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Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Proceedings International Symposium on 2nd Resource Efficiency in Pulp and Paper Technology

Crowne Plaza Hotel, Bandung, November 15-17, 2016

EDITORIAL BOARD

Hiroshi Ohi, University of Tsukuba, Japan Tanaka Ryohei, Forestry and Forest Products Research Institute, Japan Kunio Yoshikawa, Tokyo Institute of Technology, Japan Hongbin Liu, Tianjin University of Science & Technology, China Hongjie Zhang, Tianjin University of Science & Technology, Tianjin, China Zuming Lv, China Cleaner Production Center of Light Industry, China Rusli Daik, Universiti Kebangsaan Malaysia, Malaysia Leh Cheu Peng, Universiti Sains Malaysia, Malaysia Rushdan bin Ibrahim, Forest Research Institute Malaysia, Malaysia Herri Susanto, Institut Teknologi Bandung, Indonesia Subyakto, Research Center for Biomaterials-Indonesian Institute of Sciences, Indonesia Gustan Pari, Forest Product Research and Development Center, Indonesia Farah Fahma, Bogor Agricultural University, Indonesia Eko Bhakti Hardiyanto, Gadjah Mada University, Indonesia Agus Purwanto, Sebelas Maret University, Indonesia Subash Maheswari, PT. Tanjungenim Lestari Pulp and Paper, Indonesia Sari Farah Dina, Center for Research and Standardization Industry Medan, Indonesia Yusup Setiawan, Center for Pulp and Paper, Indonesia Lies Indriati, Center for Pulp and Paper, Indonesia Krisna Septiningrum, Center for Pulp and Paper, Indonesia Andri Taufick Rizaluddin, Center for Pulp and Paper, Indonesia Evi Oktavia, Center for Pulp and Paper, Indonesia Hendro Risdianto, Center for Pulp and Paper, Indonesia Syamsudin, Center for Pulp and Paper, Indonesia ------Cover Design by Nadia Ristanti Layout by Wachyudin Aziz

CENTER FOR PULP AND PAPER MINISTRY OF INDUSTRY - REPUBLIC OF INDONESIA Jalan Raya Dayeuhkolot No. 132, Bandung 40258 Indonesia

PREFACE

Proceedings of 2nd REPTech International Symposium on Resource Efficiency in Pulp and Paper Technology

After being prepared intensively by the Editorial Board consisted of distinguish Peer Reviewers, we are proudly present the Proceedings of 2nd International Symposium on Resource Efficiency in Pulp and Paper Technology (2nd REPTech). The symposium has been held in Crowne Plaza Hotel, Bandung, Indonesia during November 15-17, 2016. This symposium was organized by CENTER FOR PULP AND PAPER (CPP), Ministry of Industry, Republic of Indonesia.

In the symposium, a various effort in the development of green technology in pulp and paper production is presented including basic and fundamental aspects. This symposium also provides information on novel, and emerging industrial technologies in application of fundamental pulp and paper technology. The symposium is attended by researchers and technical experts who are active in related fields as plenary and invited speakers to enhance fruitful international exchange. In addition, research results and/or application from practitioners are also presented for more technical information and interactive discussion.

We are very much grateful to the Peer Reviewers, the esteemed members of the International Advisory Comittees and Steering Committee for their advices and guidance. The supports from the Agency for Research and Development of Industry - Ministry of Industry, Indonesian Pulp and Paper Association (IPPA), Ministry of Environment and Forestry and all parties for the successful of 2nd REPTech are truly appreciated. Thank you and hoping this proceedings provide an update information of pulp and paper technology development which are useful to the readers.

Bandung, December 2016

Dr. Andoyo Sugiharto, M.sc. The Director of CPP

TABLE OF CONTENT

Proceedings of 2nd REPTech International Symposium on Resource Efficiency in Pulp and Paper Technology

EDITORIAL BOARD i PREFACE ii TABLE OF CONTENT iii

1. Regulation Around Water Environment Related to Japanese Pulp and Paper Industry 1 Kunitaka Toyofuku*, Hiroshi Ohi *TOYOFUKU Paper Business Plan, Japan

2. Optimization of Polyester/Cellulose Carboxymethylation Process Using Pad-Bake and 11 Pad-Batch Methods Koentari Adi Soehardjo Center for Material and Technical Product, Indonesia

3. Challenges to Sustainable Wood Production of Short-Rotation Plantation Forests in Indonesia 27 Eko B. Hardiyanto Faculty of Forestry, Universitas Gadjah Mada, Indonesia

4. Assessing the Role of Ratio of Syringil/Vanillin-Based Lignin Monomers, Density of Four 35 Plantation-Forest Wood Species, and H-Factor on Delignification Intensity and Properties of Kraft Pulp Dian Anggraini Indrawan, Rossi Margareth Tampubolon, Gustan Pari, Saptadi Darmawan, Han Roliadi Center for Forest Product Research and Development, Indonesia

5. Lignin Structure of Acacia and Eucalyptus Species and Its Relation to Delignification 45 Deded S. Nawawi, Wasrin Syafii, Takuya Akiyama, Tomoya Yokoyama,Yuji Matsumoto* *The University of Tokyo, Japan

6. A Novel Paper-Based Sensor for Colorimetric and Fluorescent Detection of Copper Ions in Water 51 Yinchao Xu, Toshiharu Enomae University of Tsukuba, Japan

7. Performance of Geronggang (Cratoxylon arborescens) at 4.5 Years Old as Potential Substitute 59 for Acacia crassicarpa in Peat Land Opik Taupik Akbar, Yeni Aprianis, Eka Novriyanti Research and Development Institute for Forest Plant Fiber Technology, Indonesia

8. Kraft Pulping Condition for Sumatran Thorny Bamboo, Potential Material for Viscose Pulp 67 Kanti Rizqiania, Eka Novriyanti, Dodi Frianto Research and Development Institute for Forest Plant Fiber Technology, Indonesia

9. The Damage of Paper-Based Archives in Four Archival Institutions 73 Sari Hasanah ANRI, Indonesia

10. Energy Management in Paper Industry: A Case Study of PT X 83 Kholisul Fatikhin Serpong, Indonesia

11. Wood Supply and Sustainable Forest Management System in APRIL Group in the Province of Riau 89 Petrus Gunarso, Prayitno Goenarto APRIL, Indonesia

12. Effect of Reynolds Number at Orifice Outflow and Flotation Zone on the Fatty Acid Dispersion in 93 Correlation with Deinking Flotation Performance Trismawati, I. N. G. Wardana, Nurkholis Hamidi, Mega Nur Sasongko University of Brawijaya, Indonesia

13. Eco-friendly Material Science and Technology ― Paper in the Past, Present, and Future 99 Toshiharu Enomae University of Tsukuba, Japan

14. Comparison of Wood Properties by Age on Eucalyptus pellita Clones Using Near Infrared (NIR) 109 Spectroscopy Dian Apriyanti*, Miho Hatanaka, Ruspandi *Research and Development, Sinarmas Forestry Indonesia, Indonesia

15. Growth of Agave Germplasm in Balittas, Malang East Java 113 Parnidi, Untung Setyo Budi, Marjani Indonesian Sweetener and Fiber Crops Research Institute, Indonesia

16. Improved Oxygen Delignification by Photo Pretreatment and Additive Reinforcement: A Comparison 119 Study Between Tropical Mixed Hardwood Kraft Pulp and Oil Palm Fibre Soda-Anthraquinone Pulp Leh Cheu Peng, Chong Yin Hui, Wan Rosli Wan Daud, Mazlan Ibrahim, Poh Beng Teik Universiti Sains Malaysia, Malaysia

17. Green Technology in The Pulp Industry 127 Dominique Lachenal, Christine Chirat Grenoble INP-Pagora, France

18. Effect of Ratio Liquid Waste of Output Sedimentation and Fermentation Biogas from Palm Oil Mill 135 Effluent (POME) on Biofertilizer Production Martha Aznury, Robert Junaidi, Jaksen M. Amin, Victor Alberto Valentino Politeknik Negeri Sriwijaya, Palembang, Indonesia

19. Preparation of Polypyrrole Graphite Composite Anode Materials for Lithium Battery by Solution 143 Casting Method Jadigia Ginting, Sri Yatmani, Yustinus Purwamargapratala Pusat Sains dan Teknologi Bahan Maju-BATAN PUSPIPTEK, Indonesia

20. Development of (Recombinant) Microbial Enzymes for Application in Pulp and Paper Industry 147 Is Helianti Center for Bioindustrial Technology, Agency for Assessment and Application of Technology, Indonesia

21. The Manufacture of Bamboo Fibre Composite 155 Theresia Mutia*, Hendro Risdianto, Susi Sugesty, Teddy Kardiansyah, Henggar Hardiani *Center for Textile, Ministry of Industry, Indonesia

22. A Review: Recent Research in Paper Packaging for Food 169 Qanytah, Khaswar Syamsu, Farah Fahma, Gustan Pari* *Forest Products Research and Development Center, Indonesia

23. Study of Kinetics and Thermodynamics Adsorption Cu2+ Ion by Synthetic Zeolite From Coal Fly Ash 179 Ahmad Zakaria*, Wittri Djasmasari, Henny Rochaeni, Yustinus Purwamargapratala *AKA Bogor, Indonesia iv © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

24. Synthesis Li4Ti5O12-Sn Anode Materials as Lithium Battery with Ultrasonometry 187 Yustinus Purwamargapratala, Jadigia Ginting, Mardianto PSTBM-BATAN, Tangerang Selatan, Indonesia

25. Modified Operation of a Laboratory Refiner for Obtaining Dried Thermomechanical Pulp from 193 Non-Wood Fibers Lilik Tri Mulyantaraa, Roni Maryana, Vu Thang Do, Atanu Kumar Das, Hiroshi Ohi, Keiichi Nakamata University of Tsukuba, Japan

26. Brightness Stability of Dissolving Pulps: Effect of The Bleaching Sequence 199 Jordan Perrin, Dominique Lachenal,Christine Chirat Grenoble INP-Pagora, France

27. Building Innovation Technology Concept in Printing Industry into Printing Education 205 Muhammad Nurwahidin, Untung Basuki, Ponadi, Adi Susanto Jurusan Teknik Grafika, Politeknik Negeri Media Kreatif, Indonesia

28. Utilization of Paper Mill Rejects Waste as a Raw Material of Composite Particle Board (CPB) 215 Yusup Setiawan, Aep Surachman, Kristaufan Joko Pramono, Sri Purwati, Henggar Hardiani Center for Pulp and Paper, Indonesia

29. Study for Characterization and Drying Sludge of Paper Mill: Its Potential as Energy Source 223 Sari Farah Dina, Himsar Ambarita, Yanto Lawi, Siti Masriani Rambe Center for Research and Standardization Industry Medan, Indonesia

30. Cyan-Magenta-Yellow (CMY) Conversion Model on Digital Color Proof Printer 233 Wiwi Prastiwinarti, Noorbaity Politeknik Negeri Jakarta, Indonesia

31. The Influence of Density Tropical Hardwood to Fibers, Chemical and Pulp Quality 239 Wawan Kartiwa Haroen Center for Pulp and Paper, Indonesia

32. The Effects of Alkaline Pre-Impregnation Prior Soda-Anthraquinone Pulping on Oil Palm 249 Empty Fruit Bunch Fibre Chong Yin Hui, Ng Shi Teng, Leh Cheu Peng Universiti Sains Malaysia, Malaysia

33. Potential and Prospects of Renewable Energy Resources in Pulp and Paper Industry 257 Syamsudin Center for Pulp and Paper, Indonesia

34. Recycling of Used Beverages Cartons as An Environmental Education Program 273 Ligia Santosa, Andri Taufick Rizaluddin Center for Pulp and Paper, Indonesia

35. Utilisation of Oil Palm Biomass: Examples of Laboratory-scale and Feasibility Studies 279 Tanaka Ryohei Forestry and Forest Products Research Institute, Tsukuba, Japan

36. Research on the Preparation and Activity Test Three Types of Dry Sorbent for Flue Gas 283 Desulfurization Herri Susanto, Muhammad Arif Susetyo, David Bahrin Institut Teknologi Bandung, Indonesia

37. Pulping of Oil Palm Trunk using Environmentally Friendly Process 291 Wieke Pratiwi*, Andoyo Sugiharto, Susi Sugesty *Center for Material and Technical Product, Indonesia

38. Impact of the Internet on Consumption and Production of Paper Products 301 Kristaufan Joko Pramono, John Cameron Erasmus University of Rotterdam, The Netherlands

39. Recovery of Acetic Acid from Prehydrolysate from A Canadian Hardwood Kraft 309 Dissolving Pulp Mill Avik Khan, Laboni Ahsan, Xingye An, Baobin Wang, Jing Shen, Yonghao Ni University of New Brunswick, Canada

40. Substitution of BCTMP for Hardwood Kraft Pulp in Writing and Printing Paper 321 Lies Indriati*, Angga Kesuma, Juliani, *Center for Pulp and Paper, Indonesia

41. Isolation and Screening of Thermophilic Xylanolytic Bacterial Strains from Indonesian 327 Hot Spring Krisna Septiningrum, M. Khadafi, Saepulloh Center for Pulp and Paper, Indonesia

42. High-Yield Pulp (HYP) Application in Fiber-based Products 335 Hongbin Liu Tianjin University of Science and Technology, China

43. Biodegradable Polyesters from Biomass-Derived Monomers 337 Rusli Daik, Satriani Aga Pasma, Mohamad Yusof Maskat Universiti Kebangsaan Malaysia, Malaysia

44. Solid Fuel Production from Paper Sludge Employing Hydrothermal Treatment and its 339 Co-combustion Performance with Coal Kunio Yoshikawa, Areeprasert Chinnathan Tokyo Institute of Technology

45. Energy Efficiency Improvement and Cost Saving Opportunities for Compressed Air Supply 341 Silvy Djayanti Center of Industrial Pollution Prevention Technology

INDEX OF AUTHORS 351 LIST OF PARTICIPANT 353 DISCUSSION 360

REGULATION AROUND WATER ENVIRONMENT RELATED TO JAPANESE PULP AND PAPER INDUSTRY

Kunitaka Toyofukua1, Hiroshi Ohib2 aTOYOFUKU Paper Business Plan, the former Exective Director of Japan TAPPI, 2-19-4 Yu-karigaoka ,Sakura, chiba 285-0858, Japan bUniversity of Tsukuba, 1-1-1 Tennodai, Tsukuba Ibaraki 305-8572, Japan [email protected] [email protected]

ABSTRACT

An economy growth rate of the yearly average in Japan is less than 1% while the rate after 2000 in Indonesia is around 6%. The environmental problem called as pollution easily occurs for the period of the high growth of economy when the growth is given the priority to. Four major pollution cases occurred from 1953 through 1965 in Japan. This paper briefly reports Japanese environmental laws system. Seven pollutions to be shown in “The Environmental Basic Law” are air pollution, water pollution, soil pollution, noise, vibration, subsidence and bad smell. The laws in conjunction with the paper manufacture are (1) “Law Concerning Special Measures Dioxins”, (2) “Law Concerning Reporting, etc. of Releases to the Environment of the Specified Chemical Substance and Promoting Improvements in their Management” (so-called PRTR Law), (3) “The Basic Promotion Law of Formation Recycle Society”, (4) “Law Concerning Wastes Disposal and Public Cleaning”, (5) “Law for the Promotion of Effective Utilization of Resources”, (6) “Law for the Promotion of Sorted Collection and Recycling of Containers and Packing”. Regulation is not concentration regulation but quantity regulation of discharge of industrial waste water (effluent amount × COD, nitrogen, phosphorus) in the specific designation area. In addition, this regulation is applied to a factory with more than 50m3/day of effluent.

Keywords: environmental laws, water pollution, chemical oxygen demand, biological oxygen demand, air pollution

Introduction

Japan revived miraculously from the ruins of the end (1945) of the of World War II and was the period of the high growth of economy from 1955 through 1973. The growth rate of this period was higher than 9% a year. It was a plateau at an annual rate of 4% of growth rates until the next 1991. A growth rate of the yearly average is less than 1% after a bubble burst of 1991. The economic growth rate after 2000 in Indonesia is around 6%. The environmental problem to be said to be pollution is easy to occur for the period of the high growth of economy when economic growth is given priority to. Four major pollution cases occurred from 1953 through 1965 in Japan, and the responsibility of the cause outbreak company was investigated strictly. In addition, the conflict with fishermen by the effluent of the pulp mill in Tokyo, Edogawa occurred in 1958, and a nasty smell fish problem by the factory effluent in Mie, Yokkaichi-shi occurred in 1963. Furthermore, the issue of thick sludge (Hedoro) with the paper sludge included in the effluent of the paper mill in fishing port of Shizuoka, Tagonoura occurred in 1967. “Regulation Law such as Factory Effluent” and “Water Conservation Law of the Public Waters” were established in 1958 by the issue of effluent of the pulp mill of Edogawa. This leads to Water Pollution Control Law established in 1970. “The Environmental Pollution Prevention Basic Law” (existing “The Environmental Basic Law”) was established in 1967 by many pollution issues such as four major pollution cases. Furthermore, it was established “the Air Pollution Control Law” and “Noise Regulation Law” in 1968. Laws for prevention of pollution occurrence were established rapidly with “the Offensive Odor Control Law” in 1971. In 1971, the Environmental Agency (it becomes Ministry of the Environment in 2001) was established as the government office where was specialized in environment.

Figure 1 System of Japanese Environmental Laws

System of Japanese Environmental Laws

Japanese environmental laws system is showed in Fig.1. Seven pollutions to be shown in “The Environmental Basic Law” are air pollution, water pollution, soil pollution, noise, vibration, subsidence and bad smell. For others, laws in conjunction with the paper manufacture are: “Law Concerning special measures Dioxins” “Law Concerning Reporting, etc. of Releases to the Environment of the Specified Chemical Substance and Promoting Improvements in Their Management” (so-called PRTR Law) “The Basic Promotion Law of Formation Recycle Society” “Law Concerning Wastes Disposal and Public Cleaning” “Law for the Promotion of Effective Utilization of Resources” “Law for the Promotion of Sorted Collection and Recycling of Containers and Packing

Furthermore, as duties such as companies, it is imposed on setting of the prevention of pollution manager in the specific factory (most paper mills correspond) and promoting environmental report and the environmental education. In addition, as the standard that it is desirable to be maintained on protection of the health of the person and maintenance of the living environment, an environmental standard is determined. The environmental standard is the target that how much should keep the air, water, soil, noise, etc.. In addition, it is “the standard that it is desirable to be maintained”, and the environmental standard is an administrative policy objective. This is going to plan the achievement as the aim that it is desirable to be maintained as the lowest to maintain the health of the person more positively.

Environmental Laws to be Related to The Paper Manufacture

“Water Pollution Control Law”

“Water Pollution Control Law” regulates the effluent such as factories. Fig. 2 shows the main mill location of pulp and paper industry of Japan. The water for industrial use of the pulp and paper

2 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 industry is used mainly from the river. As Japan are surrounded in the sea like Indonesia, the effluent is discharged into river or sea area. As for the effluent regulation of the “Water Pollution Control Law”, density regulation is a basic to discharge into a public water area (general river and sea area), but in the specific designation area, the effluent is regulated in both density and quantity. Specific designation area is Tokyo Bay, Ise Bay and Seto Inland Sea, these three areas are closed sea area and correspond to it. Furthermore, the rivers flowing into these sea area correspond to it. Fig. 3 shows specific designation area. It is specific workplace to receive effluent regulation. Specific workplace is workplace having specific facilities discharging a toxic substance (all paper mills correspond). Furthermore, the workplace with more than 50 m3/day of interval discharge catches the regulation in the element related to environmental living (BOD, COD) on a day. Japanese effluent regulation (density and quantity) system is shown in Fig. 4.

Figure 2 Location of Main Mill of Paper Industry (●)

Figure 3 Specific Designation Area

Figure 4 Japanese Effluent Regulation (Concentration and Quantity) System

Regulation Discharge into General River, Lake and Sea

(1) Environmental Standard

The environmental standard of the river is with less than 1 mg/L of BOD. The environmental standard of the sea area is with less than 2 mg/L of COD. The environmental standard is accomplished at about 80% of points.

(2) Uniform Standard

Other than pH, SS, in the case of river discharge, BOD level is regulated. On the other hand, in the case of the discharge to a sea area and a lake, COD level (Mn) is regulated. This difference is a traditional reason from the past. Each Uniform Standard of (BOD and COD) that country regulation is 160 mg/L. It is 120 mg/L on the day interval average. However, there is the addition of the regulation level in the regulations and agreements. The regulation level is gradually added in the agreement with the prefecture and with the city next step. It takes severe regulation depending on a local area. Those examples are shown. a. In the Oji Paper Co., Ltd. Kasugai mill in Aichi, BOD (day interval average) is regulated to 70 mg/L in the prefecture regulations. Furthermore, it is regulated to 45 mg/L in the agreement with the city. b. In the Hokuetsu Kishu Paper Co., Ltd. Niigata mill in Niigata, BOD (day interval average) is regulated to 40 mg/L in the prefecture regulations. Furthermore, it is regulated to 24 mg/L in the agreement with the city. c. In KITAKAMI PAPER Co., Ltd. in Iwate, BOD is regulated to 40 mg/L in the agreement with the city. d. In the Lintec Corp. Kumagaya mill in Saitama, BOD (day interval average) is regulated to 20 mg/L in the agreement with the city. e. In the Lintec Corp. Mishima mill in Ehime, COD (day interval average) is regulated to 65 mg/L in the agreement with the prefecture. f. In the Daio Paper Corp. Mishima mill in Ehime, COD (day interval average) is regulated to 70 mg/L in the agreement with the prefecture. g. In the Oji Paper Co., Ltd. Tomakomai mill in Hokkaido COD is regulated to up to 160 mg/L and regulated 120 mg/L on interval average on a day Only in uniform standard of the country,. h. In the Oji Material Co., Ltd. Edogawa mill of Tokyo, BOD (maximum) is regulated to 20 mg/L in the capital regulations. Furthermore, It is regulated to 10 mg/L, very severe value in a sewer special exemption rule.

Total Amount Regulation of COD in The Specific Designated Area (Closed Sea Area)

1. Establishment of the law

The law was entered into force in June, 1979. to improve the quality of the water in the closed sea area (Tokyo Bay, Ise Bay, Seto Inland Sea).

2. Present status

A change of the quantity of COD load in the closed sea area; Tokyo Bay, Ise Bay, Seto Inland Sea, Osaka Bay (a part of Seto Inland Sea) is shown in Fig. 5. In addition, the change of the COD level with the decrease in quantity of COD load is shown in Fig. 6. Including other systems, the quantity of COD load largely decreases both in life system and industrial system. However, a reduction effort will be continued more as the environmental standard has not been yet accomplished. It is understood from Fig. 6. A country does not take severe regulation at a stroke like China in Japan, and the person concerned talks, and a method to gradually push forward regulation is often adopted as far as it is possible. Regulation is not density regulation but quantity regulation of discharge of industrial waste water (effluent amount × COD, nitrogen, phosphorus). In addition, this regulation is applied to a factory with more than 50 m3/ day of effluent.

Figure 5 Change of The Quantity of COD Load (t/day) in the Closed Sea Area

Figure 6 Change of the COD Level with The Decrease in Quantity of COD Load

Correspondence of The Pulp and Paper Industry

The situation of the reduction in each next reduction plan in the pulp and paper mill in the closed sea area is exemplified in Table 1. It is described the main capital spending carried out newly later to perform these reduction. A mill, B mill, C mill are results values, and D mill is a regulation values.

Table1 Results Example of The COD Discharge Decrease of The Closing Practices 3 Sea Area (t/ day)

Tokyo Bay Ise Bay Seto Island Sea Seto Island Sea ( A Mill ) ( B Mill ) ( C Mill ) ( D Mill ) First (1984) - 12.3 30.2 20.8 Second (1989) 2.1 10.4 27.8 20.2 Third (1994) - 8.7 22.0 18.1 Fourth (1999) 0.67 8.5 15.8 17.9 Fifth (2004) 0.32 8.0 14.0 Sixth (2008) 0.26 8.1 14.2 • The sixth lists data of 2008 • The main capital spending content is as follows. -- Tokyo Bay A mill: Reinforcement of effluent treatment such as activated sludge and catalytic oxidation; switch pulp to wastepaper pulp by CGP (1994): stopped two m/c (2000). -- Ise Bay B mill: KP generating source measures; oxygen bleaching facilities setting; reinforcement of creature film filtration facilities; reinforcement of cohesion deposition facilities; pulp switch to ECF. -- Seto Inland Sea C mill: KP generating source measures; oxygen bleaching facilities setting; reinforcement of activated sludge facilities; anaerobic waste water treatment equipment setting; reinforcement of cohesion deposition facilities; pulp switch to ECF. -- Seto Inland Sea D mill: KP generating source measures; oxygen bleaching facilities setting; reinforcement of activated sludge facilities and cohesion deposition facilities; anaerobic waste water treatment equipment and activated sludge facilities newly setting; pulp switch to ECF.

Table 2 Quantity of COD Reduction and Capital Spending Amount of Money of That Purpose

Tokyo Bay Ise Bay Seto Island Sea Seto Island Sea ( A Mill ) ( B Mill ) ( C Mill ) ( D Mill ) Quantity of COD reduction (t/day 1.8 4.3 16.2 2.9 Reduction rate for 1988 88% decrease 35% decrease 54% decrease 15% decrease Total facilities investment 26 (hundred million Japanese yen) 152 335 76 The 79-09 year • Table 1 and 2 are quoted from a document in the fifth total amount reduction specialized committee in Nov. 2009

Dioxin in a Closed Sea Area

Measuring a discharge of the dioxin from designated facilities and reporting, it was established because dioxin was included in flue gas and the burned residue of the garbage incineration site. Bleaching facilities were appointed in the pulp and paper industry. Pollution of the Baltic Sea in Fig. 7 is famous about the pollution with the dioxin (DXN) in a closed sea area. The pollution reaches maximum really from the 1960s through 70 and decreases afterwards. One of the causes includes the drainage like the pulp whitener. There was much consumption of chlorine at the time of the bleaching in Sweden and Finland at the time. Fortunately, such a thing did not happen in closed sea area in Japan. Because oxygen bleaching was introduced in front of a chlorine step to reduce an adsorbable chlorine compound (AOX) in Japan, there was largely less consumption of chlorine than North Europe. The ECF and TCF bleaching process without chlorine is used worldwide now.

Figure 7 Baltic Sea and Neighboring Areas

Table 3 Change of The Dioxin Density in Sea Crow Egg of Baltic Sea

Year 1969 1980 1992 Dioxin (ppt) 3,500 2,300 1,000 PCB (ppt) 20,000 12,000 5,000

Use of Water of Pulp and Paper Industry

Japanese annual average precipitation is at the same level as it of Indonesia (1,706 mm) at 1,718 mm (as for the world average 880 mm), and there is much in comparison with Chinese 630 mm more. Therefore the limit of the water consumption is not severe. Of course we must always keep saving water in mind that we do not use the resources idly, but the limitation is not severe unless it becomes the extreme shortage of water. The pulp and paper mill often uses water from the river, but often has the water intake right for a long time. A scramble with the agriculture water rarely occurs at shortage of water at growth time of the rice. Water consumption per 1 ton of paper is shown in Fig. 8. There is not a change at a little over 80 m3 recently.

Figure 8 Change of The New Water Consumption Per 1 Ton of Paper Year

“Air Pollution Control Law”

This law regulates exhaust gas and soot particle from a factory. 1. List of harmful air pollution material, approach materials given priority (May, 1996) a. Material which may correspond to a harmful air pollution material (234 materials) b. A list of priority approach materials: The material that it is thought that a health risk is high: Mercury and mercury compound, chloroform, etc. (22 materials) 2. Correspondence to exhaust gas and soot particle regulation a. SOx measures, Use of fuel with low content sulfur; the flue gas desulfurization equipment setting supports with regard to the scale of the factory and a local characteristic. b. NOx measures; adoption of the low NOx burner; two steps of combustion adoption, etc. c. Soot particle measures; the soot particle which occurred from a recovery boiler became the problem at one time, but it was settled by the reinforcement of a wet process scrubber and the electrostatic precipitator, etc. 3. Chloroform reduction When chlorine is used in a bleaching process of the KP pulp, chloroform is by-produced. In a bleaching process, adoption of ECF and TCF without chlorine use can approximately completely prevent by-producing chloroform. Japanese papermaker almost switches it to ECF and TCF and does not use chlorine.

“Offensive Odor Control Law”

This law regulates the bad smell around the factory.The odor of sulfur compounds such as the methyl mercaptan in the KP process of manufacture is regulated.The measurement of the odor index (sense of smell) by the sensory of the person is effective for the thing which feels an odor with the very small amount

“Waste Management and Public Cleaning Law”

1. This law regulates disposal of waste generating in a factory. a. Manifesto system, prohibition of incineration in the backyard b. Preventive measures against illegal dumping, promotion of recycling 2. Measures concerning waste disposal a. It is sludge to occupy most of the waste going out of the paper mill. In addition, small piece of wood and waste plastic are exhausted. b. The discharges of the sludge increase by increase of the wastepaper, but the most are incinerated, and it is used as energy of the mill in some cases. In addition, the left combustion ash is made good use of as cement raw materials and roadbed materials. c. It is a target that pulp and paper industry reduces quantity of last disposal to 350,000 tons by 2015, but the last disposal quantity has already decreased to 190,000 tons in 2013 and falls it approximately 86% more in comparison with 1990.

“Waste Management and Public Cleaning Law”

c. It is a target that pulp and paper industry reduces quantity of last disposal to 350,000 tons by 2015, but the last disposal quantity has already decreased to 190,000 tons in 2013 and falls it approximately 86% more in comparison with 1990.

Figure 9 Chang of Quantity of Waste Last Disposal (Quantity of Reclamation) (Source : Japan Paper Association HP data)

“Pollutant Release and Transfer Register” (PRTR)

This is a system based on the law (“Law for Concerning Reporting, etc. of Releases to the Environment of Specific Chemical Substances and Promoting Improvements in their Management”). When business operator exhausts or transfer designated chemical substance, he grasps the quantity and has a duty to tell the country. Country publishes count data. Anyone can read data on the Internet. By publication, incentive of the reduction acts on business operator.

“Law Concerning Maintenance of Pollution Control Organization in Specified Factory” (“Pollution Control Manager Law”)

“Pollution Control Manager Law” thought to be Japan’s original system was promulgated in 1971 in the next year of the “Water Pollution Control Law”. The purpose is maintenance of pollution control organization in specified factory by the election of a pollution control superviser and various pollution control manager, and prevent an environmental pollution. A qualified person (including an authorized class) is approximately 500,000 people in the whole country. This law is not a so-called regulation law such as “Water Pollution Control Law” or “Air Pollution Control Law”, but is the environmental law that plays a big role in environmental improvement of Japan. Condition of the specific factory: a. The air: Soot generating facilities (more than exhaust gas 10,000 Nm3/h) b. The water: Waste water discharging facilities (more than waste water 10,000 m3/day) c. DXN: KP, SP bleaching facilities (only in the case of an incinerator, unnecessary)

Introduction of the OJI PAPER Nantung mill in China (Jiangsu Oji Paper Co., Ltd.)

It is consistency mill from pulp to paper latest built in the river bank of the Yangtze River of Nanchung City of China. Unique waste water treatment is carried out. Summary of the mill: a. Pulp production 470,000 tons / year (the half quantity markets it) b. Coated paper production 300,000 tons / year c. Bleaching process: oxygen - ozone - chlorine dioxide - hydrogen peroxide

The process of waste water treatment is shown in Fig.10. As China government does not admit discharging pulp waste water into Yangtze River, the cleaned effluent (BOD10 ppm) by the process

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 9 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 until ozone treatment is purified enough to a drinkable level with special water treatment equipment of Nanchung City government, and it is used as drinking water in the district of the neighborhood. An article of Xinhua News Agency which introduced this system.

Figure 10 Process of Waste Water Treatment

OPTIMIZATION OF POLYESTER/CELLULOSE CARBOXYMETHYLATION PROCESS USING PAD-BAKE AND PAD- BATCH METHODS

Koentari Adi Soehardjo Center for Material and Technical Product, Jl Sangkuriang 14 Bandung 40135,Indonesia [email protected]

ABSTRACT

In the previous studies experiments on Carboxymethylation process optimization of polyester/ cellulose with Pad-Bake method has been conducted. The optimum condition was achieved using sodium chloracetate 4N, sodium hydroxide 8N and baking temperature of 120oC. The process needs a big investment because using thermosol machine that expensive and needs high energy. In order to be implemented in small scale industries, further research has been conducted by varying the same concentrations of sodium hydroxide and sodium chloracetate using the Pad-Batch method at room temperature (28oC) for 2, 4, 6, 8 and 10 hours. The experimental results were tested for polyester weight reduction, cellulose structure with an infrared spectrum using a solution of methylene blue, moisture absorption, tensile strength, crease recovery, dimensional stability and stiffness of the fabric. The optimum conditions of the two impregnation method are compared and the optimum conditions achieved in the use of pad-batch impregnation method, the use of 3N sodium chloracetate 8N sodium hydroxide and 2 hours of impregnation time at room temperature (28oC).The result showed that 7.5% weight reduction in the polyester, 94.32% absorption of methylene blue dye, 4.7% or increase 56.7% absorption of moisture, 25 kg or decrease 9.1%) tensile strength the warp direction of tensile strength and 17 , 9 kg or decrease 30.9% weft direction of tensile strength , 1580or increase 41.1% warp direction of crease recovery and in 1490 or increase 36.7% weft direction, of crease recovery, 1.02% or decrease 25% Warp direction of fabric dimensional stability and 0.44% or decrease 30.9% weft direction of fabric dimensional stability, 49 mg.cm or decrease 34.67% warp direction of fabric stiffness and 22 mg.cm or decrease 52.17% weft direction of fabric stiffness were obtained. In addition the process of polyester/cellulose Carboxymethylation using Pad Batch methods, can be done by small and medium industries because, the manufacture do not need expensive equipment investment, energy saving and lower cost for production.

Keywords: carboxymethylation, polyester/cellulose, sodium chloracetate, sodium hydroxide, pad-bake, pad-batch

Introduction

This study is a continuation of previous studies that is polyester /cellulose fabric modification using pad-bake method carboxymethylation process, which has obtained the optimal condition. The optimal condition can improve the quality of polyester/cellulose fabric by using 4N sodium chloracetate, 8N sodium hydroxide and baking temperature of 120oC. Test results showed that: 0.45% weight reduction, 94.32% methylene blue dyed absorption, 4.44% moisture regain, 21.50 kg warp direction of tensile strength and 16 kg weft direction of tensile strength, 1480 warp directions of crease recovery and 1450 weft direction of crease recovery, 0.14% warp direction of fabric dimensional stability and 0.17 of weft, 64 mg.cm warp direction of fabric dimensional stability, and 39 mg.cm of weft direction of fabric dimensional stability [1]. Processes mentioned above requires a huge investment, considering that the process carboxymethylation fabric of polyester/cellulose can be done by small and medium industries, therefore it is necessary to do further research that quality improvement Polyester/Cellulose fabric through a carboxymethylation process by comparing the pad-bake method that has previously been done before with pad-batch method, at advanced research that will be done. The purpose of this advanced research is to improve the quality of polyester cellulose fabric by overcoming the shortage of each fiber. It is also to find optimization carboxymethylation process on the use of sodium chloracetate and sodium hydroxide

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 11 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 through the comparison fixation method between pad-baking that need investment in machinery and energy with high costs compared with pad batching methods under squeeze impregnation, where the fixation process just rolled, rotated at room temperature (batching time), investment is quite simple with no energy for heating so that it can be done by small and medium industries. Polyester/cellulose (65/35%) fabric had lower moisture regains so it is not comfortable to wear. One way to overcome that is lacking by modifying the Carboxymethyl cellulose process to use sodium chloracetate and sodium hydroxide [2,5].The presence of sodium hydroxide will erode and diluting polyester fabric so that the handle of fabric will be softer [3,4]. Chemical modification by means carboxymethylation is one type of etherification process aimed at cellulose groups [5,6]. In this experiment, optimization process using pad batching method was carried out. The fabric impregnation on sodium chloracetate solution and then impregnation on sodium hydroxide solution with wet pick up 80%, rolled, rotated at room temperature in definite time of a particular fixation. The carboxymethylation process conditions will affect the degree of substitution of hydroxyl groups on the anhydroglucose unit with carboxymethyl group. [6,7] The magnitude of the degree of substitution obtained will determine the physical properties of cellulose fibers include tensile strength, crease recovery, dimensional stability and moisture regain. The presence of sodium hydroxide in addition is cellulose swelling and will hydrolyze the polyester because erosion resulted in reducing weight. The process of erosion and a reduction in weight resulted fabric handle becomes softer. Erosion polyester fibers by sodium hydroxide allows the addition of OH end groups of ester hydrolysis can increase the degree of substitution of carboxymethyl [3,4]. The carboxymethylation cellulose (see Figure 1) is a derivative of cellulose formed from alkaline and chloracetate. The chemical structure of carboxymethyl cellulose based on β- (1,4) -D-glucopyranose polymer of cellulose difference in treatment will lead to different degrees of substitution, but in general, changes in the derivatives per monomer unit of about 0.6 to 0.95. The carboxymethyl cellulose molecule structure is as follows [9]

Figure 1 The Molecular Structure of Carboxymethyl cellulose

The presence of sodium hydroxide will degrade cellulose molecules that are means degree of polymerization will decline, resulting in decreased tensile strength of the fiber. The mechanism of cellulose fiber degradations can be seen in Figure 2. [12] Oxygen will get in between the chains and the amorphous molecules into the micelle. Effect of primary valence bonds between oxygen ions and the fiber is greater than the second valence bond molecular chains. Consequently valence bonds both molecular chain breaking, finally individual molecular chains are separated from each other [12]. The occurrence of chain termination is less than perfect, still bound at some point cause the chain to change the way, this situation causes the fiber orientation to be reduced and consequently the tensile strength decrease. In the Carboxymethylation process, where the use of these types of reagents, each of which is acidic and alkaline often results in a decrease in the tensile strength of the fabric, due to the breakdown or degradation of each fiber [13]. Therefore, it is necessary to find the optimal conditions that do not cause the fiber damage, either polyester or cellulose fibers or in case of any damage as small as possible. 12 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Figure 2. Chain Termination of Cellulose Molecular by Sodium Hydroxide

Further research that will be done is the carboxymethylation process method of the pad-batch method. The fabrics is impregnation in sodium chloracetate solution corresponding variations: 2N, 3N and 4N and impregnation in 6N, 8N, 10N and 12 N sodium hydroxide solution , wet pick up 80%, rolled and rotated process at room temperature (28oC). with batching time variations of: 2 hours, 4 hours, 6 hours, 8 hours and 10 hours, respectively. The result was then washed, dried, tested, evaluation and analysis of data.

Materials and Method

Materials and Equipment

Polyester/cellulose (65%/35%) fabrics with construction: woven: plain; Warp Yarn No Tex: 13.43 and Weft Yarn No Tex 14.00, Pick Density (Number of Yarn/cm): warp density: 35 and weft density: 2 24; the dry weight of fabric/m 78.798 grams Sodium chloracetate (CH2ClCOONa) as etherification substance, sodium hydroxide (NaOH) as sodium cellulose substances forming and reducing weight of polyester. Carboxymethylation process experiment used laboratory scale pad-batch machine

Research Methods

Preparation:

Raw material of Polyester/cellulose fabric was scouring and starch removing, cut according to the testing size needs, then prepared for Carboxymethylation processing. Solution preparation for Carboxymethylation process: Sodium Chloracetate solution: 2 N, 3N, and 4N and Sodium Hydroxide solution: 6N, 8N, 10N and 12N.

Carboxymethylation process Pad –Batching methods

The fabric impregnation in sodium chloracetate solution corresponding variations: 2N, 3N and 4N impregnation sodium hydroxide solution 6N, 8N, 10N and 12 N with wet pick up 80%, rolled, and

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 13 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 rotated in batching process at room temperature (28oC). with time variations: 2 hours, 4 hours, 6 hours, 8 hours, 10 hours. The result was washed, dried, tested evaluation and analysis of the data, to find optimal conditions. Furthermore, the results were compared to the optimal conditions for obtained from the results carboxymethylation process Pad-baking method: Polyester Cellulose Fabric impregnation in sodium chloracetate solution corresponding variations: 2N, 3N and 4N and impregnation in sodium hydroxide solution 6N, 8N, 10N and 12N wet pick up 80 %, rolled, rotated at temperature variation: 120oC, 130oC, 140oC, 150oC, 160oC within 5 minutes. The result was washed, dried, tested. The optimal conditions have been obtained in previous studies that the use of 4N sodium chloracetate, 8N sodium hydroxide and baking temperature of 120oC [1].

Testing

• Fabrics Construction are woven type, Yarn Number (Tex), Pick density (number of yarn/cm): warp density and Weft Density, and dry weight of the fabric. • Infrared spectrum: FTIR characterization is performed to determine the formation of carboxymethyl groups and carboxyl expressed as a carbonyl functional group and changes the intensity of the hydroxyl functional groups of polyester. • The content of polyesters (composition): According to SNI 08-0264-89 / ISO: 1833: 2011[15] • Moisture Content /Moisture Regain: According to SNI 08-0263-1989 [16] • Tensile Strength: According to ISO 0276 – 2009 [17] • Crease Recovery: According to ISO 2313: 2011 [18] • Dimensional Stability: According to ISO 5077 – 2011 [19] • Stiffness: According to SNI 08 - 0314 - 1989 [20]

Results and Discussion

1. Identification of Carboxymethyl, Carboxyl and Carbonyl Structure Using Infra Red Spectrum.

Characteristics structure tested using FTIR has been done on cellulosic fabrics blanks/before carboxymethylation process and after Carboxymethylation process in optimal conditions. At polyester fabric and polyester/cellulose fabric 65%/35% was not necessary to be tested because the polyester has a peak absorption at carbonyl group (C = 0) which absorbs strongly in λ 1700 cm-1, so that the curves have a polyester group can not be used for determine the effect Carboxymethylation. Spectrograms generated curve turns that cause the infrared absorption peak at λ area 3300 cm-1 is a hydroxyl group in 1700 cm-1 is an area of carboxyl groups. Testing Results infrared spectrum from cellulose fabric blank (before) and after Carboxymethylation optimal conditions can be seen in Figures 3 and 4. From spectrograms on cellulose fabric which has Carboxymethylation in optimal condition indicated there are additional absorption peak at a wavelength of 1720 cm-1 and 840 cm-1, group carbonyl of the aldehyde group of compounds ketones having absorption peaks at wavelengths between 1720 cm-1 to 1740 cm-1[8]. Carboxymethylation process is a process of substitution of carboxymethyl groups to replace hydroxyl groups on the cellulose fibers. With the change of the spectrum of infrared note of wavelengths indicated by the strain group C = O in the presence of absorption peak at a wavelength of 1720 cm-1 at cellulose which Carboxymethylation can be said that there has been a substitution of the hydroxyl group with a group carboxymethyl on cellulosic fabrics . In the area of 3300 cm-1 good fabric or fabric at the beginning of the modification gives absorption peaks. This occurs because not all the hydroxyl groups experienced Carboxymethylation process, so that other hydroxyl groups still have absorption peaks. Thus the chemical modification of the fabric through a process of Carboxymethylation partial has occurred [8,10],

Figure 3. Infrared Spectrum of Cellulose Fabric (Blanks)

Figure 4. Infrared Spectrum of Cellulose Fabric in Optimal Carboxymethylation Condition

2. The Methylene Blue Absorpted by the Carboxyl Group

To determine the presence of carboxyl groups in the cellulose chain is doing by dyeing process with methylene blue dyestuff, this solution does not have an affinity for pure cellulose, but with the formation of carboxylate groups causing the cellulose can absorb methylene blue dyes [14] In Table 1 show that the entire treatment variations stain with methylene blue solution. It is identified that the hydroxyl group substitution by carboxymethyl groups have taken place, while the amount of dye that is absorbed depends on the amount of carboxymethyl group substitution that occurs in each treatment variations.

Table 1. The Absorption of Methylene Blue Dyestuff (%)

Batching Sodium Hydroxide Sodium Chloracetate (N) (Hours) (N) 2 3 4 6 92.23 93.52 93.97 8 93.15 94.32 94.76 2 10 94.01 95.20 95.61 12 94.19 95.37 95.73 6 92.44 93.96 94.04 8 93.16 94.43 95.33 4 10 94.09 95.77 96.24 12 94.27 95.82 96.27 6 92.66 94.00 94.34 8 93.21 95.44 95.74 6 10 94.40 95.87 96.52 12 94.53 95.95 96.61 6 92.76 94.32 94.37 8 93.27 95.44 95.82 8 10 94.62 95.96 97.56 12 94.66 96.01 97.72 6 93.18. 94.39 94.64 8 94.43 95.77 96.02 10 10 94.89 96.22 97.81 12 94.91 96.29 97.94 Raw material staining

From the test results shown that the concentration of sodium chloracetate up to 3N, sodium hydroxide to 8N and batching time up to 2 hours, with the use of higher concentration of sodium hydroxide and the longer time of batching in a certain extent, the absorption of methylene blue dye is higher. The amount of the dye absorbed on cellulose, not only indicate carboxymethylation reactions that occur, but also showed the presence of cellulose damage. Degradation of cellulose molecules in the presence of oxygen in sodium hydroxide (see figure 2), will enter the molecular chains of cellulose on the bond between the hydrogen and carbon atoms in position 1 glucose groups, consequently glucose circle will open and a hydrogen atom at position 1 will migration to the carbon atom at position 5, forming acid group at position 1 but remain bound to the glucose group next to it. The presence of sodium ions in solution resulting ester hydrolyzed form,thus breaking the ester bond resulting in damage oxycellulose (figure 2) which also absorb the methylene blue dyes. [1]

3. Tensile Strength

The Results of tensile strength warp and weft direction fabric can be seen in table 2. The test results shown that the Carboxymethylation process occurs the shrinkage of fabric, that means pick of yarn/cm warp and weft of fabric increased thereby increasing the tensile strength of the fabric, the highest tensile strength test results obtained on the use of a combination of 3N chloroacetate and 8N sodium hydroxide and batching time of 2 hours. The result showed: Warp direction of tensile strength 25 kg or increase of 8.2% from the beginning and the weft direction of tensile strength fabric 17.9 kg or increase 4.1%. The analysis of variances turns out, that the variations of sodium hydroxide, sodium chloroacetate concentration and batching time process have effected on the tensile strength of the fabric. At the optimal conditions, the increasing of tensile strength due to cellulose fibers swollen and helps substitution reaction of carboxymethylation, the fiber damage is smaller compared than other conditions.

Table 2. Tensile Strength of Warp and Weft Direction Fabric (Kg)

Sodium Sodium Chloracetate (N) Batching Hydroxide Warp Direction (kg) Weft Direction (kg) (hours) (N) 2 3 4 2 3 4 6 20.50 21.41 20.20 15.17 17.25 16.75 8 23.00 25.00 22.33 17.16 17.90 17.32 2 10 20.91 22.75 17.83 17.00 17.70 14.25 12 19.50 21.42 16.66 16.00 17.66 13.58 6 20.00 20.86 19.80 15.00 16.17 16.00 8 21.30 22.00 21.75 17.08 17.75 16.92 4 10 18.60 20.95 15.50 16.40 16.75 14.24 12 17.56 19.55 15.50 15.07 16.00 13.15 6 19.83 20.00 19.50 14.75 14.87 14.25 8 20.66 21.83 20.20 16.75 16.91 16.80 6 10 18.00 19.44 14.41 16.25 16.50 14.00 12 16.60 19.40 13.64 13.47 15.50 13.00 6 19.00 19.75 19.10 13.50 14.67 13.30 8 20.21 21.75 20.00 16.50 16.50 16.05 8 10 17.25 19.06 13.64 15.00 16.32 13.18 12 16.14 18.00 13.00 13.00 15.42 12.83 6 17.17 19.30 18.50 13.42 14.33 12.95 8 20.17 20.25 18.86 16.41 16.10 15.55 10 10 17.00 18.75 11.66 14.50 16.00 12.14 12 14.87 17.93 11.66 12.00 15.00 11.25 Raw material 21.15 17,20

The increasing of tensile strength after carboxymethylation process caused by the increase of the hydrogen bond and Van der walls bond, that affecting to shrinkage of fabric dimensional. , consequently pick of fabric density (warp density and weft density) will be increased [2, 12]. On the use of sodium chloracetate, the longer of batching time tensile strength tends decreased. This is because the use of sodium chloracetate which is an acid salt, cellulose can be damaged by acid is forming hydrocellulose and will be produced a shorter molecular chain. The outbreak of some glucosidal bond between units, will cause hydrolysis of cellulose, reduced unit of glucose in the chain of cellulose can occur tensile strength decrease. The sodium hydroxide is a strong alkaline, the erosion of polyester fabric turns out that the tensile strength decline and loosed the weight. At the pore where the hydrolysis happen, the polymeric molecules are not compact, molecular bonds weakened so that the tensile strength of the fabric will decreases [3],

4. Polyester Weight Reduction

The results of weight reduction polyester can be seen in Table 3.The test results shown that the use greater concentration of sodium hydroxide and the longer batching time to a certain extent occurs that weight reduction increases. The greater concentration of sodium chloracetate usage in a certain extent, the weight reduction polyester reduced, because sodium chloracetate will inhibit erosion of polyester fibers by sodium hydroxide [3, 4]. From the analysis of variance turns out that the concentration of sodium hydroxide, sodium chloroacetate concentration, and batching time effected on the test results of weight reduction

Table 3. Polyester Weight Reduction (%)

Batching Sodium Hydroxide Sodium Chloracetate (N) (Hours) (N) 2 3 4 6 7,4 4,6 4,3 8 8,4 7,5 4,6 2 10 8,9 8,7 8,4 12 9,2 9,0 8,7 6 8,6 7,9 3,9 8 8,7 7,9 8,1 4 10 9,3 9,0 9,4 12 10,2 9,4 9,4 6 8,9 8,2 7,3 8 9,5 9,4 9,0 6 10 11,2 10,0 10,2 12 11,9 10,9 10,6 6 8,9 8,4 7,5 8 10,9 9,7 9,7 8 10 14,4 10,2 10,9 12 14,7 11,4 11,2 6 9,9 10,3 8,5 8 13,8 10,8 10,3 10 10 15,9 13,8 11,1 12 16,2 14,2 11,7 Raw material 0,00

The magnitude of weight reduction depends on the duration of batching, abrasion (hydrolysis) the fiber surface by sodium hydroxide, the dissolution process leading to the fiber core, the longer of batching time, the greater of polyester erosion, so that the content of the polyester is reduced. The greater of sodium hydroxide concentration, then the bond molecular chains breaking are accompanied by dissolution in the greater part of the fiber surface, resulting in the fiber cross section of the smaller (thinner) so that the handle would be a softer fabric. Sodium chloroacetate is an acidic salt; polyester has a good resistance to acids. The impregnation polyester fabric in sodium chloroacetate will inhibited the erosion process caused by the sodium hydroxide. As a result, the higher the of sodium chloracetate used the erosion will be reduce. .The test results shown that the smallest weight reduction of the polyester obtained at combination treatment 4N sodium chloracetate, 6N sodium hydroxide and batching time of 2 hours which is 4.3% reducing weight, while the largest weight reduction of the polyester at the combined treatment of 2N sodium chloroacetate, 12N sodium hydroxide and 10 hours batching time is equal to 16.2% reducing weight. This is happen because the resulting of smaller reducing weight of fabric, carboxymethylation processed with the solution of 4N sodium chloroasetat further with 6 N sodium hydroxide 6N, this fabric has a pH of atmospheric more acidic when compared with the combination of 2N sodium chloracetate and 12 N sodium hydroxide, more acidic atmosphere prevents an erosion, because the polyester fiber is resistant to acids. So that, the weight reduction is becomes smaller. As comparison, it has also been demonstrated in previous studies [1] at Polyester Cellulose Carboxymethylation process using Pad Bake methods is the smallest weight reduction of polyester was achieved in the use of 4N sodium chloracetate, 6 N sodium hydroxide and 120oC temperature process.

5. Moisture Regains

The results of moisture regain testing can be seen in Table 4. The percentage of moisture regain in polyester cellulose fabric depends on the amount of cellulose component, the greater the cellulose components of the greater value of moisture regain. This is happen because the polyester is hydrophobic and cellulose is hydrophilic and this phenomenon related to the dimensional stability and crease recovery of the fabric properties. To increase the moisture regain of the minimum cellulose component necessary to change the physical and chemical structure with increase the absorption properties of cellulose to water. Therefore the process carboxymethyl cellulose can improve moisture regains value. Improvements moisture regains the cellulose polyester fabric depends not only on the reduction of polyester due to strong alkaline usage , but also depends on the number of carboxymethyl groups that exist and changes the cellulose molecular structure is the following: Table 4 showa the moisture regains carboximethylation processes test results, it can be seen that the process can increase the moisture regain of polyester cellulose fabric, the use of higher concentrations of sodium hydroxide up to 8N and sodium chloroacetate until 3N will be increasing the moisture regain. At the higher concentrations the moisture regains will be decreased, the increasing moisture regain is possible due to the reduction of the content of polyester is being eroded by the sodium hydroxide. The use of strong alkaline cellulose will cause a decrease in the degree of crystalline of the cellulose fibers, when the use of alkali concentration not to damage the cellulose, the degradation of cellulose fibers crystalline will lead swollen and become more open. Another thing that causes moisture regain increased is formed free hydrogen groups, carboxymethyl (-CH2COOH-) and carbonyl (-C = O) groups that are hydrophilic., Cellulose molecular structure changes due to substitution Carboxymethylation cause increased humidity [12], thus becoming more hygroscopic cellulose and cellulose resulted in an increased affinity to chemicals. It can also be demonstrated in Table 1 The absorption of Methylene Blue Dye obtained at the highest moisture regain combination in concentration 2N sodium chloroasetat, 12N sodium hydroxide and 10 hours batching times, the percentage of 5,9% moisture regain .

Table 4. Moisture Regains (%)

Batching Sodium Chloracetate (N) Sodium Hydroxide (N) (Hours) 2 3 4 6 3.6 4.0 3.5 8 4.0 4.7 4.2 2 10 4.0 4.1 4.1 12 5.0 3.9 3.8 6 4.1 4.2 3.6 8 4.1 4.8 4.8 4 10 4.6 4.2 4.2 12 5.2 4.1 4.1 6 4.2 4.3 3.6 8 4.3 5.0 4.8 6 10 4.7 4.4 4.4 12 5.4 4.4 4.2 6 4.2 4.4 3.9 8 4.6 5.2 4.8 8 10 4.7 4.6 4.6 12 5.4 4.5 4.5 6 4.4 4.5 4.4 8 4.9 5.3 5.0 10 10 5.3 4.8 4.8 12 5.9 4.6 4.6 Raw material 3.0

6. Crease Recovery

The Result of crease recovery warp and weft direction can be seen in Table 5. Crease recovery a fabric (is ability fabric to return from tangling) is fiber bending because of the pressure, due to the derailment of a molecular chain, thus changing the composition of the bonds between the molecular chains into a new arrangement. If bending is released back then the molecular chain can not be returned at the beginning position. Because the new position maintained by the arrangement of the bonds between new molecular chains. The analysis of variance it turns out that concentration of sodium chloracetate, sodium hydroxide, and batching time are affected to the crease recovery of warp and weft direction the fabric. Table 5 it is seen that the Carboxymethylation process on polyester cellulose fabrics can improve the crease recovery fabric.The highest crease recovery of warp and weft directions fabric obtained by using concentration of 3N sodium chloracetate, 8 N sodium hydroxide and 2 hours batching time, resulted 149oC warp direction and 158oC weft direction. The use of batching time up until 2 hours crease recovery fabric increase, but the longer of batching time used the crease recovery of fabric will be decreases. The use of concentration 8N sodium hydroxide and up to 3N sodium chloracetate the crease recovery increase, but using higher concentration the crease recovery will be reduced. This can be explained as follows: crease recovery fabric affected by the construction of the fabric in this case number (Tex) of yarn, pick density and stiffness of fabric. Use of sodium chloracetate cause the fabric becomes denser and treatment with sodium hydroxide causing erosion (hydrolysis) on the surface of a polyester fiber, yarn surface consequently becomes uneven (rough). Because of erosion polyester, the fabric [3,4]., becomes more refined, the woven into more rarely, and pick density reduces. Fabrics that more rarely, such as cellulose polyester fabrics processed with sodium hydroxide when folded is still possible slip. That then the crease recovery fabric becomes larger. When pick density of fabric is higher and consists of a coarse thread that makes the fabric thicker and denser, if the fabric is folded difficult to slip, then the outside of the folded fabric greater elongation than the inside. The outer fabric changes shape great. Because of a large elongation, the elasticity of the fabric decreases so that the crease recovery is decrease anyway.

Table 5. The Crease Recovery of Warp and Weft Direction Fabric (0)

Sodium Chloracetate (N) Batching Sodium Hydroxide Warp Direction Weft Direction (Hours) (N) 2 3 4 2 3 4 6 143.5 148.0 134.0 144.8 157.0 134.5 8 148.5 149.0 144.0 147.0 158.0 142.0 2 10 135.8 135.7 128.5 142.7 146.0 133.0 12 134.9 135.5 112.0 135.5 142.5 127.0 6 143.0 146.0 129.0 142.3 156.0 132.2 8 146.0 148.5 144.0 146.0 156.0 140.0 4 10 129.3 134.0 127.7 141.5 144.5 130.0 12 127.6 133.9 106.5 135.0 141.0 124.0 6 142.5 143.0 128.0 132.2 147.0 124.8 8 145.1 148.0 142.3 145.0 153.0 140.0 6 10 123.8 133.3 126.5 140.0 141.0 124.0 12 123.1 132.8 95.8 134.5 139.9 124.0 6 142.0 142.5 121.0 127.8 140.0 124.6 8 145.0 147.5 139.8 142.5 150.0 139.0 8 10 122.3 131.5 125.4 139.0 130.3 123.0 12 121.7 131.0 93.2 130.0 130.2 124.0 6 141.0 142.0 116.0 122.8 137.5 124.0 8 144.0 147.0 139.5 139.5 145.5 135.5 10 10 122.0 120.3 116.5 139.0 124.5 120.0 12 120.0 120.1 90.5 123.8 124.1 113.0 Raw material 109 112

Table 6. Dimensional Stability of Warp and Weft Direction Fabric (%)

Sodium Chloracetate (N) Batching Sodium Hydroxide Warp Direction Weft Direction (hours) (N) 2 3 4 2 3 4 6 1.02 1.20 1.42 0.94 1.18 1.23 8 0.58 1.02 1.33 0.16 0.44 0.50 2 10 1.00 1.50 2.25 0.25 0.66 1.25 12 1.11 1.57 2.26 0.36 0.72 1.26 6 1.18 1.34 1.82 1.18 1.20 1.34 8 1.10 1.42 1.81 0.33 0.48 0.58 4 10 1.23 1.92 2.47 0.42 0.85 1.33 12 1.32 1.96 2.49 0.47 0.87 1.35 6 1.42 1.84 1.89 1.18 1.28 1.34 8 1.25 1.83 1.86 0.42 0.58 1.08 6 10 1.61 2.25 2.83 0.66 0.92 1.92 12 1.65 2.29 2.87 0.71 0.96 1.97 6 1.42 2.20 2.30 1.18 1.34 1.73 8 1.42 1.85 2.03 0.42 1.16 1.33 8 10 1.74 2.27 3.25 0.98 1.50 2.17 12 1.79 2.31 3.28 1.00 1.53 2.21 6 1.60 2.78 2.57 1.23 1.67 2.07 8 1.50 2.17 2.58 1.08 1.63 2.00 10 10 1.86 2.85 3.25 1.16 1.83 3.00 12 1.91 2.88 3.31 1.19 1.88 3.09 Raw Material 1.36 1.10

7. Dimensional Stability

The test results of dimensional stability can be seen in Table 6, from the analysis of variance it turns out that the concentration of sodium chloracetate, sodium hydroxide, and the batching time of impregnation effect on dimensional change in washing and dimensional stability of fabric The higher of sodium chloracetate and sodium hydroxide concentration and the longer batching time of impregnation, the dimensional stability change (% shrinkage) produced is greater. In Table 6, it appears the polyester/cellulose fabric carboxymethylation process, that have been done can increasing dimensional stability of the fabric, that means the fabric is increasingly shrinkage towards the warp and weft direction fabric, so that the fabric more stable [13].It is because cellulose and polyester degraded, sodium chloracetate is an acidic salt and sodium hydroxide is a strong alkaline. The degradation caused initial modulus of the fabric is reduced, resulting in dimensional change increased. Beside this sodium hydroxide treatment will cause cellulose fiber swollen and shrink after washing and shrink again after drying, the fiber becomes more stable. The increasing concentrations of sodium chloracetate, sodium hydroxide and batching time of impregnation are causing degradation of the fiber. Substitution of the hydroxyl group by Carboxymethylation group can add hydrogen bonds that would be increasing the hydrogen bonding in amorphous. Furthermore, the dimensional stability testing, the resulting shrinkage smaller means the fabric more stable. Highest dimensional stability results obtained in the use of a concentration of 2N sodium chloracetate, 8N sodium hydroxide and 2 hours batching time of impregnation the result are 0.58% warp direction to 0.16% weft direction dimensional stability of the fabric.

8. Stiffness

The stiffness of warp and weft direction fabric can be seen in Table 7; from the analysis of variance it turned out that the concentration of sodium chloracetate, sodium hydroxide, batching time of impregnation effect on the stiffness of the fabric. © 2016 Published by Center for Pulp and Paper through 2nd REPTech 21 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Table 7. Stiffness of Warp and Weft Direction Fabric (mg.cm)

Sodium Chloracetate (N) Batching Sodium Hydroxide (N) Warp Direction Weft Direction (hours) 2 3 4 2 3 4 6 53 55 63 21 23 28 8 48 49 59 19 22 24 2 10 44 47 61 20 23 23 12 48 50 61 21 23 25 6 55 57 64 25 29 32 8 52 52 61 25 27 29 4 10 48 53 62 20 24 26 12 49 54 63 23 25 28 6 57 59 68 30 34 35 8 55 57 65 27 29 31 6 10 50 53 63 23 26 33 12 53 55 66 25 28 34 6 62 63 70 37 38 46 8 57 59 67 31 35 38 8 10 54 66 68 29 34 35 12 57 67 71 30 36 36 6 65 68 79 37 42 47 8 60 66 76 33 39 43 10 10 68 67 71 30 35 36 12 69 70 73 32 37 37 Raw material 75 46

On the table 7 shown that the polyester/cellulose carboxymethylation process has influenced to fabric stiffness. The higher of sodium chloracetate concentration, the fabric stiffness is getting higher and the higher of sodium hydroxide concentration, the fabric stiffness is getting lower than before treatment. The smallest fabric stiffness in the use concentration of 2N sodium choracetate, 8N sodium hydroxide and 2 hours batching time of impregnation is 48 mg.cm to the warp direction and the combination of the use of 2N sodium chloroasetat, 10N sodium hydroxide and 2 hours batching time of impregnation, the result 19 mg.cm of weft direction of fabric stiffness. As previously explained that the treatment with sodium chloracetate cause the fabric becomes denser and stiffer, while the treatment with sodium hydroxide causing erosion/hydrolysis on the surface of the polyester fiber so that the fiber cross-section is thinner so that the fabric becomes softer [2, 3], because the fabric is getting soft then the fabric is easier and faster to make curved, that means the fabric stiffness will be decreased. Besides that, the stiffness of the fabric is also determined by the fabric construction include pick density (number of yarn/cm). Polyester surface abrasion on the fabric by a sodium hydroxide solution will cause the thread diameter gets smaller and pick of Warp/ weft density of fabrics declined, so the construction of the fabric becomes rarer, the consequence fabric stiffness will be decreased. [13]. Polyester-cellulose fiber blends 65% -35% were processed Carboxymethylation processed, on the part of the polyester fiber and cellulose has a degree of crystalline different. In the process of erosion of the amorphous fiber parts polyester will be attacked by sodium hydroxide so that the degradation becomes more and more, while the amorphous cellulose fibers will be attacked by the sodium chloracetate that is increasing fiber damage, therefore the higher the concentration of chemical substances stiffness of the fabric will tend to decline.

9. Determination for Optimal Conditions of Carboxymethylation Process with Pad Batch Method

The optimal conditions selected should cover all physical test results; It make easier to determine the right optimal conditions, then each test results are given weighting in accordance to the urgency of the test.

Table 8. The Chemical and Physical properties of Polyester, Cellulose and Polyester/ Cellulose in Optimal Condition Carboxymethylation Processes of Pad-Batching Method

Polyester Cellulose Polyester/Cellulose Testing Raw Warp Weft Raw Warp Weft Raw Warp Weft 1.Construction webbing plain plain plain Number of yarn 16.60 13.45 13.67 9.80 13.43 14.00 (Tex) Pick density /cm 55 31 37 36 35 24 Dry weight m2 93.29 110.6 78.798 (g) 2.Tensile 31.50 19.58 20.87 19.53 25.00 17.90 Strength (kg) Raw material 32.58 21.78 19.13 17.43 21.15 17.20 3.Weight 4.02 reduction, % 4. Methylene Dyed stain dyed Blue dyeing 94.32 Little Raw material blank stained dyed 5.Moisture 0.70 10.7 4.7 Regains (%) Raw material 0.40 7.26 3.0 6.Crease 162.29 160.25 135.0 120.83 158 149 Recovery (o) Raw material 152.13 149.25 101.4 90.5 112 109 7 Dimensional 0.49 0.42 1.10 1.02 1.02 0.44 Stability (%) Raw material 0.63 0.52 1.69 1.55 1.36 1.1 8.Stifness (mg. 31.71 31.38 54.19 31.54 19 22 cm) Raw material 46.90 43.33 45.16 29.96 75 46

The main objective to determine the quality of polyester/cellulose Carboxymethylation process is raising the moisture regain; lack characteristic of cellulose is low crease recovery and dimensional stability of fabric. Therefore, an important parameter is given 10 weighting value, which are moisture regain crease recovery and tensile strength fabric. While the test parameters stiffness and dimensional stability of polyester/cellulose fabric has a value lower than the initial value to determine the optimal conditions are given a weighting value 5. By multiplying the value of the weighting and ranking the calculation result Newman-Keuls analysis will be obtained values to determine the optimal conditions point. The results of these calculations on table 8 showed that the optimal conditions on a treatments are: 3N sodium chloroacetate, 8N sodium hydroxide and 2 hours batching time of impregnation at room temperature (28oC)., With test results: 7 5% reduction in weight of the polyester, 94.32% absorption of methylene blue dye, 4.7% (increase 56.7%) moisture regains, 25 kg (decrease 9.1%) tensile strength of the warp direction and 17.9 kg (decrease 30.9%) of weft direction, in 158 (increase 41.1%) crease recovery of warp direction and 149 (increase 36.7%) of weft direction, 1.02% (decrease 25%) dimensional stability of warp direction and 0.44 % (decrease 30.9%) weft direction, 49 mg.cm (decrease 34.67%) stiffness of warp direction and 22 mg.cm (decrease 52.17%) of weft direction. As a comparison it has been done the carboxymethylation process on 100% polyester fabric and 100% cellulose fabric at that optimal condition, the test result shown at table 8 © 2016 Published by Center for Pulp and Paper through 2nd REPTech 23 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

11. Determination of Optimal Condition by Comparing Polyester/Cellulose Carboxymethylation Process using Pad-Batch Method that have been done and Pad Bake Method that have been done at Previous Research

The results of chemical and mechanical properties testing of polyester/cellulose fabric after carboxymethylation process using pad-batch method and pad-bake method can be seen in Table 9. From the previous research results, that has been done on optimal condition polyester/cellulose Carboxymethylation process of pad bake method reached at: concentration of 4N sodium chloroasetat, 8N sodium hydroxide and baking temperature 120oC. with the test results as follows: 0.45% weight reduction of polyester, 94.32% absorption of methylene blue dyes, 4.44% (increase 48%) moisture regains, 21,50 kg (decrease1,65%) tensile strength of warp direction, 16 kg ( decrease 6,97%) tensile strength of weft direction, 1480 (increase 32.14%) crease recovery of warp direction and 1450 (increase 33.02%) of weft direction, 0.14% (increase 89.7%) the dimensional stability fabric of warp direction and 0.17% (increase 84.54%) of weft direction, 64.0 mg.cm (decrease 14.6%) the stiffness fabric of warp direction and 39 mg.cm (decrease 15.2%)of weft directions [1]. In this study that have been done the optimal conditions polyester/cellulose fabric Carboxymethylation process using pad-batch method are: 3N sodium chloracetate, 8N sodium hydroxide and 2 hours batching time at room temperature (28oC)., with test results as follows: 7.5% weight reduction, 94.32% the absorption of methylene blue dyes, 4.7% (increase 56.7%) moisture regains 25 kg (decrease 9.1%) tensile strength of the warp direction and 17.9 kg (decrease 30.9%) of weft direction, in 1580 (increase 41.1%) crease recovery of warp direction and 1490 (increase 36.7% ) of weft direction, 1.02% (decrease 25%) the dimensional stability fabric of warp direction and 0.44% (decrease 30.9%) of weft direction , 49 mg.cm (decrease 34.67%) the stiffness fabric of warp direction and 22 mg.cm (decrease 52.17%) of weft direction. When viewed from the characteristics of the results of testing the chemical and mechanical properties in table 9 , after comparable between the two methods optimal conditions it is best of polyester/ cellulose Carboxymethylation process using pad-batch compare with pad-bake method, which in the process has result: crease recovery higher so that the fabric does not easy to crease, the stiffness is lower so that the fabric has softer handle, tensile strength of the fabric is higher because the batching process at room temperature, so it is not to cause damage for polyester or cellulose fibers, as

Table 9. The Chemical and Physical Properties of Polyester/Cellulose on Optimal Condition Carboxymethylation Process using Pad-Batch and Pad Bake Method

Pad -Batching Pad- Baking Testing Warp Weft Warp Weft Methylene Blue dyeing dyed Dyed Raw material stained Stained Moisture Regain, % 4,7 4,4 Raw material 3,0 3,0 Tensile strength (Kg) 25.00 17.90 21.5 16.0 Raw Material 21.15 17.20 21.15 17.20 Crease Recovery (o) 158 149 148 145 Raw Material 112 109 112 109 Dimentional Stability, % 1.02 0.44 0.14 0.17 Raw Material 1.36 1.1 1.36 1.1 Stiffness (mg.cm) 19 22 64 39 Raw Material 75 46 75 46

24 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 well as the value of moisture regain higher, so that the fabric absorbs sweat better thus the fabric is more comfortable to wear. Besides this, the polyester/cellulose Carboxymethylation process–batch method, can be done by small and medium industries because they do not need expensive equipment investment and energy saving.

Conclusion

The optimal condition by comparing the polyester/cellulose Carboxymethylation process using the pad batch method and pad bake method, obtained at combination treatment: 3N sodium chloroasetate 8N sodium hydroxide and 2 hours time impregnation at room temperature (28oC), The test result showed that: 7.5% weight reduction, 94.32% absorption of methylene blue dye, 4.7% or increase 56.7%, moisture absorption, 25 kg or decrease 9.1% warp direction of tensile strength and 17.9 kg or decrease 30.9%) of direction of tensile strength, 1580 or increase 41.1% warp direction of crease recovery and 1490 increase 36.7% weft direction of crease recovery, 1.02% or decrease 25% warp direction of fabric dimensional stability and 0.44% or decrease 30.9% weft direction of the fabric dimensional stability, 49 mg.cm or decrease 34.67% warp direction of fabric stiffness and 22 mg.cm or decrease 52.17% weft direction of fabric stiffness. When viewed from the characteristics and mechanical properties of the test result at optimal conditions showed that: has higher crease recovery, higher tensile strength, higher moisture regain compare than Polyester/Cellulose Carboxymethylation process using pad-bake method. In addition the process Carboxymethylation polyester/cellulose using Pad Batch methods, can be done by small and medium industries because, the manufacture do not need expensive equipment investment, energy saving and lower cost for production than pad-bake method.

Ackknowledgements

The author would like to thank and acknowledge profusely to Mrs..Gati Wibawaningsih S.Teks, MA as, Director General of Small and Medium Industry, Ministry of Industry, for all her help so that this article can be resolved.

References

1. Kuntari Adi Suhardjo, Setio Legowo 2015, Modifications fabric polyester / cellulose using a process karboksimetilasi pad-bake method “Journal of Materials Science Indonesia Vol 17 No: 3 June 2015. ISSN 1411-1098, Accreditation No. 263 / AU1 / P2MBI / 05/2010, the Center of Technology of material and Industry Nuclear Industry, BATAN, Indonesia 2. A. Hebeish et al. 2009 “Chemical Modification of Polyester/Cotton Blends Partial carboxymethylation“. American Dyestuff Reporter NewYork, 3. Addly A.M Gorravan 1980“Caustic Treatment of Polyester Filament Fabric”’ Textile Chemist and Colourist London AATCC, Volume 12 no 4, 1980 4. PT Inkali Technical Information.2009 “Alkali process, reduction of Polyester textile materials weight” 5. S. Pitchai, J. J. Moses, S. Natarajan.2014 “Study On the Improvement of Hydrophilic Character On Polyvinylalcohol Treated Polyester Fabric”.Polish Journal of Chemical Technology vol.16, no 4, pp. 21-27, 2014. 6. K. M. Hong 2013“Preparation and Characterization of Carboxymethyl Cellulose from Sugarcane Bagasse”. A project report submitted to the Department of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman,May 2013. 7. M. Gibis, V. Schuh, J. Weiss 2015. “Effect of Carboxylmethyl Cellulose (CMC) And Microcrystalline Cellulose As Fat Replacers OnThe Microstructure And Sensory CharacteristicsOf Fried Beef Patties”. Food Hydrocolloids,vol. 45, pp. 236-246, 2015. 8. A. H. Saputra, L. Qadhayna, and A. B. Pitaloka. 2014“Synthesis and Characterization of Carboxymethyl Cellulose (CMC) from Water Hyacinth using Ethanol-Isobutyl Alcohol Mixture as the Solvents”.International Journal of Chemical Engineering and Applications, vol. 5, no. 1, pp. 36-

40, Feb. 2014. 9. M. Chaplin 2014.”Water Structure and Science”, England & Wales Licences, May 2014. 10. A. Wijayani, K. Ummah and S. Tjahjani 2005. “Characterization of Carboxymethyl Cellulose (CMC) of the Water Hyacinth (Eichornia crassipes (Mart) “. Indo.J.Chem., vol. 5 (3), pp. 228-231, 2005. 11. Melisa, S. Bahri, Nurhaeni 2014“Optimization Synthesis Carboxymethyl Cellulose of Sweet Corn Cob (ZeaMays L Saccharata)”. Online Jurnal of NaturalScience, vol.3 (2), pp. 70-78, Aug. 2014. 12. Bin Xue, Qun Lie, ZhenzhenWang and Yujia Zhang, 2014.”Influencing Factor for Alkaline Degradation of Cellulose” Cellulose Research Tianjin University of Science and Technology, 2014 13. A. Bidin 2010. Reaction Conditions .Optimasi Synthesis of Carboxymethyl Cellulose (CMC) of the Water Hyacinth (Oryza sativa), , Universitas Palu, 2010. 14. D. Yan, J-X. Huang X-L. Dong, et al.2015 “Preparation Process Study On High Viscosity Sodium Carboxylmethyl Cellulose By Using Pulp As Raw Material”. Journal of Hunan Institute of Engineering (Natural Science Edition), vol. 25(2), pp. 69-72, 2015 15. SNI 08-0264-89 / ISO: 1833: 2011:”The Content of Polyesters (Composition) Testing of Fabric” 16. SNI 08-0263-1989:” Moisture Content and Moisture Regain Testing of Fabric “ 17. ISO 0276 – 2009:” Tensile Strength Testing of Fabric” 18. ISO 2313: 2011:” Crease Recovery Testing of Fabric” 19. ISO 5077 – 2011:” Dimensional Stability Testing of Fabric” 20. SNI 08 - 0314 – 1989:” Stiffness Testing of Fabric

CHALLENGES TO SUSTAINABLE WOOD PRODUCTION OF SHORT- ROTATION PLANTATION FORESTS IN INDONESIA

Eko B. Hardiyanto Faculty of Forestry, Universitas Gadjah Mada, Yogyakarta 55281, Indonesia [email protected]

ABSTRACT

Indonesia has established substantial areas of short rotation plantations, mainly to supply wood for several large industrial pulp mills with annual capacity of 7.9 million ton of pulp. Acacia was the main genera grown for pulpwood. There were around 1.2 M ha of Acacia plantations, which mainly comprise Acacia mangium on mineral soils and A.crassicarpa on peat land. The expansion of short rotation plantation was encouraged by the species’ growth rates (in 6-7 year rotation) ranging from 22 to 35 m3/ ha/year) and their excellent wood quality for pulp and paper making. In general second rotation stands grew as well or faster than the first rotation, if inter-rotation site management promoting conservation of site organic matter and weed control were deployed. During the first and second rotations there were incidences of Ganoderma root rot disease but it’s spread increased with time. This was followed by the arrival and rapid spread of Ceratocystis wilt disease, aggravated by the damages caused by monkeys. Gradually, tree mortality became so high that A. mangium was no longer viable. Based on earlier studies, Eucalyptus pellita emerged as the next best candidate species. The change of species from A. mangium to E. pellita began in 2006 by some companies. The current growth rates of E. pellita are lower than or at best comparable to A. mangium. This poses challenges to wood supply to existing mills. Good site management, including slash and litter retention has been the common practice during the last decade resulting in accumulation of organic matter and nutrients especially N. Question is, would the rates of supply of N, P and cations from these sources and soil be sufficient to support the necessary fast growth rates of eucalypts? While the disease threat in A. crassicarpa plantation on peat soil is still scanty the limited species choice adapted and suitable for pulpwood production on this soil is cause for concern. These and other issues being faced during the change of species in response to threats to sustainability would be discussed.

Keywords: change of species, productivity, site management, sustainability

Introduction

The government of Indonesia had embarked on a large planting program to rehabilitate degraded forest land dominated by alang-alang (Imperata cylindrica) grass and other unproductive land in late 1980s, mainly in Sumatra and Kalimantan. Most of the plantations are short rotation, mainly to provide wood for pulp mills with a annual capacity of 7.9 million ton of pulp [1]. One of the species suitable for this purpose is Acacia mangium. In Sumatra and Kalimantan on inherently acid and poor red-yellow podsolic soils A. mangium thrives remarkably well. In fact, it is one of the best species emerged in the species trial conducted in the region in the early 1980s. A number of studies on the utilization of A. mangium wood show that its wood is not only excellent for pulp and paper, but also good for other wood products such as plywood, furniture, flooring and light construction. The pulp properties made of A. mangium wood are comparable to those of Eucalyptus. Due to its fast growth and good adaptability to acid soil prevalent in the region which can quickly suppress the Imperata grass and suitability for making pulp and paper, A. mangium was developed into large scale plantation forests and had become a major source of wood for pulp mills in Sumatra since 1989. A. mangium plantation has also been developed in other parts of Indonesia, mainly in Kalimantan. By 2004-2005 it occupied a total land area of 700,000 ha in Sumatra and about 1.0 million ha nationally [2]. The plantations are mostly established on Red Yellow Podsolic Soil (Ultisol and Inceptisol) having generally low in nutrient reserves [3, 4].

A. mangium had been grown in more than two rotations in Sumatra and Kalimantan with productivity ranging from 20 to 35 m3/ha/year harvested at 6-8 years rotations, depending on site quality and silvicultural practices [2, 4]. However, on some sites in the third and second rotation, the incidence of Ganoderma root-rot disease and wilt/stem canker caused by Ceratocystis spp has caused the decline in plantation productivity, and even at some sites the attack of Ganoderma or Ceratocystis has reached to the point where growing A. mangium is no longer viable. These disease threats have led growers to progressively have replaced A. mangium with Eucalyptus pellita. E. pellita has been identified as the best alternative species, as it has good productivity, suitable for pulp production and tolerant to Ganoderma and Ceratocystis diseases. On peat land Acacia crassicarpa is the only species has been grown operationally for pulp plantation as other species that have been tested grow poorly on peat land. A. crassicarpa plantation in Sumatra occupies a total land area of more than 500,000 ha. The productivity of A. crassicarpa has been lower than A. mangium on mineral soil, ranging from 18 to 25 m3/ha/year grown on a 4 year rotation [5]. Currently disease outbreaks on A. crassicarpa on peat land have not been reported. A. crassicarpa has also been reported to be more resistant to Ceratocystis infestation [6]. This paper discusses the challenges in sustainable wood production in response to threats on short-rotation plantation forests in Indonesia.

Productivity Trend of Acacia Plantation

The goal of plantation forest establishment are to 1) ensure that the trend in plantation productivity is not declining, or increasing over successive rotations, 2) protect and enhance the quality of soil and water values in the plantation environment, 3) promote innovation and profit for the business of forestry and 4) provide economic, environmental and social benefits to the economy. The productivity of A. mangium in Sumatra and other SE Asian countries had recently been reviewed and reported [7]. Based on 343 and 111 inventory data plots in the first and second rotation respectively in 3 sub-regions of Sumatra. The growth rates ranged from 22.4 to 35.4 m3/ha/year in the first rotation of 7.5 to 8.3 year rotations, and from 33.9 to 35.0 m3/ha/year in the second rotation of 5.6 to 5.9 year rotations. Despite the rotation length of the second rotation decreases about 2 years the growth rates in the second rotation were in general is similar, or marginally better than those in the first rotation. Further, in the second rotation 54% of plot had mean annual increment (MAI) between 30 to 40 m3/ ha/year and 16% plot grew MAIs higher than 40 m3/ha/year. It indicates that the productivity of A. mangium plantation in these sub regions of Sumatra did not decline over two successive rotations. This was due to the use of improved genetic material, and proper silvicultural practices including organic matter conservation and weed control [3, 7]. Inventory data was also taken from 1459 and 2360 plots in the first and second rotations respectively in another 3 sub-regions of Sumatra and showed that the growth rates of A. mangium ranged from 27.3 to 33.6 m3/ha/year in the first rotation of 3.6 to 6.7 year rotations, and from 14.5 to 28.6 m3/ha/year in the second rotation. Further, the proportion of inventory plots with MAIs below 15 m3/ha/year was higher in the second rotation (22%) than the first rotation (14%). The decline in productivity of second rotation was mainly due to the incidence of Ganoderma root rot and Ceratocystis wilt/stem canker, aggravated by the attack of long-tail monkey or elephant. Long term-productivity studies on slash and litter retention management of A. mangium coordinated by CIFOR were carried out at two sites in South Sumatra and one site Riau (Central Sumatra), started in 1999. Progress of the studies had been reported [3, 4, 7, 8, 9] . In South Sumatra the volume at 10 years was 29.7 m3/ha/year in the first rotation, and increased to 47.8 m3/ha/year at 7 years in the second rotation, which is 60% increase in volume. A similar trial also located in South Sumatra harvested at 6 years showed that MAI increased from 28.9 m3/ha/year in the first rotation to 43.6 m3/ha/year in the second rotation [8]. The growth rate at third rotation (27.6 m3/ha/year) was lowered compared with that at the second rotation (50.7 m3/ha/year) at the same age of 3 years, chiefly due to high mortality caused by Ceratocystis wilt/canker disease. The survival rate at 3 years was 92.8% and 46.7 % in the second and third rotation respectively [9]. In Riau the growth rate of second rotation stand (41.5 m3/ha/year) was marginally higher than the first rotation (40.9 m3/ha/year) at 5 years [4]. The increase or maintenance in productivity of A. mangium

4.4 4.0

4.2 3.5 O) 2 4.0 3.0 C (%) BL0 pH (H

BL3 3.8 2.5

3.6 2.0 0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7

4.0 0.3 )

-1 3.0

P(mg kg P(mg 0.2

2.0 N (%)

1.0

0.0 0.1 0 1 2 3 4 5 6 7 0 1 2 3 3 5 6 7 Stand age (year)

Figure 1 Changes in Soil pH, Organic Carbon, Extractable P and Total Nitrogen on 0-10 cm Soil Depth from Planting to Harvest in The Second Rotation of A. mangium. Vertical Bars are SEs, for All

Replications at Age 0 year and For Selected Times for BL0 and BL3 Treatments in the second rotation were attributed to the good practice of organic conservation and use of improved genetic material. No data is available on the productivity of A. crassicarpa over successive rotation on peat land. However, it was reported that the the mean growth rate of A. crassicarpa in the second rotation on peatland was higher than the first rotation (29-33 3m /ha/yr).

Soil Property Changes

The maintenance of soil quality is of paramount importance for having sustainable plantation productivity and wood production. In the aforementioned long term productivity studies soil properties were regularly sampled and analysed and the changes in soil properties were evaluated. The objective is to assess whether growing short-rotation plantation over successive rotations reduce soil qualities and what kind of remedy if they happen.

In South Sumatra the changes in pH(H2O), organic C (SOC), total N, and extractable P from the harvesting of the first rotation to the mid-third rotation are illustrated in Figure 1. Values of soil properties were taken at soil depth of 0-10 cm from two slash and litter retention treatments: BL0, all slash and litter removed and BL3, double slash. Soil pH(H2O), only decreased marginally by about 0.03 for BL0 and 0.07 unit for BL3 from the end of the first rotation to the mid-third rotation. Soil organic C was about similar between the first and second rotation, and increased slightly in the mid-third rotation in BL3. Soil N followed the same trend as SOC. The capacity of A. mangium to fix atmospheric nitrogen is high. For example, the amount of N fixed ranged from 14 to 121 kg N ha-1 at 12 months, and from 26 to 142 kg/

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 29 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 ha at 18 months [10]. Extractable P decreased by 75 % from the first to second rotation then increased in the mid-third rotation in BL0 and BL3 treatments [8, 9]. In Riau soil pH increased slightly from 3.6 at the first rotation to 4.2 at the end of second rotation. SOC and total N did not change very much between first and second rotation [4]. Consequently, P input in the form of fertilizer application is of paramount importance to maintain or increase plantation productivity.

Disease Threats

Fungal root rot, caused dominantly by Ganoderma philippii [11, 12, 13) has affected significant loss in production of A. mangium plantation in Sumatra. At sites of former log-over secondary lowland rainforest root rot incidence had been observed in the first rotation, while at site of former Imperata grass land root rot was rarely found in the first rotation. The root rot incidence progressively increased over rotation, and tree mortality tended to be higher as trees get older [14]. Surveys in the second rotation A. mangium plantations in Sumatra revealed that trees showing root rot symptoms ranged from 3 to 28 % [15]. In the subsequent survey encompassing 109 compartments of A. mangium plantations in Indonesia, trees with root rot symptom increased from 5 % in the first rotation to 15 % and 35 % in the second and third rotation respectively [16] (Mohammed et al. 2012). The survey was conducted in young stand of less than 3 years old, and the mortality and production losses will be higher at the end of rotation. Ceratocystis wilt and canker diseases have also been attacking A. mangium plantation in Malaysia [17] and Vietnam [18]. Disease build-up in woody debris left behind after harvesting short-rotation plantations of five-to- seven years is associated with an accelerated development of disease such that tree death can exceed 50% in some areas within < 20 years of establishing the first rotation [16]. At some sites where the root rot incidence was so severe growing A. mangium is no longer viable to provide a commercial yield at harvest. While biocontrol agent such as Cerrena and Phleibopsis fungi have been identified as potential for reducing root rot in A. mangium plantation, its deployment in operational plantations is not yet feasible [19]. The current strategy adopted by forestry companies in Sumatra and Kalimantan is progressively replacing A. mangium with E. pellita which has been identified to be less susceptible to Ganoderma root rot. The change of A. mangium to E. pellita began in 2006 in some companies in Sumatra. The second more devastating disease of A. mangium plantation in Sumatra is wilt/stem canker caused by Ceratocystis spp.[20]. The disease was identified a decade ago, is progressively increasing its intensity over successive rotations. As the disease easily infects trees through wound [21] the wilt/ stem canker incidence is aggravated when the plantations are also attacked by monkey, squirrel or elephant which ring-bark the stem and create wounds for entry points for Ceratocystis. A trial assessing Ceratocystis resistance or tolerance in A. mangium revealed that there was little heritable variation on this trait, so that genetic improvement for resistance and tolerance to Ceratocystis is very challenging [17] . While the use of fungicide could reduce the disease incidence, its application in large scale plantation is impractical [22]. At many sites tree mortality caused by Ceratocystis wilt disease is so high, growing A. mangium is no longer feasible and has to be replaced with more tolerant species of E. pellita. A similar problem has been occurring in Sabah and Sarawak (Malaysia). While A. crassicarpa grown on peat land has been relatively free from devastating pest and disease such as Ceratocystis and Ganoderma, efforts to find alternative species should be taken seriously as relying on a single tree species planted over a large areas run a high risk of pest and disease outbreaks. In the long term diseases may adapt to the existing condition of tree plantation and start causing serious damage to the plantation which is in turn a threat to sustainable plantation productivity and wood production.

Growth of Eucalyptus Pellita

Growing large scale of E. pellita plantations is quite recent in Sumatra and Kalimantan as an alternative species for the site where growing A. mangium is economically not viable due to pest and

30 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 disease outbreak previously described. The current growth rates of E. pellita are lower than or at best comparable to A. mangium. This poses challenges to wood supply to existing mills [7]. A number of trials have been carried out to ascertain the effect of silvicultural practices on the growth of E. pellita in Sumatra. One of these studies is established on the former site of site management study in South Sumatra described previously. Results at age 2 years are reported here.

Complete removal of slash and litter (BL0) from the plot reduced the growth of E. pellita significantly. Retaining slash or slash plus litter without the addition of P fertiliser resulted in significant slower growth compared with the addition of P fertiliser on plot which had slash and litter (BL2) (Figure 2). Retaining slash and litter is inadequate to support faster growth of E. pellita. The importance of P addition to growth is supported by the trial conducted on the same site. The application of 15 kg/ha of P fertiliser increased growth significantly, further addition of P fertiliser up to 60 kg/ha improved growth marginally, particularly for the plot fertilised in the previous rotation. Positive growth response of E. pellita to P fertiliser addition was also reported from another fertilizer trials in South Sumatra. The addition of P (30 kg/ha) at 3 years had mean height, stem diameter and stem volume of 13.3 m, 12.4 cm and 77.1 m3/ha respectively, while in the unfertilized plot the mean height, stem diameter and stem volume were 10.8, 9.7 cm and 45.6 m3/ha respectively [19]. Improved growth of E. pellita due to the P fertilizer addition was also found from a trial in Riau, but the application of more than 14 kg P/ha had no additional response [19]. The addition of K (82.5 kg/ha) and Ca (368.5 kg/ha) on the plot received basal fertiliser of P (15 kg/ ha) had no additional response to growth. Plot receiving P only, and addition of K, or Ca fertiliser had volume 47.0, 44.2 and 42.0 m3/ha respectively at age 2 years. In Sumatra a number of N fertilizer trials of E. pellita grown on ex. A. mangium stand have been established to assess whether the amount of N fixed by previous A. mangium is adequate to support optimal growth of E. pellita. In South Sumatra at age 3 years the addition of N (120 kg/ha) did not increase growth significantly. However, there was a consistent though not-significant trend for 7-13% higher productivity with the application of N [18] (Mendham and Rimbawanto 2015). In Riau at age 3 years the addition of N fertilizer to E. pellita stand on site of ex. A. mangium slightly increased growth though not significantly; the mean volume of fertilized plot (126 kg N/ha) was 96.6 3m /ha, while the mean volume of unfertilized plot was 88.4 m3/ha [18] (Mendham and Rimbawanto 2015). Similarly, an application of N fertilizer on site of ex. A. mangium had marginal improvement of growth of E. pellita

50 c 45

) 40 -1 b

ha 35 b b 3 30 a 25 20 15

Volume (m Volume 10 5 0 BL0 BL1 BL2 BL3 BL2+P Slash and litter treatment

Figure 2. Growth response of Eucalyptus pellita to slash and litter retention treatment and P fertiliser

(60 kg/ha) at age 2 years. BL0 = slash+ litter removed, BL1= only slash removed, BL2= slash+litter

retained, BL3= double slash. Bars having the same letter are not significantly different according to Duncan Multiple Range Test at p=0.05.

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 31 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 in South Sumatra at 3 years of age; the volume of fertilized plot (110 kg N/ha) was 105.2 m3/ha, while that of unfertilized plot was 101.3 m3/ha [23]. These results suggest that the N supply from the soil and decomposing slash and litter is sufficient to support optimal growth ofE. pellita at the current rotation. The development of high yielding clones of E. pellita and hybrids have been in progress. Several clones of E. pellita or its hybrid have been reported to have high productivity with MAI of more than 30 m3/ha/year [24]. However, the deployment of good clones without regard to proper silvicultural practices, including better weed control, nutrient input and conservative site management will not achieve high plantation productivity. Unlike Acacia, eucalypts are more sensitive to weed competition, and consequently judicious vegetation management, particularly in the early year of plantation establishment is very crucial for growing eucalypt. Poor weed control was reported to cause significant growth loss [23].

The Way Forward

The widespread of pest and disease attacking A. mangium plantation in Sumatra and Kalimantan has caused the replacement of A. mangium with E. pellita on large scale. The time and scale of the species change is unprecedented in the history of plantation forest. The change of species can be considered as a way to sustain wood production, a similar strategy has long been applied in the management of agriculture crops where a crop such as paddy is replaced with another crop such as corn or sugar cane in the next crop rotation, for example to prevent the widespread of disease attacking paddy. It is possible that A. mangium will be replanted on the same site after 2-3 rotations of E. pellita when the population of disease has declined significantly or the resistant/tolerant A. mangium genotypes have been found. Breeding program to find genotypes of A. mangium resistant or tolerant to Ceratocystis disease is in progress. In the future we may see that the species grown in short-rotation plantation forest will change after 2-3 rotations to maintain sustainable wood production. In this perspective sustainable wood production is no longer species bound; it is one of the benefits of short-rotation plantation forest in which the plantation managers can implement the changes in responses to ecological events. In the mean time challenge of growing short-rotation plantation forest on peat land with regard to hydrology management and alternative species is also considerable for the sustainability of wood production on this site. The Government Regulation No. 7/2010 which stipulates that the water table should be maintained at least 40 cm from the peat surface will also pose another challenge.

References

1. Antara News. Kemenperin Arahkan Pengembangan Pulp di Luar Jawa. 2016 http://www.antaranews.com/ berita/547939. 2. Arisman H, Hardiyanto EB. Acacia mangium – a historical perspective of its cultivation. Heart rot and root rot in tropical Acacia plantation. Proceedings of a workshop held in Yogyakarta, Indonesia, 7-9 February. ACIAR Proceedings No. 124; 2006, pp 11-15. 3. Hardiyanto EB, Wicaksono A. Inter-rotation site management, stand growth and soil properties in Acacia mangium plantations in South Sumatra, Indonesia. In: Nambiar, E.K.S.(ed.). Site Management and Productivity in Tropical Plantation Forests. Proceedings of Workshops in Piracicaba (Brazil) 22-26 November 2004 and Bogor (Indonesia) 6-9 November 2006. CIFOR, Bogor, Indonesia.; 2008, pp.107-122. 4. Siregar STH, Nurwahyudi, Mulawarman. Effects of inter-rotation management on site productivity of Acacia mangium in Riau Province, Sumatra, Indonesia. In: Nambiar, E.K.S.(ed.). Site Management and Productivity in Tropical Plantation Forests. Proceedings of Workshops in Piracicaba (Brazil) 22-26 November 2004 and Bogor (Indonesia) 6-9 November 2006. CIFOR, Bogor, Indonesia; 2008, pp.93-106. 5. Riyanto B. Pers comm. 6. Tarigan M, Yuliarto M, Gafur A, Yong WC, Sharma M. Other Acacia species as a source of resistance to Ceratocystis. Paper presented at International Workshop on Ceratocystis Harwood Plantation. 16- 18 February 2016, Yogyakarta, Indonesia; 2016.

7. Harwood CE, Nambiar EKS. Sustainable plantation forestry in South-East Asia. ACIAR Technical Reports No. 84. Australian Centre for International Agricultural Research, Canberra. 2014.,100 pp. 8. Hardiyanto EB, Nambiar EKS. Productivity of successive rotations of Acacia mangium plantations in South Sumatra, Indonesia: impacts of harvest and site management. New Forest 2000; 45: 557- 575. 9. Hardiyanto EB. Unpubished data. 10. Wibisono MG, Veneklass E, Mendham DS, Hardiyanto EB. Nitrogen fixation of Acacia mangium Willd. From two seed sources grown at different levels of phosphorus in an Ultisol, South Sumatra, Indonesia 2015. Southern Forests 2015:1-6 11. Eyles A, Beadle C, Barry K, Francis A, Glen M, Mohammed C. 2008. Management of fungal root- rot pathogens in tropical Acacia mangium plantations. Forest Pathology 2008; 38: 332-225. 12. Glen M, Yustikanti V, Puspitasari D, Francis A, Agustini L, Rimbawato A, Indrayadi A, Gafur A, Mohammed C. Identification of basidiomycetes fungi in Indonesian hardwood plantations by DNA barcoding. Forest Pathology 2009; 44: 496-508. 13. Coetzee MPA, Wingfield BD, Golani GD, Tjahjono B, Gafur A, Wingfield MJ. A single dominant Ganoderma species is responsible for root rot of Acacia mangium and Eucalyptus in Sumatra. Southern Forest 2011; 73: 175-180. 14. Francis A, Beadle C, Puspitasar D, Irianto R, Agustini L, Rimbawanto A, Gafur A, Hardiyanto E, Junarto, Hidayati N, Tjahjono B, Mardai U, Glen M, Mohammed C. Disease progression in plantations of Acacia mangium affected by red root rot (Ganoderma philippii). Forest Pathology 2014; 44: 447-459. 15. Irianto RSB, Barry K, Hidayati N, Ito S, Fiani A, Rimbawanto, A., Mohammed, C. 2006. Incidence and spatial analysis of root rot of Acacia mangium in Indonesia. Journal of Tropical Forest Science 2006; 18:157-165. 16. Mohammed C, Beadle C, Francis A. Management of fungal root rot in plantation acacias in Indonesia. Final Report ACIAR Project FST/2003/048. Canberra, Australia. Australian Centre for Agricultural Research; 2012. 17. Brawner J, Japarudin Y, Lapammu M, Rauf R, Boden D, Wingfield M. Evaluating the inheritance of Ceratocystis acaciivora symptom expression in a diverse Acacia mangium breeding population. Southern Forests 2015; 77: 83-90. 18. Thu PQ, Quynh DH, Fourie A, Barnes I, Wiengfield MJ. Ceratocystis wilt disease-a new and serious threat to acacia plantation in Vietnam. Paper presented at the IUFRO Acacia 2014 Conference held in Hue, Vietnam, 18-21 March 2014. 19. Mendham D, Rimbawanto A. Increasing productivity of and profitability of Indonesian smallholder plantation. Final Report ACIAR Project FST/2009/051. Canberra, Australia. Australian Centre for Agricultural Research. 2015. 20. Tarigan M, Roux J, Van Wyk M, Tjahjono B, Wingfield M. A new wilt and die-back disease of Acacia mangium associated with Ceratocystis manginecans and C. acaciivora sp. nov. in Indonesia. South African Journal of Botany 2010; 77: 292-304. 21. Tarigan M, Wingfield MJ, Van Wyk M, Tjahjono B, Roux J. Pruning quality affects infection of Acacia mangium and A. crassicarpa by Ceratocystis acaciivora and Lasiodiplodia theobromae. Southern Forest 2011; 73:187-191. 22. Tarigan M, Tjahjono B, Gafur A.. Preventive spays for Ceratocystis acaciivora infection control following singling practices of Acacia mangium. In Mohammed, C., Beadle, C., Rahayu, S. (eds.). Proceedings of International Conference on the Impact of Climate Change to Forest Pests and Diseases in the Tropics, October 8th-10th 2012, Yogyakarta, Indonesia. 2012; pp.182-185. 23. Inail A, Hardiyanto EB. Unpublished data. 24. Marolop R. Pers. comm.

ASSESSING THE ROLE OF RATIO OF SYRINGIL/VANILLIN-BASED LIGNIN MONOMERS, DENSITY OF FOUR PLANTATION-FOREST WOOD SPECIES, AND H-FACTOR ON DELIGNIFICATION INTENSITY AND PROPERTIES OF KRAFT PULP*)

Dian Anggraini Indrawana 1, Rossi Margareth Tampubolona, Gustan Paria, Saptadi Darmawanb, Han Roliadic 2 a Center for Forest Product Research and Development, Bogor, Indonesia, b Center for The Technology of Non-Forest Product Research and Development, Mataram, Indonesia, c Already Retired, 1 [email protected] 2 [email protected]

ABSTRACT

Domestic consumption of pulp and its derivatives (esp. paper) during the last three years (2012-2014) steadily increased, and might be such in the future. Concerns arouse as the availability of conventional fiber sources (natural-forest woods) in Indonesia for pulp/paper becomes depleted and scarce. One way to overcome is introducing alternative fibers, e.g. plantation-forest (PF) woods. Different PF-wood species could affect pulping properties (esp. delignification extent/intensity), and the resulting-pulp/ paper products. This can lead to inefficiency in utilizing and processing different wood species for pulp/paper; and therefore deserves thorough solution. Pulping with kraft process through ingenuously manipulating process condition indicatively could tolerate species differences. Basic properties of PF woods should also be accounted (e.g. density, lignin content, and ratio of syringil-to-vanillin units in lignin). Relevantly, laboratory-scale kraft pulping was conducted on individual PF species (i.e. sengon, gmelina, meranti kuning, and kapur) employing fixed processing/cooking conditions, i.e. 16%-active alkali, 22.5%-sulfidity, and 1:4-wood-to-liquor ratio. Variable conditions were maximum cooking- temperatures at 170oC and 190oC, each held for 0-, 30-, 60-, and 90-minute durations. Combination of cooking temperatures and durations brought-out eight H-factors values (117.88-2182.67) and accordingly eight kraft-pulp varieties. Greater H-factor values induced more delignification intensity. Delignification intensity seemed more affected by ratio of syringil/vanillin units (R2=0.2026**) than by wood density (R2=0.2005*) and lignin content (R2=0.0688ns). Such intensity correlated positively with screened-pulp yield and negatively with pulp reject. The highest yield was achieved at H-factor 1502.25. As such, kraft-pulp handheets were formed without beating, and their physical/strength properties tested. Sheet properties correlated positively with syringil/vanillin ratio, negatively with wood density (less strongly), but insignificantly with lignin content. Overall, this implied greater syringil/vanillin ratio apparently enhanced active-selective delignification intensity, thereby lessening wood-carbohydrate degradation. The best/highest sheet physical/strength properties were from sengon wood, followed in decreasing order by gmelina, meranti kuning, and kapur. Meranti kuning and kapur which seemed unsatisfactory in kraft pulping can expectedly be improved by enhancing active-selective cooking liquor (e.g. regulating sulfidity and introducing AQ). These significant results seem prospectively beneficial to bring more efficient pulp/paper processing from PF woods; and lessen dependency on natural-forest woods, thereby mitigating forest-destruction intensity and sustaining natural resources.

Keywords: Lignin, siringil, vanilin, kraft, pulping

1. Introduction

Pulp signifies as half-finished product for further manufacture into paper, paperboard, fiberboard, and other pulp derivatives. Pulping with chemical processes aims for the manufacture of paper with high qualities, particularly with respect to strengths and permanency (e.g. writing/printing papers and textbooks) and other products with high cellulose-purity (e.g. rayon, cellulose nitrate, cellulose acetate, and cellulose phosphate) [1]. Consumption of those items (esp. pulp and paper) in Indonesia during the last three years (2012-2014) tended to increase (1.75-1.95 milllion tons); and indicatively will be such

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 35 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 in the future along with the advancement of human civilization and population increase. Such increase one day can not be overcome with processing results of conventional fiber stuffs (esp. natural forest woods) as their potencies become depleted and scarce [2,3]. One way to cope with those problems is introducing alternative fibers, and among them are plantation forest (PF) woods [4]. Being located in tropical region, Indonesia can have a huge diversity in its vegetations including forest trees with respect to species or related sorts. This can also lead to variation in PF wood species and hence their basic properties. Variation in wood species can bring about inefficiency in their utilization and processing into pulp/paper, and therefore deserve thorough attention [5]. Indicatively, wood pulping with kraft process can tolerate species difference to some extent through an appropriate process modification. The modification is such that kraft pulping affords effective (active-selective) delignification, high screen-pulp yield, low pulp rejects, and high pulp strengths, as those are related to qualities of paper or other pulp derivatives that result [1,6]. Variables in kraft pulping that affect those properties are among others temperature and duration of cooking. For simplification, those two variables can be expressed as a single variable, called the H-factor [7]. Relevantly, there has been experimented to assess the role of particular basic properties (wood density, lignin content, and ratio of syringil/vanillin-based monomers in lignin) of four tropical PF wood species, i.e. sengon, gmelina, meranti kuning, and kapur, on the delignification extent/intensity and properties of kraft pulp that resulted at various H-factor levels [5,8].

2. Literature Reviews

Plantation forest (PF) woods as also the case for natural forest woods and woods in common, in their fiber wall contain lignin, cellulose, and hemicellulose [5]; and accordingly PF woods are technically worth for pulp/paper processing. Several PF wood species have been adopted for the establishment of PF, e.g. sengon, gmelina, meranti kuning, and kapur (4). Different PF wood species can affect pulping properties (e.g. delignification extent and pulp yield); and further qualities/properties of pulp, paper, and other pulp derivatives [5,8]. Kraft process indicatively can tolerate wood species difference, thereby expectedly appropriate for the pulping of various tropical wood species, including PF woods through properly modifying condition of process/cooking [5,6]. Such condition (e.g. cooking temperature and duration) can also affect delignification extent, pulp yield, and ultimately kraft pulp properties. Cooking temperature and duration is inter-dependent, whereby the greater the temperature the shorter the duration; and vice versa. Further, Vroom developed a method that smartly simplified those two variables into a single variable (H-factor). Greater H-factor implies that kraft cooking condition becomes more severe and therefore intensifies the delignification action; and vice versa. In this way, accordingly, H-factor can be regarded as theoretical delignification intensity, regardless of differences in wood or other ligno-cellulose fiber species and other varying kraft cooking conditions (e.g. active alkali, sulfidity, and wood-to-liquor ratio) than cooking temperature and durations as such [1,6,7].

3. Methodology

3.1. Main Materials

The main materials were tropical plantation-forest (PF) woods that consisted of four species, i.e. sengon, gmelina, meranti kuning, and kapur (Table 1). Fist two species were obtained from Jatinangor, Sumedang (West Java), while the latter two from Berau (East Kalimantan).

3.2. Methods

3.2.1. Analysis on Wood Samples

Wood samples were prepared from each of those four FP species for the determination of basic density and lignin content (Table 1) in accordance with procedures and standards of TAPPI [9]. The

Figure 1. Phenyl-propane lignin monomer as conifery al cohol (A) with vanillin-type unit (V); and another phenyl-propane lignin monomer as sinapyl alcohol (B) with syringil-type unit (S) [6,10, 11] obtained lignin was subjected to exhaustive nitrobenzene oxidation to convert sinapyl alcohol and coniferyl alcohol monomers inside into consecutively syringil and vanillin units (Figure 1). The ratio of syringil-to-vanillin units could further be figured out (Table 1) through gas chromatography procedures developed by McNair and Bonelli [7].

3.2.2. Kraft Pulping on PF Woods and Further Related-Scrutinies

Wood samples of each PF wood species were manually reduced in size to chips measuring 3-4 cm (length) by 2.25-2.50 cm (width) by 2-3 mm (thickness), and then allowed for some time under the roof to reach their air-dry moisture content (12-14%). Afterwards, the wood chips of each PF species were cooked into pulp by kraft process in an electrically heated rotary digester of 20-liter capacity per batch. Fixed cooking conditions were active alkali (13%), sulfidity (22.5%), wood-to-liquor ratio (1:4, w/v), and ramping-duration rate to maximum/keeping temperature (1.580oC/minute). Variable conditions were two levels of maximum temperature (170oC and 175oC); and the overall (total) cooking- durations of those required from room temperature to reach each of those two maximum (keeping) temperature, added with the durations held at those maximum temperatures (i.e. 0, 30, 60, and 90 minutes). The combination of those overall cooking durations (t) and maximum temperatures (T) was further manipulated using Vroom method (Equation I), thereby bringing-out 8 varying H-factor values (117.88-2182.67) (Table 2), and accordingly 8 softened cooked-chip varieties (pulp candidates) for any of the four PF wood species (Figure 2a; Appendix A).

where: • t = particular cooking duration beginning from room temperature, ramping temperature, until end of keeping temperature; • T = absolute cooking temperature (in oK = oC + 273) at end of particular cooking duration (t), including the room temperature where the cooking starts, raising (ramping) temperature), and keeping temperature

After kraft cooking, the 8 varieties of softened chips were each vigorously agitated using a stirrer into separated fibers (pulp). Afterwards, the resulting kraft pulp was passed through a0.25-mm- slotted packer sceen. Before screening, some amount of pulp was taken for the determination of total (unscreened) pulp yield, while the portion passing through the screen was determined as screened- pulp yield. Pulp reject was calculated by subtracting unscreened-pulp yield with screened-pulp yield. Further, residual lignin content in unscreened pulp was determined according to TAPPI standards [9]. The actual delignification intensity was virtually approached ≈( ) by dividing the particular H-factor value (theoretical delignification intensity) in kraft cooking (pulping) by residual lignin content in its corresponding unscreened pulp (corrected to the total/unscreened pulp yield and then oven-dry weight of the related cooked wood chips) [6,7], and then transformed into elogarithmic (Ln), as follows:

Actual delignification intensity (Li) ≈ [ H / ΔL ] * [Y / 100% ] ------(II)

where: • H = calculated H-factor (refer to Equation I); ΔL = residual lignin content in unscreened pulp; Y = total (unscreened) pulp yield (%); the obtained actual delignification intensity (Li) was further transformed into elogarithmic (ln; e = 2.71828) or in other words went through the ln transformation (Figure 2a; Appendix A)

3.2.3. The Forming of Kraft Pulp Sheet

Kraft screened-pulp yield that reached the highest over particular H factor was selected and further formed into handsheet (without beating). Afterwards, the pulpsheets were conditioned for about 24 hours and then tested for their physical-strength properties also in accodance with the TAPPI standards [9].

4. Results and Discussion

4.1. Wood Basic Properties

The examined wood properties covered basic density, lignin content, and ratio of syringil-to-vanillin lignin monomers (Table 1). There was strong indication that those properties differed among the four FP wood species

Table 1: Basic properties of four tropical plantation-forest wood species [8] 1)

Basic density Lignin content Syrngil/Vanillin No Wood species gram/cm3 % ratio 1 Sengon (Paraserianthes falcataria (L) Nielsen 0.45 26.72 2.03 2 Gmelina (Gmelina arborea Roxb) 0.48 25.50 2.02 3 Meranti kuning (Shorea spp.) 0.57 24.89 1.87 4 Kapur (Dryobalanops spp.) 0.62 26.40 1.30 F-test for significant difference ** * ** Remarks: 1) Average of 5 replications; * = significant at P = 0.05; ** = significant at P = 0.01

4.2. The Obtained H-factors

The H-factor values as obtained are presented in Table 2. Greater H-factor values (i.e. theoretical delignification intensity) implied the more severe (intense) kraft coking condition; and vice versa.

Table 2. H-factors as obtained by manipulating cooking duration and temperature as single variable [5,8]

T max t t T (Tr à Tm) TM Tot H-factors *) oC minutes minutes minutes 170 90.00 0.00 90.00 117.88 170 90.00 30.00 120.00 579.34 170 90.00 60.00 150.00 1040.81 170 90.00 90.00 180.00 1502.25 175 93.15 0.00 93.15 173.87 175 93.15 30.00 123.15 866.56 175 93.15 60.00 153.15 1559.25 175 93.15 90.00 183.15 2182.67 Remarks:

T max = maximum cooking temperature; t (Tr à Tm) = the duration that took from the room temperature raising to maximum cooking temperature; t TM = the duration at maximum cooking temperature; t Tot = total duration of t (Tr à Tm) + t TM; *) Calculated using Vroom formula (refer to Equation I)

4.3. Properties of Kraft Pulping

Data on pulping properties varied with wood species as well as H-factors (Appendix A). Greater H-factors clearly induced actual delignification intensity (Figure 2a), causing more intensive dissolution of lignin. This was implied by the decrease of total (unscreened) pulp yield (Figure 2b). More intensive lignin dissolution also rendered fiber separation more perfect, thereby increasing screened-pulp yield to some extent (Figure 2c) and concurrently decreasing pulp reject (Figure 2d). Beyond H-factor at 1502.25, overall screened-pulp yield from four PF wood species apparently tended to decrease (Figure 2c). Presumably besides more intensive fiber separation, such was caused by more severe wood carbohydrate degradation (esp. cellulose and hemicellulose) with more severe cooking-condition (H-factor >1502.25). As described before, H-factor served just as theoretical delignification intensity, regardless of e.g. different cooked-wood species. Should the H-factor values be linked to the actual delignification intensity, there appeared a difference in such intensity among PF wood species at particular H-factors, whereby highest actual delignification intensity occurred to gmelina wood, followed in decreasing order by sengon, meranti kuning, and kapur (Figure 2a). This indicated that lignin removal (dissolution) at the first two species proceeded easier than the latest two species. It is interesting that the first two species exhibited greater ratio of syringil-to-vanillin (S/V) units, while the latest two species revealed the lower ratio (Table 1). This also implied that the active-selective actual kraft delignification intensity seemed affected by ratio of S/V units (correlation coeff: R2=0.2026**; R=+0.4501**) (Figure 3a). However, wood density also correlated with such active-selective actual kraft delignification intensity, but less strongly (R2=0.2005*; R=-0.4478) (Figure 3b); while wood initial lignin content did so, yet insignicantly (R2=0.0688tn; R=+0.2623tn) (Figure 3c). In all this suggested that S/V ratio affected the active-selective actual delignification intensity the strongest, followed in decreasing order bywood density and initial lignin content. Further, the active selective delignification correlated positively with screen-pulp yield (R=+0.3529*) (Figure 4a) and negatively with pulp rejects (R=-0.7739**) (Figure 4b). This was explicable, as such active-selective action induced more lignin dissolution and lessened carbohydrate degradation, thereby intensifying fiber-to-fiber separation

Sengon Gmelina Meranti kuning Kapur Sengon Gmelina Meranti kuning Kapur 8 65

60 6

55 5 Total pulpTotal yield,%

4 50 Delignification intensity (ln transformation) (ln intensity Delignification

3 100 400 700 1000 1300 1600 1900 2200 45 H-factor 100 400 700 1000 1300 1600 1900 2200 (A) H-factor (B)

Sengon Gmelina Meranti kuning Kapur Sengon Gmelina Meranti kuning Kapur 25 55

53 20 51

49 15 47

Pulp reject,% 10 43

Screened-pulp yield,% Screened-pulp 41 5 39

37 0 35 100 400 700 1000 1300 1600 1900 2200 100 400 700 1000 1300 1600 1900 2200 H-factor H-factor (D) (C)

Figure 2. Relationship of H-factor consecutively with delignification intensity (A), with total (unscreened) pulp yield (B), with screened-pulp yield (C), and with pulp reject (D) [8]

8 7

7 6

5 2 R = - 0,4478 (R = 0,2005) * R = +0.4501 (R2 = 0.2026) * 4 Delignification intensity (Ln. transf) (Ln. intensity Delignification 4 Delignification intensity (Ln.transf) intensity Delignification

3 3 0,4 0,45 0,5 0,55 0,6 0,65 1,25 1,45 1,65 1,85 2,05 Wood basic density, g/cm3 Syringil/Vanillin Ratio (B) (A)

5 R = + 0.2623 (R2 = 0.0688) ns 4 Delignification intensity (Ln.transf) intensity Delignification

3 24 25 26 27 Wood initial lignin content, % (C)

Figure 3. Correlation between syringl-to-vanillin (S/V) unit ratio and delignification intensity (A); between wood basic density and delignification intensity (B); and between wood initial lignin content and delignification intensity (C)

Sengon Gmelina Meranti kuning Kapur Sengon Gmelina Meranti kuning Kapur

22 51 20 49 18 R = + 0.3529 * 16 47 14 45 12 R = - 0,7739 ** 10 43

Pulp reject, % reject, Pulp 8 41 6 Screened-pulp yield,% Screened-pulp 4 39 2 37 0 3 4 5 6 7 8 3 4 5 6 7 8 Delignification intensity, ln transformation Delignification intensity, ln transformation

Figure 4. Correlation of actual delignification intensity with consecutively screened-pulp yield (A); and with pulp rejects (B)

Regarding the initial lignin content, despite significant variation among the four FP woods (Table 1), its insignicant correlation with actual delignification intensity (Figure 3c) suggested that such variation to some particular range did not affect the delignification kinetics [1,6]. About wood density, its lower role despite existing on actual delignification intensity than S/V ratio was also explicable (Figure 3b). Theoretically woods with greater density necessitated more energy input for the delignification process. This meant delignification of greater-density PF woods would require e.g. greater H-factor as well, in cooking; and vice versa. However, such was not too problematic to some extent for kraft cooking, as the strong alkaline liquor during the kraft cooking could diffuse at nearly almost equal rate in longitudinal, radial, and tangential directions of the cooked wood chips [6,8]. . The greatest role of S/V ratio at the initial wood lignin entity on delignification intensity (Figure 3a) indicatively owed to the more possibility of reaction mechanism I (Figure 5) particularly for FP

40 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 woods with higher S/V ratios, such as gmelina and sengon (Table 1), i.e. de-methylation (de-alkilation) on fragmented lignins, thereby rendering them more soluble; in addition to the regular delignification that prevalently occurs through the cleavage of α-O-4 and β-O-4 bonds at the lignin during the kraft cooking [6,10]. This situation induced more intensive fiber separation; and explained greater screen- pulp yield and concurrently lower pulp reject from meranti kuning and kapur woods (Figures 2c and 2d). Conversely, lignin with lower S/V ratio that implied containing more vanillin units (Figure 1) such as meranti kuning and meranti, might inflict more possibility on mechanism reaction II (condensation) between the fragmented lignins that afforded greater-sized fragments (aggregates) which were less soluble (Figure 6). Such phenomena besides retarding delignification rate (intensity) could also induce more severe degradation on wood carbohydrates (esp. cellulose and hemicellulose). It seemed that such condensation and degradation occurrence contributed their role significantly in decreasing the screened-pulp yields from meranti kuning and kapur woods with the elevated H-factor; and also their lower screened-yields than from gmelina and sengon woods (Figures 2c). Further beyond 1502.25 H-factor, condensation reaction during the kraft cooking of meranti kuning and kapur woods apparently became more intensive that rendered their pulp rejects increasing to the point which exceeded the rejects from gmelina and sengon (Figure 2d).

4.4. Physical and Strength Properties of Kraft Pulp Sheet

Kraft pulp handsheets were only formed and tested from the kraft cooking (pulpng) at 1502.25 H-factor, as such could achieve the highest screened-pulp yield and lowest pulp reject, particularly from gmelina and sengon woods (Figures 2c and 2d). It appeared that highest basis weight and strengths of pulp sheets were from sengon, followed in decreasing order by consecutively gmelina, meranti kuning and kapur (Table 3). Such decreasing order was seemingly correlated with the lowering S/V ratio at each of the four PF woods (R** = [+0.5665] - [+0.6542]). This again strengthened the previous indication of active-selective kraft delignification which became less effective with the more intensive condensation reaction, imperfect fiber separation, and more wood carbohydrate degradation, especially for meranti kuning and kapur woods [6,10].

Figure 5. Reaction mechanisms, in which the syringil-type monomer units in the lignin entities during the kraft cooking are partially de-methylated (de-alkilated) forming more soluble lignin fragments [6,10]

Figure 6. Condensation reactions (A and B types) that can occur between the already fragmented lignins at the unoccupied C-5 position of the vanillin-type monomers during the kraft cooking forming less soluble larger-sized lignin fragments (aggregates) [10,11]

Correlation between pulp basis weight/pulp strengths and wood density also occurred (negatively), but less strongly (R* = [-0.5078] - [-0.5663]) compared to the case for S/V ratio, whereby the greater the density, then the lower those two pulp properties. This was explicable as wood with low density tended to have thin fiber-walls, thereby intensifying fiber-to-fiber bonds and felting during the sheet forming; and vice versa. On the other hand, insignificant correlation between initial lignin content and pulp basis weight/strengths (Rns = [+0.3219] - [+0.4646]) seemed strongly attributable to the insignificant correlation between lignin content and delignification intensity (Figure 3c)

Tabel 3. Basis weight and strength properties of unbeaten kraft pulp from four plantation forest’s wood species [8]1)

Basis weight Tear factor Breaking length Wood species g/m2 mN.m2/g Km Sengon 61.55 5.09 5.55 Gmelina 61.13 2.29 2.67 Meranti kuning 61.08 0.33 0.36 Kapur 57.23 0.24 0.26

Correlation (R) with Syringil/Vanillin Ratio: + 0.5857 * + 0.6542 ** + 0.5665 * (Highest) Correlation (R) with Wood Basic Density: - 0.5391 * - 0.5663 * - 0.5078 ns (Second Highest) Correlation (R) with Lignin Content: + 0,3219 ns + 0,4646 ns + 0,4518 ns (Lowest) 1) Average of 5 replications

4. Conclusions and Suggestions

Satisfactory qualities of kraft pulp from four plantation forest (PF) wood species can be obtained by thoroughly accounting for their varying wood basic properties (i.e. density, initial lignin content, and ratio of syringil-to-vanillin lignin monomers) as well as implementing appropriate cooking condition (varying theoretical delignification intensities or H-factors at 117.88-2182.67). Supporting details are forthcoming: Actual delignification intensities increased with the elevated H-factors. At 1502.25 H-factor was obtained the kraft pulp apparently with highest screened-pulp yield, lowest pulp reject. Therefore, highest pulp strengths were strongly presumed at such H-factor Actual delignification intensity, screened-pulp yield, and pulp strengths seemed affected by ratio of syringil-to-vanillin (S/V) units (the strongest), followed by wood density (less strongly) and initial wood lignin content (insignificantly). Such phenomena implied that increasing S/V ratio besides enhancing active-selective kraft delignification also concurrently lessened wood carbohydrate degradation; and vice versa. Based on such implication, sengon wood afforded the greatest prospect for kraft pulp, followed in decreasing order by gmelina, meranti kuning, and kapur woods. PF woods which were less prospective for kraft pulp (i.e. meranti kuning and kapur) expectedly can be improved by enhancing active-selective kraft cooking liquor, e.g. regulating sulfidity and introducing little amount of additives (anhtraquinone/AQ and polysulfide/PS). The seemingly prospective results of kraft pulping on those four PF woods expectedly can bring benefits towards more efficiency in fibrous stuff utilization and lessening dependency on conventional fiber sources (natural forest woods), thereby reducing forest degradation rate and sustain renewable natural sources.

References

1. Smook, G.A. Handbook for Pulp and Paper Technologists. Atlanta, Georgia. USA Joint Textbook Committee of the Paper Industry; 2002. 2. Anonim. Indonesia’s Statistics. Jakarta, Indonesia. Agency for Statistics Center; 2015. (Heading and Content in Indonesian as well as in English) 3. Anonim. Forest Resources: Current Indonesia’s deforestation rate at 0.5 million ha per year. Environment. Kompas Newspaper, May 9, 2012, p. 13 Jakarta, Indonesia; 2012. (Heading and Content in Indonesian) 4. Anonim. The management and governance of industrial plantation forest evaluated. Republika On- line. 11 August 2012. Accessed on 28 January 2013 (Heading and Content in Indonesian) 5. Anggraini, D., Efiyanti, L., Tampubolon, R.M. Pulp manufacture for wrapping paper. Draft still under evaluation for publication. Bogor, Indonesia. Center for Forest Products Research and Development; 2014. (Title and Abstract in Indonesia as well as in English; Content in Indonesian 6. Casey, J.P. Pulp and Paper: Chemistry and Technology. 3rd ed. Vol I. New York USA. A Wiley - Interscience Publisher; 1980. 7. Anonim. Kraft pulping kinetics. Derivation of H-factor. PSE. Lecture 12. Seattle, Washington, USA. College of Forest Resources. Univ. of Washington; 2009. website: http://se/s.washington. edi>powerpoint. Accessed on 17 January 2016. 8. Roliadi, H. and Rahmawati, N. Explicability of the H-factor to account for the delignification extent and properties of plantation forest wood in the kraft cooking process. Bogor, Indonesia. Center for Forest Products Research and Development Center. Journal of Forest Products Research, vol. 24 (4): 275-299; 2006. (Title and Abstract in English as well as in Indonesian; Content in English) 9. Technical Association of the Pulp and Paper Industries (TAPPI)’s Test Methods. Atlanta, Georgia, USA. TAPPI; 2007. 10. Lourenci, A., Cominho, J., A. VeletPeresa, M.H. Reactivity of syringil and guaiacyl lignin units and delignification kinetics in kraft pulping of Eucalyptus globulus using Py-GC - MS/FID. DOI: 10.1016/9.biotech.2012.7.092. Portugal. Bioresource Technology, 123: 296-32; 2012 website: http://www.researchgate-net > publication. Accessed on August 17, 2015. 11. Prentti, O. Wood: Structure and Properties. New York, USA. Trans Technical Publications; 2006.

Appendix A. Kraft pulping properties of four plantation-forest wood species [8]1)

Residual Residual Actual Total- Screened- lignin lignin Actual delignification Pulp Wood species H-factor pulp pulp content content delignification intensity (ln reject,% yield,% yield,% in pulp, (ΔL), intensity transformation) % % 2) 3) Sengon 117.88 63.02 42.75 20.27 4.97 3.13209 37.63616 3.62797 173.87 60.75 44.51 16.24 4.72 2.86740 60.63681 4.10490 579.34 57.05 48.55 8.50 4.65 2.65283 218.38606 5.38626 866.56 55.40 49.15 6.25 4.37 2.42098 357.93769 5.88036 1040.81 54.32 49.15 5.17 4.12 2.23798 465.06588 6.14218 1502.25 51.32 49.98 1.34 3.34 1.71409 876.41358 6.77584 1559.25 50.94 50.02 0.92 3.23 1.64536 947.66380 6.85400 2182.67 48.81 47.83 0.98 3.02 1.47406 1480.71787 7.30028 Gmelina 117.88 61.35 44.25 17.10 4.90 3.00615 39.21295 3.66901 173.87 59.62 44.25 15.37 4.91 2.92734 59.39518 4.08421 579.34 59.05 44.40 14.65 4.52 2.66906 217.05769 5.38016 866.56 59.22 44.37 14.85 4.09 2.42210 357.77248 5.87990 1040.81 57.40 49.15 8.25 3.80 2.18120 477.17312 6.16788 1502.25 54.59 49.90 4.69 3.04 1.65954 905.22291 6.80818 1559.25 54.20 48.79 5.41 2.95 1.59890 975.20170 6.88264 2182.67 49.68 46.72 2.96 2.48 1.23206 1771.55570 7.47961 Meranti kunng 117.88 65.40 43.60 21.80 6.30 4.12020 28.61026 3.35377 173.87 64.58 43.00 21.58 6.04 3.90063 44.57483 3.79717 579.34 61.94 40.80 21.14 5.26 3.25804 177.81835 5.18076 866.56 55.10 39.91 15.19 4.76 2.62276 330.40004 5.80030 1040.81 52.15 39.48 12.67 4.61 2.40412 432.92854 6.07057 1502.25 50.18 38.55 11.63 4.52 2.26814 662.32801 6.49576 1559.25 51.65 39.45 12.20 4.43 2.28810 681.46209 6.52424 2182.67 49.67 38.01 11.66 4.08 2.02654 1077.04477 6.98198 Kapur 117.88 61.12 44.65 16.47 6.01 3.67331 32.09093 3.46857 173.87 60.33 43.96 16.37 5.96 3.59567 48.35541 3.87858 579.34 57.44 42.07 15.37 5.42 3.11325 186.08861 5.22622 866.56 55.88 40.86 15.02 5.03 2.81076 308.30052 5.73108 1040.81 55.02 39.70 15.32 4.76 2.61895 397.41469 5.98498 1502.25 52.91 40.20 12.71 4.50 2.38095 630.94563 6.44722 1559.25 52.67 40.86 11.81 4.41 2.32275 671.29567 6.50921 2182.67 50.17 39.14 11.03 4.08 2.04694 1066.31082 6.97196

Remarks: 1) Average of 5 replications; 2) Corrected to total-pulp yield and original oven-dry weight of the cooked wood chips; 3) Ln transformation

LIGNIN STRUCTURE OF ACACIA AND EUCALYPTUS SPECIES AND ITS RELATION TO DELIGNIFICATION

Deded S. Nawawia,b, Wasrin Syafiia, Takuya Akiyamab, Tomoya Yokoyamab,Yuji Matsumotob1 aDepartment of Forest Products, Faculty of Forestry, Bogor Agricultural University (IPB), Bogor, Indonesia bWood Chemistry Laboratory, Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo, Japan [email protected]

ABSTRACT

Lignin structure of 15 acacia woods and 13 eucalyptus woods were analyzed and the relationships between lignin structure and lignin reactivity were examined. Generally hardwood lignins are different from softwood lignins by the presence of syringyl type aromatic nuclei. In addition, there are wide varieties in the structure and amount of hardwood lignins depending on wood species, environment of growing site, portion in the wood, portion in the cell wall, and so on. We have shown that the wide variety of lignin structure and amount can be sorted out by taking the syringyl/guaiacyl ratio as an index. Furthermore, we have also shown that lignin structure can be quantitatively related to the chemical reactivity such as delignification during chemical pulping by taking the syringyl/guaiacyl ratio as an index. In this report, we review our recent achievements about the quantitative relationships between lignin structure and reactivity .

Keywords: lignin; structure; delignification; pulp; aromatic; stereo structure

Lignin Aromatic Structures and b-O-4 Structures

Generally, hardwood lignin contains syringyl nuclei and guaiacyl nuclei as aromatic ring types (Fig.1). Syringyl/guaiacyl ratio is a very important structural characteristics of lignin and greatly different each other depending on the difference of wood species, position in the wood, environment of growing site, portion in a cell wall, and so on.

CH2OH CH2OH H C O H C O H C OH HO C H OCH3 OCH3

OCH3 H3CO OCH3 OCH3 OCH3 OCH3 OCH3 O O OH O C O O

guaiacyl syringyl phenolic non-phenolic erythro β-O-4 structure threo β-O-4 structure

aromatic ring type aromatic ring type side-chain stereo structure

Fig. 1 Important Chemical Characteristics of Lignin from the Point of Reactivity

Another important difference of aromatic structure is phenolic or non-phenolic. Although the difference of whether guaiacyl or syringyl doesn’t change the reaction mechanism, it greatly affects the reactivity. On the other hand, difference of whether phenolic or non-phenolic sometimes results in the different reaction mechanism. As a most important structure in lignin, b-O-4 structure is present in both hardwood and softwood lignins. This structure has two stereo isomers, erythro and threo at its side-chain (Fig. 1). All of these differences affect the reactivity of lignin. Therefore, if lignin structure is different, the pulping performance can be greatly different.

General Tendency of Lignin Chemical Structure

Based on the analysis of 21 wood species, Akiyama et al. (2005) reported that the general tendency of lignin chemical structure can be visualized by taking syringyl/guaiacyl ratio as an index. General tendency was as following: the higher the syringyl/guaiacyl ratio, the higher the erythro/threo ratio of b-O-4 side chain stereo structure, the higher the proportion of b-O-4 structure, the higher the proportion of non-condensed structure, the lower the lignin content, and so on. These general tendency can be seen not only among different wood species, but also in different portions of the same wood. For example, Akiyama et al. (2003) demonstrated that the tension part of reaction wood can be characterized by higher syringyl/guaiacyl ratio, higher erythro/threo ratio, higher proportion of b-O-4 structure, and, lower lignin content compared with the compression part by the analysis of samples obtained from the different portion within the same wood disc of yellow poplar stem which was standing on the slope before harvest. Later, Nawawi et al. applied the same analysis to various type of reaction wood samples and confirmed the same tendency (Nawawiet al. 2016A, B). The relation can be recognized not only in the wide range of wood species but also in the same group of trees in which the structural difference is rather small. If the structural difference is small, it will be difficult to establish a correlation between two structural factors. However, Nawawi et al. (2016C) successfully demonstrated that the general tendency can be well recognized among the same group of trees, such as genus Acacia and genus Eucalyptus (Table 1).

Table 1. List of wood samples examined in this study

Sample Wood species Sample Wood species Genus Acacia Genus Eucalyptus 1 Acacia auriculiformis 16 Eucalyptus camaldulensis A 2 Acacia hybrid A *1 17 Eucalyptus camaldulensis B 3 Acacia hybrid B*1 18 Eucalyptus deglupta 4 Acacia hybrid C*1 19 Eucalyptus dunii 5 Acacia hybrid D *1 20 Eucalyptus globulus A 6 Acacia hybrid E*1 21 Eucalyptus globulus B 7 Acacia hybrid F*1 22 Eucalyptus grandis A 8 Acacia mangium A 23 Eucalyptus grandis B 9 Acacia mangium B 24 Eucalyptus grandis C 10 Acacia mangium C-1*2 25 Eucalyptus hybrid *3 11 Acacia mangium C-2*2 26 Eucalyptus nitens 12 Acacia mangium D 27 Eucalyptus saligna 13 Acacia mangium E 28 Eucalyptus urophylla 14 Acacia mangium F 15 Acacia meransii Same wood species with different alphabets are from different growing area. *1: Hybrid of Acacia mangium and Acacia auriculiformis with different mother trees *2: Same species from the same plantation area but C-1 was 8 years and C-2 was 12 years old *3: Hybrid of Eucalyptus camaldulensis and Eucalyptus deglupta

For example, Fig. 2 shows the relation between lignin content and syringyl/guaiacyl ratio. Here, the ratio between syringyl and guaiacyl is expressed as syringyl ratio (proportion of syringyl among the total of syringyl and guaiacyl). It is clearly shown that lignin content is significantly related to the syringyl ratio within each genus. Among the general tendency of lignin chemical structure, the correlation between the syringyl/ guaiacyl ratio and erythro/threo ratio of b-O-4 side-chain stereo structure is very high and this relation is quite important from the point of chemical reactivity of lignin as will be seen in the following sections. This correlation was first established by Akiyama et al. (2005) for 21 wood species (15 hardwoods and 6 softwoods) and later we have demonstrated that all the native lignins fit this correlation. Fig. 3 shows the correlation between the syringyl/guaiacyl ratio and erythro/threo ratio when they are expressed as

46 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 erythro ratio (proportion of erythro) and syringyl ratio, respectively). In this figure, the correlation found for 21 wood species by Akiyama et al. (2005) and that found for genus Acacia and genus Eucalyptus by Nawawi et al. (2016C) are expressed together. Since softwood has no syringyl nucleus, the erythro ratio is exactly 0.5, which means the amount of erythro and threo b-O-4 structure is equal.

Fig. 2 Relationship between lignin content and Fig. 3 Correlation between erythro ratio syringyl ratio. ◇ Acacia ◆ Eucalyptus of b-O-4 structure and syringyl ratio. ◇ syringyl ratio = syringyl/(syringyl+guaiacyl) Acacia ◆ Eucalyptus ○ 21 wood species by Akiyama et al. (2005) erythro ratio = erythro/(erythro+threo)

Structure-Reactivity Relationships of Lignin

During alkali pulping including kraft pulping, the most important reaction is the cleavage of non- phenolic b-O-4 structure shown in Fig. 4. In this mechanism, ionized a-hydroxyl group nucleophilically attacks the b-carbon from the backside of b-O-4 ether resulting in the cleavage of this linkage.

Fig. 4 Alkaline cleavage of non-phenolic b-O-4 structure

Considering the presence of 2 types of aromatic structures (syringyl and guaiacyl) and 2 types of side-chain stereo structures (erythro and threo), basically 8 types of b-O-4 structures are possibly present in lignin. In Fig. 5, structures of model compounds which represent these 8 types of b-O-4 structures are shown. The number below each structure is the alkali cleavage rate constant obtained by the alkali treatment under 160 ºC at 2 molar NaOH concentration. Since softwood lignin has only guaiacyl type aromatic nucleus, there are only two types of b-O-4 (erythro and threo of GG, Fig. 5) in softwood. The ratio between erythro and threo of softwood lignin is exactly 1:1. On the other hand, hardwood lignin has totally 8 types of b-O-4 (erythro and threo of GS, SG, SS in addition to GG, Fig. 5). Proportion between GG, GS, SG and SS can be different in different lignins depending on the ratio between syringyl and guaiacyl of the lignin. Reactivity of these 8 types of b-O-4 structures can be summarized as following: 1. erythro isomer is always more reactive than threo isomer when the aromatic composition is the same 2. substitution of guaiacyl with syringyl nucleus at any position results in the increase of reactivity 3. the effect of substitution from guaiacyl to syringyl is greater when etherifying guaiacyl is substituted than when guaiacyl in the carbon main skeleton is substituted. It is very important to note that syringyl ratio could be higher than 0.8 in some wood species (Fig.

3). Since the proportion of erythro b-O-4 becomes higher when the syringyl ratio is higher, erythro type of SS can be predominant b-O-4 structure in these wood species. In softwood lignin, half of b-O- 4 structure is threo GG type, while majority of b-O-4 structure is erythro SS type in these hardwood species. The alkali cleavage rate constant of the former type is 16.7 and that of latter is as high as 217. By this comparison, it is easily predicted that hardwood lignin with higher proportion of syringyl nuclei is much more easily degraded during alkali pulping process such as kraft pulping than softwood lignin or hardwood lignin with lower syringyl proportion (Shimizu et al. 2012, 2013, 2015).

Fig. 5 Model compounds of 8 types of non-phenolic b-O-4 structures and their alkali cleavage reaction rate constant in 2 molar aqueous NaOH under 160 ºC. S: syringyl, G: guaiacyl (Shimizu et al., 2012)

Pulping Result

In the previous section, it was predicted that hardwood with higher proportion of syringyl is easily delignified from the point of chemical reactivity of non-phenolic b-O-4 structures. One more factor which benefits the woods with higher syringyl proportion is the lower lignin content of such woods. Nawawi et al. confirmed this prediction by subjecting wood species belonging to genus acacia and eucalyptus to kraft pulping (Nawawi et al. 2016C). Fig. 6 clearly shows that woods with higher syringyl ratio needs less alkali charge to reach kappa 19.

Fig. 6 Relationship between syringyl ratio and delignification. ◇ Acacia ◆ Eucalyptus

References

1. Akiyama, T., Matsumoto, Y., Okuyama, T., Meshitsuka, G. Phytochemistry 64, 1157–1162 (2003) 2. Akiyama, T., Goto, H., Nawawi, D.S., Syafii, W., Matsumoto, Y., Meshitsuka, G. Holzforschung, 59(3), 276-281 (2005) 3. Nawawi, D.S, Syafii, W., Akiyama, T., Matsumoto, Y. Holzforschung 70(7):593-602. (2016A) 4. Nawawi, D.S., Akiyama, T., Syafii, W., Matsumoto, Y. 2016. Holzforschung (Holz.2016.0100: Accepted 12-Aug-2016). (2016B) 5. Nawawi, D.S., Syafii, W., Tomoda, I., Uchida, Y., Akiyama, T., Yokoyama, T., Matsumoto, Y. Submitted to Journal Wood Chemistry and Technology. (2016C) 6. Shimizu, S., Yokoyama, T., Akiyama, T., Matsumoto, Y. J. Agric. Food Chem., 60, 6471−6476 (2012) 7. Shimizu, S., Posoknistakul, P., Yokoyama, T., Matsumoto, Y. BioResources, 8 (3), 4312-4322 (2013) 8. Shimizu, S., Yokoyama, T., Matsumoto, Y. J. Wood Sci., 61 (5), 529-536 (2015)

A NOVEL PAPER-BASED SENSOR FOR COLORIMETRIC AND FLUORESCENT DETECTION OF COPPER IONS IN WATER

Yinchao Xu a1, Toshiharu Enomae b2 a Research fellow of Japan Society for the Promotion of Science; Graduate School of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8572, Japan b Faculty of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305- 8572, Japan 1 [email protected] 2 [email protected]

ABSTRACT

In this research, we have developed a user-friendly, low-cost, sensitive and ion-species-selective paper-based sensor to inspect drinking and industrial water for excessive levels of copper ions. The paper-based sensor was simply fabricated by printing an anthraquinone derivative acetone solution onto filter paper. In the colorimetric detection, by 10 min immersion in a 5 mL test water sample, the paper- based sensor was proven to be feasible to indicate a Cu2+ concentration of as low as 2 ppm, through the visible colour change from yellow to light purple. In the instrumental fluorescence detection, the linear relationship was successfully obtained between the resulting surface fluorescence intensity of the paper- based sensor and Cu2+ concentration. Based on this linear relationship, more accurate concentrations are available. In addition, the high selectivity of the paper-based sensor ensured applications to detect practical contaminated water samples.

Keywords: copper ion detection, inkjet printing, paper-based sensor

Introduction

Heavy metals, commonly defined as metals with densities higher than 5 g/m3[1], exist naturally in the environment. However, in past decades, heavy metals have caused serious environmental pollution, originating from industrial effluents and, more recently, metal ions leached from soil by acid rain.[2] As heavy metals form complexes with nitrogen, sulfur, and oxygen ligands in biosystems, excessive concentrations of heavy metals are harmful, or even deadly, to human and animals.[3] Copper, one of the most abundant and fundamental trace elements, can adopt distinct redox states, oxidized Cu(II) or reduced Cu(I), allowing the metal to play a pivotal role in cell physiology as a catalytic cofactor in the redox chemistry of enzymes, mitochondrial respiration, iron absorption, free radical scavenging, and elastin cross-linking.[4] In contrast, excessive concentrations of copper cause oxidative stress and related symptoms, which can lead to diabetes and many neurodegenerative disorders, such as Alzheimer’s disease[5], and Menkes disease[6], and Wilson disease[7]. Conventionally, inductively coupled plasma–optical emission spectroscopy (ICP–OES) is the most common and sensitive method used to determine metal ion concentrations [8].However, it is an expensive and laborious analytical method, limited to high-demand laboratory research analysis and, thus, inaccessible to nonprofessionals. To explore other analytical approaches, published alternative methods are mostly based on colorimetric analysis and fluorescence spectroscopy, combining modified dyes, synthesized organic compounds, or nanomaterials to achieve highly selective and sensitive detection. Mahapatra et al. developed a colorimetric and turn-off fluorimetric sensor for Cu2+ detection using a synthesized triphenylamine-based indolylmethane derivative [9]. Liu et al. developed a colorimetric Cu2+ sensor using DNA-functionalized gold nanoparticles [10]. Chen et al. developed a fluorescence sensor for Cu2+ detection using synthesized highly-fluorescent glutathione-capped gold nanoparticles [11]. Maity et al. [12] used thiourea-salicylaldehyde to realize visible and near-IR sensing of Cu2+ based on the coordination reaction.Many more effective synthesized chemicals and methods have also been proposed and developed, all showing remarkable sensing selectivity and sensitivity. However, these approaches are still costly and limit the methods to laboratory use as an alternative to ICP–OES.

Therefore, the development of a high-performance, user-friendly method to detect heavy metal ions, such as Cu2+, in water is in strong demand, and would allow nonprofessionals to determine water safety, especially in Third World countries. Herein, we proposed and developed a simple low-cost method, using inkjet printing technology to fabricate a paper-based copper ion sensor for both qualitative and quantitative detection. A commercial anthraquinone dye and common filter paper were used as the main chemical and substrate, respectively, for sensor fabrication. Consequently, the developed paper- based sensor can realize both qualitative detection of Cu2+ in water and quantitative detection based on fluorescence spectroscopy for high ion species selectivity and sensitivity.

Experimental

2.1 Materials

An anthraquinone derivative (Sigma-Aldrich) and filter paper (No. 1, Advantec) were used as the sensing dye and substrate of the sensor, respectively. Metal nitrate salts, including sodium, potassium, calcium, ferric, cobalt, cadmium, manganese, mercury, lead, nickel, zinc, and silver nitrates (Japanese Industrial Standard [JIS] special grade, Wako Pure Chemical), were used in the experiment to evaluate interference by metal ions other than Cu2+. Copper standard solution (Cu 100, Wako Pure Chemical) was used to calibrate Cu2+ concentrations measured by ICP–OES (Optima-7300DV, PerkinElmer, USA) and the paper-based sensor.

2.2 Fabrication

A lab-made ink, comprising a 1 g/L anthraquinone derivative acetone solution, was first prepared. An inkjet printer (DMP-2831, Dimatix, Fujifilm, Japan) was then used to fabricate the paper-based sensor by printing this ink onto filter paper. The designed printing pattern was a rectangle with a 30-mm length and 20-mm width, which was the most appropriate size for the sample holder in fluorescence spectroscopy in fluorescence detection. The ink dried in 10 s after printing, and the anthraquinone derivative was adsorbed onto the cellulose fibers through non-covalent interactions. Filter paper printed with the rectangular pattern is denoted as the “paper-based sensor” throughout. The paper-based sensors were cut out from the filter paper for further use.

2.3 Characterization

In the experiment, a confocal laser scanning microscope (CLSM) (LSM-700, Carl Zeiss, Germany) was used to observe the distribution of the anthraquinone derivative on fiber surfaces and in fiber networks. The filter paper was first stained with a 0.01 g/mL Nile blue–acetone solution by pipetting. After drying, a 0.5 g/L anthraquinone derivative acetone solution was printed onto the stained filter paper using the Dimatix inkjet printer. A paper sample with a 45° beveled cross-section was then prepared by cutting paper sandwiched between polystyrene blocks with a 45° beveled plane using a razor blade. The prepared paper sample was then pasted onto a glass slide and observed using CLSM. Double-track mode was applied to the laser scan. In one laser scanning track, the Ar laser at 488 nm was selected to excite and detect anthraquinone derivative, while in the other track, the He–Ne laser at 634 nm was selected to excite Nile blue in order to reveal the whole fiber network. The scanning depth was 200 μm, which was approximately equal to the filter paper thickness. Finally, 3D images of the paper-based sensor were captured.

2.4 Visible and Fluorescence Detections

In the visible detection, also referred to as qualitative detection, the paper-based sensors fabricated using 0.6 g/L anthraquinone derivative acetone solution were immersed in 5-mL Cu2+ aqueous solutions with concentrations of 1, 2, 3, 4, and 5 ppm for 10 min. After immersion, the sensor color was observed by the naked eye and captured using a digital camera.

In the fluorescence detection, also referred to as quantitative detection by applying fluorescence spectroscopy (F-4500, Hitachi, Japan), the surface fluorescence intensity of the paper-based sensor was measured. The excitation and emission wavelengths were 490 nm and 567 nm, respectively. As anthraquinone derivative was quenched by Cu2+ in solution, the surface fluorescence intensity of paper- based sensors immersed in Cu2+ solutions of various concentrations was determined. Paper-based sensors, fabricated using a 1 g/L anthraquinone derivative acetone solution, were immersed in 5-mL Cu2+ solutions with concentrations of 1, 2, 3, 4, 5, and 6 ppm for 10 min. Additionally, to achieve higher sensitivity, paper-based sensors were fabricated using an anthraquinone derivative acetone solution of lower concentration (0.4 g/L). Subsequently, these fabricated sensors were immersed in 5-mL Cu2+ solutions with concentrations of 200, 400, 600, and 800 ppb for 10 min. After immersion, excess water was removed with a paper wiper. Before drying, the surface fluorescence intensity of the paper-based sensors was measured, and the relationship between surface fluorescence intensity and Cu2+ concentration was determined. All aqueous samples in this research were adjusted to pH 7 using a buffer solution containing 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) and NaOH, which is widely used in research related to heavy metal solutions.

2.5 Interference

To determine the selectivity of the paper-based sensor, interference by other metal ions was studied in both visible and fluorescence detections. Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+ were tested. The paper-based sensors were immersed in a 5-mL 20-ppm aqueous solution of each metal ion. After 10 min immersion, the color of the sensor was observed by the naked eye and captured using a digital camera. In fluorescence detection, excess water on the paper-based sensors was removed and surface fluorescence intensity was measured.

Results and Discussion

3.1 Fabrication and Characterization

A quick and easy fabrication method was developed using inkjet printing technology. The anthraquinone derivative was firmly adsorbed on cellulose fiber surfaces through non-covalent bonds, including hydrogen bonds, hydrophobic forces, and CH–π interactions.16 The fabrication method developed in this research has the following advantages: (i) although acetone evaporated quickly, perhaps causing anthraquinone derivative to block the nozzle of the printer head, the ink easily flowed in the nozzle, redissolving anthraquinone derivative and preventing the printer head nozzle from being blocked; (ii) acetone is non-destructive to the filter paper fiber network; and (iii) inkjet printing technology makes flexible pattern design and homogeneous distribution of anthraquinone derivative possible. Furthermore, as shown in Fig. 1, anthraquinone derivative is only concentrated in the top layer with a total thickness of 150 μm, suggesting that it was possible to easily control and reduce the amount of anthraquinone derivative, and accelerate and accentuate the color reaction, compared with other fabrication methods, such as immersion. Fig. 2 shows a CLSM image of the anthraquinone derivative distributed evenly on cellulose fibers by inkjet printing. Even distribution was important for detection, especially for fluorescence detection, and difficult to achieve using any other method. Consequently, inkjet printing appeared to be an ideal method for this fabrication regarding pattern design, operation, and cost.

3.2 Qualitative and Quantitative Detection

Fig. 3 shows a photograph of paper-based sensors immersed in Cu2+ aqueous solutions. The color of the dye on the paper-based sensors changed from yellow to purple with increasing Cu2+ concentration. This result confirmed that the paper-based sensor was able to detect Cu2+ at concentration as low as 2 ppm, which is the maximum allowed amount in drinking water, according to the WHO. The entire

Fig. 1. CLSM image representing the 3D structure and the anthraquinone derivative distribution of a paper-based sensor cross-sectioned at 45o on one side.

Fig. 2. CLSM image of the anthraquinone derivative distribution on cellulose fibers.

Fig. 3. Paper-based sensors after immersion in Cu2+ aqueous solutions at different concentrations for 10 min. detection process took only 10 min and sensitive detection of Cu2+ was successfully achieved. The 10-min immersion time was determined in the preliminary test, in which no additional obvious color change was observed with immersion times longer than 10 min. This user-friendly detection provided the possibility for non-professionals to perform an on-site water safety check. Fig. 4 shows the fluorescence spectra of paper-based sensors after immersion inCu2+ aqueous solutions. As the Cu2+ concentration increased, the fluorescence intensity at 567 nm decreased. Fig. 5 shows a linear relationship between the surface fluorescence intensity of the paper-based sensor and Cu2+ concentration, which provided the possibility for quantitative detection of Cu2+ concentration using the paper-based sensor by simply combining with fluorescence spectroscopy. In addition, low2+ Cu

54 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 concentrations, at ppb levels, were detected accurately by applying a low-concentration anthraquinone derivative acetone solution in the fabrication, as shown in Fig. 6. The detection mechanism can be explained by the quenching effect of Cu2+ on the anthraquinone derivative. The complexation between Cu2+ and the anthraquinone derivative results in electron or energy transfer from the anthraquinone derivative moiety to Cu2+, quenching the fluorescence emission17. Regarding the kinetics of the chemical reaction at the solid–liquid interface, the amount of the anthraquinone derivative per unit area and the Cu2+ concentration were important factors in the detection reaction. After 10 min, the paper-based sensors printed with a certain amount of anthraquinone derivative decreased the fluorescence intensity because of an increasing quenching level, caused by the formation of more Cu2+ and the anthraquinone derivative complexes with an increasing Cu2+ concentration, within a certain range. In this research, the paper-based sensor printed with 5.7 × 10–9 mol/cm2 anthraquinone derivative was suitable for the visible detection of a 2 ppm Cu2+ aqueous solution, while the paper- based sensors printed with 9.5 × 10–9 and 3.8 × 10–9 mol/cm2 anthraquinone derivative were suitable for measuring Cu2+ concentrations in the ranges 0–5 ppm and 0–600 ppb, respectively. This revealed the positive correlation between the amount of the anthraquinone derivative per unit area and the detection range of Cu2+ concentration. Based on this relationship, paper-based sensors for various detection ranges could be fabricated by controlling the amount of the anthraquinone derivative printed.

Fig. 5. Fluorescence intensity of paper-based Fig. 6. Fluorescence intensity of paper-based sensor, fabricated with 1 g/L anthraquinone sensor fabricated with 0.4 g/L anthraquinone derivative solution, after immersion in Cu2+ derivative solution, after immersion in Cu2+ aqueous solutions of various concentrations, aqueous solutions at various concentrations, from from 0 to 5 ppm. 0 to 600 ppb.

3.3 Interference

Fig. 7 shows that, after immersion in each 20 ppm aqueous solution of Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+, no color change was observed in the paper-based sensors, except with the Cu2+ solution, even though the concentrations of other metal ions were all ten times that of Cu2+. This strongly indicated the high selectivity of the anthraquinone derivative for detecting Cu2+ without interference by other metal ions. In addition, Fig. 8 shows a result measured by fluorescence detection, which revealed that among these metal ion species, only Cu2+ could quench the anthraquinone derivative, and other metal ions had little impact on the surface fluorescence intensity of the paper- based sensors. Therefore, the paper-based sensors could function adequately in the detection of practical contaminated water.

Fig. 4. Fluorescence spectrum of paper-based sensors after immersion in Cu2+ aqueous solutions of various concentrations.

Fig. 8. Surface fluorescence intensity of paper-based sensors after immersion in 20 ppm aqueous solutions of Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+.

Conclusions

A quick, low-cost, and flexible method for fabricating an effective paper-based sensor using inkjet printing technology has been developed. Inkjet printing proved to be a standout fabrication method for the paper-based sensor, due to its low cost, flexible pattern design, and homogeneous distribution of the anthraquinone derivative. The paper-based sensor provided dual-function detection of Cu2+ in water. Visible detection provided semi-quantitative detection of Cu2+, which was beneficial for nonprofessionals, especially people in Third World countries, to quickly ascertain the safety of drinking water on-site. Fluorescence detection enabled the paper-based sensor to be an alternative method for ICP–OES, providing high measurement accuracy at a lower cost and with less laborious analysis and instrumental maintenance than ICP–OES. In addition, the high selectivity of the paper-based sensor ensured applications to detect practical contaminated water samples. In conclusion, a dual-functional paper-based sensor was successfully fabricated using inkjet printing technology for the semi-quantitative and quantitative detection of Cu2+ in water, and has great potential in practical applications, due to its low-cost fabrication, user-friendly operation, and high-accuracy detection.

Acknowledgements

This research is financially supported by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant Number 15J01942). The authors would like to thank the Research Facility Center for 56 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Science and Technology and Gene Research Center of University of Tsukuba for providing frequent opportunities to use their measurement equipment.

Fig. 7. Paper-based sensors after immersion in 20 ppm aqueous solutions of Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+.

References

1. Jarup L. Hazards of heavy metal contamination. Brit Med Bull 2003; 68: 167–182. 2. Khan M. Biomanagement of metal-contaminated soils. Springer Dordrecht 2011. 3. Aragay G, Pons J, Merkoçi A. Recent Trends in Macro-, Micro-, and Nanomaterial-Based Tools and Strategies for Heavy-Metal Detection. Chem Rev 2011; 111: 3433–3458. 4. Tapiero H, Townsend D, Tew K. Trace elements in human physiology and pathology. Copper. Biomed Pharmacother 2003; 57: 386–398. 5. Barnham K, Masters C, Bush A. Neurodegenerative diseases and oxidative stress. Nat Rev Drug Discov 2004; 3: 205–214. 6. Copper in drinking water. National Academy Press Washington, D.C. 2000. 7. Fatemi N, Sarkar B, Molecular mechanism of copper transport in Wilson disease. Environ Health Perspect 2002; 110: 695–698. 8. Ponce de León Hill C. Inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectoscopy used in the determination and speciation of trace elements, PhD Thesis, University of Cincinatti, 2001. 9. Mahapatra A, Hazra G, Das, Goswami S. A highly selective triphenylamine-based indolylmethane derivatives as colorimetric and turn-off fluorimetric sensor toward Cu2+ detection by deprotonation of secondary amines. Sensor Actuat B-Chem 2011; 156: 456–462. 10. Liu J, Lu Y. An invasive DNA approach toward a general method for portable quantification of metal ions using a personal glucose meter. Chem Commun 2007; 46: 4872–4874. 11. Chen W, Tu X, Guo X. Fluorescent gold nanoparticles-based fluorescence sensor for Cu2+ ions. Chem Commun 2009; 13: 1736–1738. 12. Maity D, Govindaraju T. Highly Selective UV/Visible-Near Infrared and Fluorescence Sensing of Cu2+ 13. Based on Thiocarbonohydrazone System in Aqueous Media. Chem Eur J 2011; 17: 1410–1414.

PERFORMANCE OF GERONGGANG (Cratoxylon arborescens) AT 4.5 YEARS OLD AS POTENTIAL SUBSTITUTE FOR Acacia crassicarpa IN PEAT LAND

Opik Taupik Akbar 1, Yeni Aprianis 2, Eka Novriyanti 3 Research and Development Institute for Forest Plant Fiber Technology / Balai Penelitian dan Pengembangan Teknologi Serat Tanaman Hutan (BP2TSTH) Ministry of Environmental and Forestry Jl. Raya Bangkinang-Kuok Km. 9 PO. BOX 4/BKN Bangkinang 28401, Indonesia 1 [email protected] 2 [email protected] 3 [email protected]

ABSTRACT

Geronggang (Cratoxylonarborescens) is fast growing, medium to large sized, evergreen tree, usually found in freshwater or peat-swamp forest or sandy or sandy-loamy soils, and sometimes in coastal dipterocarp swamp forest. Geronggang trees often occur abundantly in secondary forest (after felling), and they grow rapidly. Preliminary works have been carried out by Research and Development Institute of Forest Plant Fiber Technology (BP2TSTH) to cultivate geronggang as alternative species in peatland. At 4.5 years, the survival rate, mean annual increment (MAI), and current annual increment (CAI) were 85%, 12.79 m3/ha/year, and 27.17 m3/ha/year respectively. The survival rate was higher than that of Acacia crassicarpa but the MAI and CAI were lower. The 4.5 years old geronggang was analyzed for its wood and pulp properties. The results showed that specific gravity of geronggang was 0.43 (0.38-0.50), and fiber dimension and derivatives were in quality I-II. The resulted pulp yield, pulp lignin, pulp reject, and kappa number were 48.15%, 2.09%, 0.08% and 16.09, respectively. Overall, based on specific gravity, fiber dimension, and pulp properties, geronggang is suitable as raw material for pulp and paper.

Keywords: Cratoxylon arborescens, Acacia crassicarpa, wood properties, pulping properties, pulp and paper, peat land

Introduction

Indonesia has the largest peat-land among tropical countries, which is about 21 million hectares, scattered mainly in Sumatra, Kalimantan and Papua. On the island of Sumatra itself, peat-land area is about 6.2 million hectares which most of it, about 4 million hectares is located in Riau Province. In addition to having the largest peat-land area, Riau also has one of the largest pulp and paper industry in Indonesia. In 2013 Riau Province contributes 86.35% of the total pulp production in Indonesia [1]. There are two pulp factories i.e. PT. Indah Kiat Pulp and Paper (IKPP) and PT. Riau Andalan Pulp and Paper (RAPP). Until recently, the main source of raw wood material of peat areas is Acacia crassicarpa [1]. Both companies develop plantation of A. crassicarpa in their respective concession area. This monoculture plantation and the invasive nature of acacia species may cause an imbalance in the local ecosystem. The likely of using native wood species in pulp and paper plantation may reduce the imbalance in the local ecosystem. A potential local wood species for the purpose is geronggang (Cratoxylon arborescen). Previous exploration by Research and Development Institute of Forest Plant Fiber Technology (BP2TSTH) showed geronggang population in Riau ranging from 93 to 168 trees/ha that suggested relatively abundant potential yet there is no adequate utilization [2]. Using local species in plantation also has several advantages, i.e. the planting and maintaining would be considerably easier because they are proven to be able to adapt to local conditions; tolerant to environmental conditions i.e. including pests and diseases; may maintain or even improve the ecological function and biodiversity; possibility to optimize its productivity through tree breeding/improvement program; providing balance and sustainability of habitats for other organisms (fauna and flora) because it is a natural part of the © 2016 Published by Center for Pulp and Paper through 2nd REPTech 59 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 ecosystem; may contribute to the bigger land productivity and can create typical landscape(s) [3],[4]. Geronggang (Cratoxylon arborescens) is in family of Gutiferae or Hypericaceae. It is a fast growing, medium to large-sized, evergreen tree up to 50 m tall, and bole up to 65 cm in diameter. It can be found in Sumatra, Borneo, Southern Burma, and Peninsular Malaysia. Geronggang tree is pioneer species. They are abundantly and grow rapidly in secondary forest (after felling or fire) [5]. Geronggang typically occurs in freshwater or peat-swamp forest on sandy or sandy-loamy soils, and sometimes in coastal dipterocarp swamp forest. It generally appears scattered but it sometimes abundantly clustered and can even become dominant. Several enrichment plantings with nursery-cultivated seedlings of geronggang in experimental scale by various institutions in Indonesia showed good results in swamp forest. [5] According to Center for Pulp and Paper, the characteristic of wood needed as a raw material for pulp are low density (0.3-0.8), fiber length 0.8 mm or more, lignin content less than 23%, cellulose content 40-45%, pulp yield more than 40% (un-bleached pulp). From silviculture point of view, wood species to be developed as raw material for pulp industry must meet certain criteria such as fast growing, short cycle on harvesting, fewer tree branches, bole height or straight trunk, easy to grow and easy to cultivate, and free of pests and diseases [6] This paper provides data to support geronggang as an alternative species for pulp raw material that could potentially replace A. crassicarpa plantation in peat-lands. The study presented in this paper addressed growth characteristic, wood density, fiber dimension, and pulp properties of geronggang as a potential pulp wood.

Methods and Materials

This paper is half review and half research paper. Data of A. crassicarpa and geronggang growth characteristic are review from other paper. Wood density, fiber dimension, and pulp properties were conducted by authors. Geronggang sample was harvested from Lubuk Ogong, Pangkalan Kerinci, Riau Province, Indonesia. The trees planted in research area of Research and Development Institute of Forest Plant Fiber Technology (BP2TSTH). Three trees of 4.5 years old with different diameter at breast height (1.3 m) were selected. The log s were sent to BP2TSTH to prepare and analyzed. Specific gravity was determined in accordance with ASTM D 2395 – 07a using B method (volume by water immersion). Meanwhile, wood sticks sample (0.5 mm x 20 mm) for fiber dimension analysis was taken from middle part of knotless trunk. The sticks were immersed in glacial acetic acid and 35% hydrogen peroxide (1:20 v/v) and boiled for 1-2 hours until the stick’s color turned white. After the removal of chemical with distilled water, the now-separated wood fiber was colorized with 10-15 drops of 2% safranin and then mounted to slide-glass and the fiber dimension was measured under light microscope. The pulping process used in this study was kraft method that was done at sulphidity of 25% and active alkali of 18%, with 4:1 liquor to fiber ratio. The cooking was using rotary digester with maximum temperature was set at 165oC and cooking time 90 minutes. The resulted pulp was washed, screened, dried, prior to determination of pulp yield, reject, and kappa number.

Results and Discussion

The performance of geronggang (i.e. tree growth, wood density, fiber dimension and pulping condition) was firstly compared withA. crassicarpa by reviewing previous works.

Growth

Geronggang showed higher survival rate than A. crassicarpa, yet it had inferior growth performance (height and DBH) than A. crassicarpa (Table 1). But it must be noted that geronggang in this study was originated from wildlings while A. crassicarpa was supplied from advanced tree improvement program. Nonetheless, supposedly geronggang already accustom to their natural habitat (e.g. better in overcoming the threat of pests or diseases) thus it showed higher survival rate than the introduced-A.

60 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 crassicarpa. Termites and fungi Ceratocystis sp were suspected to be the main cause of higher mortality of crassicarpa [7].

Table 1. The growth of geronggang (Cratoxylon arborescens) and Acacia crassicarpa at age of 3 - 4.5 years old in drained-peatland experimental plots [7]

MAI CAI Age Survival rate Species Height (m) Dbh (cm) 3 -1 3 -1 - (yo) (%) (m ha (m ha year year-1) 1) Cratoxylon 3 86.4 ± 1,60 6.83 ± 0.394 7.81 ± 0,823 5.25 11.03 arborescens 3.5 85.6 ± 2,19 7.72 ± 0.245 8.44 ± 0,385 8.68 17.26 4.5 85.6 ± 2,19 10.01± 0.50 10.16 ± 0,50 12.79 27.14 3 53.6 ± 4,49 16.6 ± 0.662 15.69 ± 1,64 No data 18,31 ± No data 3.5 28.8 ± 15,00 18.04 ± 1.528 available Acacia 1,349 available crassicarpa 4.5 25.6 ± 11.17 18.87 ± 0.99 22.99 ± 2,33 32.54 Note: Dbh = Diameter at breast height; MAI = Mean Annual Increment; CAI = Current Annual Increment.

The high mortality may greatly diminish the higher growth performance of A. crassicarpa and eventually may reduce its standing stock (MAI and CAI) in the further future. On the other hand, higher survival rate may favour geronggang to increase its standing stock, especially once its growth performance is improved through tree breeding/improvement program. Maintaining a broad genetic base is very important for large scale tree improvement program. Although have lower survival rate, A. crassicarpa provide higher productivity because has larger dimension in diameter and height. There was no intersection curve of MAI and CAI of geronggang at the measurement period of 2.5 - 4.5 years old, they even tended to still sharply increase. The result suggested that optimal volume was not obtained yet at those periods. Thus, it is necessary to further observe the growth and productivity of geronggang (figure 1) [7].

Figure 1. MAI and CAI curve of geronggang in drained-peatland experimental plots [7]

The MAI can be improved by progeny test, clonal test, control pollination, and tissue culture. After using the program of silviculture and the improvement method of vegetative and clonal in fact can increase the productivity of MAI (Table 3) [8]. The chance to improve the growth of geronggang and in turn increase MAI through tree breeding/improvement program, however, is still widely open to match the impressive growth of the improved-A. crassicarpa.

Table 2. The MAI of Acacia mangium, Acacia crassicarpa, and Eucalyptus pellita in PT. RAPP after tree improvement program [8]

Species Age (year) MAI (m3/ha/year) Remark Acacia mangium 7 22 No improvement (in 1996) 6 29 With tree improvement (in 2006) 6 >40 Using vegetative family forestry materials (in 2009) Acacia crassicarpa 7 18 No improvement (in 2001) 6 29 Using vegetative family forestry materials (in 2009) Eucalyptus pellita data not 20 No improvement (in 2000) available 35 Using clonal materials (in 2009)

Thus far, A. crassicarpa dominated peatland plantation for pulp and paper. However, in the recent years, A. crassicarpa shows various serious problems. In addition, few cases of broken trunk or even uprooted tree were found in the plot of A. crassicarpa which were not occurred in the nearby plot of geronggang [7]. Tree’s biomass increases with age and the development of biomass of A. crassicarpa was considerably large. This immense biomass development was not equal to the low fitness of the root system to the less favorable characteristics of peat soil thus A. crassicarpa is prone to fell or uprooted by severe wind blows. PT Arara Abadi [9] reported the stands of A. crassicarpa at age 3 years old showed survival rate of 49.82% and noticeably decreased to only 27.38% at age of 4 years old.

Table 3. Potency and stand volume of A. crassicarpa [9]

Plant of Age Height Dbh (cm) Survival Volume MAI (m3/ha/ CAI (years) (m) rate (%) (m3/ha) year) (m3/ha/year) 1 4.1 4.6 22.89 1.9 1.9 - 2 9.3 8.4 38.18 22.9 11.5 21.0 3 14.0 11.8 36.96 66.5 22.2 43.6 4 17.9 15.0 29.79 110..2 27.6 43.7 5 20.9 18.0 21.97 136.9 27.4 26.7 6 23.4 20.8 16.32 152.0 25.3 15.1 7 25.2 23.5 12.36 158.3 18 6.3

Specific Gravity

Specific gravity (SG) is a complex physical property corresponded to both anatomical structure and chemical composition of the wood, and considerably responsive to genetic, environmental and physiological influences. On the other hand, SG is also corresponded to the most of the resistance properties of the timber (durability, shrinkage, etc.) as well as many aspects of wood processing (chipping, transporting, pulping) and product quality. In fact, SG and pulp yield are considered as key parameters in tree-selection for pulping, in addition to tree growth (wood biomass). SG is important consideration in determining wood species for raw material of pulp. General requirement of SG for pulp-wood is 0.3-0.8 [6]. The specific gravity of 4.5 years old geronggang was 0.43 (0.38-0.50), which was almost similar to that of crassicarpa [7]. The density of geronggang is classified as class I-II and is categorized as low to medium [10]. In this range of wood density, diffusion and penetration of chemicals in pulping process will take place easier thus it will more effectively dissolve lignin in the middle lamella and consequently will resulted better fibers separation [11].

Table 4. Specific density of geronggang Cratoxylon( arborescens) and Acacia crassicarpa

Age Species Specific density Class Source (years) Cratoxylon - 0.4-0.47 I-II [10] arborescens - 0.47 (0,36-0,71) I-II [13] - 0.35-0.71 [5] 4.5 0.43 (0.38-0.50) [7] 4.5 0.44 (0.37-0.51) [7] Acacia crassicarpa -s 0.67-0.71 [5]

Fiber Dimension

Fiber dimension can be used to determine the value of the fibers parameter i.e. runkle ratio, felting power, mulsteph ratio, flexibility ration, and coefficient of rigidity. Fiber dimension parameters, i.e. fiber length, fiber diameter, cell wall thickness, and lumen diameter have complex relation of each other and have a fundamental influence on the physical properties of pulp and paper [12]. The 4 and 5 years old A. crassicarpa had relatively long fibers (Table 5) classified as quality II (medium). Meanwhile fiber diameter is classified as quality I (good). Long fibers produce higher tear strength and wide diameter fibers produce better paper compact [13]. The values of fiber derivative ofA. crassicarpa showed almost similar class quality. Based on the fiber dimensions in Table 5, the 4-5 years old A. crassicarpa were classified in class quality I - II. In general, the fiber properties of crassicarpa meet the requirement of the pulp and paper industry [2]. The resulting data of fiber dimensions and their derivatives values were compared with the criteria standard. The quality of fiber as a raw material for pulp is categorized into classes I and II. Generally, Geronggang has thin to medium cell wall with wide lumen. In making pulp’s sheet, fiber is easy to be flat. The connectivity between fiber and derivatives was good. Meanwhile, it was made for paper that was predicted has tensile, tearing, and burst strength medium to high [10].

Table 5. Fiber dimension and its derivatives of geronggang (Cratoxylon arborescens) and A. crassicarpa [9],[12],[14]

Cratoxylon Species Acacia crassicarpa arborescens Ages 4 years old Unknown [11] Unknown [14] 5 years old [9] [9] Properties Value Class Value Class Value Class Fiber length 1.180 II 1.230-1.327 II 1.343 II 1.307 II (mm) Fiber diameter 22.3 II 28.09-31.18 II 35.68 I 34.24 I (µm) Runkle ratio 0.3 II 0.16-0.18 I 0.14 I 0.14 I Felting power 53 II 43.63 III 38.01 III 38.09 III Mulsteph ratio 41.2 II 26.27 I 22.00 I 20.20 I Flexibility ratio 0.77 II 0.86 I 0.88 I 0.88 I Coeff. of rigidity 0.12 II 0.07 I 0.06 I 0.06 I

Pulp Properties

Kraft process was conducted to determine pulp properties of geronggang wood. The kraft method was 25% sulphidity, 18% active alkali (AA) at 165oC of cooking temperature and 90 minutes of cooking time at the maximum temperature, as generally conducted in pulp and paper industry. The resulted pulp properties of the process are presented in Table 6 [15],[16]. Pulp yield, kappa number and pulp lignin have been considered as adequate parameters to describe pulp quality. Pulp yield of geronggang in this study is in consent with which stated pulp yield of hardwood is ranging from 45-50% [17]. Pulp yield is substantially affected by specific gravity (SG), and since SG of geronggang is lower than that of A. crassicarpa (SG is 0.49) thus it is understandable that pulp yield of geronggang was lower than that of A. crassicarpa as well (Table 6).

Table 6. The pulp properties of geronggang (Cratoxylon arborescens) and Acacia crassicarpa [16]

Parameter C. arborescens A. crassicarpa [16] Pulp yield (%) 48.15 53.48 Kappa Number 16.09 17.77 Pulp lignin (%) 2.09 2.31

Kappa number determination is an indirect method to estimate the residual lignin in the pulp and thus an indicator of the degree of lignin dissolution in the pulping process. Kappa number is very important tool to identify 1) the degree of delignification during cooking process, 2) to determine the chemical concentration in bleaching process [18]. Kappa number bigger than 20 means that it is not feasible to bleach the pulp because it will require higher concentration of bleaching chemical. In this study, kappa number of crassicarpa was bigger than that of geronggang which implied the suitability of geronggang for pulp wood [19]. Pulp lignin is a function of the Kappa number of pulp, where a high kappa number reflect a high content of lignin remaining in the pulp [20]. In this research pulp lignin as Klason lignin. Lignin content in the pulp was calculated as 0.13 x Kappa number [22]. In this case, pulping condition of geronggang produced the highest residual lignin and caused the pulp lignin of geronggang lowest than pulp lignin crassicarpa. Pulp lignin of geronggang and crassicarpa were 2.09 and 2.31 respectively (Table 6). Based on data, geronggang was more effective for delignification of lignin polymer than crassicarpa. In the sulfate process, sulfur enters the lignin molecule to form alkali-soluble thiolignin [19]

Conclusion

Geronggang had higher survival rate but lower MAI and CAI than Acacia crassicarpa. Specific gravity of geronggang was 0.43 (0.38-0.50) thus it is suitable for pulp wood. Fiber dimensions and values of fiber derivative of geronggang were in class quality I-II. The resulted pulp yield, pulp lignin, pulp reject, and kappa number of with 25% sulphidity and 18% active alkali (AA) at 170oC for 90 minutes were 48.15%, 2.09%, 0.08% and 16.09, respectively. Although SG, fiber dimension, and pulp properties of geronggang at 4.5 years old are suitable as raw material for pulp and have potential to substitute A. crassicarpa, but the wood productivity (MAI & CAI) still lower than A. crassicarpa. Wood productivity of geronggang needs improvement in diameter and height to substitute A. crassicarpa. Geronggang not optimal productivity at the age 4.5 years old because the wood productivity not optimal yet.

Acknowledgments

We would like to express our gratitude to Ahmad Junaedi (Institute of Research and Development on Forest Plant Fiber Technology) for sharing his knowledge in silviculture of geronggang and prepare the sample.

References

1. Statistik Kehutanan Indonesia. Ministry of Forestry Statistic 2013. Kementerian Kehutanan Indonesia. Jakarta. 2014 2. Suhartati, S. Rahmayanti, A. Junaedi & E. Nurrohman. Sebaran dan Persyaratan Tumbuh Jenis Alternatif Penghasil Pulp di Wilayah Riau. Kementerian Kehutanan. Badan Penelitian dan Pengembangan Kehutanan. Jakarta. 2012 3. Johnson, H. & Stawell. The benefits of using indigenous. Plants.Landcare Notes.State of Victoria Department of Natural Resources and Environment. Australia. 2001 4. Harrison, S., T.J. Venn, R. Sales, E.O. Mangaoang& J. F. Herbohn. Estimated financial performance of exotic and indigenous tree species in smallholder plantations in Leyte Province. 2005.Annals of Tropical Research 27(1): 67-80 5. Soerinegara, I dan R.H.M.J. Lemmens (eds). Plant resources of South-East Asia. Timber trees, Major Commercial Timber 5 (1): 143-148. Prosea. Bogor. 2001. 6. Mindawati, N. Beberapa Jenis Pohon Alternatif untuk Dikembangkan Sebagai bahan Baku Industri Pulp. Mitra Hutan Tanaman 2 (1) : 1-7. Pusat Penelitian dan Pengembangan Hutan Tanaman. Bogor. 2007. 7. Junaidi, A., Novriyanti E., Rahmayanti, S., Hendalastuti, H., Aprianis, Y. Akbar, O.T., Rizqiani, K.D. Silvikultur jenis Pohon Lokal Potensial (Native Sspecies) Pada lahan Kritis (Marginal) di Riau. Laporan Hasil Penelitian Tahun 2015. Balai Penelitian Teknologi Serat Tanaman Hutan. Riau. 2015. 8. Suhartati, Y. Aprianis, A. Pribadi, Y. Rahcmayanto. Study of Reduction Cycle Impact of Acacia crassicarpa A. Cunn Plantation to Production Value and Social Aspect. Jurnal Penelitian Hutan Tanaman Vol. 10 No. 2Junu 2013. 9. Golani, G.D., Siregar, S.T.H., Gofur, A. Tree Improvement and SIlviculture Research Progress at PT Riau Andalan Pulp and Paper APRIL Group-Chalenges and Opportunitie. Proceedngs International Seminar Research on Plantation Forest Management: Challenges and Opportunities. Bogor 2009. 10. Pasaribu R.A. and tampubolon. Persyaratan Teknis Bahan Baku, Air dan bahan Penolong untuk Industri Kertas dan rayon. Diklat Pelatihan Verifikasi Eksportir Terdaftar Produk Industri Kehutanan (ETPIK). Puslitbang Hasil Hutan. Bogor. 2007. 11. Casey, J.P. 1980. Pulp, Paper Chemistry and Chemical Technology. Third Edition. Vol I. Willey Interscience Publisher Inc. New York. 12. Nurrachman, A and T. Silitonga. DImensi serat beberapa jenis kayu Sumatra Selatan. Laporan No. 2, Lembaga Penelitian Hasil Hutan, Bogor. 1972. 13. Martawijaya, A., Kartasujana, I., Kadir, K., Prawira, S.A. Atlas Kayu Indonesia Jilid I (edisi revisi). Departemen Kehutanan. Balai Penelitian dan Pengembangan Kehutanan. Bogor. 2005. 14. Rinanda. R. Sifat dasar dan Kegunaan Kayu Sumatera. Laporan Hasil Penelitian. Balai Penelitian Teknologi Serat Tanaman Hutan. Riau. 2012. 15. Aprianis, Y., Novriyanti, E., Wahyudi, A., Akbar, O.T., Rizqiani, K.D. Diversifikasi Produk Serat: Bambu Sumatera dan Kayu Potensial Gambut. Laporan Hasil Penelitian Tahun 2015. Balai Penelitian Teknologi Serat Tanaman Hutan. Riau. 2015. 16. PT. Arara Abadi. Rencana Kerja Periode Tahun 2008-2017. Riau. 2008. 17. Fengel, D & Wegener, G,. Chemistry, ultrastructure, reaction. Walter de Gruyter, Berlin. 1989. 18. Smook, A.G. Handbook for pulp and paper technologist Second Edition. Angus Wilde Publication Inc. Bellingham. 1992. 19. Casey, J.P. Pulp and paper chemistry and chemical technology Second Edition. Vol. 1, Interscience Publishers, Inc., New York. 1980.. 20. Fatriasari, W., Suriyanto & Iswanto, A.P. The kraft pulp and paper properties of sweet sorghum bagasse (Sorghum bicolor L Moench). 2015.Journal Engineering Technology Science. Vol. 47 (2): 149-159. 21. Sjöström, E. Wood chemistry: fundamental and application Second Edition. Academic Press, San Diego, USA. 1981. 22. TAPPI. Kappa Number of Pulp. TAPPI Press, Atlanta, Georgia. 1996

KRAFT PULPING CONDITION FOR SUMATRAN THORNY BAMBOO, POTENTIAL MATERIAL FOR VISCOSE PULP

Kanti Rizqiani1, Eka Novriyanti2, Dodi Frianto3 Research and Development Institute for Forest Plant Fiber Technology / Balai Penelitian dan Pengembangan Teknologi Serat Tanaman Hutan (BP2TSTH) Ministry of Environmental and Forestry Jl. Raya Bangkinang-Kuok Km. 9 PO. BOX 4/BKN Bangkinang 28401, Indonesia [email protected] [email protected] [email protected]

ABSTRACT

Thus far, Sumatran thorny bamboo, namely duri bamboo (Bambusa blumeana), has not utilized economically by communities or business holders. Given the best quality of bamboo fiber in general and in an effort to determine the suitability of Sumatran thorny bamboo for viscose pulp, B. blumeana were pre-hydrolyzed with 0%, 2.5% and 5% acetic acid prior to kraft pulping process. Chemical analysis on pre-hydrolyzed bamboo chips showed that 2.5% acetic acid gave the optimum result. The kraft method was done in 3 levels of active alkali (AA, 18%, 20% and 22%) and 3 levels of sulfidity (22%, 25% and 28%). The analyses on the kraft method showed that the best holocellulose, a-cellulose and lignin values were resulted by combined-treatment of AA 20% and sulfidity 22%, AA 22% and sulfidity 22%, and AA 22% and sulfidity 25%, respectively. In general, kraft method with AA 22% and sulfidity 25% gave the optimum result for this Sumatran thorny bamboo. The yield resulted from this treatment was 51.91%, reject 0.32%, kappa number 13.11, ash content 0.52%, total extractives 14.57%, holocellulose 93.72%, a-cellulose 79.08% and lignin content 4.46%. This condition of kraft pulping could be considered for the procedure in further observation of the suitability of duri bamboo for viscose pulp.

Keywords: Bambusa blumeana; pre-hydrolyzed; kraft pulp; viscose; active alkali; sulfidity.

Introduction

Bamboo is a perennial plant in the family Graminaeae sub family Bambusoideae. Among 1250 of the world-recorded bamboo species, 159 species are found in Indonesia. Most of bamboo species grow in tropical or subtropical regions, but some are spread along temperate area such as in China and Japan (Widjaya 1998). In Indonesia, although bamboo spreads widely from the outmost western to the foremost eastern part of the country’s islands, the utilization of bamboos is economically less recognized. Bamboo could be found from lowland to 3000 m asl in highland (Latif & Razak 1991), on various types of habitat and almost on all of soil types except on alkaline, desert and mangrove (Lee et al. 1994). Bamboo reaches it maximum height at 4-6 months old with daily increment of 15-18 cm. A well grown bamboo’s clump could consist of 40-50 culms with rate of addition of 10-20 culms/year (Aminuddin & Latif 1991). According to Lee et al. (1994) mature 3-5 years old bamboo culm in a well- managed clumps can be harvested in 3 years rotation. These conditions enlighten the immense potency of bamboo’s stock. Mostly, bamboo is used to substitute wood in construction due to its equal strength (Marsoem et al. 2009). Fiber of bamboo is categorized as long or semi long fiber to which it usually being compared with that of softwood (Ma et al. 2012). Bamboo fibers have been used in production of high grade-papers and other high grade products, e.g. ester-cellulose, ether-cellulose, textile fibers, etc. (Christov et al. 1998). The big potency of bamboo’s stock and the high grade fibers have encourage various bamboo-related researches in Indonesia. Chemical content in bamboo define its suitability as material for pulp industry. This lignocellulose material contains 60-70% holocellulose, 20-25% pentose, 20-30% lignin, a small percentage of resin, © 2016 Published by Center for Pulp and Paper through 2nd REPTech 67 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 tannin and wax. In general, the chemical content of bamboo is similar to that of hardwood, but bamboo has higher silica and NaOH-soluble extractives (Ogunsile & Uwajeh 2009). Anatomically, bamboo fiber is classified as long fiber and is categorized in quality class I for pulp. Fatriasari and Hermiyati (2008) revealed the length of bamboo fibers are varied from 2299 to 4693 µm. Based on its chemical content and fiber anatomy feature, bamboo is highly suitable material for pulp and paper industry. The high grade of bamboo fiber has made this material usually used for high grade paper or high grade derivative- cellulose products. This recent study addresses the possible utilization of Sumatran thorny bamboo, called duri bamboo, for viscose pulp; yet this paper presented the progress up to the results of kraft pulping process of this bamboo. Pulping process for lignocellulosic-material is similar for wood and bamboo; it depends on what the final product to be made. In order to produce viscose pulp, the Sumatran thorny bamboo (Bambusa blumeana Schult. f.) was undergone kraft pulping process.

Materials and Methods

The internode sections from culms of 3-4 years old Sumatran thorny bamboo (Bambusa blumeana Schult. f.) were debarked and de-pitted and subsequently chipped with size 2.5 x 2.5 x 0.5 cm and air dried. Prior to kraft process, the chips were pre-hydrolyzed with 5% acetic acid in a stainless steel kettle at ±100°C for 60 minutes. The pre-hydrolysis was aimed to enhance the removal of lignin from this lignocellulosic material. The chips were then pulped in kraft process as presented in Table 1.

Table 1. Conditions of kraft process on duri bamboo

Condition Level Active alkali (%) 18 (A1), 20 (A2), 22 (A3) Sulphidity (%) 22 (S1), 25 (S2), 28 (S3) Chips to liquor ratio 1:4 Maximum temperature (°C) 165 Cooking time at max Temperature 60

The resulted pulp was washed to free it from the cooking liquor, screened and dried with centrifuge drier. The brown pulp was determined for yield, reject, kappa number, and chemical content e.g. cellulose, holocellulose and lignin. The lignin content was determined in accordance with SNI 0492- 2008, holocellulose with SNI 01-1389-1989 and cellulose with SNI 14-0444-1989.

Results and Discussion

Pre-hydrolysis prior to kraft pulping is aimed to obtain dissolving pulp with higher degree of cellulose content and lower hemicellulose (Li et al. 2015). With pre-hydrolysis process, the hemicellulose was degraded in two stages, which are prior to and at the kraft cooking process (Asim 2012). Water pre- hydrolysis at a particular temperature and cooking time will break xylan chains and separate acetyl groups as the result of hydrolysis reaction by hydronium ions. In the further stage of hydrolysis, acetic acid resulted from the acetyl group provides extra hydronium ions that may enhance the hydrolysis kinetic (Li et al. 2015). The duri bamboo chips’ yield after pre-hydrolyzed with 5% (v/w) acetic acid was 67.08% with kappa number 69.29, while the water-hydrolyzed chips had yield and kappa number of 81.94% and 78.72, respectively. In the previous study, it was noted that the higher the concentration of acetic acid used in the pre-hydrolysis the lower the resulted yield and kappa number. Kappa number is a considerable-predictor for lignin content in particular material. Lower kappa number usually indicates lower lignin content in wood chip or pulp. Pre-hydrolysis with 5% (V/W) acetic acid considerably reduced ash and extractives content, as well as lignin content, compare to those of bamboo without pre-hydrolysis (Table 2). As lignin content was lower in hydrolyzed-bamboo than that in un-hydrolyzed one, alpha-cellulose of pre-hydrolyzed bamboo

68 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 was also lower than that of un-hydrolyzed bamboo (Table 2). The lower lignin content in the hydrolyzed- bamboo suggested the occurrence of lignification in the bamboo’s chips, as expected. This hydrolysis, however, cost the bamboo a reduce content of alpha-cellulose as it may degraded as well in the process of delignification (Table 2).

Table 2. Chemicals content of pre-hydrolyzed and un-treated bamboo chips

Content (%) after pre-hydrolyzed Parameter Without pre- with 5% (V/W) acetic hydrolysis acid Moisture content 7.52 5.55 Ash content 2.68 5.13 Extractives soluble in benzene 1.23 4.32 Extractives soluble in hot water 5.07 9.26 Extractives soluble in cold water 3.86 6.23 Holocellulose 79.87 79.59 Alpha-cellulose 48.55 51.28 Lignin 11.53 17.57

Despite it lower content of alpha-cellulose, pre-hydrolysis noticeably lowered ash and extractives content in duri bamboo which unwanted in the further process of viscose production. Thus in this case, pre-hydrolysis with acetic acid may favor the process in term of lower lignin, ash and extractives content. However, concerning the also lowered content of alpha-cellulose due to pre-hydrolysis with acetic acid, thus it is necessary to find the proper condition and acid concentration in the pre-hydrolysis for duri bamboo to obtain optimum alpha-cellulose, lignin, ash and extractives content. The hydrolyzed-chips of duri bamboo were then pulped in kraft method to obtain brown kraft pulp prior to further process to produce viscose pulp. The resulted pulp yield, reject percentage and kappa number of the brown pulp are presented in Table 3. Although active alkali (AA) 20% separately with sulphidity 28% seemed to give highest pulp yield, 60.20% and 57.74% respectively (Table 3). However, since both AA and sulphidity altogether are accounted in kraft process that they must not credited separately, thus AA 20% and sulphidity 25% gave the highest pulp yield in this study, 64.46% (Table 3). Reject is the percentage of fibers that could not pass through mesh in the screening process. Usually, higher AA and sulphidity will cause smaller reject in kraft pulping. This lower reject is because more fibers would be effectively separated with higher AA and sulphidity thus could pass through the screener. Combination of AA 22% and sulphidity 25% gave the lowest reject in this study, 0.32% (Table 3). Separately from sulphidity, AA 22% gave the lowest reject which was 0.69%. Sulphidity, in the other hand, showed insignificant different in affecting reject. In similar magnitude with reject, the higher the AA and sulphidity the lower the resulted kappa number (Table 3). This suggested the bigger portion of lignin had been effectively removed from the pulp. Although statistically showed insignificant different, however combination of AA 22% and sulphidity 25% tended to give the lowest kappa number which was 13.11 (Table 3). ANOVA test revealed that ash content was significantly affected by AA, although Duncan-Wallis Test showed that AA 20% did not give significantly different result with AA 22% in reducing ash content of the pulp. Separately from AA, sulphidity had no different effect on ash content of the pulp as it was shown by one way ANOVA. However, combination of AA 22% and sulphidity 28% significantly gave the best lowest ash content, 0.31% (Table 4).

Table 3. Pulp yield, reject and kappa number of brown pulp of duri bamboo resulted by various level of active alkali and sulphidity in kraft process

Active alkali Sulphidity Yield Reject Kappa number (%) (%) (%) (%) (%) 22 56.04 ± 0.95 6.38 ± 0.71 30.46 ± 2.47 18 25 56.03 ± 0.48 8.47 ± 2.19 35.45 ± 4.47 28 57.85 ± 5.36 8.74 ± 3.38 42.05 ± 7.14 Total 56.64 ± 2.88 7.86 ± 2.33 35.99 ± 6.68 22 59.88 ± 4.74 9.70 ± 4.23 37.16 ± 11.19 20 25 64.46 ± 6.36 7.05 ± 1.65 36.38 ± 5.81 28 56.26 ± 12.06 6.82 ± 0.41 37.09 ± 3.35 Total 60.20 ± 8.05 7.85 ± 2.67 36.88 ± 6.54 22 55.59 ± 7.27 1.09 ± 1.27 16.62 ± 6.48 22 25 51.91 ± 1.36 0.32 ± 0.23 13.11 ± 0.60 28 59.11 ± 3.52 0.66 ± 0.16 14.52 ± 1.25 Total 55.54 ± 5.15 0.69 ± 0.73 14.75 ± 3.65 22 57.17 ± 4.82 5.72 ± 4.37 28.08 ± 11.21 Total 25 57.47 ± 6.43 5.28 ± 4.02 28.31 ± 11.99 28 57.74 ± 6.94 5.40 ± 4.03 31.22 ± 13.32 TOTAL 57.46 ± 5.89 5.47 ± 3.99 29.20 ± 11.81 Remarks: ANOVA test with a= 0.05

Table 4. Chemical properties of kraft brown pulp of duri bamboo in various level of active alkali and sulphidity

Active Ash Extractive Extractive Extractive Alpha Sulphidity Holocellulose Lignin alkali content (Benzene) (Hot water) (Cold water) cellulose (%) (%) (%) (%) (%) (%) (%) (%) (%) 22 0.39 3.57 6.60 3.92 91.41 77.21 5.14 18 25 0.69 3.07 5.99 3.32 91.68 71.90 5.29 28 1.04 3.32 9.10 3.99 90.36 70.85 7.00 Total 0.71 3.32 7.23 3.75 91.15 73.32 5.81 22 1.43 3.72 8.30 4.50 90.28 72.04 6.64 20 25 0.54 1.94 4.02 2.19 92.61 73.09 5.84 28 0.66 3.02 5.77 3.04 92.44 78.12 5.04 Total 0.88 2.89 6.03 3.25 91.78 74.42 5.84 22 0.54 2.18 5.72 2.64 92.63 79.11 5.52 22 25 0.52 2.48 7.67 4.42 93.72 79.08 4.46 28 0.31 2.40 7.92 4.05 92.77 78.44 5.66 Total 0.46 2.35 7.10 3.70 93.04 78.88 5.21 22 0.79 3.16 6.88 3.69 91.44 76.12 5.77 Total 25 0.58 2.50 5.89 3.31 92.67 74.69 5.20 28 0.67 2.91 7.59 3.70 91.86 75.80 5.90 TOTAL 0.68 2.86 6.79 3.57 91.99 75.54 5.62 Remarks: ANOVA test with a= 0.05

The analysis of extractives content of the pulp was approached by three extractives solubility, namely solubility in alcohol-benzene, hot water and cold water. The AA and sulphidity, separately or in combination, significantly affected extractive dissolved in alcohol-benzene. The AA 22% gave the lowest extractive in alcohol-benzene which was 2.35%, meanwhile sulphidity 25% gave the lowest extractive

70 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 in alcohol benzene which was 2.50%, and combination of AA 20% and sulphidity 25% gave the lowest extractive in alcohol benzene, 1.84% (Table 4). Combination of AA and sulphidity significantly affected extractive in hot water in which AA20% and sulphidity 25% gave the lowest 4.02% of extractive in hot water. However, there was no different result found on extractive in cold water cause by various levels of AA and sulphidity and their combination. In general, combination of AA 20 % and sulphidity 25% gave the lowest extractive content in the pulp of duri bamboo (Table 4). Holocelluose can be used to predict the hemicellulose content in the pulp. The adequate dissolving pulp must have higher content of alpha-cellulose (≥ 95%), low holocellulose (≤ 10%) and lignin content (≤ 0.05%). In this study, brown pulp kraft of duri bamboo was have not yet bleached to further dissolved hemicellulose and lignin. The resulted alpha-celluose was only ± 79% and the holocellulose content ±93% which suggested hemicellulose may around 14% (Table 4). These results had not yet meet the requirement for dissolving pulp thus bleaching must be conducted to further reduced holocellulose and lignin from the brown pulp. Active alkali (a 0.05), sulphidity (a = 0.05) and their combination (a = 0.1) significantly affected holocelluose content of duri bamboo’s brown pulp in which AA 20% and sulphidity 22% resulted the lowest holocellulose, 90.22%. Alpha-cellulose and lignin were significantly (a = 0.1) affected by combination of AA and sulphidity. Duncan-Wallis test showed that combination of AA 22% and sulphidity 22 or with sulphidity 25% did not give different result and gave the highest alpha-cellulose content, ±79%. Meanwhile, combination of AA 22% and sulphidity 25% gave the lowest lignin content which was 4.46% (Table 4). In this study, higher AA was likely gave higher alpha-cellulose and tended to reduce lignin content better. In general, combination of AA 22% and sulphidity 25% gave the optimal result for kraft brown-pulp of duri bamboo. This cooking condition gave pulp yield 51.91%, reject 0.32%, holocellulose 93.72%, alpha-cellulose 79.08% and lignin 4.46%. This result was different with that of Ma et al (2012) that examined dissolving pulp from Dendrocalamus oldhamii. The bamboo was water pre-hydrolyzed (max temperature 170°C, 60’, in rotary digester) and kraft cooking condition AA 23%, sulphidity 26%, max temperature 170°C for 60 minutes. They obtained pulp yield 32.4%, kappa nuber 6.3, pentosan 5% and alpha-cellulose 90.2%. Although this study had higher pulp yield and lower lignin content, yet the resulted alpha-cellulose was lower than Ma et al. (2012). Presumably, the different bamboo species used in this study and in Ma et al (2012) gave that different result. The using of rotary-digester in pre-hydrolysis may also accountable for the different result in Ma et al (2012). Rotary digester would distributed pre-hydrolysis process evenly in the whole bamboo chips and kept the higher and stabile temperature than stainless steel kettle.

Conclusion

The kraft process for duri bamboo that gave the best result was AA 22% and sulphidity 25%, chips to liquor ratio 1:4, max temperature 165 °C and cooking time 60’ at the max temperature. The resulted kraft brown pulp had pulp yield 51.91%, reject 0.32%, kappa number 13.11, ash content 0.52, total extractives 14.57%, holocellulose 93.72%, alpha-cellulose 79.08% and lignin content 4.46%.

Acknowledgement

Authors would like to express our sincere gratitude to Dissemination Division of BP2TSTH for supporting this manuscript, Sub District of Puhun Pintu Kabun, Bukittinggi City, for providing bamboo materials, and Center for Forest Product Technology for providing laboratory facility, Center for Pulp and Paper for discussion input.

References

1. Widjaya, EA. Bamboo genetic resources in Indonesia In Vivekanadan K, A.N. Rao, V, Ramanatha Rao (eds). 1998. Bamboo and rattan genetic resources in certain Asian countries. IPGRI-APO, Serdang, Malaysia.1998.

2. Lee, AWC, Xuesong, B, Perry NP. Selected physical and mechanical properties of giant timber bamboo grown in South Carolina. Forest Prod J 1994; 44(9): 40-46. 3. Aminuddin, M. and Latif MA. Bamboo in Malaysia: past, present and future research. In 4th International Bamboo Workshop, Bamboo in Asia and the Pacific, Chianmai, Tahiland, 27-30 November 1991. Proceedings, pp 349-354. 4. Marsoem SN, Prasetyo, VE, Rachman WB, Sudarwoko, AD. Pemanfaatan serat monokotil bambu legi (Gigantochloa atter) sebagai bahan baku pulp secara mekano-organosolv. Proceeding National Seminar MAPEKI XII Bnadung, West Java, 23-25 July 2009. 5. Ma, X, Huang, L, Cao, S, Chen, Y, Luo, X, Chen, L. Preparation of dissolving pulp from bamboo for textile application. Part 2: Optimation of pulping condition of Hydrolyzed bamboo and its kinetics. Bioresources 2012; 7(2): 1866-1875. 6. Christov, LP, Akhtar, M, Prior, BA. The potential of bio-sulphite pulping in dissolving pulp production. Enzyme and Microbial Tech 1998; 23: 70-74 7. Ogunsile B.O and Uwajeh C.F. Evaluation of the pulp and paper potentials of Nigerian grown Bambusa vulgaris. World Applied Science Journal 2009; 6(4): 536-541 8. Li, G, Fu, S, Zhou, A, Zhan, H. Improved cellulose yield in the production of dissolving pulp from bamboo using acetic acid in prehydrolysis. BioResources 2015; 10(1): 877-886.

THE DAMAGE OF PAPER-BASED ARCHIVES IN FOUR ARCHIVAL INSTITUTIONS

Sari Hasanah ANRI, Jl. Ampera Raya, Jakarta 12560, Indonesia [email protected]

ABSTRACT

The objective of this research is to study the archives damage so that the results can support preservation of paper-based archives. The research was conducted on static archives which have historical value and kept permanently in four archival institutions. Archives damage was analyzed based on Archives Damage Atlas and Universal Procedure Archives Assessment. Several damage profiles were shown for each category and were classified according to severity: slight damage, moderate damage, and serious damage. Damage was divided into the five categories: Binding and text block damage, chemical damage, mechanical damage, pest infestation, and water damage. The data clearly reveal slight damage in most archives (54-87%). For the accessibility issues, 4-28 percent of archives should not be made accessible. It is also discovered that chemical damage was found in most archives. Finally based on these results, both preventive and curative preservation could be improved and archival institution also should endeavour to create more awareness in using archives.

Keywords : archives damage; damage atlas; historical value; paper

Introduction

Archives provide information and evidence of activities. Organizations include Governments create and use archives in their daily activities and relationships with others. Archives have administrative functions so archives produced by organizations have to be managed by archivist to support good governance. The International Council on Archives (ICA) said that effective records and archives management is an essential precondition for good governance, the rule of law, administrative transparency, the preservation of mankind’s collective memory, and access to information by citizens [1]. The reasons of governments in managing archives are to assist in scrutinizing every decision and activity, to enable communities in transferring knowledge, to learn from the past and to protect the collective interest of society and citizens, and to fulfill the interest of society in decision which affect to public [2]. Histories of archives generally start by referring to archives in the ancient world, tracing the record keeping practices of ancient Greece and Egypt, the repositories of the Roman Empire and the links from these written archives to legal and political developments [3]. The history of archival institution in Indonesia was begun on January 28, 1892 when the Dutch government established Landsarchief in Batavia. On May 18, 1971, the Law Number 7 Year 1971 was issued and then celebrated as the National Archives Day. Not all archives produced by the governments should be preserved in archival institution. Governments discard quickly most archives and some are still kept for longer periods because their continuing value to nation. This value is called as secondary value which is the additional historical value to the organization and wider. This can include evidential value derived from the way the record documented the history, structure and functions of an organization, and informational value in providing research material on persons, places and subjects. The opposite of secondary value is primary value which is the value to the organization that created them for administrative, legal and fiscal purposes[ 4]. Law of the Republic of Indonesia Number 43 of 2008 stated that the administration of archives shall be the responsibility of archival institution. Archival institution shall mean an institution that has the functions, duties, and responsibilities in managing static archives and maintaining development in the administration of records and archives [5]. Static archives here mean archives which have historical/ secondary value. Archives are created in any media like paper, film, magnetic tape, optical disk, video,

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 73 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 microfilm. Today, most archives kept are in paper media/format. Paper based archives are vulnerable to deterioration. Paper are subject to intrinsic decay which is degradation that is inherent in the material itself. Patkus called it as ”inherent vice”, a term that describes inherent weaknesses in the chemical or physical structure of an object [6]. There are also external agents of deterioration like water, pests, pollutants, moisture, temperature, light and human agency. In addition to changing environmental conditions, many archives have been exposed to different forms of damage. Careless handling of collections, theft and vandalism also contributes the deterioration of archives. The multitude of preservation research activities being carried out worldwide indicates an international awareness of the need for scientific tools to tackle the problem of degradation of the world’s cultural heritage. Research is providing new insights into why and how objects deteriorate and is informing the development of new active and passive (preventive) conservation procedures [7]. Archiving services are required by law, moreover, to pass on archival documents to future generations in good, well-ordered and accessible condition. For this reason it is important to be aware of the condition, not only of the individual documents but also of the archive as a whole. By determining how many archival documents in a piece (or a part of it) are in poor or even bad condition, a general statement can be made about its quality and accessibility. At the same time, a vision can be developed on the need for future preservation work [8]. The research was conducted on archives stored in four archival institutions. Consideration four archival is based on geographical considerations. It is known that the environment influences the life of the archives. The objective of this research is to study the archives damage in four archival institutions so that the results can support preservation of paper-based archives.

Method

Archives damage was analyzed based on Archives Damage Atlas and Universal Procedure Archives Assessment. The Archives Damage Atlas is a tool that can be used to recognize and classify damage to archival documents in order to establish the level of accessibility [8]. The atlas should also provide more insight into the types and causes of damage. Universal Procedure Archives Assessment is a model for calculating the assessment or consultability of archives [9]. Damage was divided into the following categories: 1. Binding and text block damage 2. Chemical damage 3. Mechanical damage 4. Pest infestation 5. Water damage

Several damage profiles were shown for each category and were classified according to severity. This division distinguishes between: 1. Slight damage. The damage to the object is not exacerbated when the archival document is handled (when it is moved, for instance, or paged through). 2. Moderate damage The damage to the archival document is not exacerbated when it is calmly and carefully handled. However, if the piece is subjected to handling or treatment that is a bit too rough, there is a good chance that the damage will worsen. 3. Serious damage Even careful and painstaking handling of the archival document (for instance, when paging through) will result in aggravation of the existing damage. It should also be noted that if there is a danger of information loss, the damage to the archival document should always be regarded as serious. Even if only part of a single leaf of an objectis seriously damaged,the entire object should be considered seriously damaged and therefore should not be made accessible.

Sampling method was random sampling so that each element has an equal probability of selection. The Sample size was determined using Table of Stephen Isaac and William B. Michael [10]. Population was all collection of paper based archives stored in four archival institutions. The population size and the sample size are shown below: 1. Institution A Population size : 2000 boxes of archives Sample size: 322 boxes of archives 2. Institution B Population size: 1200 boxes of archives Sample size : 304 boxes of archives 3. Institution C Population size: 3500 boxes of archives Sample size : 356 boxes of archives 4. Institution D Population size: 12428 boxes of archives Sample size : 98 boxes of archives In this institution, sample size was not large enough because there was the fumigation process in the time of research.

Results and Discussion

Level of Archives Damage

Identification of Level of Archives Damage are presented in Table 1, Table 2, Table 3, and Table 4 :

Table 1. Level of Archives Damage in Institution A

No Level Number % 1 Good 63 20 2 Slight damage 219 68 3 Moderate damage 32 10 4 Serious damage 8 2 Total 322 100

According to Universal Procedure Archives Assessment, moderate and serious damage need serious attention. Table 1. shows that 20% of archives are in good condition, 68% of archives are in slight damage, 12% of archives are in damaged condition (10% of archives are in moderate damage and 2% of archives are in serious damage). These mean that most archives stored are accessible to the public and only 12% of archives should not be made accessible.

Table 2. Level of Archives Damage in Institution B

No Level Number % 1 Good 28 9 2 Slight damage 265 87 3 Moderate damage 11 4 4 Serious damage 0 0 Total 304 100

Table 2. shows that 9% of archives are in good condition, 87% of archives are in slight damage, 4% of archives are in damaged condition. These mean that most archives stored are accessible to the public and only 4% of archives should not be made accessible.

Table 3. Level of Archives Damage in Institution C

No Level Number % 1 Good 64 18 2 Slight damage 193 54 3 Moderate damage 77 22 4 Serious damage 22 6 Total 356 100

Table 3. shows that 18% of archives are in good condition, 54% of archives are in slight damage, 28% of archives are in damaged condition (22% of archives are in moderate damage and 6% of archives are in serious damage). These mean that most archives stored are accessible to the public and only 28% of archives should not be made accessible.

Table 4. Level of Archives Damage in Institution D

No Level Number % 1 Good 7 7 2 Slight damage 70 72 3 Moderate damage 17 17 4 Serious damage 4 4 Total 98 100

Table 4. shows that 7% of archives are in good condition, 72% of archives are in slight damage, 21% of archives are in damaged condition (17% of archives are in moderate damage and 4% of archives are in serious damage). These mean that most archives stored are accessible to the public and only 21% of archives should not be made accessible. Table 5. shows the age of archives. From this data, we can see that most archives are under 100 years of age and it supports the accessibility of archives because the majority of archives are in slight damage.

Table 5.Archives’s Age

No Institution Year Created Archives’s Age 1 A 1820-2011 197-6 2 B 1958-2005 59-12 3 C 1926-2005 91-12 4 D 1936-1989 81-28

Law of the Republic of Indonesia Number 43 of 2009 Article 36 mandated that Archival institutions shall provide information services on records and archives, consultation, and guidance in managing records and archives of the community. Besides having an obligation to provide information to the community, archival institution shall ensure the protection of archives as the responsibility of the nation in preserving the national identity of the community, the nation and the state. To what extent an object can be accessed is closely connected to how damaged the documents are. These are the kind of damages that were found:

Figure 1. (a) Slight Damage (b) Moderate Damage (c) Serious Damage 76 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Categories of Archives Damage

Categories of damage assessed by Universal Procedure Archives Assessment are binding and text block damage, chemical damage, mechanical damage, pest infestation, and water damage. According to Universal Procedure Archives Assessment, moderate and serious damage need serious attention. The percentage of archives damage based on categories of damage in institution A is shown on this Table 5. :

Table 6. Categories of Archives Damage in Institution A

Number of Number of Categories Total % Moderate Damage Serious Damage Binding and text block damage 2 0 2 3,3 Chemical damage 42 6 48 78,7 Mechanical damage 6 1 7 11,5 Pest infestation 1 2 3 4,9 Water damage 1 0 1 1,6 61 100

Table 6 shows that the percentage of chemical damage (78.7%)>mechanical damage (11.5%)>pest infestation (4.9%)>binding and text block damage(3%) >water damage (1.6%). Moreover, the percentage of archives based on type of archives damage is shown in this Table 7:

Table 7.Type of Archives Damage in Institution A

Number of Moderate and Category Type of Damage % Serious Damage Surface 0 0 Binding and text Warping 0 0 block damage Spine damage 0 0 Loose binding 2 3,3 2 3,3 Fire damage 0 0 Foxing 17 27,9 Ink corrosion 3 4,9 Chemical damage Rust 18 29,5 Acidification 9 14,8 Old repairs 1 1,6 48 78,7 Damage through use 6 9,8 Mechanical damage Damage through 1 1,6 violence 7 11,5 Damage by insect 3 4,9 Pest infestation Damage by rodents 0 0 3 4,9 Staining 1 1,6 Felting 0 0 Water damage Mould 0 0 Stuck sheet 0 0 1 1,6 Total 61 100

The percentage of archives damage based on categories of damage in institution B is shown on this Table 8:

Table 8. Categories of Archives Damage in Institution B

Number of Number of Categories Total % Moderate Damage Serious Damage Binding and text block damage 1 0 1 7.7 Chemical damage 6 0 6 46.2 Mechanical damage 2 0 2 15.4 Pest infestation 3 0 3 23.1 Water damage 1 0 1 7.7 13 100

Table 8 shows that the percentage of chemical damage(46.2%)>pest infestation (23.1%) >mechanical damage (15.4%) > binding and text block and water damage (7.7%). Moreover, the percentage of archives based on type of archives damage is shown in this Table 9.

Table 9. Type of Archives Damage in Institution B

Number of Moderate and Category Type of Damage % Serious Damage Surface 0 0 Binding and text Warping 1 7.7 block damage Spine damage 0 0 Loose binding 0 0 1 7.7 Fire damage 0 0 Foxing 2 15.4 Ink corrosion 0 0 Chemical damage Rust 0 0 Acidification 4 30.8 Old repairs 0 0 6 46.2 Damage through use 1 7.7 Mechanical damage Damage through 1 7.7 violence 2 15.4 Damage by insect 2 15.4 Pest infestation Damage by rodents 1 7.7 3 23.1 Staining 1 7.7 Felting 0 0 Water damage Mould 0 0 Stuck sheet 0 0 1 7.7 13 100

The percentage of archives damage based on categories of damage in institution C is shown on this Table 10. Table 10 shows that the percentage of chemical damage (48.6%)> binding and text block damage(28.9%)>mechanical damage (11.9%)>water damage (7.8%)>pest infestation(2.8%). Moreover, the percentage of archives damage based on type of archives damage is shown in this Table 11. The percentage of archives damage based on categories of damage in institution D is shown on this Table 12.

Table 10. Categories of Archives Damage in Institution C

Number Number of Categories of Serious Total % Moderate Damage Damage Binding and text block 44 19 63 28.9 damage Chemical damage 83 23 106 48.6 Mechanical damage 21 5 26 11.9 Pest infestation 6 0 6 2.8 Water damage 13 4 17 7.8 13 100

Table 11. Type of Archives Damage in Institution C

Number of Moderate Category Type of Damage % and Serious Damage Surface 22 10.1 Binding and text Warping 3 1.4 block damage Spine damage 22 10.1 Loose binding 16 7.3 63 28.9 Fire damage 0 0.0 Foxing 25 11.5 Ink corrosion 10 4.6 Chemical damage Rust 11 5.0 Acidification 52 23.9 Old repairs 8 3.7 106 48.6 Damage through use 23 10.5 Mechanical damage Damage through 3 1.4 violence 26 11.9 Damage by insect 5 2.3 Pest infestation Damage by rodents 1 0.5 6 2.8 Staining 7 3.2 Felting 4 23.5 Water damage Mould 4 1.8 Stuck sheet 2 0.9 17 7.8 218 100

Table 12. Categories of Archives Damage in Institution D

Number of Number Categories Moderate of Serious Total % Damage Damage Binding and text block 0 0 0 0 damage Chemical damage 21 5 26 72.2 Mechanical damage 7 0 7 19.5 Pest infestation 1 2 3 8,3 Water damage 0 0 0 0 36 100

Table 12 shows that the percentage of chemical damage (72.2%)>mechanical damage (19.5%)>pest infestation(8.3%). Moreover, the percentage of archives based on type of archives damage is shown in this Table 13 :

Table 13. Type of Archives Damage in Institution D

Number of Moderate and Category Type of Damage % Serious Damage Surface 0 0 Binding and text Warping 0 0 block damage Spine damage 0 0 Loose binding 0 0 Fire damage 0 0 Foxing 7 19.4 Ink corrosion 5 13.9 Chemical damage Rust 4 11.1 Acidification 10 27.8 Old repairs 0 0 Damage through use 7 19.5 Mechanical damage Damage through 0 0 violence Damage by insect 3 8.3 Pest infestation Damage by rodents 0 0 Staining 0 0 Felting 0 0 Water damage Mould 0 0 Stuck sheet 0 0 0 0 Total 36 100

Based on Table 7, Table 9, Table 11 and Table 13. it can be seen as the following matters: 1. Binding and text block damage Binding and text block damage in institution A was caused by loose binding and in institution B wasonly caused by warping. There were all types of binding and text block damages in institution C and there were not types of binding and text block damage in institution D. Binding and text block damage can be caused by improper and incorrect storage, wear and tear caused by use and transportation, incorrect use of material. 2. Chemical damage In institution A, chemical damage was caused mostly by rust and in institution B, C, and D, chemical damage was caused mostly by acidification. Besides rust and acidification, another factor caused chemical damage (with big percentage) was foxing. 3. Mechanical damage In institution A, C, and D, mechanical damages mostly was caused by damage through use. In institution B, percentage of damage through use and violence is same. 4. Pest damage In institution A and D, pest damage was caused only by insect. In institution B and C, percentage of insect damage is bigger than percentage of rodents damage. 5. Water damage In institution A and B, water damage was caused only by stain. In institution C, water damage was caused by staining, felting, stuck sheet, and mold. In institution D, there was not water damage.

Based on above description, moderate and serious damage were caused mostly by chemical factors. Therefore it is necessary to improve preventive and curative preservation programme. The aim of archival preservation is to prolong the usable life of useful research information in two ways. First, preventive preservation seeks to reduce risks of damage and to slow down the rate of 80 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 deterioration. This aim is usually accomplished by selecting good quality materials and by providing suitable storage environments and safe handling procedures. Secondly, prescriptive preservation is a means of identifying and treating or copying damaged materials to restore useful access to the information [11]. These days, preservation science is a speciality in its own right in which scientists develop an understanding of why and how archive materials deteriorate and then, in co-operation with conservators, research into methods and materials for arresting that deterioration. Most advances in preservation knowledge and practice concentrate on the following three categories decay: cause and mechanism of degradation: treatment: active conservation; storage: passive conservation and damage prevention [12]. Storage plays a successful (preventive) preservation programme. Proper storage temperature and relative humidity can extend life of archives. The control of temperature and relative humidity is generally accepted as a means to prevent degradation of collections. Observation of temperature and relative humidity in four archival institutions shows that storage doesn’t yet meet requirement of norms for both temperature and relative humidity. If the temperature and humidity are always changing, over time the paper becomes weak because of the disruption of chemical bonds in cellulose polymer. The most common reaction is a hydrolysis reaction. The reaction speed is affected by temperature and moisture content in the paper. The moisture content is influenced by humidity in the storage room [13]. Archives should be stored in environmental conditions that appropriate to their format. Other preventive preservation programme is reproduction. When paper based archives are in moderate and serious damage, archival institution should reproduce the archives and make the copies available for use. The originals are then kept in safe storage or sent for conservation treatment. According to Moses, reproduction is something that is made in imitation of an earlier style and acces copy is a reproduction of a document created for use by patrons, protecting the original from wear or theft; a use copy [14]. Roper and Millar said that reproduction is a preservation tool [11]. The aim of reproduction is to protect physical archives so the original doesn’t be used for access to public. Paper based archives can be copied/converted into microfilm or digital format [15]. Besides preventive programme, moderate and serious archives also need restoration. Moses defined restoration as the process of rehabilitating an item to return it as nearly as possible to its original condition [14]. Restoration may include fabrication of missing parts with modern materials, but using processes and techniques that are similar to those originally used to create the item. In the restoration, there is acid removal process. Caminiti said that current paper preservation is thus based, overall, on deacidification- treatments and physical reinforcement [16]. Archival institution also should endeavour to create more awareness in using archives. All element shall participate in utilization of archives by promoting the utilization of archives as a culture in accordance with the appropriate procedure. Handling methods have a direct impact on the useful life of collections and the accessibility of information. Normal use causes wear, but inexpert and rough handling can quickly lead to extensive damage to collections requiring expensive repair.

Conclusion

Finally based on the above analysis, it can be concluded that The results showed that the biggest damage on paper-based archives was in slight damage (54-87%), Percentage of archives which is in moderate and serious damage is vary from 4% until 28% so for archives which are in these levels should not be made accessible, Moderate and serious damage were caused mostly by chemical factors, Both preventive and curative preservation could be improved, Archival institution also should endeavour to create more awareness in using archives. Training and education of staff is crucial to overall preservation of the archives.

References

1. The International Council on Archives. About ICA. In: http://www.ica.org/en/international-council- archives-0. Accessed September 6, 2016.

2. Azmi. Reformasi Birokrasi dalam Perspektif Penyelenggaraan Kearsipan. Jurnal Kearsipan 2009; Vol 4 (1): 1-34. 3. Shepherd, E. Archives and Archivists in 20th Century England. Surrey England:Ashgate Publishing Limited; 2009. 4. The National Archives. What is Appraisal. Kew UK: The National Archives; 2013. 5. Undang-Undang No. 43 Tahun 2009 tentang Kearsipan. 6. Patkus, B. Assessing Preservation Need, A Self – Survey Guide. Massachusetts: Northeast Document Conservation Centre; 2003. 7. Porck, H.J., Teygeller, R. Preservation Science Survey An Overview of Recent Developments in Research on the Conservation of Selected Analog Library and Archival Materials. Washington D.C: Council on Library and Information Resources; 2003. 8. Van der Most, P., Defize, P., Havermans, J. Archives Damage Atlas A Tool for Assessing Damage. The hague: Metamorfoze; 2010. 9. Nationaal Archief. Universal Procedure Archives Assessment. Den Haag; Workshop Collection Management and Care; 2010. 10. Isaac, S., Michael, W.B. Handbook In Research And Evaluation. In: Silalahi, U. Metode Penelitian Sosial, Bandung: Refika Aditama; 2010. 11. Roper, M., Millar, L., 1999. Managing Public Sector Records: A Study Programme, Preserving Records. International Records Management Trust, London. 12. Teygeller, R. Preserving Paper: Recent Advances. in (J.Feather [ed.]): Managing Preservation for Libraries and Archives, Current Practice and Future Developments. Ashgate: Aldershot; 2004, p 83– 112. 13. Porck, H.J. Rate of paper Degradation, the Predictive Value of Artificial Aging Tests. Amsterdam: European Commission on Preservation and Acces; 2000. 14. Moses, R.P. A Glossary of Records and Terminology. Chicago: The Society of American Archivists; 2005. 15. Arsip Nasional Republik Indonesia. Peraturan Kepala ANRI No. 23 Tahun 2011 Tentang Pedoman Preservasi. Jakarta: ANRI; 2011. 16. Caminiti, R., Campanella, L., Plattner, S.H., Scarpellini, E. Effects of Onnovative Green Chemical Treatments on Paper, Can They Help in Preservation?. International Journal of Conservation science 2016; Vol. 7 (1): 247-258.

ENERGY MANAGEMENT IN PAPER INDUSTRY: A CASE STUDY OF PT X

Kholisul Fatikhin Serpong, Banten 15320, Indonesia [email protected]

ABSTRACT

The pulp and paper sector is one of the most energy-intensive sectors. Energy is a significant production-cost component (about 15 – 25 percent), so the sector made efforts to reduce its energy costs by switching the energy sources and or improving energy efficiency. Energy efficiency is a key metric, both in terms of environmental impact and financial performance of the company. PT X has implemented energy efficiency since 2000s. Some projects to improve its energy performance have been made such as install variable speed drive, improve power factor, fixed steam leakage and other losses. In 2012, PT X implemented Energy Management System ISO 50001. Energy efficiency was carried out better and more systematic using PDCA approach. Energy was managed day to day through daily operating control and involves all the function in the company. After implementing EnMS, PT X achieved about 15.2% energy reduction in 2015 from baseline 2011. Total energy saving is 428,000 GJ.

CO2e reduction is 60,605 tons or reduces about 30% from the baseline.

Keyword: energy; energy management; energy conservation, energy efficiency; ISO 50001

Introduction

Since the strengthening of the issue of global warming and rising fuel prices, management of PT X decided to implement Energy Management System (EnMS). ISO 50001 is an international standard that give a guidelines or a framework for industry which will implement Energy Management System After implementing EnMS ISO 50001, energy efficiency was carried out better and more systematic. Energy was managed day to day through daily operating control and involves all the function in the organization such as design, procurement, operation, maintenance, training, quality assurance and so on. Top management fully support the system by providing the resources needed to establish, implement, maintain and improve the EnMS and energy performance. Commitment from top management has poured into the company policy.

Related Work

Climate change is one of the driving forces behind a new wave of energy management systems. Most of the currently available energy management systems in domestic environment are concerned with real-time energy consumption monitoring, and display of statistical and real time data of energy consumption. The motivation behind this approach is to provide households effective advice on their energy consumption by enabling them to take focused and effective actions towards efficient energy use [1]. Energy management program is a systematic and scientific process to identify the potential for improvements in energy efficiency, to recommend the ways with or without financial investment, to achieve estimated saving energy and energy cost. Thus the need to conserve energy, particularly in industry and commerce is strongly felt as the energy cost takes up substantial share in the overall cost structure of the operation which is relevant to our work [2]. Manufacturing managers need to understand the interrelated links between advanced manufacturing technology, primary and alternative energy choices, energy output values and costs, and energy conservation over the life of a project [3].

EnMS Development and Implementation

ISO 50001 give a guidelines or a framework for industry which will implement EnMS. The process to develop and implement the system is described in the diagram below [4], see Fig 1.

Fig. 1.EnMS ISO 50001 implementation process

Energy Policy

Energy policy is a statement to demonstrate that the commitment of top management to improve the energy efficiency continually, ensure the availability of information and of necessary resources to achieve objectives and targets, comply with applicable legal requirements and other requirements, supports the purchase of energy efficient products and services and design for energy performance improvement, provides the framework for setting and reviewing energy objectives and targets and conduct energy review periodically. PT X set the energy policy into the company policy. Top management has decided to communicate about the energy policy, EnMS and energy performance both internally and externally. All the suppliers have been informed about the energy policy and that procurement is partly evaluated on the basis of energy. Top Management has pointed a management representative and energy manager. The energy management team was formed to support the EnMS that consist of representatives of the related department such as Engineering, Production, Quality Assurance, Purchasing, Human Resource and Finance. Main responsibility of the team as follow: 1. Collecting and analyzing the energy data 2. Determine the Significant Energy Users (SEU) 3. Determine the factors that influence energy consumption 4. Establish baseline and Energy Performance Indicators (EnPI) 5. Identify the things desired by legal and other requirement 6. Identify opportunities for improvement 7. Identify the people who are responsible for the SEU area 8. Establish energy objectives and targets 9. Establish, implement, and maintain action plans

Energy Planning

Energy planning is process to analyze energy use and consumption, identify areas of significant energy use (SEU) and consumption, and identify opportunities for improving energy performance. The input of this process is the past and present data of energy use and relevant variable affecting SEU. The output is energy baseline, energy performance indicator (EnPI), objectives, targets and action plan. PT X use energy in the form of electricity and steam. Using Pareto Chart was founded that Paper Machine (PM) and Stock Preparation (SP) consumes more than 80% of electricity and steam, see Fig 2. Therefore, SP and PM were considered as SEU. EnMS implementation is focused on the SEU.

40.0% 120.0% 40.0% 120.0% 35.0% 35.0% 100.0% 100.0% 30.0% 30.0% 80.0% 80.0% 25.0% 25.0%

20.0% 60.0% 20.0% 60.0% 15.0% 15.0% 40.0% 40.0% 10.0% 10.0% 20.0% 20.0% 5.0% 5.0% 0.0% 0.0% 0.0% 0.0% PM#3 PM#2 PM#1 SPConv&Chip SP PM1 FIN WWT WT

Percent % ACC Percent % ACC

Fig. 2.(a) Pareto chart of electric consumption; (b) Pareto chart of steam consumption

After determine the SEU than we should identify the relevant variable that affecting to SEU (energy drivers). A method to identify the energy driver is a simple regression for single variable or multiple regressions for two or more variables. Correlation test using the past data in PT X, was founded that there are significant correlation between production level and energy consumption (R-square = 0.865), see Fig 3.Therefore, the regression equation obtained in the test is reliable and able to use as a model to predict the future energy consumption. The equation is called as energy baseline.

Fig. 3. Regression analysis between production level and energy consumption

Energy performance can be demonstrated by comparing the actual energy consumption with the prediction. If the actual energy consumption is lower than the prediction, it means that the energy performance improves and vice versa. The energy conservation opportunities (ECO) is identified, prioritized and recorded by conducting the energy audits. Action Plan was established and implemented in PT X for achieving their objective and target, see Table 1.

Table 1. Energy Conservation Opportunities in PT X

Annual saving Description (GJ) Reduce Air Compressor Pressure 483 Install interlock (Auto Off) 105 Install Variable Speed Drive 512 Replace V-Belt with Timing Belt 879 Upgrade PM Drive from line shaft to sectional 3,521 drive(3 lines) Rebuild Steam & Condensate System (3 lines) 3,600 House keeping -

Implementation and Operation

After implementing EnMS ISO 50001, energy efficiency has been managed better from day to day through daily operation control. All critical parameters for operation and maintenance related to SEU are identified, monitored, measured and analyzed at planned intervals. Design and procurement process also consider the energy conservation opportunity. All employees related to SEU are trained to improve their competency and awareness. The objectives of the training as follows: • Employees who work especially in the area SEU has adequate competence • Employees care about the importance of EnMS • The employees concerned will benefit from improved energy performance. • Employees concerned that the activities and behavior contribute to the achievement of the objectives and targets companies.

All employee especially in SEU areas also involved in the energy efficiency improvement through focused improvement activities such as Small Group Activity (SGA) and Skill Development Activity (SDA). Each employee also may give a suggestion through e-suggestion (intranet base). Every year PT X conducts a competition to choose the best project and best suggestion. Some action plan has been established was implemented, monitored and recorded. Some investment has been made to improve energy performance in SEU such as install VSD, upgrade steam and condensate system, upgrade line shaft with sectional drive.

Checking

PT X ensures that the key characteristics of its operations that determine energy performance are monitored and measured and analyzed. Energy consumption is tracked monthly and compared with predicted energy consumption. Energy team reviews the EnPI to determine the energy performance quarterly. Preventive and corrective action is also reviewed at that time, EnMS audit carried out regularly once a year by internal and external auditors. This audit aims to verify whether the company’s activities are still consistent with the EnMS ISO 50001 requirements, whether the company still meets the legal and other requirements, whether EnMS are carried out effectively. A Technical audit is conducted every 3 years by professional auditor. It is helpful for the company to find the opportunities for improvement.

Management Review

Management review is conducted once a year to review if any decisions or actions related to changes in the energy performance of the company, energy policy, EnPI, objective and target, and allocation of the resources. Management review is attended by top management, management representative, energy manager, energy team and all department head.

Result and Benefit

Energy efficiency improvement gives a positive impact to the company. Production volume increased significantly in 2015 compared to baseline. Energy intensity also improves continually. Energy Intensity decreased by 15.2 % in 2015 compared to baseline, see Fig 5.

Fig. 5. (a) Trend of energy consumption & production; (b) Energy intensity (GJ/Ton of product)

Energy performance can be demonstrated by comparing actual energy consumption with the predicted energy consumption. Actual energy consumption is lower than energy prediction. Gap between actual and prediction is saving. Accumulative energy saving from 2012 – 2015 is about 428,000 GJ, see Fig 6.

Fig. 6. (a) Trend of actual energy consumption & prediction; (b) CUSUM Graph

Conclusion

Energy is a controllable resource. Therefore, using it efficiently will help the company to improve their financial performance and increase the company image. EnMS ISO 50001 is an international standard that give a framework for organization which will implement Energy Management System. This standard applies internationally so it can provide added value to the product in the global market Commitment from Top Management is mandatory. Barrier for implementation is if Management just focuses on production and not on energy efficiency.

References

1. Kuo-Ming Chao, Shah, N., Farmer, R., Matei, A., Ding-Yuan Chen, Schuster-James, H., Tedd, R., “A Profile Based Energy Management System for Domestic Electrical Appliances”. 2. Irawati Naik, Prof.S.S.More, Himanshu Naik, “Scope of Energy consumption and Energy Conservation in Indian Auto Part Manufacturing Industry”. 3. Jeffrey M. Ulmer, Troy E. Ollison, “Alternative Energy Choices, Conservation, and Management: A Primer for Advanced Manufacturing Managers” 4. Badan Standarisasi Nasional, “Sistem Manajemen Energi – Persyaratan dengan Pedoman Penggunaan”. SNI ISO 50001:2012

WOOD SUPPLY AND SUSTAINABLE FOREST MANAGEMENT SYSTEM IN APRIL GROUP IN THE PROVINCE OF RIAU

Petrus Gunarso1, Prayitno Goenarto2 APRIL, Jl. M.H. Thamrin No.31, Jakarta 10230, Indonesia [email protected] [email protected]

ABSTRACT

Indonesia is a rapidly developing country, but millions still live in poverty. Responsible plantation forestry helps the economy grow, creates jobs and improves local livelihoods. Through forest plantations, Indonesia can become a key player in sustainability - meeting the world’s need for wood and fiber and at the same time providing jobs, and economic growth. In 2014 APRIL Group - an integrated pulp, paper, and forest plantation introduced an upgraded Sustainable Forest Management Policy that commits the company to implement a moratorium on plantation development in areas where High Conservation Value Forests (HCVF) assessments have not been completed. The company is also committed to supporting conservation areas through HCVF assessments and has obtained ecosystem restoration concessions with a target of maintaining conservations areas equal in size to its plantation areas. With the implementation of Sustainable Forest Management Policy, the company is guaranteeing sustainable wood supply for the pulp and paper mill with improved quality and efficient mill operation. While most efficiency evaluations focus on mill operations, this paper focuses on the sustainable production of timber and fiber, eliminating deforestation from the supply chain, improving environmental conservation to protect and enhance biodiversity within production forests, and addressing the issues of poverty and climate change.

Keywords: wood supply; sustainable forest management; HCVF assessment; biodiversity conservation.

Introduction

Indonesia’s forest cover is decreasing rapidly due to deforestation and illegal logging leading to a shortage of timber resources available for domestic use. Due to current laws and regulations the economic viability for timber plantations other than for pulp and paper to supply domestic markets are questionable. This situation leads most companies to focus on foreign markets and exports, which in turn causes a shortage of timber for domestic consumption and contributes towards a gap between local supply and demand. The large discrepancies between the demand and supply for domestic timber consumption then forces individuals to seek alternative sources to fulfil these needs. Discrepancies between domestic market price and estimated price for legally supplied wood suggest that the majority of timber sold domestically does not come from legal sources [1].

The Role of Forest Plantation in Indonesia

Deforestation and Illegal Logging

Landsat Satellite imagery from 2000, 2005, and 2010 shows the increasing trend in degraded forests [2]. Primary forest cover decreased from 49 million ha (Mha), to 44 Mha to 42 Mha ha while degraded forests increased from 28.4 million, to 30.9 million ha, to 31 million ha. The trend in forest degradation is also supported by data from Indonesia’s Ministry of Environment and Forestry indicating a deforested area of about 727,981 ha during the years of 2012-2013[3]. The factors contributing towards the rapid deforestation rates and loss of primary natural forests include historic political, technical and economicmotivations. Before the system of logging permits (Hak Pengumutan Hasil Hutan-HPHH and Izin Pemungutan dan Pemanfaatan Kayu-IPPK) was stopped early in the first decade of this century, district governments

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 89 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 were issuing numerous logging permits, with various individuals and companies vying for land. A lot of these small-scale district logging licenses were issued because the Ministry of Forestry did not have the capacity to block them under the conditions of decentralization of forest administration that existed at that time[4].Massive land use and land-cover changes occurred as a result of poor governance and law enforcement. Many companies were under pressure to adopt non-sustainable strategies in order to access the timber stock in their concessions before the illegal loggers [5].Under these conditions it has been estimated that less than ten percent of forest was being managed for continuous productivity[6]. The prevalence of illegal logging, and the corruption that ensued following the decentralization of logging permit issuance, was linked to substantial financial losses into the billions of dollars [7]. The non-sustainable forest management response resulted in land clearing, with no plans to restore or reforest.As a result a majority of licenses were revoked by government leaving open access land vulnerable to encroachment or conversion. The extent of the impact of this process is evident from the fact that of the 560 concessions that existed in 1985 now only around 200 remain. The massive increase in unmanaged forest land has created a potentially enormous pool for conversion to other uses. For example, the projected demand for oil palm land expansion is set to increase by7% annually [8].The expansion and conversion of degraded or unused forest into palm oil plantationshas further reduced the availability of land for timber plantations and has fed a positive-feedback loop.As the gap between demand for timber and potential to supply it under sustainable management widens, the motivation for people to illegally log leaves behind further cleared open access land that is then left unproductive or converted for other purposes. Acknowledging the limit of land availability left for timber, the next most intuitive solution to addressing the gap would be to increase productivity and maximise efficiency of timber production on the already available land through improved plantation productivity.

Forest Plantation Productivity

Although slow in progress, forest plantations have the potential to sustainably produce large quantity of timber for fibre and wood. Forest plantations Hutan( Tanaman) in Indonesia produced more than 20 million m3of log wood in 2013. Indonesia has the potential to increase this output by a level of magnitude and if managed well, according to scientific principles, high productivity, intensely managed plantations may also serve the potential to help meet the world’s need for timber [9]. In contrast natural forests (Hutan Alam) currently produce less than 6 million m3of logwood per year [10].The lower yield of timber from natural forests (around 1m3/ha/annum) from a range of species means that this resource should be reserved for high value selective markets and not included in the same market space as that targeted by plantations. April Group (APRIL) is one of the largest, most technologically advanced and efficient makers of pulp and paper products in the world. It makes products that are used by millions of people every day in liquid packaging, printing and writing paper, tissues, shopping bags, food packaging, magazines and books. APRIL is an integrated Pulp, Paper Mill and Sustainably managed plantation forest - located in Riau Province, Indonesia. In its operation APRIL has shown that forest plantations are capable of reaching 20-25m3/ha/annum through a 5 year rotation, allowing for a greater quantity of timber to be harvested more frequently, and providing a stable income base. Certain forest plantations have the potential to restore productivity and rehabilitate degraded tropical production forests[11]. As the forest plantations convert high diversity of forests into monoculture, it is therefore APRIL has initiated a mitigation measures through allocating larger proportion of conservation or protection of its concession with so called one to one. Every one hectare of plantation forest is mitigated with one hectare of protected or conserved natural forests in the concession and implement restoration efforts.

Sustainable Forest Management Policy

In June 2015 APRIL unveiled its Sustainable Forest Management Policy version 2.0 (SFMPv2) [12]. with the objective of “eliminating deforestation from our supply chain and protecting the forest

90 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 and peat land landscapes in which we operate”. The APRIL Policy is being implemented by ensuring its plantations are developed on areas that are not forested and peatland. APRIL has also placed a moratorium on clearing natural forest pending HCV - High Conservation Value and HCS - High Carbon Stocks assessment. It has no plans to establish further pulp mills or other related infrastructure until plantation fibre self-sufficiency is achieved. The SFMPv2 pushes APRIL towards maximising its efficiency and productivity based on the timber resources it has on its existing lands.APRIL is also committed to implementing actions that go beyond legal compliance of micro and macro delineation such as the implementation of HCV assessments since 2005. The purpose of the HCV Assessment is to assess and identify forests/areas which have High Conservation Values, these values pertain to “biological, ecological, social or cultural values which are considered to be outstanding significance or critical importance at the national, regional or global scale” [13]. At the landscape level, the Kampar Peninsula, total protected areas that include ERC and HCV areas is greater than 300,000 ha. The current landscape unit of Forest Management -Kesatuan Pengelolaan Hutan Produksi (KPHP) covers the total area of 513,000 ha. With the current ERC - Ecosystem Restoration Concession and HCV of more than 300,000 ha, the proportion of protected areas in the KPHP - Production Forest Management Unit Tasik Besar Serkap is now more than 58%; higher than the APRIL target of 1 to 1. The landscape of Kampar Peninsula is a perfect example for implementation of both one to one principle and ring buffer and core conservation principles.

Poverty Alleviation

Sustainable Development rests on three related pillars: environmental; social and economic. The first Goal of the UN Sustainable Development Goals addresses poverty by targeting an end to extreme poverty by 2030[14]. Experience has shown that in order to end poverty those suffering from it need to be engaged and supported in finding solutions.An important element of this approach is to create jobs to reduce unemployment. Rural unemployment has been identified as an important factor contributing towards local conflict in Indonesia. Unlike local conflict in Java Island, the situation in Sumatrain particular is exacerbated by uncertainty of tenure, so legal assignment of forests land to a company is not necessary perceived and seen by local community as a legal assignment but more seen as legally supported central government of land occupation. This in particular relates to the boundary marking process that each concession has to mark its boundary at own cost. [15]With large populations dependant on land and with no land allocated to them, this will subsequently increased un-employment. Companies operating in this context therefore need to address local un-employment through land sharing and labor force openings. The APRIL Policy supports this approach. Between 1999 and 2014 APRIL has increased employment opportunities in Riau from 42,000 people working in 2000, to 59,000 in 2010 and 58,000 in 2014. The benefits of increased job creation during the study period also translated to a rise in economic output as the agriculture accounted for nearly 70.7% of Pelalawan District economic output.[16] Pelawan is the location of Pulp, Paper and Power Mill of APRL. With household income expected to continue to rise, the economic benefits from the agriculture will hopefully continue and the effects felt by the surrounding communities for generations to come. Past situations where communities were not in a good position to deal and negotiate with companies, and single representatives led negotiations have often resulted in unfavourable gains that did not benefit the community and only benefited a few individuals resulting in confusion and distrust[17].Therefore, it is imperative to provide long term economic support for local community instead of short-term economic fixes and to ensure that benefits are widespread affecting a majority of the communityand not just a few.

Conclusion

This paper focuses on resource efficiency upstream of the industrial timber process towards the idea of responsible forestry which involves various concepts of sustainability and benefits across environmental, economic and social aspects.As part of responsible plantation forestry, APRIL implements sustainable

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 91 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 practices through policies such as the SFMPv2 - Sustainable Forest Management Policy version 2 that ensure no deforestation of forests and legal sources of wood supply. Establishment of pulp mills and sustainable forest plantations also addresses socio-economic issues, with agricultural assistance improving local livelihoods through increased employment opportunities and economic growth.

References

1. Klassen AW. Domestic demand: the black hole in Indonesia’s forest policy. European Tropical Forest Research Network News2010; 52: 15-22 2. Gunarso P. Darurat tutupan hutan Indonesia. In: Nugraha A, Santoso H, Ardiansyah I, Imron MI, Sanyoto R, Awang SA, Yuwono T, Istoto YEB, editors. Darurat Hutan Indonesia, Banten; Wana Aksara;2014, p. 235-57 3. Data and Information Centre, Ministry of Environment and Forestry of Indonesia. 2015. Ministry of Environment and Forestry Statistics 2014. Jakarta, Ministry of Environment and Forestry. 4. Barr CM, Resosudarmo IAP, Dermawan A, McCarthy J, Moeliono M, Setiono B. Decentralization of forest administration in Indonesia: Implications for forest sustainability, economic development, and community livelihoods.Center for International Forestry Research 2006: 90-1 5. Jepson P, Jarvie JK, MacKinnon K, Monk, KA. The end of Indonesia’s lowland forests?Science 2001; 292: 859-61 6. Dauvergne P. The politics of deforestation in Indonesia.Pacific Affairs1993;66: 497-518 7. Smith J, Obidziinski K, Subarudi, I. Suramenggala. Illegal logging, collusive corruption and fragmented governments in Kalimantan, Indonesia.International Forestry Review 2003; 5:293-302 8. [8] Gunarso P, Hartoyo ME, Agus F, Killeen TJ.Oil palm and land use change in Indonesia, Malaysia and Papua New Guinea. 2013.Reports from the Technical Panels of the 2nd Greenhouse Gas Working Group of the Roundtable on Sustainable Palm Oil 2013; 29-64 9. Fox TR. Sustained Productivity in intensively managed forest plantations. Forest Ecology and Management 2000; 138: 187-202 10. Kementerian Kehutanan. 2014. Statistik Kawasan Hutan 2013. 11. Parrotta JA. The role of plantation forests in rehabilitating degraded tropical ecosystems.Agriculture, Ecosystems & Environments 1992; 41: 115-33. 12. APRIL. APRIL Group’s Sustainable Forest Management Policy 2.0. 2015: 1-4. 13. Jennings S, Nussbaum R, Judd N, Evans T. The High Conservation Value Forest Toolkit. 2003. Proforest. Edition 1; 1-27 14. United Nations. Transforming our world: the 2030 Agenda for Sustainable Development. 2015. A/ RES/70/1 15. Barron P, Kaiser K, Pradhan M. Understanding variations in local conflict: Evidence and implications from Indonesia. World Development2009; 37: 698-713 16. Lembaga Penyelidikan Ekonomi dan Masyarakat – Fakultas Ekonomi dan Bisnis Universitas Indonesia. Analisis Dampak Ekonomi & Fiskal Analisis Dampak Ekonomi & Fiskal APRIL Group Riau Complex (AGRC): Update 2014. p. 1-124 17. Obidzinski K, Barr C.The effects decentralisation on forests and forest industries in Berau district, East Kalimantan.In: Case studies on decentralisation and forests in Indonesia. Bogor, Center for International Forestry Research; 2003, p. 1-31

EFFECT OF REYNOLDS NUMBER AT ORIFICE OUTFLOW AND FLOTATION ZONE ON THE FATTY ACID DISPERSION IN CORRELATION WITH DEINKING FLOTATION PERFORMANCE

Trismawati a1, I. N. G. Wardana 2, Nurkholis Hamidi 3, Mega Nur Sasongko 4 a Doctoral Student of Mech. Engineering, Univ of Brawijaya, Malang 65144, Indonesia Department of Mechanical Engineering, University of Brawijaya, Malang, 65144, Indonesia, [email protected] [email protected] [email protected] [email protected]

ABSTRACT

The importance mechanism of bubbling is to generate suitable Reynolds number to create hydrodynamic shear force in flotation. The critical Reynolds number at orifice outflow (Reo) and in flotation zone (Revt) are defined as the maximum Reynolds numbers of fluid at some distance from nozzles and in flotation zone to create turbulence without the appearances of proper mixing. The ink and froth is collected at the upper part of the flotation tank, the fibers free of ink are discharged from the bottom part of flotation tank. ONP pulp slurry of 5,0 % consistency is poured into the flotation thank that has been filled with water up to 70 % of volume so that 1,0 % consistency is achieved. From the bottom part of flotation tank, air with difference flow rate is injected into the flotation tank through orifice with difference sizes. Fatty acid from Morinda oil is injected into the flotation tank. The Reynolds numbers that are able to disperse the fatty acid is evaluated by the achievable brightness and ERIC. As a benchmark synthetic surfactant is used to evaluate the effectiveness of fatty acid as a surfactant for flotation deinking. From the experiment it is concluded that fatty acid need higher Reynolds number for its dispersion and creates hydrodynamic shear force that able to detach ink from fiber surfaces. To high Reynolds number gave proper mixing instead of flotation, results poorer flotation performances and give poor results. Difference lipophilic and hydrophilic character of substance used in the deinking flotation need difference region of turbulence (Reynolds number) to achieve the proper results. The critical Reynolds number suitable for this deinking flotation is 4,0 – 5,0 x 107 at some distance escape from orifice, and 1,0 – 1,3 x 107 in flotation zone.

Keywords: hydrodynamic shear force, Reynolds number, ink detachment, fatty acid dispersion, orifice outflow, flotation zone

Introduction Flotation deinking is a separation process of the detached ink from fiber by the use of air that injected into flotation tank. The injected air will create bubbles move upward with the ink particles into the froth zone. For being able to carry up the detach ink, an interaction between ink particles and bubble should be exist. In this case, a substance that has interconnection between ink particles (oil based) and bubbles (bubble - water interface) is needed. In order so, the used of surfactant in deinking flotation to assist the separation of ink particles from fibers is unavoidable. Surfactant can be distributed evenly in a flotation medium (water) because its head has hydrophilic properties, in other side its tail that has lipophilic properties, able to penetrate into the disperse ink particles. This process is apparently simple as long as the surfactant has the appropriate HLB value. Research concerning HLB value of surfactant for deinking flotation has been done. Surfactant with high HLB value is favorable for cellulose activity and low HLB value is favorable for ink removal [1]. HLB value of surfactant is closely relate to the hydrocarbon structure, the longer the hydrocarbon chain and the more the un-saturated structure presence, the better the surfactant performance for deinking flotation [2]. The probability of surfactant and ink interaction is modeled by the probability of ink attachment on bubbles [3].

Nomenclature

𝑣𝑣𝑗𝑗𝑗𝑗 𝐴𝐴 :𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑏𝑏𝑏𝑏 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑒𝑒

𝑣𝑣𝑓𝑓𝑓𝑓 𝐴𝐴 : 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑐𝑐 𝑏𝑏𝑏𝑏 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑑𝑑𝑜𝑜 :𝑑𝑑𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜

𝐵𝐵𝑗𝑗 𝑑𝑑 :𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑒𝑒

𝐵𝐵𝑓𝑓 𝑑𝑑 :𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑏𝑏 𝑎𝑎 𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑓𝑓 𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑒𝑒

𝑒𝑒𝑗𝑗𝑗𝑗 𝑅𝑅 :𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑒𝑒𝑓𝑓𝑓𝑓 𝑅𝑅 : 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑓𝑓𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑗𝑗𝑗𝑗 𝑣𝑣 :𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑓𝑓𝑓𝑓 𝑣𝑣 : 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑏𝑏 𝑎𝑎𝑎𝑎 𝑓𝑓 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑣𝑣𝑜𝑜 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑎𝑎𝑎𝑎𝑎𝑎 𝑡𝑡ℎ𝑟𝑟𝑟𝑟𝑟𝑟 𝑟𝑟ℎ 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜

𝜌𝜌 ∶ 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑓𝑓 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

𝜇𝜇Numerical∶ 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 code:𝑜𝑜𝑜𝑜 20,𝑓𝑓 𝑓𝑓𝑓𝑓40,𝑓𝑓 𝑓𝑓𝑓𝑓60 are orifice diameter of 2, 4, and 6 mm

To know the turbulence performance, Reynolds number at orifice outflow and flotation zone is evaluated:

In this case:

With vfz is the velocity of bubbles at the flotation zone and is measured by dividing the distance of bubble path by the increment of time in 0.25 second (by controlling the video of bubbles movement).

The bubbles diameter dBf and dBj was measured as the average bubbles size using Image J.

With Avjz and Avfz is the area covered by bubbles at orifice outflow and flotation zone respectively, and it was measured by Image J. If air is injected continuously through a nozzle into water medium, the air jet immediately breaks up into an array of bubbles which range in diameter from almost zero up to a maximum value. This diameter is depends upon the air discharge and the gravitational acceleration g [4]. The used of surfactant has certain effect on the physical properties of water when it is dissolved on water, such as decreasing water surface tension, decreasing mean diameter of bubbles, increasing gas hold up and gas movement [5, 6, 7]. These all might be related with the hydrogen bonding presence between the hydrophilic part of surfactant and water molecule. In case of fatty acid is used instead of surfactant, hydrogen bonding does not available abundantly. The only interaction is between the fatty acid and fatty ester presence in ink structure. This might be happened when fatty acid can reach (contact) the fatty ester of ink. In order to disperse fatty acid evenly, turbulences should be created and the hydrodynamic shear forces presence will assisting the separation of ink particle from fiber. The critical Reynolds number to create hydrodynamic shear forces is elucidated in this research. The result is compared with the critical Reynolds number when surfactant is used in flotation deinking.

Experiment

Experiment was performed in the flotation tank as it is depicted in Fig. 1. Air was injected at difference flow rate through orifice. The Reynolds number was calculated based on the speed of outflow air through orifice (Reo), and based on the average speed of rising bubble (Revt). The orifices used in this experiment were 2, 4, and 6 mm of diameter. Old newspaper pulp was prepared by disintegrate it in a pulper at 5 % of consistency for 10 minute. Sodium Lauryl Sulfate was injected as a foaming agent at 0.6 % of dosage. fatty acid of Morinda oil (FA) and synthetic surfactant used for deinking flotation was studied comparatively. The achievable brightness and ERIC was measured with Technidyne – Color Touch 2 models ISO. The maximum Reynolds number that able to create the necessary hydrodynamic shear force for ink liberation without proper mixing was studied to know the lipophilic character of any surfactant or fatty acid for ink liberation. To evaluate the deinking flotation performance, brightness (Tappi T 452) and ERIC (Tappi T 567 om-04) measurement was performed.

Froth Zone

Flotation

Zone

Shear force

zone zone

ead ead Jet zone D D

Fig. 1. Experimental arrangement, ink detachment from fibres and ink attachment on bubble.

Ink Detachment Analysis

It is assumed that the bonding between fiber and ink particles has been rupture by the hydrodynamic shear force and friction force during pulping. In deinking flotation hydrodynamic shear force is also presence. When hydrodynamic shear force is created, the ink particle will be pulled out of intact from the fiber surface. Hydrodynamic shear force is created by pressurized air escape from nozzles. This force is a function of Reynolds number. In case of synthetic surfactant is used for flotation, the surfactant will distribute easily into flotation medium because of its HLB value is properly designed. In case of fatty acid is used for flotation, the fatty acid does not easily distribute into the flotation medium, because it has higher lipophilic character, and it will easily penetrate into ink particles when they are in touch to each other. The maximum Reynolds number to create hydrodynamic shear force without proper mixing is searched in this experiment. When both synthetic surfactant and fatty acid is able to reach the ink particle, then the ability to detach ink particle is resembles, the created hydrodynamic shear force is sufficient to remove ink particle from the fiber surface. If the ability to detach ink particle is quite difference, the lipophilic character (fatty acid diffusivity into ink particle) of fatty acid should be improved. Reynolds number is the property of turbulence. In flotation deinking, there are dead zone, jet zone, flotation zone and froth zone. The ink detachment is mostly happened in jet zone, and the separation of detached ink from fiber is mostly happened in flotation zone. Dead zone is dominated by sedimentation of fiber. In froth zone, the detached and floated ink particles are collected. When the deinked pulp quality is almost the same, this mean the ink separation in the flotation zone has the necessary Reynolds number to create turbulent for flotation deinking. In other case, when the ability of flotation is resembles, this can be inferred that the hydrophilic character of surfactant and fatty acid is quite strong enough to keep in touch the ink particle from bubbles.

Result and Discussion

From Fig. 2, it is shown that: (a) the addition of synthetic surfactant and FAMC result the higher velocity of rising bubbles; (b) the addition of synthetic surfactant and fatty acid reduces the diameter of rising bubbles. This was happened because the effect of synthetic surfactant and fatty acid addition to the water is reducing its surface tension. This result is supported by other research experiment that the used of surfactant give effect on decreasing of water surface tension, decreasing of mean diameter of bubbles, increasing of gas hold up and gas movement [5, 6, 7, 10].

Fig. 2. Correlation of (a) bubble velocity and air flow rate; (b) Diameter of bubbles and air flow rate - through nozzle; (c) Image J of bubbles for air flow rate of 5 L/s from orifice of 5 mm (in flotation zone).

From Fig. 3 (a) it is shown that brightness was increase as the Reynolds number increase but at a certain Reynolds number the brightness was declined. For synthetic surfactant the optimum Reynolds number at orifice outflow is in the range of 2,0 – 4,0 x107 and for Fatty acid in the range of 4,0 – 5,0 x107 when orifice with diameter of 4 mm and 6 mm was used. If orifice with diameter of 2 mm was used higher Reynolds number is needed. From Fig. 3 (b), the ERIC reaches the lowest value at the same Reynolds number as it was performed for brightness. From this result it can be concluded that fatty

96 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 acid need higher Reynolds number for its dispersion. Fatty acid and water is immiscible, fatty acid has hydrophobic properties so it needs higher turbulence (Reynolds number) for its dispersion. In other case, synthetic surfactant has a good balance in oil and water properties (good HLB value), so synthetic surfactant need lower Reynolds number for its dispersion. When fatty acid has been disperse well, as it was in the above Reynolds number, the brightness and ERIC achievement is approaching of the deinking flotation result using synthetic surfactant, so it can be inferred that the lipophilic properties of fatty acid is almost the same with the lipophilic properties of synthetic surfactant. Fatty acid can reach the best performance as surfactant at Reynolds number of 4,0 X 107. In case of the achievable brightness (“and ERIC”) of deinking pulp with fatty acid is still lower (“higher”) than the one with synthetic surfactant, this might be correlated with its hydrophilic properties.

Fig. 3. (a) Brightness of floated pulp; (b) ERIC of floated pulp vs Reynolds number at orifice outflow

From the result presented on Fig. 3 it is clearly seen that Reynolds number of 4,0 x107 at the orifice outflow seems the most appropriate for the above system. It gives the best performance for deinking flotation result. At this Reynolds number, the created hydrodynamic shear force gave the best performance for ink particles detachment. From Fig. 2 and Fig. 3, it is clearly seen that orifice with diameter of 4 mm gave the most appropriate bubbles size suitable for deinking flotation. It produces the deinked pulp with highest brightness and lowest ERIC. This may correlates with the ability of suitable bubbles size in lifting the detached ink into froth zone, and the probability of collision between ink particle and bubble [8,9].

Fig. 4. (a) Brightness and; (b) ERIC of deinked pulp vs Reynolds number at flotation zone

Fig. 4 shows, the correlation of Reynolds number in the flotation zone with the quality of deinked pulp. Bubbles diameter produces from orifice diameter of 4 mm, gave the best performance for deinking flotation. In this case, when synthetic surfactant was used, Reynolds number of 7,5 – 11,5 x 106 is the appropriate Reynolds number for deinking flotation to achieve highest brightness and lowest ERIC. When fatty acid was used, the appropriate Reynolds number is higher (1,0 – 1,3 x 107). © 2016 Published by Center for Pulp and Paper through 2nd REPTech 97 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Conclusion

From the above experiment, it is conclude that fatty acid need higher Reynolds number for its dispersions, and synthetic surfactant need lower Reynolds number. The Reynolds number needed is 4,0 – 5,0 x 107 in the orifice outflow zone and 1,0 – 1,3 x 710 in flotation zone for fatty acid dispersion, and 2,0 – 4,0 X 107 in the orifice outflow zone and 7,5 – 11,5 x 106 in the flotation zone for synthetic surfactant dispersion. Orifice diameter of 4 mm gives the suitable bubbles size for flotation deinking at the above Reynolds number. This could achieve the best performance for both fatty acid and synthetic surfactant dispersion, and for deinking flotation results. It can be inferred that when the disperse fatty acid can reach ink particles, the ability of bubbles to lift the detached ink is still questionable and this could be improved. It may relate with the interaction among air bubbles, bubbles – water interface, and the hydrophilic character of fatty acid.

Acknowledgements

The authors are grateful for the financial support of the Indonesian Directorate General of Higher Education (DGHE or DIKTI), Grant. No: 1014/UN10.14/KU/2013; PT KAO Indonesia Branch Surabaya for Papyrase enzyme and synthetic surfactant; Darono Wikanaji, M. Eng., Pulp and Paper Technology lecturer and consultant for helpful thinking and educated suggestions.

References

1. Mayeli, N., Talaeipour, M. Effect of different HLB value and Enzymatic treatment on the properties of old newspaper deinked pulp. Bioresources 2010; 5(4), 2520 – 2534. 2. Khalek, M. A. Performance of different surfactants in deinking flotation process. Elixir Appl. Chem. 2012; 46: 8147-8151. 3. Heindel, T. J., Maruvada. K. S. A Methodology for Flotation Deinking Model Validation. Institute of Paper Science and Technology. Profect F00903, Report 7. Atlanta, Gergia. 1998. 4. Kobus, H. Bemessungsrundlagen und Anwendungen fur Luftscheier im Wasserbau. Heft 7. Schriftenreiche “Wasser und Abwasser in Forschung und Praxis”, Erich Schmidt Verlag. Berlin. 1973. 5. Asari, M. Hormozi, F. American Journal of Chemical Engineering, 1(2), 50 (2013). 6. Chaumat, Helene, Billet, Anne Marie, Delmas, Henry. Hydrodynamic and mass transfer in bubbkle column: Influence of liquid phase surface tension. Un-published. Laboratoire de Genie Chimique, Z. A. Basso Cambo, France. 7. Chaumat, Hélène and Billet, Anne-Marie and Delmas, Henri Hydrodynamics and mass transfer in bubble column: Influence of liquid phase surface tension. Chemical Engineering Science. 2007 vol. 6 (24): 7378-7390. ISSN. 8. Emerson, Z. I., Particle and bubble interactions in flotation systems. Doctor of Philosophy Desertation, Auburn University, Alabama, 2007. 9. Emerson, Z. I., Bonometi, T., Khrishnagopalan, G. A., Duyke, S. R., Visualization of toner ink adsorption at bubble interfaces, Peer Reviewed Deinking, Tappi Journal 2006; 5 (4): 10 – 16. 10. Maedeh A., Faramarz H., Effects of Surfactant on Bubble Size Distribution and Gas Hold-up in a Bubble Column, American Journal of Chemical Engineering, Vol. 1 (2), 50-58

ECO-FRIENDLY MATERIAL SCIENCE AND TECHNOLOGY - PAPER IN THE PAST, PRESENT, AND FUTURE

Toshiharu Enomae Faculty of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8572, Japan. [email protected]

ABSTRACT

Paper is one of the greatest inventions over the course of human history and a multifunctional and ecological material that deserves such an admiration: manufacturing from bio-resources such as plants and animals as well as natural inorganic materials such as calcium carbonate, no need of external energy for manufacturing because black liquor supplies a total energy required, and recycling at a high ratio of recycled pulps as a fiber source. Such an environmentally-friendly material should be utilized more broadly for people and societies in the future. However, the demand of printing paper is decreasing in developed countries, due to the replacement of information carrier with digital media. New fields with a large demand are now being explored. In view of this point, we have developed new paper tools such as a power generator from vibration of paper, paper-based sensor to detect copper ions in water, a paper-based bacterial culture system using ink jet printing technology. Also, a new insight for paper conservation to carry over paper-made cultural assets from the past into future by preventing them from oxidation over the lapse of time and inhibiting mold growth after flood damage was obtained.

Keywords: bacterial detection, paper sensor, visual awareness

Introduction

In this article, papermaking technology and paper products will be reviewed from the origin of paper, importance of paper in the present age, and prospective paper-related products under development in our research group.

History of Papermaking Technology

Origin of Paper

Fig. 1 Fangmatan Paper

Papermaking technology is considered to be invented in ancient China. The world oldest paper was found and estimated to be buried as a burial good between 179 and 142 BC (early Western Han Dynasty) This paper was used as a map, where mountains, waterways and roads were drawn as shown in Figure 1. The papermaking technology was summarized by Ts’ai Lun in A.D. 105, and spread all over the world, for example, to Japan in 610, Samarkand, Uzbekistan in the central Asia in 751, Baghdad, Iraq in 793, Fabriano, Italy in 1276, England in 1494, and USA in 1690. The fundamental concept characteristic of this modern papermaking technology is dispersion of fibers into water and the fiber slurry is dehydrated to form sheets. Historically, there were many traditional and local paper-like raw-plant-based products by the preceding sheet making technology of beating and spreading out inner bark layers without dispersing © 2016 Published by Center for Pulp and Paper through 2nd REPTech 99 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 fibers into water.Included in this category are Hawaiian Tapa, Polynesian Kapa, Mexican Amate (Figure 2a), Indonesian bark paper (Figure 2b) all from various species of mulberry plants, and African tapa (Figure 2c). Papyrus is produced from the pith in stems of the papyrus plant. There are recording materials using a part of raw plants that are different from modern paper, bark paper or papyrus. Sastra is a Cambodian document written on leaves of treang trees (palm) that are tied loosely with strings like a book as shown in Figure 3. Holy texts are recorded as a religious custom. Similar documents were produced in the Southeast Asia.

Fig. 2 Bark paper occasionally called “Tapa”; a) AD 16-18 c, Mexico, b) Batak, Sumatra, Indonesia, c) Africa all exhibited in Deutsches Museum, Munich, Germany.

Fig. 3 “Sastra”, a document made on tied leaves of treang trees (palm) that is preserved in temples of Cambodia.

Technology of Japanese Paper

The history of Japanese paper called “Washi” dates back to A.D. 610 when the papermaking technology was imported. Ancient documents written in the 8th century are still securely stored in Shosoin, Nara, Japan. The Shosoin documents include a census register written on a sheet of Japanese paper in A.D. 702 at the earliest in Japanese history. Japanese papermaking craftsmen have invented new technology historically. Fiber length is an important factor on paper strength and formation; too short fibers do not realize high strength paper although too long fibers do not realize good formation. Initially since the import, long hemp fibers from Cannabis with a fiber length of approximately 100 mm had been widely used partially together with shorter segments of fibers after cutting.Then , Japanese papermaking craftsmen shifted to bast (skin) fibers extracted from low trees such as paper mulberry (Kozo) with a fiber length of approximately 10 mm to avoid the laborious process “cutting”. Furthermore, they proceeded to Thymelaeaceae (Gampi) and then, Edgeworthia chrysantha (Mitsumata) with fiber lengths of approximately 5 mm and 4 mm, respectively. The choice for shorter fibers had been improving the writing performance with an ink brush because of less bleeding due to the dense sheet structure, as well as providing comfortable touch feeling of the paper surfaces. Another notable innovation was the discovery and introduction of a fiber dispersing agent called “Neri”. This agent is extracted from roots mainly of Abelmoschus manihot and composed of uronic acids[1] that have negatively charged functional groups on the surface. This negative charge provides repulsive force between fibers in pulp slurry as well as the increased viscosity to prevent a quick dehydration. This effect results in good fiber dispersion

100 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 and therefore good formation of the finished paper in the flow sheet-making technique by declining the papermaking wire (actually, bamboo splints woven together with silk threads). During dehydration in the static sheet-making process on the contrary, a papermaking wire is commonly allowed to stand and fibers tend to aggregate together in the meanwhile, making the formation worse.

Paper Competitive to Digital Media in The Present Age[2]

A Recent Trend in Paper Production in Japan

Recently, the amount of paper produced in Japan suddenly decreased immediately after the financial crisis in 2008 following a stable production period for about 10 years. The depressed economy definitely still continues to inhibit paper production; however, that is not the only reason for such decreasing paper production. Figure 4 shows the chronological change in the amount of paper production in Japan. Sanitary paper, represented by facial and toilet tissue papers only has increased the amount of production, whereas printing paper, whether coated or uncoated, has severely decreased the production. Newsprint paper decreased less; however, when it is compared to the largest amount of production for these 15 years that was recorded in 2007, the decrease rate is as high as ▲21.5%. Although printing paper had been the most suitable material to deliver information publicly, this status is now being replaced with digital media such as tablet computers and smartphones that eliminate on-paper printing processes to obtain information.

Fig. 4 Chang in amount of paper production for each category. “▲” denotes a decrease rate from 2000.

Comparison Between Paper and Digital Media

One problem typical of digital media is visual recognition that might be inferior to that of paper media. People perform proof reading on a computer display and think they have corrected all the errors in their manuscript, but sometimes cannot find last few errors before additional proof reading on a paper- based document. Such an experience suggests an idea that paper media is more advantageous to visual recognition. On the other hand, ICT (Information and Communication Technology)-based education has been introducing digital devices even into elementary schools. Therefore, we examined the reading performance between paper and digital (tablet) media for Indonesian elementary schoolers.

Visual Recognition in Reading Texts on Paper Versus Tablet for Indonesian Elementary SchoolErs

The objective of this survey is to examine the difference in reading performance between paper and tablet at the elementary school level. However, the overall goal is a consideration on an ideal choice of media for reading at the elementary school level and smooth introduction of digital devices in combination with paper media to achieve the best possible education effect.

Fig. 5 Paper and tablet containing the same content and dimension.

Materials

The media used were a tablet (Galaxy Tab S 10.5 type SM-T800, Samsung, with a matrix size of 2560 x 1600 pixels) and paper (Recycle PPC, Daio Paper Corporation, A4 size copy paper containing 70 % recycled pulps). The same document containing a proof reading task was displayed or printed practically to the same dimension as shown by Figure 5.

Test Method

Proofreading of two tasks, that is, texts with purposely misspelled words was assigned to elementary schoolers. Below is a task example including three misspelled words underlined although actual tasks were written in Indonesian language.

Table 1 Misspelling patterns set in tasks

Misspelling pattern Example 1. Substitution of letter(s) Makan → Makin 2. Adding or eliminating letter(s) Awan → Kawan 3. Change of the order Disalurkan → Disalukran

“Once upon a time there was a zebra and a giraffe who were best friend. The giraffe was showing off to the zebra because he had a long deck and he could eat the leaves on the trees. So, the zebra got mad and tried to eat the leaves off the trees, too. But he was too sohrt. Then the zebra remembered that he could do things that the girafe couldn’t do.” Table 1 shows three patterns of misspelling. Each pattern has a sub-pattern in which the misspelled word can be a meaningful word in a different context like “deck” in the task example above. Tasks A and B were edited to the elementary 3rd grade level and both the tasks included each 18 misspelled words in a total of 862 and 870 words, respectively. Every schooler in the 4th (n = 31), 5th (n = 36), and 6th (n = 38) grades in one elementary school in Indonesia answered each task on a different medium on different days: for example, schooler S answered task A on paper on May 5 and task B on tablet on May 7. Prior to the test, they were asked to find misspelled words simply with check marks without correcting them and read at their own reading paces, but not to read over again. The length of time they spent was also measured.

Analytical Method

Analysis of variance (ANOVA) was applied to the proof test results. Dependent variables were set to the total number of misspelled words found (Total number of finding) (ANOVA), Misspelling pattern (MANOVA), and sub-misspelling pattern: whether the misspelled words can be a meaningful word in a different context or not (Meaningful misspelled word). Independent variables are Task, Grade, and Media. Our focus is especially on Media.

Fig. 6 Total number of finding and spent time for grades 4, 5, and 6.

Results and Discussion

Total Number of Finding

Figure 6 reveals that the Total number of finding in grades 4 until 6 consecutively increased with the grade, with the differences in spent time decreased also consecutively with the grade. The difference in the number of finding was not observed between the two media (F(1,198) = 2.38, p= 0.124). Note that p value > 0.05 means no significant difference between them.

Table 2 Effect of media, task and grade on misspelling pattern

Variable Wilks’ Ʌ F df Error df p Media 0.953 3.20 3 196 0.025 Task 0.755 21.32 3 196 0.000 Grade 0.790 8.18 6 392 0.000

Table 3 Interaction between misspelling pattern and media

Variable F df Error df p Substitute 3.90 1 198 0.050 Add or Eliminate 4.82 1 198 0.029 Order change 0.37 1 198 0.546

Fig. 7 Finding among misspelling patterns.

Table 2 shows that the interaction between the misspelling pattern and media appears significant because the p value 0.025 is lower than 0.05 suggesting 95% confidence in significance. Table 3 shows

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 103 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 that significant differences appear in substitute and add or eliminate with larger numbers of finding for paper media although it does not appear in order change. Figure 7 graphically shows this tendency.

Meaningful Misspelled Word

Figure 8 revealed that in task A, grades 5 and 6 schoolers skipped more significantly “Meaningless misspelled word” than “Meaningful misspelled word”, but there is no such tendency with significance in Task B. Presumably, whether it is meaningful or meaningless is not related to awareness recognition. No significant relationship was found between the media and number of finding in the interactions( F(2, 197) = 1.44, p =0.239).

Chapter Conclusion

Fig. 8 Finding between ‘Meaningful’ and ‘Meaningless’ words

There was no significant difference in visual awareness performance between paper and digital media. However, after analyzing it on a misspelling pattern basis, paper media help children improve their visual awareness efficiency.

Paper Devices in The Future

Bioassay System using Paper and Ink-Jet Printing

Formation of Hydrogel Medium using a Printer

We created an automated bioassay system based on ink-jet printing[3]. Compared to conventional manual bacterial culture systems, our printing approach improves the quality as well as the processing speed. A hydrophobic/hydrophilic pattern as a container supporting a culture medium was built on filter paper using a toluene solution of polystyrene for hydrophobization, followed by toluene printing to create several hydrophilic areas. As culture media we used a standard calcium alginate (CA) hydrogel.

The calcium alginate hydrogel was formed by chemical reaction between sodium alginate and CaCl2 solutions as shown in Figure 9. A multi-cartridge system (MCS) printer for color printing equipped with four ink cartridges loadable with four different solutions was applied. Figure 10 shows how to load ink cartridges with all solutions required to compose a hydrogel medium. In addition, the ejected amount of each solution was controlled by specifying CMYK percentages. Together with nutrients, both solutions for forming hydrogel were successfully printed on paper by means of the modified ink-jet printer. The amount of each solution was demanded simply by outputting CMYK values.

Bacterial Growth on CA Hydrogel Medium

In the last step, bacterial cells were printed. Figure 11 confirms E. coli growth on the printed CA hydrogel medium 6 h after inoculation. Consequently, the average number of colonies per hydrophilic area was consistently approximately 5-6 colonies with low 95% confidence intervals. This low deviation suggests that liquids containing E. coli cells could be dispensed evenly and regularly onto a culture medium. Finally, we achieved a stable bacteria growth which was confirmed by microscopically imaging the growing bacterial colonies.

Fig. 9 Reaction Between Sodium Alginate and CaCl2

Fig. 10 Processing of MCS Printer and Procedure of Medium Printing

Fig. 11 E. coli Colonies Growing on CA Medium After 6 h

Electrical Detection of Bacterial Growth on Medium

Fig. 12 Setup of Paper-Based Bacterial Sensor.

This work is now being applied to an electrical detection system[4] for acquiring the condition of bacterial growth. Two electrodes were built on ink-jet paper and a cuboid-shpaed Luria-Bertani (LB) culture medium was placed over them as shown in Figure 12. When a cyclic electric field was applied, current-voltage characteristic or I-V curves were measured and assinged to each growth phase of the bacteria.

Paper-based Cu2+ ion sensor

Fabrication of Sensor using Ink-Jet Printer

Water containing excessive amounts of Cu2+ is extremely harmful to human health and the biology of other animals. Therefore, we developed a user-friendly, low-cost, sensitive, and ion-species-selective paper-based sensor to inspect drinking water and industrial waste effluent for excessive Cu2+ levels, for use by people especially in developing countries. A dual-function paper-based sensor was fabricated simply by printing an acetone solution of an anthraquinone derivative onto a filter paper[5].

Fig. 13 Paper-based sensors after immersion in Cu2+ aqueous solutions at different concentrations for 10 min.

Fig. 14 Fluorescence spectra of paper-based sensors after immersion in Cu2+ aqueous solutions of various concentrations.

Response of The Sensor

In visible detection, the color of the dye on the paper-based sensor changed from yellow to purple with increasing Cu2+ concentration. Figure 13 shows a photograph of paper-based sensors immersed in Cu2+ aqueous solutions. This result confirmed that the paper-based sensor was able to detect Cu2+ at concentration as low as 2 ppm, which is the maximum amount allowed in drinking water according to the World Health Organization. The entire detection process took only 10 min and sensitive detection of Cu2+ was successfully achieved. In fluorescence detection, linear relationships observed between the surface fluorescence intensity and Cu2+ concentration in the dilute solution samples, as shown in Figure 14, indicates successful quantitative detection. Furthermore, the accuracy of the Cu2+ concentration measurements was proven by comparison with measurements using inductively coupled plasma-optical emission spectroscopy. With regards to detection conditions, pH 7 was optimum and the increase in temperature promoted the detection reaction. Furthermore, although slight color fading of the paper-based sensor was observed with exposure to strong ultra-violet light, protection from light during storage would prevent this photoredox reaction.

Acknowledgements

Siti Dian Mardiyani, a master candidate is greatly appreciated for research work on “Visual awareness performance in reading texts on paper versus tablet for Indonesian elementary school children” described in Chapter 3. Tithimanan Srimongkon, a post-doctoral research fellow, National Institute of Advanced Industrial Science and Technology is appreciated for the collaborative work on “Bioassay system using paper and ink-jet printing” described in Chapter 4.1. Yinchao Xu, a PhD candidate is appreciated for his pioneering work “Paper-based Cu2+ ion sensor” described in Chapter 4.2.

References

1 Han, Y.-H., Yanagisawa, M., Enomae, T., Isogai, A. and Ishii, T., “Analyses of mucilaginous compounds used in making traditional handmade paper”, Japan Tappi J., 59(7): 1067-1076(2005). 2 Mardiyania, S. D., Higuchi, N., Enomae, T., "Paper or tablet? - Media effect on visual awareness performance of elementary schoolers-", Ag-ESD symposium, Tsukuba, Japan, Sept., 2016. 3 Srimongkon, T., Mandai, S., Enomae, T., “Application of biomaterials and inkjet printing to develop bacterial culture system”, Advances in Materials Science and Engineering, Vol. 2015, 290790(2015). 4 Srimongkon, T., Buerkle, M., Enomae, T., Ushijima, H., Fukuda, N., "Study of the electrical response of culture media during bacterial growth on a paper-based device", Proc., ICFPE2016, Yamagata, Japan, Sept., 2016. 5 Xu, Y., Enomae, T., "Development of a novel paper-based copper ion sensor using inkjet printing technology", Proc., the 135th Res. Conf., JSPST, Tokyo, Japan, pp.73-76, May, 2016.

COMPARISON OF WOOD PROPERTIES BY AGE ON EUCALYPTUS PELLITA CLONES USING NEAR INFRARED (NIR) SPECTROSCOPY

Dian Apriyantia1, Miho Hatanakab2, Ruspandic3 aResearch and Development, Sinarmas Forestry Indonesia bUniversity of Tsukuba, Japan cResearch and Development, Sinarmas Forestry Indonesia [email protected] [email protected] [email protected]

ABSTRACT

Eucalyptus pellita is one of fastest growing trees species for raw material of pulp and paper industries that has received a lot of attention from many researchers. Nevertheless, information on wood properties could enhance additional gains manifesting in the end product. The evolution of wood properties in age (1-5 years) was observed in two clones growing at two sites classes (named: medium texture (SC I) and sandy texture (SC III). Research was conducted by drilling up to 100 standing trees, collecting the core from clones at different ages. Furthermore, the samples were screened by near infrared (NIR) spectroscopy. NIR spectroscopy is known as a powerful tool that can provide quantitative information on chemical and physical properties. Thus, NIR predictions of pulp properties were undertaken. NIR was used to evaluate pulp yield and properties of two clones of E. pellita at different ages in two site classes. The results showed that basic wood density and lignin content increase with age. For the particular comparison between clones, wood consumption of the clone EPB is 11% lower than the clone EPA but lignin content 11% higher.

Keywoods: Eucalyptus pellita; wood; NIR

Introduction

Eucalyptus pellita is one of fast growing trees species for raw material of pulp and paper industries that has received a lot of attention from many researchers. Currently, high performing clones in the field are finally selected by wood properties.1 Assessing the wood quality is a big challenge for the forest industry, because Eucalyptus wood, as raw material is highly heterogeneous. It is therefore important to have high technology, able to predict wood properties using non-destructive and a rapid analysis method for routine activity.2 NIR spectroscopy has gained widespread acceptance in recent years because it is a rapid, non- destructive analysis, reliable for determination and the multiplicity of analysis with one operation. Spectra within the NIR region consist of overtone and combination bands of fundamental stretching vibrations of fundamental groups that occur in the middle infrared region, mainly CH, OH and NH, which represent the backbone of all biological compounds.1 E. pellita is not an exception and NIR was used to evaluate pulp yield and wood properties. This study evaluates by using NIR spectroscopy the variation in wood properties of E. pellita clones according to different site classes from 1 to 5 years of age. Evolution of the wood properties and differences between clones are reviewed based on its characterization as raw material for pulp and paper industry.

Materials and Methods

Materials

The E. pellita clones EPA and EPB were taken from plantations in Riau, Indonesia, district Rasau Kuning, Gelombang and Sorek (Table 1). The locations are around latitude 00º46’ N; 100º31’ W, altitude

44-57 masl, mean annual rainfall of 2,152 mm/year and average temperature of 30.30 Celsius. There are two site classes of soils represented; one medium texture (Site Class I) and another sandy texture (Site Class III). The samples were taken from 20 trees in each age class (1 to 5 years) per clone. A total of 200 samples from site class I were processed and 120 samples from site class III (because not all ages were available in the field).

Table 1. Plantation area where samples were taken by site class and age

Age EPA EPB (year) SCI SCIII SCI SCIII 1 Gelombang 208 Gelombang, 197 Sorek, 64 Sorek, 2 Rasau Kuning, 195 Rasau Kuning, 260 Rasau Kuning, 195 Rasau Kuning, 019 3 Rasau Kuning, 96 na Gelombang, 169 na 4 Rasau Kuning, 77 Rasau Kuning, 120 Rasau Kuning, 80 na 5 Rasau Kuning, 63 na Rasau Kuning, 008 Gelombang, 007 Note: SC = site class; na = not available

Methods

The 320 samples were drilled up from two different clones at different ages. The samples are drilled sample where each tree was drilled at 1.3 m from the ground. Furthermore, the hole made was covered by plugging a tightly-fitting wooden peg (pasak). Then, tree-cote was applied on the bark surface completely in order to prevent the infection of the sampled tree from outside. The drilled samples were kept in the plastic bag and labeled immediately. Drilled samples were sent to the preparation room to dry and process up to the 40-60 mesh required. Furthermore all the samples were ready to be screened by NIR spectroscopy.

NIR Spectroscopy and Data Processing

Wood analyses were carried out on the Foss NIRSystems NIR spectroscopy 6500.3 Absorbance spectra up to 1440 scans were collected at 2.0 nm intervals over the range 400-2500 nm. Basic wood density, cellulose, extractive, lignin, pulp yield were observed. Statistical analysis of the data were undertaking using PLS regression model and software winISI III upgrade to 1.60, a FOSS statistical analysis for predicting wood properties.4 In addition, wood consumption was estimated as follows: The significance of the main factors (clone,site class and age) on wood properties such as basic wood density, cellulose, extractive, lignin, pulp yield and wood consumption were estimated by univariate GLM using SPSS program version 20.

Results and Discussion

There were statistically significant differences between clones for basic wood density, lignin, pulp yield and wood consumption; between site classes for basic wood density, extractive and wood consumption; and between ages for all parameters except cellulose content (Table 2). A comparitive evaluation of the wood properties between the clones at different ages and site classes is illustated in Fig. 1.

Probability of a larger value = 0.05

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1 2 3 4 5 1 2 3 4 5 I III I III 53 4.8

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Fig. 1 Comparison of EPA (dot) and EPB (cross) on (a) basic wood density, (b) cellulose, (c) extractive, (d) lignin, (e) pulp yield and (f) wood consumption along the age in site class I and III.

Table 2 Probability of difference within groups (clone, site class and age) from univariate ANOVAs for each wood property

Description Basic wood density Cellulose Extractive Lignin Pulp yield Wood consumption Clone 0.000 0.148 0.557 0.000 0.000 0.000 Site Class 0.000 0.125 0.000 0.061 0.141 0.000 Age 0.000 0.155 0.000 0.000 0.000 0.000

Basic wood density and lignin content trend to increase with age for the two clones in the two site classes, having clone EPB higher values than EPA (Fig. 1a and 1d). A similar increasing trend was reported for basic wood density in few Eucalyptus sp.5 Five years is the current rotation age for comercial plantation of E. pellita in Riau Province, Indonesia. At 5 years of age in site class I, which include the full set of age measurements, clone EPB was 12% higher than clone EPA for basic wood

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 111 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 density and 11% higher in lignin content. Basic wood density of clones EPB and EPA achieved average values of 560 kg/m3 and 489 kg/m3, respectively (Table 3). In the case of lignin content of EPB and EPA were 34.3% and 30.5% respectively.

Table 3 Phenotypic means for all wood properties traits assessed from each clone by site class and age and respective units.

Basic Age Cellulose Extractive Lignin Pulp yield Wood Clone SC density (year) (%) (%) (%) (%) consumption (m3) (kg/m3) EPB 5 I 559.9 48.8 2.14 34.3 47.2 3.78 EPB 5 III 529.5 51.3 1.72 33.5 47.9 3.97 EPA 5 I 487.6 50.4 2.10 30.5 48.4 4.24 EPA 4 III 499.0 51.1 1.98 31.3 49.2 4.08 Note: SC= site class;

Not significant differences between clones was achieved for extractives (Table 2) but a trend to incraese with age is shown in Figure 1c. The same trend was explained by Erikson and Arima for Douglas-Fir during the first 6 years of age.6 Extractive content of EPB and EPA were 2.14% and 2.10% respectively. Although not completely clear, but still a trend of decreasing values with age occured in pulp yield for clone EPB (Fig. 1e). Even the clones showed significant differences for pulp yield at the age of 5 years (47.2% and 48.4% for clones EPB EPA, respectively), 1.2 difference is negligible. Cellulose showed not significant differences between any of the groups studied (Table 2). In case of Douglass-fir wood, the alpha cellulose increased to age 25 years, but there was no significant difference between the yields of plot treatment and control trees.6 Cellulose content of EPB and EPA were 48.8% and 50.4% respectively. The consistent lower wood consumption of clone EPB in site class I does not seem so clear in site class III but still significantly different to comment on the performance of clone EPB. According to the results in site class I, this clone is 11% more efficient in the mill(Table 3).

Conclusions

The results of the study of the wood properties on E. pellita by age demonstrated that there was a clear trend of increasing basic wood density with age. This trend seems to impact in the reduction of wood consuption with age but moderated by the pulp yield. Clone EPB had 11% lower wood consumption than EPA, and on the other hand it had higher lignin content of 11%.

References

1 Bailleres, H. NIRS Analysis as a tool rapid screening of some major wood characteristics in a Eucalyptus breeding program. Ann. For Sci. 59 479-490. 2002 2 Schimleck LR. Near infrared spectroscopy: a rapid, non-destructive method for measuring wood properties and its application to tree breeding. New Zealand Journal of Forestry Science 38 (1): 14- 35. 2008 3 Ndlovu ZTL, Swain TL, Zbonak A, Fossey A. Development of a non-destructive near infrared sampling technique to determine screened pulp yield of Eucalyptus macarthurii. IUFRO Durban 2007 4 Yamada T, Yeh TF, Chang HM, Li L, Kadla JF, Chiang VL. Rapid analysis of transgenic trees using transmittance near-infrared spectroscopy (NIR).Hozforschung, Vol. 60, pp 24-28. 2006 5 Backman ME, Leon J. Correlations of pulp and paper properties at an early age and full rotation age of five Eucalyptus species. Lisboa, EUCEPA, 9, 2003 6 Erickson HD, Arima T. Douglas-Fir Wood quality studies Part II: Effect of age and stimulated growth on fibril angle and chemical constituents. Wood Science and Technology Vol. 8 255-265. 1974

GROWTH OF AGAVE GERMPLASM IN BALITTAS, MALANG EAST JAVA

Parnidi1, Untung Setyo Budi, Marjani Indonesian Sweetener and Fiber Crops Research Institute Jl. Raya Karangploso Km. 4, Kotak Pos 199, Malang [email protected]

ABSTRACT

Agave or sisal is a crop producing non - wood fibers are widely used for textile materials, ropes, paper, craft, building materials and construction. The growth and diverse plant morphology are reflection of the wide genetic diversity,which is needed in the Sisal variety assembly program. Until now, the collection of sisal germplasm in Balittas has not been characterized their morphologic characters.Sisal accession characterization was carried out from 2012 to 2015 in Karangploso Experimental Station in Malang is located at an altitude of 515 meters above sea level with the climatic conditions of type D (medium) Smith Ferguson, rainfall of 1,500 mm/year, and the type of soil GleymosolGleik/inceptisol. Each accession was planted in experimental plots, 6 plants for each accession at a spacing of 2 m between plants and 5 m etween accessions. Fertilization was done 2 times at the beginning and end of the rainy season at the following rates: 200 kg Urea (92 kg N) + 400 kg Phonska (79.1 P)+ 15 tons of manure per hectare. At age 3 years Balittas 15 was the tallest with an average growth rate of 157.34 cm. The highest number of leaves was shown by Balittas 19, with mean increase of 56.33 sheets for 3 years. The greatest length of leaf was shown by Balittas 13 with average growth rate of 87.75 cm for 3 years. The greatest width of leaf was shown by Balittas 14 with average growth rate of 9.20 cm for 3 years. The highest of fiber content was shown by Balittas 22 with average 4.59 %.

Keyword: growth, morphological characteristics, fiber yield, germplasm.

Introduction

Agave is a crop that can grow in tropical and sub-tropical areas. Agave fiber is used for textile, cordage, waiver, paper, craft [1], bio-fuel [2], food and beverages [4], medicines [5] and [5] construction materials, synthetic fiber manufacture material and as composite material for packaging such as cement bag [6], [7], and [8]. Agave fiber has some advantages among others it is renewable, recyclable and also degradable in environment [9]. The agave plant is easy to be cultivated, can be harvested in relatively short time compared with fiber from wooden trees. The success of superior excellent variety breeding program is greatly determined by the availability of germplasm, as a source of diversity and genetic resource. The great diversity of genetic resources increases the chances of success in the assembly of new excellent varieties. The role and function of germplasm is important as the plant genetic resources, its presence should be maintained in order to avoid extinction, so that it can meet human needs such as food, clothing and shelter [10]. In addition, it is also necessary to obtain as much as possible genetic information through characterization and evaluation of germplasm. This can be as a source of genetic material in assembling new variety in breeding programs. Sweetener and fiber crops research institute (Balittas) is a national research center applying the mandate to conduct research on fiber crops.Balittas has as 23 accessions of agave germplasm collection. The addition of agave germplasm is done by introduction and exploration. This study aims to evaluate the performance of Agave germplasm owned by Balittas.

Materials and Methods

Agave germplasm was planted in Karangploso Experimental Station, Malang, at an elevation of 515 m asl, D Smith Ferguson climate type, rainfall 1500 mm/year, and soil type Gleymosol Gleik/Inseptisol in 2012-2015. Each accession was planted in a plot of trial with the 6 populations in each accession with

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 113 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 the planting distance of 2 m x 2 m and inter-accession distance of 5 m. The fertilization was done twice in the beginning and at the end of rainy season. The rate of fertilizer used was 200 kg Urea (92 kg N) + 400 kg Phonska (79.1 kg P) + 15 tonnes of manure per hectare. The morphology qualitative characters being assessed were color of leaves, edge leaf color, the present of leaves in the edge and the color of leaves in the tip. This was done when the plant aged 24 months. Meanwhile the quantitative characters includes height of plant, number of leaves, length and width of leaves, fresh weigh of 25 leaves, dried fiber weight and fiber content. This was done every year. The descriptive statistic analysis was carried out to know the performance of growth and result components.

Results and Discussion a. Qualitative Character Performance

The agave germplasm in Balittas consists of three groups, namely Agave angustifolia, Agave cantala and Agave sisalana. The qualitative characters of each accession are presented in Figure 1-4 as well as Table 1. Agave cantala has bluish gray leaves, big, sharp and closely spine in the tip of leaves, dark brown thorn in the tip of leaves. A. sisalana has green grayish leaves, big and small prickle in leaves margin and some has no prickle, also dark brown spine in tip of leaves. According to [1] A. cantala is more resistant to drought than A. sisalana. However, the fiber production of fiber ofA. cantala is lower than A. sisalana. The characteristics of A. sisalana which has glaucous leaves with spine in the tip of dark brown [5]. The width of leaves reaches 10 cm and the length of leaves can reach more than 1.5 m. All A. cantala are type of agave with big prickles in the tip of leaves. The prickle in the margin of A. sisalana leaves is catergorized into a number of groups, namely no prickle, small and many prickles and big and rarely prickles as well as big and many prickles.

Figure 1.Agave angustifolia Figure 2. Agave cantala

Figure 3.Agave sisalanawith green leaves Figure 4. Agave sisalanawith grey leaves

Agave sisalana has very short basal stems, usually less than 0.5 m tall. Mature plants have relatively large green or greyish-green leaves (usually 90-130 cm long) that are usually very rigid. These leaves do not have any prickles along their margins [11]. Meanwhile, A. angustifolia has light green leaves, short leaves, great number of leaves, sharp and closed thorny leaves in the edge. A. angustifolia has very short basal stems, usually less than 0.5 m tall. Mature plants have relatively small light green, grayish-green or variegated leaves (usually 30-60 cm long) that are usually very rigid. These leaves have numerous small prickles (2-5 mm long) along their margins. This species produces large capsules and sometimes also develops numerous plantlets (i.e. bulbils) on the branches of its flower clusters [11].

Table 1. Qualitative Charachters of Agave germplasm in Balittas.

Collection Margin of leaves Prickle of leaves Color of tip Agave type Leaves color name color margin spine Balittas 1 A.angustifolia Green Light green Notched, big prickly Dark-brown Balittas 4 A.angustifolia Green Light green Notched, big prickly Dark- brown Balittas 5 A.angustifolia Green Light green Notched, big prickly Dark- brown Balittas 9 A.angustifolia Green Light green Notched, big prickly Dark- brown Balittas 19 A.angustifolia Green Yellowish green Notched, big prickly Dark- brown Balittas 2 A.cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 3 A.cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 6 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 7 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 8 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 11 A.Cantala Dark green Dark green Notched, big prickly Dark- brown Balittas 15 A.Cantala Greyish-green Green Notched, big prickly Dark- brown Balittas 20 A.Cantala Grey Yellowish green Notched, big prickly Dark- brown Balittas 21 A.Cantala Grey Green Notched, big prickly Dark- brown Balittas 22 A.Cantala Grey Grey Notched, big prickly Dark- brown Balittas 26 A.Cantala Grey Green Straight, big prickly Dark- brown Balittas 10 A.Sisalana Dark green Dark green Rare, straight prickly Dark- brown Balittas 12 A.Sisalana Dark green Yellow Straight, Small prickly Dark- brown Balittas 13 A.Sisalana Dark green Yellow Straight, Small prickly Dark- brown Balittas 14 A.Sisalana Green Light green Notched, big prickly Dark- brown Balittas 16 A.Sisalana Grey Grey Without prickly Dark- brown Balittas 24 A.Sisalana Grey Grey Without prickly Dark- brown Balittas 25 A.Sisalana Grey Green Without prickly Dark- brown

b. The Growth, Growth Rate and Fiber Content of Agave Germplasm

At age 3 years the average height and length of A. cantala leaves were, respectively 1.68 m and 1.18 m, while the average height and length of A. sisalana leaves were 1.41 m and 0.97 m respectively. Meanwhile Agave angustifolia has average height of 106.41 cm and average length of leaves of 82.8 cm. For the length of leaves, A. sisalana has 10.46 cm that is wider than A. cantala which is 9.43 cm and also A. angustifolia which is 7.79 cm. According to [12] stating that Agave americana until the flowering phase, the height of Agave plant can reach of 2.4 - 7.6 m with the length of leaves reaches of 1.8 m. in the agave sisala, the height of plant until the flowering phase can reach of 7- 9 m, with the length of leaves reaches 1.5 m [5]. In agave angustifolia, the height of plant ranges from 70 to 90 cm, with mature leaf length ranging from 110 to 130 cm and width from 8 to 10 cm [13]. The number of A. angustifolia leaves reaches 77.18 sheets per year. This shows greater number than A. sisalana (49.77) and A. cantala (53.94). Brown mentioned that during the life until before the flowering phase, the agave can produce 220 sheets of leaves per planting process. The research result by

[12] showed that in Agave Americana, the growth of number of leaves each year can reach 40-50 sheets. Based on the data in Table 2, it shows that until the fourth year, the height of plant, length of leaves and width of leaves are still lower than the growth of agave plant in other countries. The coefficient value of agave germplasm in Balittas of for the characters of height of plant, length and width of leaves show the diversity less than 50 %. The diversity of genetic of agave germplasm in Balittas is categorized as medium. This is based on the grouping on the diversity coefficient value conducted by [14]. The coefficient of genetic diversity is classified into 4 criteria, namely: coefficient value of 0% - 25% is categorized as low coefficient value, 25% - 50% is medium coefficient value. The coefficient value of 50% - 75% is categorized as high coefficient value and coefficient value more than 75% is categorized as the highest coefficient value. The Agave germplasm in 2015 has been in the second year of production. The first harvesting is conducted when the plant has been in the second year. The harvest is conducted for the leaves that have been old and formed angle of 45oC with the length is not less than 1 meter [15]. Meanwhile, [12] made a limitation that the harvest of agave leaves is conducted after the plant is three years old. The harvest of agave leaves is conducted twice in a year, namely in May and November. The harvest of agave can be conducted until the plant is in flowering phase. The agave plant can produce until it reaches the age of 8-30 years old [12]. Leaves can be harvested after two years of age, which will postpone the “bolting” for 15-20 years. After “bolting”, the plant dies. Based on Table 2. It shows that the growth rate of agave germplasm of Balittas collection keeps increasing. The greatest increase of Agave angustifoliais in accession Balittas 9 and the lowest one is in accession Balittas 1. The growth rate of Agave angustifolia germplasm height of collection Balittas is 61.45 – 107.41 cm for 3 years. The average number of leaves reaches of 29.08 – 56.33 sheets for 3 years. The average of lenght of leaves reaches of 30.79 - 65.53 cm. Meanwhile, the average growth of width of leaves reaches of 2.66 - 4.73 cm for 3 years.

Table 2. The Growth rate and fiber content of Agave germplasm

Plant height Leave number Lenght of Width of Fibers NamaAksesi (cm) (sheet) leaves (cm) leaves (cm) content (%) Agave Balittas 1 61.45 29.08 30.79 2.66 2.95 angustifolia Balittas 4 77.43 29.67 57.83 3.80 2.82 Balittas 5 106.42 39.00 63.29 4.73 2.32 Balittas 9 107.41 40.17 63.10 4.65 2.50 Balittas 19 82.15 56.33 65.53 4.41 3.81 Agave cantala Balittas 2 114.95 34.34 48.68 3.40 3.64 Balittas 3 138.00 24.50 46.45 5.19 3.99 Balittas 6 106.77 29.42 73.48 4.2 2.93 Balittas 7 110.23 39.92 75.00 4.68 4.13 Balittas 8 118.04 37.17 69.27 4.28 3.50 Balittas 11 137.40 25.50 43.70 6.17 3.76 Balittas 20 141.78 33.09 58.07 6.14 3.51 Balittas 21 150.70 54.75 60.19 6.48 3.55 Balittas 22 141.06 36.75 43.84 6.25 4.59 Balittas 26 93.86 29.50 81.21 4.75 4.42 Agave Balittas 10 100.25 34.17 25.25 6.75 2.77 sisalana Balittas 12 145.89 37.33 56.38 8.33 2.66 Balittas 13 98.00 29.52 87.75 5.20 2.79 Balittas 14 131.29 38.08 74.75 9.20 2.95 Balittas 15 157.34 31.84 61.12 7.48 3.36 Balittas 16 60.96 21.42 28.88 2.88 2.95 Balittas 25 74.91 8.59 51.05 2.82 3.07 Rerata 110.80 35.65 59.04 5.41 3.26 KK 20.90 14.42 5.64 12.01 20.30

The greatest growth rate of Agave cantala is in accession Balittas 21 and the lowest one is in accession Balittas 26. The growth of Agave cantala germplasm height of Balittas collection is 93.86 - 150.70 cm for 3 years. The average growth of number of leaves reaches of 24.50 – 54.75 sheets for 3 years. The average growth of lenght of leaves reaches of 43.84 – 81.21 cm. Meanwhile, the average growth of width of leaves reaches of 3.40 – 6.48 cm for 3 years. Meanwhile, the greatest growth rate of Agave sisalana is in accession Balittas 15 and the smallest one is in accession Balittas 16. The growth of Agave cantala germplas height of Balittas collection is 60.96 – 157.34 cm for 3 years. The average growth of number of leaves reaches of 8.59 – 38.08 sheets for 3 years. The average growth of length of leaves reaches of 25.25 – 87.75 cm. Meanwhile, the average growth of width of leaves reaches of 2.82 – 9.20 cm for 3 years. In general, it shows the normal growth of morphology characters from the three types of agave, namely Agave angustifolia, Agave cantala and Agave sisalana. The growth of Agave germplas is more determined by each genetic. The growth of Agave angustifolia tends to be slower than Agave sisalana and Agave cantala. The greatest average of A. angustifolia fiber level is 3.81 %, the greatest average of A. cantala fiber level is 4.59 % and the greatest average of A. sisalana fiber level is 3.36 %. According to [12] stated that the agave fiber level can reach of 4-5%. The lenght of leaves, the number of leaves, the width of leaves and weight of leaves are an important determinant of result component for fiber producer plants from the leaves. The length of leaves, number of leaves, and weight of leaves have positive correlation on the agave fiber results. Meanwhile, according to [16] there was a significant interaction between the characters of number of leaves, lenght of leaves, results of dried fiber and all parameters of fiber quality in the environment.

Conclusion

Based on the morphology characters of agave germplasm collection in Balittas, it can be divided into 3 types, namely agave angustifolia, agave cantala and agave sisalana. Based on the plant morphology characters, it shows that the agave cantala has greater characters of height of plant and lenght of leaves than sisalana or agave angustifolia. Meanwhile, for the character of number of leaves, the greatest is in agave angustifolia. The agave sisalana has most significant character in its width of leaves. The growth of agave cantalagermplasm shows it has faster growth than sisalana or angustifolia. A. Cantala has the highest value of production component than other agave types.

References

1. Santoso B. Peluang Pengembangan Agave Sebagai Sumber Serat Alam. Perspektif 2009; 8.2: 84 – 95. 2. Nu~nez, HM. Biofuel Potential in Mexico: Land Use, Economic and Environmental E_ects (Work-in-Progress). Department of Economics Centro de Investigaci_on y Docencia Econ_omicas Aguascalientes, Mexico. Agricultural and Applied Economics Association Annual Meeting. Boston, Massachusetts. 2016. 3. Almaraz AN, Amanda EDA, Antonio JÁR, Natividad JUS, Silvia LGV. The Phenols of the Genus Agave (Agavaceae). Journal of Biomaterials and Nanobiotechnology 2013; 4: 9-16. 4. Monterrosas BN. Martha LAO, Enrique JF, Antonio RJA, Zamilpa A, Manases GC, Jaime T, and Maribel HR. Anti-Inflammatory Activity of Different Agave Plants and the Compound Cantalasaponin-1. Molecules 2013;18: 8136-8146. 5. Tewari DYC, Tripathi and Anjum N. Agave sislana: a plant with high chemical diversity and medicinal importance. Pharmaceutical Research 2014; 3. 8: 238-249 6. Budiman I, Aulya FS, Subyakto, Subiyanto B, Laporan akhir tahun, UPT BPP Biomaterial LIPI, Penelitian pemanfaatan serat sisal (Agave sisalana) untuk pembuatan komposit serat semen: hubungan antara temperatur hidrasi dengan kuat tekan. UPT Balai Penelitian dan Pengembangan Biomaterial LIPI. 2006. 7. Subyakto, Hermiati E, Heri DYY, Fitria. Proses pembuatan serat selulosa berukuran nanodari sisal (Agave sisalana) dan bamboo betung (Dendrocalamusasper). Beritaselulosa 2009; 44.2: 57- 65.

8. Kusumastuti A, Aplikasi Serat Sisal sebagai Komposit Polimer. .J.KompetensiTeknik 2009; 1.1: 27-32. 9. Zimmermann T, Pohler E, Geiger T. Cellulose Fibrils for Polymer Reinforcement. Advanced Engineering Science 2004; 6.9: 754-761 10. Gajatri SB, Status Pengelolaan Plasma Nutfah Jagung. Plasma Nutfah 2007;13. 1: 11-18. 11. Anonymous, Weeds of Australia - Biosecurity Queensland Edition Fact Sheet. Agave sisalanahttp:// www. keyserver.lucidcentral.org/weeds/data/.../agave_sisalana.pdf. 2016. 12. Hulle A, Kadole P, and Katkar P. Review Agave Americana Leaf Fibers. Fibers 2015; 3: 64-75. 13. Hidalgo MR, Magdaleno CC, Luis HHG and Guillermo UC, 2015. Chemical and morphological characterization of agave angustifolia bagasse fibers. Botanical sciences 2015; 93. 4: 807-817. 14. Rebin RW. and DS Decker W. Cucurbits. Central for Agricultural and Bioscience International. USA. 1995. 15. Brown K. Agave sisalana Perrine. University of Florida, Center for Aquatic and Invasive Plants, 7922 N.W. 71st Street, Gainesville, FL 32653; www.se eppc.org/.../pdf/summer2002-brown- pp18-21.pdfdiaksestanggal 9 September 2016. 16. La-Vina HC. Stability of Yield and fiber fineness in rami(Boehmerianivea[L.]Gaud).http://agris.fao. org/agrissearch/search/display.do? F=1994% 2FPH%2FPH94008.xml%3BPH9410635. Diakses 20 Mei 2016.

IMPROVED OXYGEN DELIGNIFICATION BY PHOTO PRETREATMENT AND ADDITIVE REINFORCEMENT: A COMPARISON STUDY BETWEEN TROPICAL MIXED HARDWOOD KRAFT PULP AND OIL PALM FIBRE SODA-ANTHRAQUINONE PULP

Leh Cheu Penga1, Chong Yin Hui, Wan Rosli Wan Daud, Mazlan Ibrahim and Poh Beng Teik aBioresource, Paper and Coatings Technology, School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Pulau Pinang [email protected]

ABSTRACT

Oxygen delignification (O) is an important process in pulp and paper industry for enhanced elemental chlorine-free (EFC) or totally chlorine-free (TCF) bleaching. The application of an O could remove the residual lignin from unbleached pulp up to 50 percent and therefore, reduce the burden to the bleaching plant. The major drawback of O is its relatively lower selectivity between delignification and cellulose degradation in comparison to other bleaching agent. For attaining a more efficient chlorine-free (ECF or TCF) bleaching, as the first bleaching stage, the selectivity of the O has to be improved. In this study, the selectivity of O was improved through three different modification approaches—additive reinforcement, pre-treatment and the combination of the two modifications toward two different pulps namely tropical mixed hardwood kraft pulp and oil palm empty fruit bunch (EFB) soda-anthraquinone pulp. The results obtained showed that all the modification approaches were capable of improving the bleaching selectivity up to 90% by retaining higher pulp viscosity and achieving better kappa number reduction. The simple photo pretreatment could even eliminate the hexenuronic acid more than 60%. These indicated that the beneficial effects of improved Os were repeatable on the two different pulps.

Keywords: anthraquinone; bleaching selectivity; hexenuronic acid; oxygen delignification; photo pretreatment

Introduction

Among all the chlorine-free bleaching agents, oxygen delignification (O) is commonly used as the first bleaching stage to eliminate residual lignin in bulk from the brown stock. However, in comparison to conventional chlorination (C) bleaching, O shows relatively lower selectivity in between delignifying power and carbohydrates degradation, and the delignification is generally limited to no more than 50% to prevent unwarranted carbohydrates degradation[1-2]. As a result, chlorine-free bleached pulps commonly show relatively lower strength properties as well as pulp brightness [3-4]. Hence, the improvement of O is very important as it may alleviate the number of bleaching stage required to avoid undesired degradation of cellulose and increase the brightness of pulp as well. Over the past thirty years, many attempts have been made to improve the selectivity of the O with minor modifications such as additional of additives or implementation of a pre-treatment prior to the process. In 2010, Ng and co-worker (2010) were recommended a higher H2O2 charge (> 0.5%) and small amount of anthraquinone (AQ) added in the O on oil palm empty fruit bunch (EFB) soda-AQ pulp. The results of study have proven that the addition of H2O2 and AQ during O generally gives a satisfactory acceleration on the pulp brightness and minimizes cellulose deterioration while retain a rather high degree of delignification [5-6]. Nevertheless, there is no further modified O’s research carried out or continued on different chemical pulps even thought the capability of the OpAQ bleaching process is remarkable. On the other hand, some researchers have also found that photo pretreatment can increase the bleaching selectivity due to the generation of reactive radicals during the treatment and they may degrade the lignin into smaller molecules [5-7] and thus, increase the delignification efficiency in the subsequent bleaching stage. In this study, the improved O by both additive reinforcement and photo pretreatment, and also

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 119 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 the combination of two approaches were applied on two different chemical pulps viz. mixed tropical hardwood kraft pulp and oil palm empty fruit bunch (EFB) soda-anthraquinone pulp. The effectiveness of the three modification approaches on the two chemical pulps were compared based on pulp properties such as kappa number, viscosity, selectivity, hexenuronic acid content and pulp brightness.

Experimental

Materials

Sabah Forest Industries Sdn. Bhd, Sabah, Malaysia provided the mixed tropical hardwood brown kraft pulp with kappa number of 16.4, pulp viscosity of 30.4 cP, and 36% ISO brightness. The oil palm empty fruit brunch (EFB) was provided by by Eco Fibre Bhd., Johor, Malaysia. The EFB was soaked in water for one day and washed, in order to remove contaminants (such as sand, dust and oil), then it was air-dried and kept in plastic bags prior to pulping.

Soda-Anthraquinone Pulp Preparation

Pulping of EFB was carried out in a 6 L stainless steel digester. Four hundred gram of oven-dried (o.d.) EFB was cooked at 160oC with 25% of sodium hydroxide and 0.1% anthraquinone (on the oven dry basic of EFB), material-to-liquor ratio of 1:7, time-to-temperature of 90 min and time-at-temperature of 120 min. After the completion of cooking, the collected EFB soda-AQ pulp was defiberized in a hydropulper for 10 min and washed thoroughly with tap water in a stainless steel mesh filter. The pulp was further disintegrated mechanically in a three bladed disintegrator for 1 minute at a pulp consistency of 2.0% and then screened by Somerville flat-plate screen with 0.15mm slits. The pulp was then spin-dried and kept in the fridge (4oC) before used.

Methods

Photo Pretreatment

Twenty five grams of hardwood kraft pulp was soaked in the acid solution with pH 5 (adjusted by adding 0.5M sulphuric acid solution) for 15 min. The pulp stock was then squeezed to remove excess acid solution to reach 10% consistency. After that, the pulp sample was transferred into a polyethylene bag and photo irradiation was carried by placing the pulp sample under ultraviolet, 369 nm (6 watt) for a desired duration of time. The distance between the lamp and pulp sample was 3 cm for blue light and 5 cm for the UV light. After the completion, the pulp was washed and spins dried, and then continued with oxygen delignification.

Improved Oxygen Delignification (O) with Hydrogen Peroxide (Op) and Anthraquinone (OpAQ)

Oxygen delignification (O) was carried out using a 650-mL stainless steel autoclave equipped with a gas inlet and stirrer, manufactured by the Parr Instrument Company, USA. Twenty-two gram (oven- dry basis) of pulp sample was mixed with 0.5% magnesium sulfate and 2.5% sodium hydroxide and distilled water was added to adjust the pulp consistency to 10%. After the cover was fastened, the air in the autoclave was replaced by oxygen gas through a gas inlet, and the pressure inside the autoclave was kept at 0.55 MPa and 95°C for 30 min. At the end of the delignification process, the autoclave was cooled and the oxygen pressure was released. The pulp was then washed, spin-dried, and analyzed.

The procedures of the improved O, viz. hydrogen peroxide reinforced O (Op) and anthraquinone

(AQ) aided hydrogen peroxide-reinforced O (OpAQ) were same as the O, additional hydrogen peroxide and AQ were added according to the amount shown in Table 1. (All the chemicals used above were based on oven-dry basis of pulp sample).

Table 1. Amount of reinforced additives added to oxygen delignification.

Type of raw material Type of improved O H2O2, % Anthraquinone, % O 1.4 - SFI hardwood kraft pulp p OpAQ 1.4 0.04 O 1.2 - EFB soda-AQ pulp p OpAQ 1.2 0.02

Pulp Properties

The delignified pulp was analyzed by the Technical Association of the Pulp and Paper Industry TAPPI T236 (2013) to find the kappa number, TAPPI T230 (2008) to establish pulp viscosity, ISO2470 (2008) to determine pulp brightness, and TAPPI T282 (2013) to determine hexenuronic acid content of the chemical pulp. Bleaching selectivity is defined as the relative reactivity of a bleaching process toward the lignin and carbohydrate components of pulp and it was calculated as the ratio between the difference in kappa number to the difference in pulp viscosity (cP) before and after the process [5,6].

Analysis of Residual Lignin and Delignified Pulp by FTIR Absorption Spectroscopy

FTIR spectral data were obtained using the potassium bromide (KBr) pellet technique. Infrared spectra were recorded using a Shimadzu FTIR spectrometer, model 8201PC (Japan). Small amounts of sample pulp or lignin were mixed with the KBr powder at a concentration of 1 mg/100 mg KBr. The mixture was then ground for 3 to 5 min. The powder was pressed for 2 min to form a KBr pellet. The collar was placed with the pellet onto the sample holder. The spectra were recorded in the absorption band of 4000 to 400 cm−1.

Result and Discussion

The results demonstrated in Table 1 demonstrated that the kappa number (Kn) reduction of both the hardwood kraft and EFB Soda-AQ pulps by O was not quite impressive, which was limited to not more than 38% and 30% (Figure 1), respectively. Hence, it would substantially limit the role of O as the first bleaching stage in the chlorine-free bleaching sequence. Therefore, to improve the bleaching selectivity of the O, some modification such as additional of additives or implementation of a pretreatment prior to the delignification process were carried out. Fig. 1 shows that bleachability of the EFB pulps by O was higher than that of hardwood kraft pulp with the selectivity of 0.63 and 0.53, respectively, even though the latter showed higher kappa number (Kn) reduction (Figure 1), it experienced more severe drop in pulp viscosity (Table 1).

Improved Oxygen Delignification by Additive Reinforcement

As shown in Table 2 and Figure 1, it is quite notably that the additional of hydrogen peroxide into an

O, known as H2O2 reinforced O (Op), offered a greater improvement on delignification and brightening effects for both chemical pulps, in which the Kn reduction and ISO brightness of hardwood pulp was increased to 55.6% and 52%, while those of EFB pulp were increased to 42.1% and 66.8%, respectively.

The addition of H2O2 in an O causes the generation of more reactive species such as hydropeoxide - anion (HO2-), hydroxyl radical (OH·) and superoxide anion radical (O2· ) due to the decomposition of

H2O2 [2,5]. Since the generated radicals react actively with organic compounds, they would degrade the residual lignin in the pulp and at the same time destroy the chromophoric structures in lignin. As a result, it increased both the kappa number reduction and pulp brightness. However, since the radical reactive species generated in the system attacked both lignin and carbohydrates unselectively, the cellulose degradation was accelerated as well [2,5-7]. Nevertheless, in comparison to delignification, the effect of

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 121 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 hydrogen peroxide on cellulose degradation was relatively smaller, and thus, ended up that the bleaching selectivity of the hardwood kraft and EFB pulps was improved to 0.71 and 0.74, respectively (Figure 2).

Table 2. Bleaching conditions of oxygen and improved oxygen delignification

Pretreatment Delignification Responses Stage Stage 360nm UV Pulp Type of Oxygen Kappa Brightness Hexenuronic Viscosity Exposure time, Delignification Number (ISO, %) acid, μmol/g min (cP) SFI Hardwood Unbleached pulp 16.4±0.4 30.4±0.3 36.0±1.8 55.5±2.3 - O 10.2±0.2 18.7±0.1 43.2±1.5 49.3±3.1

- Op -stage 7.3±0.5 17.5±0.5 52.0±1.8 52.6±5.7

- OpAQ-stage 8.4±0.2 20.4±0.2 52.6±1.8 46.2±6.3 30 O 7.6±0.1 21.7±0.4 47.8±2.3 24.8±2.9

30 Op-stage 6.7±0.2 17.1±0.5 60.3±0.9 20.4±3.1

30 OpAQ-stage 7.2±0.5 18.3±0.2 50.9±1.2 28.0±2.0 EFB Soda-AQ Unbleached pulp 11.1±0.3 18.8±0.4 47.5±0.6 47.2±2.3 - O 7.8±0.4 13.6±0.5 55.3±1.2 42.9±3.2

- Op-stage 6.4±0.2 12.5±0.3 66.8±1.1 40.7±3.9

- OpAQ-stage 7.2±0.3 14.2±0.4 65.6±0.9 41.3±4.3 30 O 6.9±0.1 15.1±0.5 56.9±1.3 20.9±4.6

30 Op-stage 5.9±0.3 13.1±0.4 67.0±0.5 18.9±3.6

30 OpAQ-stage 6.3±0.2 14.6±0.3 65.1±0.7 22.6±3.3

On the other hand, the addition of an optimum amount of anthraquinone (AQ) in an Op, named as AQ- aided H2O2 reinforced O (OpAQ), was capable of preserving the cellulose from degradation. As shown in Table 2, the pulp viscosities of both hardwood and EFB pulps were retained even higher than that of the ordinary O one. Different from Op, which its selectivity was increased mainly due to the extended delignification, the OpAQ improved the bleaching selectivity through both carbohydrate stabilization and extended delignification. Nevertheless, in comparison to pO , the Kn reduction of OpAQ was lesser.

Fig. 1. Kappa number reduction of oxygen delignified pulps with and without modification

According to previous studies, when AQ was added in an alkaline bleaching system, it would reduce to anthrahydroquinone (AHQ) through oxidizing cellulose reducing end groups to alkali-stale aldonic acid groups. Since AHQ was readily being oxidized by strong oxidants such as hydroxyl radicals, thus,

Fig. 2. Selectivity of oxygen delignification with and without modification. the AQ added in the bleaching system acted as a hydroxyl radical scavenger [5-6,8-9] and therefore might diminish the happening of cellulose degradation caused by hydroxyl radical. However, at the same time the delignification due to radical attack was also moderated. Even so, there was no significant effect of

AQ on the pulp brightness as the OpAQ bleached hardwood and EFB pulps remained the same brightness as Op bleached pulped. On the other hand, improved O by Op and OpAQ did not show significant effect on the reduction of the hexenuronic acid (HexA) content for both the pulps used in this study. This indicated that the addition of the additives (hydrogen peroxide and AQ) in the O did not help in reducing the HexA content. By comparing the hardwood pulp and EFB pulp, it was found that OpAQ gave better improvement on bleaching selectivity to the former (37.7%) than the latter (23.8%). Nevertheless, due to the initial properties of the unbleached pulp, the EFB Soda-AQ pulp achieved lower Kn and higher ISO brightness.

Improved Oxygen Delignification by Photo Pretreatment

The application of UV photo pretreatment for only 30 min prior to O on both chemical pulps showed positive effects on delignification and pulp viscosity preservation. As shown in Table 2, the Kn of both hardwood and EFB pulps was reduced to 7.6 and 6.9, hence the Kn reduction was enhanced to 57.3% and 37.8% (Figure 1), respectively. On the other hand, it was very surprise to see that the increase of delignification by the photo pretreatment not only did not cause more serious cellulose degradation, it even diminished cellulose degradation during the subsequent O and thus, enhanced the bleaching selectivity of the hardwood and EFB pulps to 1.01 and 1.14 (Figure 2), respectively, which accounted to 90% and 80% improvement on selectivity. Moreover, photo pretreatment also showed an overwhelming effect of on eliminating HexA from pulp. The Ph-O was capable of removing more than 55% of HexA from both the unbleached pulps, which was much more effective than the ordinary O or even improved Os (Op and OpAQ). As reported by many researchers, HexA groups could be only hydrolysed under drastic acidic condition and which was strongly influenced by reaction temperature and pH [13,14]. However, in this study, a simple photo pretreatment in mild acidic medium (pH5) for 30 min without heating process could easily remove the HexA more than 50%. It was believed that the unsaturated double bonds in the HexA could absorb the energy/proton released from the irradiation process and subsequently initiated the hydrolysis of the HexA [15,16]. Nevertheless, the Ph-O pulp showed merely a small improvement on pulp brightness in comparison to the O as there was no additional brightening agent such as H2O2 added. Based on the results of the two chemical pulps, it was found that the UV photo-pre-treatment was applicable on different pulps and gave the similar effect as well. Nevertheless, the augmentation of selectivity of EFB pulp was better than that of hardwood pulp. On the other hand, the enhancement of

Kn reduction of latter was much greater than that of the former. This was possibly due the initial Kn of unbleached EFB pulp was rather low and might contain lesser phenolic groups, which are easier to be attacked under alkaline O, it its residual lignin.

Improved Oxygen Delignification by Combination of Photo Pretreatment and Additives Reinforcement

Both the additive reinforced O and photo-pre-treatment O were capable of improving the bleaching selectivity of the two chemical pulps with different approaches. Furthermore the former enhanced the brightness increment while the latter increased the removal of HexA. However, based on the results in

Table 2, the combination of both approaches offered merely slightly increase in Kn reduction but there was no further improvement on the bleaching selectivity. This indicated that single modification of O might have achieved the asymptotical limit of delignification, therefore, the extended delignification become least feasible. Nevertheless, the resultant pulp bleached by combination approaches attained the benefits of higher pulp brightness and low in HexA content, which were never achieved at once by applying only single approach neither via additive reinforcement nor photo pretreatment. Based on selectivity, the combination modification of O was more workable for EFB pulp than hardwood pulp, wherein the selectivity of the EFB Ph-Op and Ph-OpAQ was still retained considerably high whereas the selectivity of both the hardwood bleached by combination approaches was lower than that of single approach.

Conclusion

The modifications of oxygen delignification (O) by additives reinforcement and pre-treatment were successfully improved the performance of O in all aspects—kappa number reduction, pulp viscosity preservation, brightness increment and removal of hexenuronic acid. Additive reinforcement gave better effect on brightness increment whilst the photo pretreatment enhanced the cellulose stability and removal of hexenuronic acid. In comparison to single approach, modification of O by combination approaches attained the benefits of both higher pulp brightness and lower in HexA content. The effect of improved O on the hardwood pulp and EFB pulps was basically in similar trend. Based on the improvement of selectivity, the photo-pretreatment and combination modification of O was more workable for EFB pulp than hardwood pulp

Acknowledgment

The authors would like to acknowledge the financial support from grants funded by Universiti Sains Malaysia [FRGS Grant 203-PTEKIND/6711327] and USM fellowships scheme and scholarship sponsored by the Ministry of Higher Education (MOHE) Malaysia (Mybrain15 MyPhD) to Miss Chong Yin Hui.

References

1. Barroca MJMC, Marques PJTS, Seco IM and Castro JAAM. selectivity studies of oxygen and chlorines dioxide in the pre-delignification stages of a heardwood pulp bleaching plant. Ind Eng Chem Res 2001; 40:5680-5685 2. Suchy M and Argyropoulos DS. Catalysis and activation of oxygen and peroxide delignification of chemical pulps: A review. TAPPI J 2002; 785(4):2-43 3. Ismail D and Guniz G. Dimensionless parameter approach for oxygen delignification kinetics. Ind Eng Chem Res 2008; 47(16): 5871–5878 4. Leh CP, Wan Rosli WD, Zainuddin Z and Tanaka R Optimization of oxygen delignification in production of totally chlorine-free cellulose pulps from oil palm empty fruit bunch fibre. Ind Crop Prod 2008; 28:260-267 5. Ng SH, Ghazali A, and Leh CP. Anthraquinone-aided hydrogen peroxide reinforced oxygen delignification of oil palm (Elaeis guineensis) EFB pulp: A two-level factorial design. Cell Chem Technol 2011; 45(1-2):77-87 6. Chong YH, Ng SH, and Leh CP. Improved oxygen delignification selectivity of oil palm EFB Soda-

AQ pulp: Effect of photo pre-treatment and AQ-aided H2O2 reinforcement. Cell Chem Technol 2013; 47(3-4):277-283

7. Sun YP, Kien Loi NY and Wallis AFA. Totally chlorine-free (TCF) bleaching of radiata pine kraft pulp involving a UV-peroxide stage. APPITA J 1996; 49:96-99 8. Liu Z, Cao Y, Yao H, and Wu S. Oxygen delignification of wheat straw soda pulp with anthraquinone addition. BioResources 2013; 8(1):1306-1319 9. Dence CW and Reeve DW. Pulp Bleaching: Principles and Practice. Atlanta, GA: Tappi Press; 1996, pp. 213-239. 10. Hon DNS. Photochemical degradation of lignocellulosic materials. In Grassie, N. (Ed.) Developments in Polymer Degradation-3. London: Applied Science Ltd; 1983, p 229-281 11. Bikova T and Treimanis A. UV-absorbance of oxidized xylan and monocarboxyl cellulose in alkaline solutions. Carbohyd Polym 2004; 55(3): 315-322 12. Sjöström E. Wood chemistry: Fundamentals and applications. San Diego: Academic Press Inc; 1993 13. Jiang ZH, Audet A, Sullivan J, Lierop BV and Berry R. A new method for quantifying hexenuronic acid groups in chemical pulps. Pulp Pap Sci 2001; 27(3):92-97 14. Vuorinen T, Burchet J, Teleman A and Fagerstrom P. Selective hydrolysis of hexenuronic acid groups and its application in ECF and TCF bleaching of krafts pulps. Pulp Pap Sci 1997; 25(5):155-162 15. Sixta H and Rutkowska EW. Comprehensive kinetic study on kraft pulping of Eucalyptus Globulus Part 2. O Papel 2007; 68(2): 68-81. 16. Bajpai P. Environmentally Benign Approaches for Pulp Bleaching. Amsterdam, The Netherlands: Elsevier, 1st Edition; 2005

GREEN TECHNOLOGY IN THE PULP INDUSTRY

Dominique Lachenal1, Christine Chirat Grenoble INP-Pagora BP 65, 38402 Saint Martin d’Hères Cedex France, [email protected]

ABSTRACT

Kraft cooking and ECF bleaching has become the universal way of producing cellulose pulp fibers from wood. These processes have been so well optimized that impressive progresses have been made in the last decades in reducing the environmental impact of pulp manufacture. However there is still some matter of improvement. Two on-going new developments are presented in this paper. The first one concerns the conversion of pulping process into a biorefinery operation in which prehydrolysis is performed prior to cooking. Such an approach is already an industrial reality for the production of dissolving pulp. In a near future the prehydrolysis filtrate will be recovered since it represents an important source of hemicellulosic sugars. The main point discussed here is that after prehydrolysis, cooking is much easier. Among the likely reasons are the lower occurrence of lignin carbohydrate linkages, the cleavage of some ether bonds and the better accessibility of the lignin. The change in kinetics is such that the kraft cook could be replaced by a soda cook. In an optimum situation the caustic soda cook is stopped at higher kappa number and is continued by an extensive oxygen delignification. Using a sulfur free caustic soda cook in place of a kraft cook represents a major process simplification and a move toward greener technology. The second development deals with the implementation of green bleaching for chemical pulps. Because the common bleaching process uses chlorine dioxide, it remains the cause of significant water consumption, release of organic materials in the aqueous effluent and formation of hazardous chlorinated compounds. Replacing chlorine dioxide by ozone is a most straightforward means to develop an environmentally friendly bleaching process. Ozone offers many advantages compared to chlorine dioxide: it is a more powerful oxidant, it produces a chloride-free effluent that can be recovered and burnt. Ozone-based totally chlorine-free sequences are proposed which do not affect pulp quality and are economically attractive. These improvements have been made possible thanks to close examination of the chemistry of ozone with pulp components. It is thought that pulping and bleaching operations will necessarily evolve in a near future because a green product such as cellulose deserves to be produced by the best available technologies.

Keywords: sulphur-free cooking; caustic soda cooking; prehydrolysis; totally chlorine-free bleaching; ozone

Introduction

The kraft process has become the universal way of producing cellulose for paper making. The reason is the unbeatable quality of the extracted cellulose fibres and the overall efficiency of the process which allows for the production of cellulose from wood without any consumption of the cooking chemicals which are entirely recovered, and with a marginal use of fossil fuel, the energy needed being provided by the combustion of the cooking liquor which contains around 50% of the original weight of the processed wood. The energy balance is so favourable that the kraft pulp mills are net producers of energy under the form of green electricity. No other process so far has met such records. However, despite its global performance, the kraft process suffers from several drawbacks: • more than 50% of the wood components (lignin and most of the hemicelluloses) are burned, which is not the most valuable usage of these sophisticated macromolecules. • methylmercaptan and dimethyl sulphide are released in the atmosphere. Although they do not present any toxicity, their smell is spoiling the environment of a kraft pulp mill over dozens of kilometres. Progress has been made to capture these gases at their point of emission, but the odour problem can only be efficiently tackled in new kraft pulp mills. • bleaching of the kraft cellulosic fibres still uses chlorinated organic chemicals (mainly chlorine

dioxide). This practice not only generates potentially toxic chlorinated chemicals but also prevents the combustion of the bleaching effluent because it contains chloride ions. As a result, bleaching is by far the main contributor to the water pollution of a kraft pulp mill.

This paper summarizes the research efforts which address these problems and will contribute to the development of a sustainable cellulose industry.

The Kraft Biorefinery Concept

Converting a kraft pulp mill to a biorefinery represents the most realistic mean to develop a sustainable production of chemicals from lignocellulosic biomass. In theory, many other processes may be used to this purpose. They are not described here. For many reasons, it makes more sense and is technically and economically more attractive to take profit of existing cellulose production mills to develop such a chemical platform. The challenges are then to extract the hemicelluloses prior to the delignification and to recover some of the lignin dissolved in the cooking liquor, which are today industrially feasible. Therefore, many people consider that pulp mills are going to be the future large scale biorefineries. One example will be the start up in 2017 of the new Metsa mill at Aanekoski in Finland which should produce both 1.3 million tons of cellulose per year and a series of bioproducts and biofuels, including sulfuric acid, methanol, textile fibres, lignin derivatives, fertilizers, biogas [1]. Figure 1 gives a general scheme of a kraft biorefinery. In this process the wood is treated at high temperature with vapor prior to kraft cooking. During this step named autohydrolysis, the hemicelluloses are depolymerized and made soluble in water. Part of them is recovered as simple sugars or oligomers which may be the raw material for sugar chemistry [2]. Some of the lignin present in the liquor after cooking is precipitated and recovered as a source of phenolic compounds. However the drawbacks of the kraft process are not addressed. Moreover, the presence of sulfur in the recovered lignin may be a problem for subsequent applications. Our recent work has been devoted to the understanding of the reactions taking place during the autohydrolysis step.

Figure 1. Scheme of the kraft biorefinery mill

2.1 Impact of Autohydrolysis on Lignin and Lignin-Carbohydrates Complexes

In wood, lignin and carbohydrates are covalently linked. Several types of linkages have been described. Some of them will not be cleaved during the kraft process which means that even though lignin is depolymerized, it may not go into solution. This hinders lignin removal and contributes to the well known fact that residual delignification has a very slow rate. The quantity of lignin linked to

128 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 carbohydrates (LCC) has been investigated for both hardwood (mixed) and softwood. The procedure for the measurement of LCC was adopted from Due et al (2013) [3]. Table 1 shows that most of the lignin in wood is linked to carbohydrates. After hydrolysis, it is clear that in softwood some lignin carbohydrates linkages are cleaved, since some lignin is left free of carbohydrates. This demonstrates that autohydrolysis has the capability of detaching some lignin from the carbohydrates. In hardwood lignin remains linked to carbohydrates. However it does not mean that no lignin carbohydrates linkages have been cleaved since one lignin molecule may be originally linked to carbohydrates at many locations. The lower proportion of carbohydrates engaged in LCC after autohydrolysis can be consistent with the cleavage of lignin carbohydrates bonds [4]. This should help delignification. The effect of autohydrolysis on lignin itself is difficult to study. The reason is that, due to the lack of in situ analytical techniques, lignin is usually extracted by acidolysis for analysis. This extraction procedure is known to introduce some modification to the lignin, which weakens the validity of the conclusions. We have developed an in situ method to measure the phenolic OH groups [5]. The method is based on the fact that at low temperature chlorine dioxide reacts exclusively with the free phenolic groups in lignin. The consumption of chlorine dioxide is then correlated to the content in these groups

(the higher the ClO2 consumption, the higher is the phenolic OH content). Some secondary reactions may happen and consume further ClO2. However at low temperature (0°C here) and appropriate pH (phosphate buffer pH 6.7) the extent of these reactions is minimized. Figure 2 compares the consumption of ClO2 for hardwood chips before and after autohydrolysis. It appears that autohydrolysis introduces new free phenolic groups. Since these groups originate from the cleavage of aryl ether linkages, one may conclude that partial depolymerisation of lignin occurs during autohydrolysis, at least in a first step, since the possibility of recondensation of lignin fragments cannot be totally excluded.

Table 1. Proportion of lignin and carbohydrates engaged in LCC before and after prehydrolysis of softwood and hardwood chips

Lignin in LCCs/ GGM in LCCs/ Xylans in LCC/ Cellulose in LCCs/ Ratio LCC/wood lignin in wood GGM in wood xylans in wood cellulose in wood Control softwood 0.98 0.61 0.63 0.83 Prehydrolysed 0.79 0.66 0.41 0.81 softwood Control hardwood 0.92 0.67 1.03 0.83 Prehydrolysed 0.90 0.47 0.86 0.62 hardwood Note: The values do not take into consideration the acetyl and methylglucuronic acid groups in carbohydrates.

Figure 2. Consumption of ClO2 by milled hardwood chips before ( ) and after ( ) autohydrolysis (0°C, pH 6.7)

As a consequence, cooking should be much facilitated after autohydrolysis. Moreover the removal of part of the hemicelluloses which are the main responsible for caustic soda consumption should allow for a substantial decrease in the alkali requirement. Finally, the departure of hemicelluloses must have resulted in a more porous and accessible lignocellulose matrix. This has not been investigated so far but appears logical. Many trials have confirmed that kraft cooking is much easier after autohydrolysis.

2.2 Replacing The Kraft Cook by A Caustic Soda Cook

Considering the effect of the autohydrolysis step on lignin-carbohydrate bonds and lignin structures, alkaline delignification must be much easier, which is actually observed. Then, replacing the kraft cook by the simple sulphur-free caustic soda cook becomes possible. Table 2 illustrates the exceptionally good performance of the caustic soda delignification after prehydrolysis in the case of Eucalyptus Globulus. Even though the residual lignin content (visualized by the corrected kappa number) is higher after NaOH cook, its absolute value is quite acceptable. After oxygen delignification a very low residual lignin is reached. Therefore, in the perspective of biorefinery the caustic soda cooking process associated with autohydrolysis allows for the production of high quality cellulose, sugars (monomers and oligomers) and for the availability of a sulfur-free lignin. Bleaching may still be an issue. However the next part of this paper will detail the progress which has been made to develop a high performance totally chlorine- free bleaching process.

Table 2. NaOH cooking of prehydrolysed (PH) Eucalyptus chips. Comparison to Kraft cooking of untreated chips.

Kappa Kappa Cooking Kappa HexA, Xylans, Cooking Pretreatment number DPv number process number µmol/g % Yield % (corrected)* after O* no Kraft 165°C 16.2 9.5 66.4 1460 17.3 51.2 2.4 NaOH / PH 160°C 9.5 9.2 3.1 1500 2.5 52.8 2.9 AQ** 155°C PH 160°C NaOH 165°C 17.0 16.4 3.6 1580 2.3 51.0 5.0

Kraft: Effective Alkali 23%, 30% sulfidity, L/W ratio 3.5, 45 min NaOH cooking: 18.9% NaOH, L/W ratio 3.5, 0.1% AQ (NaOH AQ), 45 min PH : 160°C, L/W ratio 3, 2 h *HexA contribution is substracted (10 µmol/g hexA = 1 kappa unit)

O oxygen delignification : 100°C, 1 h, 0.3% MgSO4, 7H2O, 5 bars O2, 1% NaOH for Kraft and NaOH/ AQ pulps, and 1.5 % for NaOH pulp **AQ: Anthraquinone

Green Bleaching

Pulp bleaching with oxygen derived reagents (green bleaching) would offer many advantages for the sustainability of a cellulose production unit: • no AOX formed, • no chloride ions in the bleaching effluent • lower water consumption because of the possible recovery of the bleaching effluent for the washing after oxygen delignification • possible combustion of the beaching effluent • dramatic reduction of the DBO and DCO charges in the effluent going to the water treatment unit • replacement of caustic soda by oxidized white liquor in the alkaline extraction stages

For chemistry reasons green bleaching must include oxygen gas (O) (the cheapest delignification chemical), ozone (Z) (the most efficient delignification reagent) and hydrogen peroxide (P) (the better whitening agent for the removal of the last chromophores). However some oxidation of the pulp

130 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 carbohydrates takes place, which results in lower pulp viscosity. Ozone is partly responsible for this drawback. Ozone is a powerful delignifying agent which reacts very readily with unsaturated organic compounds. Applied to the phenolic moieties, this reaction causes lignin degradation and dissolution. The parallel degradation of cellulose during pulp ozonation is generally explained by the formation of hydroxyl radicals when ozone reacts with lignin. We have found that the formation of hydroxyl radicals is much more general than anticipated since it occurs also when non aromatic carbon-carbon double bonds react with ozone [6]. Acetovanillone, maleic acid, and 2,5-dimethyl 2,4-hexadienedioic acid which are models for lignin, HexA and muconic acids respectively (Figure 3) were treated by ozone under the conditions of pulp ozone delignification and the formation of hydroxyl radicals was followed by ESR spectroscopy, using 5,5-dimethyl-pyrrolidine-1-oxyl (DMPO) as the spin trapping substance. In all cases, OH radicals were observed (Figure 4). Several blank experiments, including the addition of H2O2, one possible product of the Criegee general reaction, indicated that the OH radicals would result from the direct reaction of ozone with the compound. This finding suggests that OH radicals are formed not only when ozone reacts with lignin, but also with hexenuronic acids (hexA), and muconic acid derivatives which are the primary oxidation products of lignin. Therefore, the key to improved selectivity of ozone delignification would be to minimize the reaction of ozone with carbon-carbon double bond structures. One way is to reduce the amount of HexA prior to ozone application (e.g. by hot acid treatment (A)). Another way is to limit the presence of muconic acids as much as possible. This can be achieved by splitting the ozone charge and applying an alkaline extraction after each ozonation phase. Some of the muconic acid derivatives formed by the ozone are made soluble and are eliminated in the next washing stage before addition of the new ozone charge. Both ways must be taken in the case of hardwood paper pulp. For softwood paper pulp and dissolving pulps, the content in HexA is generally too small to justify the implementation of A stage. Selective TCF bleaching sequences were designed based on these principles. One promising approach is the A(ZE)(ZE)(ZE) type sequence in which the Z stages are carried out with 1-2 kg O3/o.d. t pulp in a mixer at 70°C for a very short time, immediately followed by an alkaline extraction at the same temperature.

HOOC

O OH COOH

OXyl

OH COOH

Acetovanillone Maleic acid HexA

HOOC COOH COOH COOH

Muconic acid derivative 2,5-dimethyl 2,4-hexadienedioic acid

Figure 3. Models used for the detection of OH radicals during ozonation. Structures of HexA and muconic acid derivative are given for comparison.

Figure 4. ESR signal given by a solution of maleic acid (MA) during ozonation in the presence of DMPO

An example of bleaching line flowsheet is given in Figure 5. The whole sequence is carried out at medium consistency. The AQ stage is a high temperature (90°C) acid (pH 3.0) treatment (2h). Q stands for chelating agent like EDTA. Q is optional. The A effluent is released to the water treatment plant. This effluent contains most of the metal ions present in the pulp before bleaching. Countercurrent washing of the 3-stage (ZE)(ZE)P sequence is proposed here with fresh water added at the P wash press. The corresponding alkaline effluent is used to wash the pulp after oxygen delignification in combination with fresh water. One drawback of the sequence is the higher consumption of caustic soda. In theory oxidized white liquor might be used since the alkaline effluents are ultimately burned in the recovery furnace of the mill. Then extensive oxidation should be performed to be able to use oxidized white liquor in P. If not, some other effluent recycling strategies will have to be looked for.

Figure 5. Flowsheet of the A(ZE)(ZE)P sequence for the bleaching of eucalyptus kraft paper pulp

Two sequences are proposed where the alkaline extraction stages are reinforced with oxygen and where hydrogen peroxide is added at the end to destroy the last colored chromophores and improve brightness stability: A(ZEo)(ZEo)P for paper pulp (Table 3) and (ZEo)(ZEo)(ZP) for dissolving pulp (Table 4) [7]. We have shown that they lead to pulp qualities equivalent to their ECF counterparts.

Table 3. Chlorine-free bleaching sequence for eucalyptus kraft paper pulp (Kappa number 9 after oxygen delignification)

ClO O H O 3 3 2 2 NaOH Brightness Treatment on pulp DP on pulp on pulp on pulp (%) (%) (%) (%) (%) No - 60 1350

Dhot(Ep)DP 0.55+0.25 0.35+0.2 1+0.8 90.5 1180 Z(Eo)P 0.8 0.6 1+1 86 800

AQ(ZEo)(ZEo)P - 0.25+0.18 0.6 1.1+1.1+0.8 90.5 1000

Table 4. Chlorine-free bleaching sequence for eucalyptus prehydrolysis- Kraft dissolving pulp (Kappa number 3.0 after oxygen delignification)

ClO2 O3 H2O2 NaOH Brightness Treatment DP on pulp on pulp on pulp on pulp (%) (%) (%) (%) (%) No - 57 920

D (Eop)DP 0.4+0.4 0.1+0.1 1+0.5 89 740

ZP - 0.4 0.6 0.8 86 400

(ZEo)(ZEo)(ZP) - 0.1+0.1+0.1 0.2 1+1+1 90 620

Conclusion

Although cellulose manufacture has already reached a high degree of sustainability, some improvements are still possible. Among them, the recovery of sugars and oligomers from the wood hemicelluloses prior to cooking by autohydrolysis allows for the conversion of the kaft process to caustic soda process. This change is possible because delignification is made easier by the effect of the acidic conditions and the removal of hemicelluloses. Sulfur-free cooking will simplfy the mill operations, reduce the impact on the air in the vicinity of the mill and improve the potential quality of the lignin which may be extracted from the black liquor. Another progress would be the development of a new generation of chlorine-free bleaching process based on the implementation of multi-stage ozonation. Because most of the washing filtrates can be recovered and ultimately burned, this change may reduce the impact of bleaching on water consumption and effluent quality.

References

1. http://bioproductmill.com/articles/metsa-group-to-build-next-generation-bioproduct-mill-in- aanekoski 2. Boucher et al. Extraction of hemicelluloses from wood in a pulp biorefinery, and subsequent fermentation into ethanol, Energy Conversion and Management 2014; 88:1120–1126. 3. Due et al. Universal fractionation of lignin–carbohydrate complexes (LCCs) from lignocellulosic biomass: an example using spruce wood, Plant J. 2013;74:328-338. 4. Claire Monot et al. Characterisation of lignin and lignin-carbohydrate complexes in control and prehydrolysed wood chips, Holzforschung, 2017 (to be published). 5. Delmas et al. Titration of free phenolic groups in pulps, Holzforschung 2009;63:705-710. 6. Pouyet et al. On the origin of cellulose depolymerization during ozone treatment of hardwood kraft pulp, Bioresources 2013;8(4):5289-5298. 7. Perrin et al. New chlorine-free bleaching for dissolving pulp production presented at 18th ISWFPC. Vienna; 2015.

EFFECT OF RATIO LIQUID WASTE OF OUTPUT SEDIMENTATION AND FERMENTATION BIOGAS FROM PALM OIL MILL EFFLUENT (POME) ON BIOFERTILIZER PRODUCTION

Martha Aznury1, Robert Junaidi, Jaksen M. Amin, Victor Alberto Valentino Department of Chemical Engineering, Politeknik Negeri Sriwijaya, Palembang Jl. Srijaya Negara Bukit Besar,Palembang 30139, Indonesia [email protected]

ABSTRACT

Palm oil mill effluent (POME) can pollute the waters because of high organic matter content, low acidity levels, and contain macro nutrients such as nitrogen (N), phosphorus (P) and potassium (K) that need treatment before being discharged to the river. Palm oil mill effluent when processed exactly it will produce biogas. Palm oil mill effluent is processed into biogas will produce of liquid waste from output sedimentation and fermentation biogas digester. This study aims to determine effect ratio of output sedimentation and fermentation biogas digester for liquid organic to biofertilizer. The method used is anaerobic fermentation process in two stages from two outputs biogas digester. Variables measured are the ratio of liquid waste volume percent of the output of biogas and bio-activator additions. The results of ratio 10:0 (sedimitation: fermentation) with bio-activator showed nitrogen, phosphorus, potassium 2.66%, 0.07%, 1.11%, approximately. The highest result without the addition of bio-activator with ratio 10:0 had2.44%, 0.07 and 1.03%, nitrogen, phosphorus, and potassium, approximately

Keywords: Palm oil mill effluent, biogas, sedimentation, fermentation, biofertilizer

Introduction

Palm oil mill effluent (POME) from palm oil industries contained substances high organic and macro nutrients such as nitrogen (N), phosphorus (P) and potassium (K). POME needs treatment before being discharged in the bank of river (Eyrani, 2014). If the waste is not managed well and just directly discharged waters it will be very disturbing the surrounding environment. Most industries would dispose of waste are required to process them beforehand to prevent contamination of the surrounding environment (Widhiastuti et al, 2006). POME cannot be directly discharged to the river n because it has a concentration of Chemical Oxygen Demand (COD) is high to 50,000 mg/ (Ibrahim et al., 2013). POME can generate on biogas production and waste. Waste biogas was through from sedimentation and fermentation could be used as bio fertilizer, which contains organic substances. POME due process in bioreactors is methanogenesis fermentation which will also produce organic substances. The rest of the biogas output has undergone anaerobic fermentation so that it can be directly used to fertilize crops. Organic fertilizers including compound fertilizer because it contains nutrient more than one element and micronutrients. The content of nutrients in bio fertilizer was not high when compared to inorganic fertilizer but bio fertilizer could to improve the nature of physical and biological soil, loosening soil surface layer, increase the number of microorganisms, as well as increase the absorption and store water so that the whole can improve soil fertility. Bio fertilizers produced from waste biogas output is organic fertilizer as the main material is organic waste. Waste output in the form of biogas and liquid slurry. The waste can be processed into liquid bio fertilizer. Bio fertilizer itself has several advantages over solid organic fertilizer for application more easily and nutrients contained therein more easily absorbed by plants. Processing biogas output is expected to reduce the waste from the biogas output resulting in lower levels of pollution to the environment. The process of composting or anaerobic decay of organic material is carried by the microorganisms in the fermentation process (Polprasert, 1980). The nutrient content of the waste contained biogas can be seen in Table 1.

Table 1. Nutrient Content of Waste Biogas

Material N (%) P2O5 (%) K2O (%) Solid 0.64 0.22 0.24 Liquid 1.00 0.02 1.08 (Junus, 1998)

Table 1 shows the nutrient content of the output from biogas installations which are a by-product of anaerobic composting system that is free of pathogenic bacteria and can be used as fertilizer to maintain soil fertility and increase crop production (Food and Agriculture Organization, 1997). Effluent contains macro elements that are essential for plant growth as an element of N, P, K, and micro elements, namely Cu, Fe, Mg, S, and Zn (Suzuki et al., 2001). Park (1984) stated that the effluent from biogas if used as fertilizer for crops can improve agricultural yields and improve soil fertility. Fermentation is a process in which the chemical components generated as a result of the growth and metabolism of microbes. Bio fertilizer production process can be accelerated by the addition of bio- activator that is a source of microorganisms. Microorganism activity is influenced by concentration of sugar as sucrose contained in the sugar solution is the substrate that is easily digested and utilized for growth of microorganisms. Bio fertilizer production by the fermentation of success marked by a white coating on the surface, a characteristic odour, and colour changes from green to brown and fertilizer produced brownish yellow. White coating on the surface of the fertilizer is actinomycetes, which kinds of mushrooms grow after bio fertilizer production [6]. Based on this, the authors conducted a study of POME by utilizing the output of the digester sedimentation and fermentation biogas production. The output of the sedimentation and fermentation is directly discharged into the environment can damage the soil and pollute the environment. It is necessary for the processing of these outputs by anaerobic fermentation process using gallons media to be more effective and efficient. Bio fertilizer as a product can be applied to oil palm plantations for itself and other plants. Output processing using gallons media this is an effective and efficient in terms of place, time, and cost of processing. The purposes of this study include: 1. Utilize a byproduct of sedimentation and fermentation digester output into bio fertilizer. 2. Obtain appropriate concentration variation between the byproduct of the digester output sedimentation and fermentation digester to be used as organic manure. 3. Determine the influence of bio-activator to the content of N, P, and K are produced from bio fertilizer.

Methodology

Palm oil mill effluent (POME) from PT. Mitra Ogan Tbk was fermented with activator microorganism (activator) from cow manure obtained from slaughter houses in Gandus area, as well as the chemicals used are available in the laboratory of Chemical Engineering Department of the Polytechnic of Sriwijaya. In the output processing effluent from sedimentation and fermentation biogas digester uses advanced anaerobic fermentation methods using such media gallon. Both liquid waste digester biogas output will be used as organic manure by using anaerobic fermentation in the media about a gallon for 10 days. Production of bio fertilizer will be the effect of comparisons percent bio-activator volume and also influence the nutrient content contained in the organic fertilizer will be produced.

Process Preparation of raw materials 1. Tools a. Funnel b. Jerry can c. Bucket 2. Procedure: a. Opening the pipeline that is below bioreactors biogas. b. Accommodate the output from the digester sedimentation and fermentation into jerry cans and return pipe shut bioreactor. 136 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Output from Fermentation Digester Output from Sedimentation Digester

Figure 1.Output from Sedimentation and Fermentation Digester.

Fermentation Process 1. Materials and Equipment a. Materials • Materials from output sedimentation and fermentation biogas digester

• bio-activator EM4 • Brown sugar • Water b. Tools • Gallons of water 2.5 liter • Hose • Plasticine • Measure Iwaki glass 500 mL • Cutter • Knife • Plastic bottles of 600 mL • Former syrup bottles 2. Procedure: a. Prepared materials as follows: the liquid waste digester output sedimentation and fermentation that has been accommodated, 54 grams sugar, 27 mL of bio-activator and water at a certain ratio. b. Gallons of water prepared as media fertilizer, 1 meter transparent aerator hose (diameter approximately 0.5 cm), and plastic bottles of 600 mL size. Close gallon sized perforated hose aerator. c. The second output of the biogas digester was added to a gallon by comparison as follows:

Ratio of output of sedimentation and fermentation digesters in sample 1, 2, 3, 4, 5, and 6 can be seen in Table 2.

Table 2. Ratio of output of sedimentation and fermentation digester with number of sample

Output Digester Sample (%v/v) 1 2 3 4 5 6 Sedimentation 0 20 40 60 20 0 Fermentation 100 80 60 40 80 100

Analysis Procedures

Having obtained a bio fertilizer through a fermentation process, then did the analysis procedure. The analysis includes the determination of macro and micro levels of bio fertilizer by using Atomic Absorption Spectroscopic (AAS) and UV Spectrophotometer for Chemical Oxygen Demand (COD) and Biological Oxygen Demand (BOD). Procedure BOD and COD used SNI 6989.2-2009 Determination of concentration nitrogen in bio fertilizer used ISO 2803: 2010. Analysis of levels Phosphorus used ISO 2803: 2010 and concentration potassium used SNI 2803:2010.

Results

Preliminary Analysis of Bio fertilizer

In the initial analysis of bio fertilizer from output of sedimentation and fermentation digesters add bio- activator and without bio-activator. Results samples with the addition of bio-activator, nitrogen obtained ranged from 1.0211 to 1.4150%, while the sample without the addition of bio-activator have 0.9981 to 1.3878% nitrogen. In a phosphorus element analysis for samples with the addition of bio-activator have ranged from 0.0352 to 0.0488%, and without bio-activator phosphorus have ranged from 0.0352 to 0.0439%. The content of phosphorus is very small because it is based on Junus (1998) mentions that are element phosphorus contain in the waste liquid biogas that is equal to 0.02. The content of the element potassium in bio fertilizer in the initial analysis for samples with the addition of bio-activator ranged from 0.8341 to 0.8843%, and without the addition of bio-activator ranges from 0.8172 to 0.8743%. The content contained in the initial organic liquid fertilizer that has not actually meet the standards fermented bio fertilizer based on the Minister of Agriculture No.28 / Permentan / OT.140 / 2/2009 is <2%. But the elements of value Nitrogen, phosphorus, and potassium need to be improved in order to produce a bio fertilizer which has a better quality. That was why a process of anaerobic fermentation to enhance the existing content in the liquid organic fertilizer. Anaerobic fermentation processing is preferred because it carried the potential for handling POME because it has the characteristics of organic matter (Zhang et al. 2008).

Nitrogen Analysis

Nitrogen (N) is an essential macro nutrient that is needed for growth in the bio fertilizer plant. Nitrogen serves to prepare proteins that function in the metabolism of plants which will further stimulate cell division and elongation (Parman, 2007). The results of the analysis of the nitrogen content can be seen in Figure 2.

Figure 2. Concentration Nitrogen after Fermentation Anaerobic Treatment

From Figure 2 it can be seen that the nitrogen content after the process of anaerobic fermentation ranged from 1.7853 to 2.6625% of the samples with the addition of bio-activator, while for the samples without the addition of bio-activator obtained nitrogen levels ranged from 1.5257 to 2.4373%. From these data it is seen that the samples with the addition of bio-activator tend to have a greater nitrogen content compared to samples without bio-activator. This is because there is a bio-activator in the nitrogen- fixing bacteria, namely Rhodopseudomonas sp. According Koh.et al, (2007), Rhodopseudomonassp bacteria capable of increasing the content of nitrogen in organic fertilizer. The analysis of this study showed that the nitrogen content obtained in this study is still much to exceed the standard liquid organic fertilizer, defined by the Minister of Agriculture No.28 / Permentan / OT.140 / 2/2009 where the required standards, i.e. < 2%, Provision of excess nitrogen will result in very rapid vegetative growth, leaf colour to dark green, and more fertile, inducing the plant to be susceptible to pests and diseases (Prawiranata and Tjondronegoro, 1992). From Figure 2 can also be seen that the nitrogen content was lowest for the first sample where sample 1 is a sample that contains only the output of the digester fermentation alone. Levels of nitrogen will increase concurrently with increasingly smaller percent volume of fermentation digester. This is because the fermentation digester contains little organic materials compared to the digester sedimentation so that if the mixture contains more fertilizer output from the digester fermentation, the levels of nitrogen obtained will be smaller too.

Phosphorous Analysis

The element phosphorus (P) on the plant be functioning in the formation of flowers, fruits, and seeds as well as accelerate the ripening of fruit. Provision of P in adequate amounts can improve the quality of seeds that include the potential for germination and seedling vigour (Mugnisjah and Setiawan, 1995). Results of analysis of phosphorus levels after treatment in the anaerobic fermentation can be seen in Figure 3.

Figure 3. Concentration Phosphorus after Fermentation Anaerobic Treatment

Figure 3 the levels of phosphorus to the sample with the addition of bio-activator ranged from 0.0579 to 0.0701%, while for the samples without the addition of bio-activator obtained phosphorus levels ranged from 0.0527 to 0.0689%. Phosphorus levels were highest in the study contained in the sample 6 with the addition of bio-activator, is equal to 0.0701, while the lowest levels of phosphorus are present in the sample 1 without the addition of bio-activator. From Figure 3 can also be seen that the addition of bio-activator has a role in increasing the content of phosphorus in bio fertilizer. Phosphorous levels will also increase concurrently with the decrease in percent volume fermentation digester. Levels of phosphorus in liquid organic fertilizer in this study are now eligible liquid organic fertilizer quality standards based on the Minister of Agriculture No.28 / Permentan / OT.140 / 2/2009 is <2%. Phosphorus content value is worth very little by Junus (1998) biogas output has value only phosphorus content of 0.02%. From the data obtained it was not much different when compared to the research conducted Anwar (2015) mentions that the phosphor obtained by 0.07%. According to Manan (2006) P

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 139 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 element is also a very important substance, but always in a state of less deep. P element is very important as a source of energy (ATP). Therefore, P deficiency can inhibit the growth and reactions of plant metabolism. To increase the content of P fertilizer, during the process of making organic fertilizer can be added-rich material P such as bone meal (Prariesta and Winata, 2009).

Potassium Levels

Potassium (K) plays a role in the formation of proteins and carbohydrates, hardening of the wooden parts of the plant, increase plant resistance to disease, and improving the quality of seeds and fruits (Mulyani, 1994). Results of analysis of potassium levels after processing performed by the anaerobic fermentation can be seen in Figure 4.

Figure 4. Concentration Potassium after Fermentation Anaerobic Treatment

From Figure 4, the levels of potassium to the sample with the addition of bio-activator ranged from 0.8693 to 1.1055%, while for the samples without the addition of bio-activator obtained potassium levels ranged from 0.8574 to 1.0335%. Potassium levels were highest in the study contained in the sample 6 with the addition of bio-activator, in the amount of 1.1055%, while the lowest potassium levels found in sample 1 without the addition of bio-activator, in the amount of 0.8574%. From Figure 4, it can also be seen that the addition of bio-activator has a role in increasing the content of potassium in liquid organic fertilizer. Potassium levels will also increase concurrently with the decrease in percent volume fermentation digester. Potassium levels obtained in this study is greater than the levels of potassium in the research conducted by Anwar (2015) is only 0.07%. This is due to the addition of bio-activator that helps in increasing the nutrient content contained in a liquid organic fertilizer. Potassium levels obtained in this study also have to meet the standards set by the Minister of Agriculture No.28/Permentan/OT.140/ 2/2009 is < 2%. The element potassium is needed by plants because plants that lack the element of K will experience symptoms of dryness at the end of the leaves, especially older leaves. Dry end will increasingly spread to the leaf base. Sometimes it seems like the plants that lack of water. K element deficiencies in fruit trees, affecting the sweet taste of fruit (Winata. 1998).

Analysis of Chemical Oxygen Demand (COD) and Biological Oxygen Demand (BOD5)

COD value indicates the amount of oxygen needs is equivalent to the content of organic substances in wastewater (effluent) that can be oxidized by a strong chemical oxidant. Oxidation of organic material produces CO2 and H2O. High COD value in waste biogas output is directly discharged into the water can contaminate the environment. If the waste is directly discharged into the water, then some will sink, decompose slowly, consume dissolved oxygen, causing turbidity, emit a pungent smell and can damage aquatic ecosystems. For the analysis of COD liquid organic fertilizer after processing performed by the anaerobic fermentation can be seen in Figure 5.

with without

Figure 5. Concentration COD from Bio fertilizer after Fermentation Anaerobic Treatment

Figure 5 shows that COD value increases with the addition of bio-activator and the COD value will decrease without a bio-activator. This can be seen in the sample 5 and sample 6 with a bio-activator COD value increased by 310 mg/L and 325 mg/L approaching the maximum allowed by the government. Viewed from the South Sumatra Governor Regulation No. 08 of 2012 About Liquid Waste Quality Standard for Palm Oil Industry maximum limit that is collected is equal to 350 mg/L to be discharged directly into the environment. Bio fertilizer thus generated good COD value is without the use of bio-activator. Bio-activator has a function as change materials - organic materials and accelerates the fermentation time. This case can causes fermentation in the COD value by using bio-activator increases. As for the BOD value of POME can be seen in Figure 6.

with without

Figure 6. Concentration of BOD from Bio fertilizer after Fermentation Anaerobic Treatment

Figure 6 show that BOD values increase with the addition of bio-activator, but when no bio-activator addition, BOD value will decrease. This can be seen in the sample 5 and sample 6 with a bio-activator BOD value increased by 103.5 mg/L and 104.6 mg/L has passed the maximum allowed by the government whereas without bio-activator decreasing. The maximum allowed by the government in the amount of 100 mg/L. This causes Liquid Organic Fertilizer produced viewed from the BOD i.e. without using a bio-activator.

Conclusion

Production bio fertilizer with bio-activator plays an important role in increasing the nutrient content. This can be seen in the sample with the addition of bio-activator has the nutrient content greater than that of samples without the addition of bio-activator. This is because in a bio-activator there are microorganisms that contribute in decomposition of organic matter © 2016 Published by Center for Pulp and Paper through 2nd REPTech 141 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Acknowledgements

1. The authors would like to acknowledge the financial suport of Penelitian Stategis Nasional, Directorate General of Higher Education provides funding research project grants NOMOR SPPK : 189/SP211/LT/DRPM/III/2016, Date: 7 Desember 2015, entitled Rancang Alat Biodigester Untuk Pengolahan Air Limbah Industri Minyak Kelapa Sawit Untuk Memproduksi Biometan Dan Pupuk 2. PT. Perkebunan Mitra Ogan was a suport of POME.

References

1. Eyrani, K.A,. 2014. Design Alat Sedimentasi dalam Pengolahan Air Limbah Industri Kelapa Sawit. Laporan Akhir. Jurusan Teknik Kimia. Politeknik Negeri Sriwijaya. Palembang 2. Widhiastuti, R., Suryanto, D., Wahyuningsih, H., 2006 Pengaruh Pemanfaatan Limbah Cair Pabrik Pengolahan Kelapa Sawit Sebagai Pupuk Terhadap Biodiversitas Tanah.Jurnal Ilmiah Pertanian Kultura Vol. 41, No. 1, 1-6. 3. Ibrahim A.L, Dahlan I., Adlan M.N., dan Dasti A. F. (2013): Characterization of palm oil mill effluent: a comparative study, Caspian Journal of Applied Sciences Research, 2, 262-268 4. Polprasert, C.1980. Organic Waste Recycling. John Wiley and Sons, Chicester. 5. Food dan Agriculture Organization. 1997. China:in Agriculture. FAOS oils Bulletin Volume 40.FAO Rome. 6. Suzuki, K., W.Takeshi, and Lam. 2012. Consentration and cristalization of phosphate, ammonium and minerals in the effluent of biogas digester in the Mekong Deltha,Vietnam. Jircan and Cantho University, Cantho Vietnam.Japan Agriculture ResearchQuarter.32 (4):271-276. 7. Park, Y.D.1984. Biogas research and utilization in Korea. Procedings of International Symposium, Alternative Source of Energy for Agriculture.Food and Fertilizer Technology Center for the Asian PasificRegion. 8. Junus,M.1998.Rekayasa Penggunaan Sludge Limbah Ternak Sebagai Bahan Pakan Dan Pupuk Cair Tanaman. Jurnal Penelitian Ilmu-ilmu Hayati (Life Science). 10 (2):93-106. 9. Zhang,Y., L.Yan, L.Chi, X.Long, Z.Mei, and Z.Zhang.2008.Startup and operation ofanaerobic EGSB reactor treating palm oil effluent.J. Environ.Sci.20: 658-663. 10. Parman, Sarjana. 2007. Pengaruh Pemberian Pupuk Organik Cair terhadap Pertumbuhan dan Produksi Kentang (Solanum tuberosum L.). Buletin Anatomi dan Fisiologi Vol. XV, No. 2. 11. Koh, R. Hyun and H.G. Song, Effects of Application of Rhodopseudomonas sp. On Seed Germination andGrowth of Tomato Under Axenic Conditions, J. Microbiol. Biotechnol. (2007), 17(11), 1805– 1810 12. Prawiranata,W.S.H. dan P.Tjondronegoro.1992. Dasar-dasar Fisiologi Tanaman.Jurusan Biologi, Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor, Bogor. 13. Mugnisjah, W.Q.dan A.Setiawan. 1995. Pengantar Produksi Bersih. PT.Raja GrafindoPersada,Jakarta. 14. Prariesta, D dan Winata, R. 2009. Peningkatan Kualitas Pupuk Organik Cair Dari Limbah Cair Produksi Biogas. Tugas Akhir Jurusan Teknik Kimia. Institut Teknologi Sepuluh Nopember. Surabaya. Tidak diterbitkan 15. Mulyani,S.1994. Pupuk dan Cara Pemupukan. Rineka Cipta,Jakarta. 16. Anwar, Dedy 2015. Kajian Awal Pembuatan Pupuk Cair Organik dari Effluent Pengolahan Lanjut Limbah Cair Pabrik Kelapa Sawit (POME) Skala Pilot. Medan: Universitas Sumatera Utara. 17. Winata, L.1998. Budidaya Anggrek. Penebar Swadaya, Jakarta

PREPARATION OF POLYPYRROLE GRAPHITE COMPOSITE ANODE MATERIALS FOR LITHIUM BATTERY BY SOLUTION CASTING METHOD

Jadigia Gintinga1, Sri Yatmani b2, Yustinus Purwamargapratalac3 a,cPusat Sains dan Teknologi Bahan Maju-BATAN PUSPIPTEK, Serpong, Tangerang Selatan 15314 bTeknik Elektro ITI , Jl Raya Puspiptek Serpong Tangerang Selatan 15320 [email protected] [email protected] [email protected]

ABSTRACT

Preparation of Polypyrrole Graphite Composite Anode Materials For Lithium Battery By Solution Casting Method. Preparation and characterization measurement have been practisized recently in our anode study progression. The research was focused to observ the effect of the composition polypyrrole to graphite composite that proposed could increase the anode performance. Sample composition were 0 %; 2 %; 4 %; 6 % and 8 % of polypyrrole. Identification of the polymeric electrolyte composite forming were realisized using FTIR spectroscopy, the optical instrument and XRD diffractometer. Homogenity was observed with SEM. The conductivity measured using LCR apparatus. The result indicated the conductivity of the graphite polymeric composite decreased after the addition of polypyrrole respectively : for 0 % ppy was 10 -0.3; 2 % was 10 -0.55; 4 % was 10 -0.62; 6 % was 10 -0.8 ; and for 8 % polypyrrole added the conductivity was 10 -0.7 SCm-1. All measurements operated at frequency of 40 - 105 Hz. Microscopies observation data showed the homogeneous particles distribution. No interesting result was found by thiese method experiment.

Keywords : anode, polypyrrole, lithium batteries, solution casting

Preliminary

Pyrrole is a natural material that can be polymerized with commercial graphite SFG10 by polymerization technique.[1] . This materials can be made to produce gellic electrolyte that having specific charge capacity of the cathode or an anode and could discharge the system tohave0.4 Volt and showing no less capacity when cycled to 100 cycles [2]. The electronically conducting polymers ( ECPs ) like polypyrrole ( ppy ) are known to give unusually high electrical conductivity especially in doping process.[3] Conducting polymers like this can be processized either chemically or electrochemically. The electrochemical synthesis is the most common method as it is simpler, quick and perfectly controllable.[3-4]. Polypyrrole are applicable to make anode and cathode materials for ion lithium battery. [2]. This experiment propose to find an easier and productable result for material anode preparation with solution casting technique.

Methodology

Materials and Instruments

All materials used in this workis coming from commercials grade like MTI and Aldrich Catalog. The instruments used in the study is a spatula, micro balance, measuring cups, glass beaker, magnetic stirrer hotplate, mortar, ultrasonic, vacuum filter, compacting, furnace, X-ray diffraction (XRD), FTIR spectroscopy, impedance capasitance resistance (LCR) meter, optical microscopy.

Experimental Methods

To fix the mixture forming composite, treatment was applied by hand made using the mortar tools. After a certain amounts of polypyrrole and graphite weighted with hyphothetic composition for every 2 grams sample graphite was added polypyrrole of 0; 2%; 4%; 6% and 8% , the materials were treated to make smoothing in size with hand made and solved with acetone. Then dried at room temperature and continued in the oven at 50oC. The powder samples was compacted with 4000 psi for 1 minute to form pellets for conductivity measurements.

Results and Discussion

Microscope Optic Analysis

Figure 1. Observation the morphology of polymers composite polypyrrole/graphite composized: 0; 2%; 4%; 6%; and 8% ppy

Microscopy figure above indicate the morphology of distribution of polypyrrole unto graphite, seemed the best distribution is the concentration of 8% ppy that should have better conductivity.

Diffractometric Analysis

Figure 2. The pattern of X-Ray Diffractionintensity for ppy/gra in divers composition of ppy

After this difgfraction we consider that at the angel of 2Ɵ at 12 has formed polymeric composite of polypyrroly/graphite, considering that no bulk peak formed

Conductivity Measurements

Figure3. Conductivity of polypyrrole/graphite composite of divers composition of ppy.

LCR meter measurements showed that the conductivity graphite decrease by addition the ppy, respectively as follow: 0, 2%, 4%, 6%, and 8 % PPY are 10-0,3, 10-0,55, 10-6,2, 10-0,8, dan 10-0,7 S.cm-1 at frequency measurement range 40-105 Hz .

Conclusion

No satisfaction result found after these experiments according to Powder Metallurgical Technique and even with Solution Casting Technique. More detail and serious study needed to explore these materials development and its application. Solution Casting Technique not worthy in preparation of anode and cathode materials using polypyrrole polymers.

Acknowledgements

The writers would like to thank to all those who have participated helping this research, especially to Head of Advanced Materials Science And Technology, PSTBM Batan Serpong.

References

1. Basker Veeraraghavan, et.al, “ Study of polypyrrole graphite composite as anode material for secondary lithium-ion batteries”, Journal of Power Sources 109 ( 2002 ) 377-387. 2002 2. J.G. Killian, et.al . “Polypyrrole Composite Electrodes in an All-Polymer Battery System”,Journal of The Electrochemical Society, 1996 volume 143, issue3, 936-942. 1996 3. R.N. Singh, Madhu and R. Awasthi, “ Polypyrrole Composite : Electrochemical,Synthesis, Characterization and Application “, Banaras Hindu University, India. www.intechopen.com 4. C.M. Li, C.Q.Sun, W. Chen, L. Pan , “ Electrochemical thin film deposition of polypyrrole on different substrates”, Surface and coating Technology 198 ( 2005 )474-477. 2005 5. A. Manuel Stephan, K.S. Nahm, “ Review on Composite Polymer Electrolytes for Lithium Batteries,”Polymer 47 ( 2006 ) 5952-5964. 2006

6. L. Yu, D. Cai, H. Wang, M.M. Titirici, “Synthesis of Microspherical LiFePO4-Carbon Composites for Lithium Ion Batteries”, Nanomaterials, Vol. 3, pp. 443-452, 2013 7. Wang J,Chen y and Qi L, The Development of Silicon Nanocomposite Materials for Li-ion Secondary Batteries, The Open Materials Journal, 2011, 5, (Suppl 1:M5) 228-235

8. I.S. Kim and P.N. Kumta, High Capacity Si/C nanocomposite anodea for Li-ion batteries, Journal Of Power Sources, Vol 136, Issue1, 10 Sept 2004,pages 145-149. 9. J.M. Tarascon, M. Armand, “Issues and challenges facing rechargeable lithium batteries”, Nature, Vol. 414, pp. 359-367, 2001. 10. Y.P. Wu, E. Rahm, R. Holze, “Carbon anode materials for lithium ion batteries”, J. Power Sources, Vol. 114, pp. 228-236, 2003 11. H. Azuma, H. Imoto, S. Yamada, K. Sekai, “Advanced carbon anode materials for lithium ion cells”, J. Power Sources, Vol. 81- 82, pp. 1-7, 1999 12. Z.X. Chen, J.F. Qian, X.P. Ai, “Preparation and electrochemical performance of Sn-Co-C composite as anode material for Li-ion batteries”, J. Power Sources, Vol. 189, pp. 730-732, 2009 13. E. Kendrick, A. Swiatek, J. Barker, “Synthesis and characterization of iron tungstate anode materials”, J. Power Sources, Vol. 189, pp. 611-615, 2009. 14. F. Sauvage, J.M. Tarascon, E. Baudrin, “In Situ Measurements of Li ion Battery Electrode Material

Conductivity: Application to LixCoO2 and Conversion Reaction”, J. Phys. Chem. C., Vol. 111, pp. 9264-9269, 2007

15. J.Y. Luo, Y.G. Wang, H.M. Xiong, Y.Y. Xia,”Ordered Mesoporous Spinel LiMn2O4 by a Soft Chemical Process as a Cathode Material for Lithium Ion Batteries”, Chem. Mater., Vol. 19, pp. 4791-4795, 2007.

DEVELOPMENT OF (RECOMBINANT) MICROBIAL ENZYMES FOR APPLICATION IN PULP AND PAPER INDUSTRY

Is Helianti Center for Bioindustrial Technology, Agency for Assessment and Application of Technology (BPPT) Building No 611, LAPTIAB-BPPT, Puspiptek-Serpong, Tangerang Selatan, Banten, INDONESIA [email protected]

ABSTRACT

Enzyme is protein that catalyzes the biochemical reaction in living cells. Because of their specificity and high efficiency, many microbial enzymes are applied in the various fields, from pulp and paper industries to food industries. The use of enzymes in the pulp and paper industry started in the late 1980’s. Although enzyme usage leads to better and greener processes in industries, its use is still relatively insignificant. This presentation will discuss the development of recombinant enzymes to increase their productivity in different microbial hosts, using our own experience in the improvement of the production of xylanase, lipase, and cellulase, three enzymes commonly used in pulp and paper application.

Keywords: enzymes; bleaching; deinking; pulp and paper industries

Introduction

The paper and pulp production and consumption increase annually. Globally, paper and paper board production exceed 270 million metric tons; while in North America, more than 50 million metric tons of paper is produced every year (https://www.greenamerica.org/PDF/PaperFacts.pdf). In Indonesia, as 7th rank of the ten largest paper producer in the world (Table 1), in 2015 the amount of pulp export reached 3.5 million tons, worth USD 1.72 billion, whereas paper export reached 4.35 million tons, worth US$3.74 billion. It is predicted that the global paper demand will increase from 394 million to 490 million tons by 2020 (http://tempo.co.id).

Table 1 Paper and Paper Broad Producer in the World in 2011

Rank Production in 2014 Share Country 2014 (1,000 ton) 2014 1 China 107,579 26.5% 2 United States 73,188 18.0% 3 Japan 26,471 6.5% 4 Germany 22,540 5.5% 5 South Korea 11,702 2.9% 6 Canada 11,076 2.7% 7 Indonesia 10,943 2.7% 8 India 10,866 2.7% 9 Sweden 10,419 2.6% 10 Finland 10,409 2.6% Total 295,193 72.6% 11 Others 111,298 27.4% World Total 406.491 100.0%

Source: http://www.jpa.gr.jp/states/global-view/index.html#topic01

However, actually, the pulp and paper industry has been held responsible as one of the causes of several environmental problems, from deforestation to the environmental pollution. For these problem, enzyme is a smart solution. Enzyme-based processes could gradually replace the chemical processes in

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 147 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 this industry, since they can save energy, reduce water, chemicals, prevent environmental pollution, and improve the product quality (Kenealy and Jeffries 2003). In Indonesia, only 15% of the domestic pulp and paper industry uses enzymes in the process (BPPT 2006). Even if only a fraction of all pulp and paper production in Indonesia or globally uses enzymatical processes, , it could mean a great expansion of the existing enzyme industry. The development of enzymes and their application also support the sustainability of industry in economical, environmental, and social aspects. In this short review, we will discuss the enzymes that have potential application in pulp and paper industry, their production, and the technology advancement related to the production such as recombinant DNA technology. We discuss them based on our own experience combined with information gathered from various reports.

Potential Enzymes in Pulp and Paper Industries

Several enzymes are known for their potential application in pulp and paper industries, such as xylanases, lipases, cellulase, amylase, etc. The majority of these enzymes come from microorgainisms. For instance, amylase has been applied in modifications of raw starch in paper industry for a long time; however, other enzymes application only emerged from the late of 1980’s. Xylanases could be applied in bleaching of pulp and reduce the amount of chemicals required for bleaching, it also enhances deinking process (Sunna and Antranikian 1997). Cellulases can smooth fibers, enhance drainage, and promote ink removal, so that it can also be used in deinking process. Whereas, lipases reduce pitch; laccases and lignin-degrading enzymes reduce color in effluents, and promote lignin removal (Kenealy and Jeffries 2003). The prominent enzymes used in pulp and paper industry were summarize in Table 2.

Table 2 Types of Enzymes in Pulp and Paper Industry, Respective Substrates, and the Applications

Enzymes Substrates Application References

Amylase Starch • Reduce viscosity by cleaving Venditti http://www4.ncsu. starch molecules edu/~richardv/documents/cs irEnzymeApplicationsinPul • Used for surface sizing and for pandPaperrav.pdf starch in coatings

Cellulase Cellulose fibers Deinking process of waste paper Venditti http://www4.ncsu. edu/~richardv/documents/cs • Cellulase enzymes hydrolyze the irEnzymeApplicationsinPul microfibrils that stuck with ink, pandPaperrav.pdf releasing the adhesives

• Enzyme assisted deinking reported to remove 30-60% more toners and (Kenealy and Jeffries improve brightness by 4-5 points 2003).

• Cellulase could improve softness becauses its partial depolymerization of cellulose and swelling of fibers to becoming more flexible fibers

•Reduction of fines

Xylanase Hemicellulose Bleaching process Venditti http://www4.ncsu. edu/~richardv/documents/cs • Used to cleave hemicelluloses in irEnzymeApplicationsinPul fiber, making the bleaching process pandPaperrav.pdf more effective

• May be able to reduce bleaching chemicals by up to 30% Kenealy and Jeffries 2003; Helianti et al. 2014a; • Can improve brightness Viikari 1994; Bajpai 2012

Deinking of waste paper

• Xylanase enzymes hydrolyze the microfibrils that stuck with ink, releasing the adhesives

• Enzyme assisted deinking reported to remove 30-60% more toners and improve brightness by 4-5 points

Lipase Glycerol Pitch treatment http://www4.ncsu. backbone, pitch edu/~richardv/documents/ • Used to control pitch in pulping csirEnzymeApplicationsin processes PulpandPaperrav.pdf • Converts tri-glycerides to fatty acids which are more stable in water, so it will not be accumulated Esterase Ester, stickies Stickies treatment http://www4.ncsu. edu/~richardv/documents/ • Used to break ester bonds in csirEnzymeApplicationsin polymers used in toners and PulpandPaperrav.pdf adhesives

• Improved paper cleanliness

Lacasse Lignin • Used in delignification and Virk et al. 2012; Upadhyay brightening of the pulp et al. 2016

• To remove the lipophilic extractives responsible for pitch deposition from both wood and nonwood paper pulps

• Improving properties of pulp by forming reactive radicals with lignin or by functionalizing lignocellulosic fibers

• Degrade coloured and toxic compounds released as effluents from pulp and paper industry

Nowadays, the most significant application of enzymes from economical and environmental aspects in pulp and paper industry is in bleaching process. Xylanase treatment can improve lignin extraction, change carbohydrate and lignin associations linkage, or cleave reaccumulated xylan (Viikari et al. 1994). It is the most effective enzymes for the prebleaching of kraft paper, and now used in several mills in the world (Viikari et al. 1994, Bajpai 2012). Xylanases hydrolize the xylan of the pulp fiber structures, so that fibres more permeable. Hence, the xylan hydrolysis in inner fiber layer also enhance

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 149 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 the bleachability. However, the main target of the enzymes usage in the bleaching is to counteract the environmental issue, namely the reduction of chlorine chemicals and finally lowering the adsorbable organic halides (AOX) in the effluents. Another important application of xylanase is in the process of deinking waste paper. Deinking waste paper is the prefered paper processing to counter the deforestation and global warming issues. One of the main applications of enzymes in fiber recycling is to remove print. Waste paper usually consists of uncoated papers printed with copy and laser printer toners that are often difficult to remove by conventional, alkaline deinking processes. With xylanase, cellulase also plays significant roles in deinking process. Enzyme assisted deinking reported to remove 30-60% more toners, and also reported improve brightness by 4-5 points (http://www4.ncsu.edu/~richardv/documents/csirEnzymeApplicationsinPulpandPaperrav. pdf). From our own experience, the xylanase usage in deinking process could improve the whiteness and brightness of recycled paper (Helianti et al. 2014a).

3. (Recombinant) Enzyme Production for Pulp and Paper Industry and Its Prospect in Indonesia

From the above description, we know that enzymes are green chemicals that can improve the process and the product quality in pulp and paper industry, as well as support the sustainability of the industry through energy saving, environmentally friendly process, etc. Although enzymes are very important for domestic pulp and paper industry, Indonesia depends on imported enzymes to meet its domestic demand. Indonesia imports almost 100% of its demand in industrial enzymes (BPPT 2006). The demand of industrial enzymes is shown in table 3, where it is also shown that the enzyme demand for pulp and paper industry is significant. Only 15% of total pulp and paper industry uses enzymes in their processes, because imported enzymes are expensive. Therefore, it is high time to produce affordable enzymes for domestic market.

Table 3 The Demand of Industrial Enzymes in Indonesia at 2006

Total production User enzymes (%) Enzymes needed in 1 Prediction of total Industry (ton/year) kg product enzymes needed (kg)

Detergent 372,285,536 53 1.80 354,766,217 Feed 9,442,303 46 0.04 174,319 Textile 1,098,776 n.a 219,848 Leather 71,800 76 38.52 2,114,975 Pulp and paper 12,781,730 15 26.18 50,921,301 Source: BPPT 2006

To meet the pulp and paper industry’s requirements, the most important characteristics are the optimum pH and temperature of the enzyme, high specific activity, and strong resistance to metal cations and chemicals. Other specifications include cost-effectiveness, eco-friendliness, and ease of use. Therefore, most of the reported xylanases do not possess all of the characteristics required by this industry (Motta et al. 2013). The discovery of ideal enzyme for pulp and paper industry is still required. Three decades ago, there is only one approach to produce enzyme namely to find new organisms and new enzymes. However, nowadays, besides this conventional method we have recombinant DNA technology that can clone the enzyme-encoding gene of from known producer, difficult to culture microbes, unculturable microbes, or even just the DNA sequence (and based on it we can synthesize DNA). Using this recombinant DNA technology, we can increase the productivity of enzymes and efficiency of production, for instance by cloning the enzyme genes into microbe with faster growth or do not need expensive medium, etc. Using similar technology, modification of optimum temperature, pH, and stability of the cloned enzymes might be performed, for instance by random mutagenesis, gene shuffling, directed evolution, and site-directed mtagenesis. It is also possible to design and create

150 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 enzymes that are not presently found in nature. Thus, recombinant DNA technology make the ideal enzymes for pulp and paper industry available and accessible. Today, by combining the recombinant DNA technology, bioprocess engineering, and large scale fermentation, several enzymes needed by the pulp and paper industry are manufactured (http://www.novozymes.com/en/solutions/pulp-and-paper). When we want to produce recombinant enzymes, the productivity of the enzymes (the production rate and yield) is the main consideration. We have to choose which microbial host is the most appropriate for the cloning. Recombinant enzymes have been expressed in bacteria (e.g., Escherichia coli, Bacillus), filamentous fungi (e.g., Aspergillus) and yeasts (e.g., Pichia pastoris, Saccharomyces cerevisiae). Prokaryotic system or bacterial hosts such as E. coli and Bacillus can be used to quickly and easily overexpress recombinant enzymes; however, the bacterial systems cannot express very large proteins (more than 100 kD) and proteins that require post-translational modifications. Large proteins (> 100 kD) are usually expressed in eukaryotic systems, such as yeast or filamentous fungi. Indeed, E. coli expression system continues to dominate the bacterial expression systems, however, if we want to express the extracellular enzymes, E. coli is not the best choice. Rather than E. coli, Bacillus systems are better choices, since the bacteria is a high secretors and, thus, mainly preferred for the homologous expression of recombinant extracllular enzymes. For larger proteins and those need translational modification, yeast and filamentous fungi are good choices. However, compared to yeast, the relatively less understanding of the basic knowledge about fungi still hinders the development of the fungal host. Yeast can be grown rapidly to high density, and the level of product expression can be regulated by simple manipulation of the medium (Motta et al. 2013). We (BPPT team) have isolated, identified, and characterized an alkalothermophilic xylanase producer from local hot spring (Ulfah et al. 2011). A native alkalothermophilic xylanase have been produced from this bacterial strain and characterized. We designated this bacterial strain Bacillus halodurans CM1. The native xylanase of this bacterial strain and the recombinant xylanase from E. coli have been produced and applied in deinking process, and proven to increase the brightness and whiteness of the paper (Helianti et al. 2014a). Currently, we are still establishing this native xylanase production in pilot scale using corncobs and fish flour as the main medium component (Helianti et al. 2015). Since the Bacillus halodurans CM1 is thermophilic, its fermentation is conducted at 50 °C, which, although reduces contamination, need higher energy for fermentation. Therefore, the cloning and expression into more economically feasible microbial host must be considered. Previously, we have cloned and expressed family 11 xylanase from Bacillus subtilis AQ1 in both E. coli and B. subtilis DB104 (Helianti et al. 2010; Helianti et al. 2016). The high level expression of this gene in these bacterial host seemed regulated constitutively by the promoter. At present, we have isolated and cloned an alkalotermophilic xylanase gene from the B. halodurans CM1 in three microbial hosts, namely E. coli, Bacillus subtilis, and Pichia pastoris. This alkalothermophilic xylanase is family 10 glycosyl hydrolase and the expression is induced greatly by the presence of xylan. We found the expression of this gene in E. coli was very low, therefore we we continue the cloning and expression procedure into Bacillus and yeast Pichia pastoris (not published yet). Expression via plasmid in Bacillus subtilis gave higher extracellular alkalothermophilic xylanase. Expression of the gene in Pichia pastoris gave the highest activity, however, the production time was longer (table 4). In this Pichia system, the xylanase productivity was induced by methanol not xylan since the xylanase gene was integrated in alcohol oxidase locus. These recombinant xylanases are produced in lab scale, and still need further bioprocess engineering before continuing into pilot production. We also cloned the cellulase gene from Bacillus licheniformis F11 in E. coli and Bacillus megaterium. The cellulase gene expressed well both in E. coli and Bacillus megaterium. The characteristics of the enzyme was good, however, the level of the intrinsic activity must be increased for pulp and paper process application (Helianti et al. 2014b). The synthetic gene encoding of Thermomyces lanuginosus lipase has also been cloned and expressed in E. coli and Bacillus (Haniyya et al. 2016). The lipase gene expresion was very faint as we expected, as these prokaryotic bacteria were not the the proper choice for eukaryotic lipase gene expression. Therefore, we continued to clone and express of the gene in Pichia pastoris, and now still on progress. Based on our experience in producing (recombinant) microbial enzymes we can conclude that, the wild type bacterial strain must have excellent characters to be used in large scale enzymes production.

To find this kind of strain is not easy, and it took several years to isolate the best one. Hence, recombinan DNA technology must be applied to obtain more feasible condition for enzyme production. The choice of microbial host and the finding the most suitable promoter for the gene expression are the keys to achieve good level of recombinant enzymes production.

Table 4 Comparison of alkalothermophilic xylanase, lipase, and cellulase gene expression in E.coli, Bacillus subtilis DB104, and Pichia pastoris in our laboratory

Host Expression Time of production Actvity Recombinan xylanase Low, extracellular and E.coli Via plasmid 24 h intracellular Bacillus subtilis Via plasmid 24 h Good, extracellular Better than in Bacillus, Integrated into DNA Pichia pastoris 5 days extracellular chromosom

Recombinant lipase E.coli Via plasmid 24 h Low Bacillus subtilis Via plasmid 24 h Low Integrated into DNA Pichia pastoris Under development Under development chromosom Recombinant cellulase Low, intracellular and E.coli Via plasmid 24 h extracellular Bacillus subtilis Via plasmid 24 h Moderate, extracellular

References

1. Bajpai P. 2012. Biotechnology for pulp and paper processing. Springer US, Boston, MA; 2012. 2. BPPT.2006. Kajian prospek pasar enzim-enzim industri. 3. Haniyya. 2016. Karakterisasi produk gen sintetik lipase Thermomyces lanuginosus yang diekspresikan oleh Bacillus subtilis DB104 rekombinan yang mengandung pSKE194-lip (skripsi, Universitas Indonesia). 4. Helianti I, Nurhayati N, Ulfah M, Wahyuntari B, Setyahadi S. 2010. High level of constitutive expression of endoxylanase gene from newly isolated Bacillus subtilis strain AQ1 cloned in Escherichia coli. J Biomed Biotechnol. http:// dx.doi.org/10.1155/2010/980567. 5. Helianti Ia, Ulfah M, Wahyuntari B, Nurhayati N, Wahjono E, Vitianingrum DF. 2014. Properties of Native and Recombinant Thermoalkalophilic Xylanase(s) from Bacillus halodurans CM1, and Application of the Enzymes in Waste Paper Deinking Process. The 1st ASEAN Microbial Biotechnology Conference 2014 (AMBC2014), Bangkok, 19-21 Februari 2014. 6. Helianti Ib, Ulfah M, Nurhayati N, Mulyawati L. 2014. Cloning, sequencing,and expression of the gene encoding a family 9 cellulase from Bacillus licheniformis F11 in Escherichia coli and Bacillus megaterium, and characterization of the recombinant enzymes. Microbiol Indones 8(4): 147-160. Doi DOI: 10.5454/mi.8.4.2. 7. Helianti I, Ulfah M, Nurhayati N, Wahyuntari B, Nurhasanah A, Suhendar D, Wahjono E. 2015. Proses produksi xilanase yang bersifat tahan panas dan tahan basa untuk diaplikasikan pada industri kertas. Paten terdaftar Oktober 2015. 8. Helianti I, Ulfah M, Nurhayati N, Finalissari AK, Wardhani AK. 2016. Production of Xylanase by Recombinant Bacillus subtilis DB104 Cultivated in Agro-Industrial Waste Medium. Hayati “Journal of Life Science” (accepted).

9. Kenealy WR, Jeffries TW. 2003. Enzyme processes for pulp and paper: A Review of Recent Developments. US Government work. 10. Motta FL, Andrade CCP, Santana MHA. 2013. A review of xylanase production by the fermentation of xylan: classification, , characterization and applications. Intech: 251e75. http://dx.doi. org/10.5772/53544. 11. Sunna A, Antranikian G. 1997. Xylanolytic enzymes from fungi and bacteria. Critical Reviews in Biotechnology 1997;17: 39–67. 12. Ulfah M, Helianti I, Wahyuntari B, Nurhayati N. 2011. Characterization of a new thermoalkalophilic xylanase-producing bacterial strain isolated from Cimanggu Hot Spring, West Java, Indonesia. Microbiol Indones 5(3): 139-143. doi: 10.5454/mi.5.3.7. 13. Upadhyay P, Shrivastava R, Agrawa PK. 2016. Bioprospecting and biotechnological applications of fungal laccase. 3 Biotech. 6(1): 15. 14. Viikari L, Kantelinen A, Sundquist J, Linko M. 1994. Xylanases in bleaching: From an idea to the industry. FEMS Microbiology Reviews 13: 335–350. 15. Virk AP, Sharma P, Capalash N. 2012. Use of laccase in pulp and paper industry. Biotechnol Prog. 2012 Jan-Feb;28(1):21-32. doi: 10.1002/btpr.727. Epub 2011 Oct 19.

THE MANUFACTURE OF BAMBOO FIBRE COMPOSITE

Theresia Mutiaa1, Hendro Risdiantob, Susi Sugestyb, Teddy Kardiansyahb, Henggar Hardianib aCenter for Textile, Ministry of Industry Jl. Ahmad Yani, Bandung, Indonesia bCenter for Pulp and Paper, Ministry of Industry Jl. Raya Dayeuhkolot 132, Bandung, Indonesia [email protected]

ABSTRACT

Fiber and bamboo pulp have not been used optimally as a substitute for wood in wood manufacture industry, whereas bamboo planting period is much shorter. Therefore, study of three bamboo species from West Java, namely Gigantochloa apus (Tali bamboo), Gigantochloa pseudoarundinacea (Temen bamboo) and Bambusa vulgaris v. green (Haur bamboo) have been conducted as raw material for composite. The objective of this study was to manufacture bamboo composite for sound absorber material which is expected can be used as a fiberboard too, using bamboo fiber and pulp from selected bamboo. Bamboo cooking chemicals for G. apus require the least, so it was chosen to make pulp by Kraft cooking process and to get its fiber by soda cooking process, than be made for composite. The composite was made with Hot Press Machine at a pressure of 60 kg/cm2, using epoxy resin and bamboo fibers or pulp with a certain ratio. From the test results was known that composite of bamboo fiber and pulp at 5000 Hz (reference frequency) can reduce noise 28% and 77% consecutively, so it can be used as sound absorber material (ISO 11654:1997). The quality of bamboo fiber composite was higher than bamboo pulp composite and at 2500 Hz can reduce noise up to 97%. Furthermore, bamboo fiber composite also comply with the physical properties of the applicable standards as fiberboard (SNI 01 – 4449 - 2006).

Keywords : bamboo fiber, bamboo pulp, fiberboard, natural fiber, sound absorber composite

Introduction

Manufactured wood (plywood, chipboard and fiberboard) is all wood derived products are made in factories by binding fibers, particles with an adhesive to form a composite material [1, 2 in 3]. Fiberboard is classified by types of raw materials, production methods and density, but the best way to classify is based on density [4 in 5]. Manufactured wood made of wood (fiber) and plastic primarily used in outdoor use such as park bench, deck boats and can also be used for indoor use, such as furniture, sound absorber materials, automotive purposes, etc. [6, 7]. The advantage of manufactured wood compared with natural wood is consistent and uniform shape, not rotten and cannot be eaten by insects, does not absorb water and does not require periodic painting. Nowadays, wood products having problems, because the availability of raw material is limited [8]. This causes inequality between the availability of wood production with the needs of national timber. One solution to overcome this problem, i.e. by utilizing materials containing lignocellulose as wood substitute in the manufacture of composite boards [9]. There are many choices for alternative raw materials and available in large quantities, such as bamboo of various types (species). Bamboo fibers is a long fiber with shorter planting period (3 - 5 years) compared to wood (8 – 20 years) [10, 11]. In addition, bamboo produces cellulose per hectare 2 - 6 times greater than pine and increased biomass per day is higher (10 - 30 %) than wood (2.5%) [12]. The content of cellulose in bamboo is also quite high, between 40 % - 54 % [13 in 14]. Bamboo is widely used as home building materials, household appliances, paper pulp, composites, and others [15, 16]. Composite is a material formed from a combination of two or more different components, for example, resin/plastic and reinforcing materials such as fibers/webbing or other [17, 18, 19, 20 in 21]. Plastics are widely used for composite products, because it has advantages compared with other materials, are easily molded, lightweight, and inexpensive [22 in 23 ]. Fibers function in the composite is to strengthen the © 2016 Published by Center for Pulp and Paper through 2nd REPTech 155 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 product, so the product will be strong and sturdy [6, 9, 14, 21]. Besides it can reduce the use of resin and synthetic fibers [15]. In an effort to get the appropriate raw materials, various materials have been used for composites, but up to this moment, bamboo fiber or bamboo pulp have not been optimally used as a substitute for synthetic fibers, and other materials, such as glass, plastic, metal or other conventional materials; which is used to make composite for various products, such as fiberboard or sound absorber material. In addition, composite bamboo fiber, as well as composites from natural fibers are expected to have better characteristics, i.e. easily available, cheaper, lighter, environmentally friendly and can reduce the use of synthetic fibers and resins. Therefore, study has been done on three types of bamboo plants that are endemic in West Java, namely Tali bamboo (G. apus), Temen bamboo (G. pseudoarundinacea) and Haur bamboo (B. vulgaris v. Green) in order to know the characteristics of pulp and bamboo fiber that can be used as composite raw material. This initial study focused on getting the method of pulp and fiber processes of some species of bamboo and then selected types of bamboo that use minimal chemicals. The objective of this study was to manufacture bamboo composite for sound absorber material which is expected can be used as a fiberboard too, using bamboo fiber and pulp from selected bamboo.

Materials and Method

Raw Materials and Chemicals

The raw material used come from three types of bamboo plants that are endemic in West Java, namely Tali bamboo (G. apus), Temen bamboo (G. pseudoarundinacea) and Haur bamboo (B. vulgaris v. Green)

Equipment

Wood chipper, glassware, Rotary Digester, Mechanical Softening & Brushing Machine, Hot Press Machine.

Method

Pulping Process

Bamboo was cut into small pieces (chip) by wood chipper, then made into pulp by Kraft process (with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours with various concentrations of active alkali and sulfidity, and followed by 2 times of refining process) and soda process for selected bamboo (with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours with caustic soda 12%, and followed by 2 times of refining process).

Decomposition Bamboo Fiber

For getting unravel fiber bamboo of pieces of bamboo (for selected bamboo), the bamboo is cut along approximately 25 cm and then digested to remove most lignin by soda process (caustic soda 12%), with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours, then combed and leveled through Mechanical Softening and Brushing equipment. Composite Making

In this study, the process of making composites was performed by epoxy resin matrix. Natural fibers as reinforcement composites used in this study were pulp and bamboo fiber from selected bamboo. The composite was made using epoxy resin and pulp or fibers with a certain ratio with Hot Press Machine at a pressure of 60 kg/cm2. 156 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Testing

Bamboo a. Bamboo fiber morphology b. Chemical components analysis • The water content, in accordance with SNI 08-7070-2005, Determination of the moisture content of pulp and wood by heating in oven method • Levels of ash and silicate levels, in accordance with ISO 776: 2010, Pulp- determination of acid insoluble ash • Lignin, in accordance with SNI 0492-2008, Pulp and wood – Determination of lignin – Klaxon method • Pentose, in accordance with SNI 14-1304-1989, Determination of pentose content in wood pulp • Extractive (Extract Alcohol-Benzene), in accordance with SNI 14-1032-1989, Determination of extractive (alcohol-benzene extract) in wood and pulp • Hollocellulose, in accordance with SNI 01-1303-1989, Determination of holo cellulose in wood • Alpha Cellulose, in accordance with SNI 0444:2009, Determination of alpha, beta and gamma cellulose • Solubility in cold water and hot and cold water, according to SNI 01-1305-1989, Determination of wood solubility in cold water and hot water c. Microstructure analysis (SEM) d. Functional groups analysis (FTIR Spectroscopy)

Composite a. Microstructure analysis ( SEM ) b. Functional groups analysis (FTIR Spectroscopy) c. Sound absorption coefficient determination [24]

Results and Discussion

Raw Material

Fiber Dimension

Fiber dimension of these bamboo fibers can be seen at Table 1.a., while fiber dimension of seven wood species as a comparison, can be seen at in Table 1.b. [25].

Table 1.a. Dimension of Bamboo Fiber

Species of bamboo Parameter Haur Tali Temen Fiber length, mm 3.24 3.14 3.76 Outer diameter, µm 20.32 25.62 27.58 Inner diameter, µm 11.13 13.71 15.43 Wall thickness , µm 4.60 5.96 6.08

Fiber dimension is one of the important properties of raw materials that can be used as the basis for selecting raw materials for the production of pulp and paper. From Table 1.a. and Table 1.b. [25], known that the length of the bamboo fiber is generally above 3 millimeters and higher than wood fiber. According to the classification IAWA, bamboo fiber including to a long fiber grade that is at least 1.6 mm, maximum 4.4 mm and an average of 2.7 mm [26].

Table 1.b. Fiber Dimension of Seven Wood Species [26]

Fiber Fiber Lumen Fiber wall No. Species length diameter diameter thickness (µ) (µm) (µm) (µm) 1. Anthocephalus cadamba (jabon) 1.561 23.956 2.788 18.380 2. Octomeles sumatraa (binuang) 1.427 27.058 1.976 23.108 3. Macaranga hypoleuca (mahang putih) 1.455 36.822 2.277 32.267 4. Macaranga pruinosa (mahang keriting) 1.607 33.810 3.071 27.667 5. Macaranga tanarius (setutup) 1.207 20.164 2.627 14.909 6. Macaranga conifera (Bodi) 1.053 21.515 2.591 16.333 7. Macaranga gigantea (sekubung) 1.598 26.344 2.363 18.039

From previous studies known that the longer the wood fibers, the pulp produced will have high strength [26, 27]. This is due to the long fibers provide a wider field of contiguity and better webbing between one fiber to another, which allows more occur hydrogen bonds between the fibers. Furthermore, long-fiber pulp is more difficult to pass the filter, so it is easily washable. Fiber length affects certain properties of pulp and paper, including tear resistance, tensile strength and folding endurance. Haur bamboo fiber diameter is smaller than Temen and Tali bamboo. Similarly, lumen diameter of Haur bamboo is smaller than Temen and Tali bamboo. Haur bamboo fiber wall thickness is thinner than the Tali dan Haur bamboo. From Table 1.a. and Table 1.b. it’s known that the wall thickness of bamboo fibers are higher than wood fibers, but the inner diameter are smaller. Thin-walled fiber will more easily be flattened, resulting in pulp and paper sheet denser and better bursting strength compared to thick- walled fibers. Instead, thick-walled fibers produce sheet that has high tear strength, but low bursting strength. To obtain bursting strength and high tear, thick-walled fibers need to be mixed with long and thin-walled fibers [26, 28].

Chemical Components

Chemical components of bamboo fiber can be seen at Figure 1.

80 3.5 70 3 60 2.5 Lignin Ash content 50 2 Pentosan 40 1.5 Extractive Alpha cellulose 30 1 Hollocellulose 20 0.5 10 0 0 Tali Temen Haur Tali Temen Haur

Figure 1. Chemical Components of Bamboo Fiber

There are two major chemical components in wood, i.e. lignin (18 – 35)% and carbohydrate (65– 75)% (comprises of 40 to 50% cellulose and 25 to 35% hemicelluloses), and minor amounts of extraneous materials (usually 4– 10%), mostly in the form of organic extractives and inorganic minerals (ash) [29]. From the chemical components analysis of the fiber (Figure 1.) is known that the fiber used in this study contains alpha cellulose, hemicellulose and lignin of about 44% - 53%, 21% - 23% and 21% - 23% respectively. Lignin and extractives contain of tali bamboo relatively lower than temen and haur bamboo. As for the contents of cellulose, temen bamboo is the highest, while the lowest is haur bamboo. Therefore it is necessary for cooking by using caustic soda solution to reduce/eliminate the content of

158 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 these substances, especially lignin so that the surface roughness of fiber increased and fiber has better adhesion with the matrix resin, because it is so critical in composite manufacture [30]. Compare to wood fibers, bamboo contains lignocelluloses whose levels are relatively equal and can be used as an alternative raw material for particleboard or fiberboard [9], but as wood fiber also contains extractive substances, hemicellulose and other impurities [31, 32]. These substances can hinder the adhesive to react with cellulose, especially extractive substances which affect the consumption of adhesive and durability of fiber board. In addition extractive materials that evaporate can cause blowing or delaminating at the compression process [2 in 3]. From Figures 1 and the results of evaluation of fiber dimension is known that the three types of bamboo potential to produce good pulp [28, 33].

Bamboo Pulp

In this study, the cooking process is done with Kraft process by varying the concentration of active alkali and sulfidity, in order to determine the influence of the process variation to the Kappa number and yield of bamboo pulp. From the preliminary study found that variations condition of cooking process for Tali bamboo will generate Kappa numbers smaller than the Temen and Haur bamboo. This might be due to the levels of lignin and extractives of Tali bamboo is the lowest. It found that the total yield of Temen bamboo is relatively higher compared to Tali and Haur bamboo. This might be due to alpha cellulose content of Temen bamboo is the highest. In the manufacture of composites, lignin in natural fibers as reinforcement is necessary, because of its nature as an adhesive, so that the fibers do not easily break or has a lower tensile strength. Therefore, the experiment was continued to obtain pulp with Kappa number of about 30 (lignin content + 5% ), using different concentration of alkali active and sulfidity, based on the results of the cooking at preliminary study. The results of the test are presented in Figure 2.

60 25

20 45 15 Kappa Number Fiber length (mm) 30 Total Yied (%) 10 Diameter ( μm )

Fines (%) 15 5

0 0 Tali Temen Haur Tali Temen Haur

Figure 2a. Cooking Results to Get Kappa Number Figure 2b. Pulp Morphologi at Kappa 30 Number 30

5 90

4 Ash content (%) 60 3 Extractive (%) Pentosan (%) Lignin (%) 2 Alpha cellulose (%) 30 1

0 0 Tali Temen Haur Tali Temen Haur

Figure 2c. Pulp Chemical Components at Kappa Figure 2d. Pulp Chemical Components at Number 30 Kappa Number 30

From the previous research knew that to produce bamboo pulp with a certain lignin content or have a certain Kappa number, it is necessary to use active alkali and sulfidity with different concentrations. Furthermore, from the test result knew that to produce pulp with a lignin content of about 5% or have a Kappa number of about 30, it is necessary to use active alkali and sulfidity with different concentrations. Cooking of Tali, Temen and Haur bamboo require active alkali and sulfidity consecutive ie, 16% and 25%, 18% and 25% and 22% and 32%. Thus it is known that Tali bamboo requires the lowest chemicals concentration, while Temen bamboo and especially Haur bamboo require chemicals that are relatively higher. This is due to the levels of lignin and extractives of Tali bamboo is the lowest. The use of chemicals is higher on haur bamboo caused by several factors, including ash, extractive and lignin content. From Figure 2. it is known that the cooking conditions as above will produce pulp with Kappa Number and total yield at range between 30.43% - 32.71% and 44.13% - 53.82%. Note also that the value of Tali bamboo pulp relatively better than the two other bamboo. All the pulp has fiber length between 2 mm - 2.3 mm, diameter of 18.9 μm - 20.8 μm and fines between 5.1% - 6.65%, while the lignin content of about 4.21% - 4.89%; alpha cellulose 83.86% - 84.82%; and hemicellulose between 14.07 % - 15.59%. Cooking Tali bamboo requires the lowest chemicals, so the it was chosen to be the raw material for reinforcing composites by mixing with a resin.

Characteristics of Fiber and Bamboo Pulp {Tali Bamboo (G. apus)}

Fiber and bamboo pulp characteristics after cooking are presented in Figure 3, while the microstructure test results of pulp and bamboo fiber by SEM analysis are presented in Figure4 . From Figure 3 known that the levels of lignin, ash and extractive of bamboo pulp from Kraft Process is smaller than bamboo fiber, whereas higher levels of cellulose. As has been described above, that it is caused by the cooking process for bamboo fiber using lower caustic soda concentration than pulp cooking by Kraft process, so that lignin, ash and extractive in the fibers can not be degraded/dissolved entirely. It is known also, that the fiber length is about (2 - 4.5) mm, and fiber from soda cooking process is longer than pulp, especially than pulp from Kraft cooking process. It may be caused by the concentration of chemicals in Kraft cooking process is higher than the soda cooking process, thus it can partially degrade cellulose fibers. From the test results it is known that the water content of fiber and pulp is still below 10%, so it is expected does not affect the quality of the composite; because the optimum water content in the manufacture of composites is about 10 % - 14 % (if it is too high, then the flexural rigidity and internal bonding strength of the particle board will decrease) [9]. From Figure 4. can be seen that the microstructure of specimen material at a vertical and horizontal position, the material making up the specimen pulp in a vertical position seem their air cavities between the fibers in the pulp, while the bamboo fiber specimen at the position appears more compact than pulp.

Lignin, % Moisture content, % Hemi cellulose Alpha cellulose Ash content Extractive Fiber length, mm 90 15 75 5 60 4 12

% 45 3 9 % 30 2 6 15 1 3 0 0 0 1 2 3 1 2 3 1 2 3 1. Fiber 2 Pulp (Soda) 1. Fibre 2 Pulp (Soda) 3. Pulp (Kraft) 1. Fiber 2. Pulp (Soda) 3. Pulp (Kraft) 3. Pulp (Kraft)

Figure 3. Pulp and Fiber Characteristics of Tali Bamboo (after cooking)

Vertical position Horizontal position Vertical position Horizontal position Bamboo pulp Bamboo fiber (after cooking)

Figure 4. Micro Structure of Pulp and Fiber Tali Bamboo (SEM, 500 X)

Bamboo Composite

Characteristic

As described in the method, the manufacture of composites made with variation of pulp or fiber fraction of the resin fraction (epoxy) at certain condition. From the literature it is known to obtain optimal composite manufacturing condition and from preliminary experiments results known that the optimal ratio for pulp or bamboo fiber and epoxy matrix is about 1 : 1.5. The characteristic ofthe resulting composites are presented in Table 2.

Table 2. Characteristic of Bamboo Fiber and Pulp (Kraft Process) Composite

Bamboo Parameter Pulp Fiber Thicness, cm 0.95 2.20 Volume, cm3 7.01 16.18 Volume/weight, m3/g 0.78 1.46 Specific gravity, g/cm3 1.27 0.69

From Table 2 it is known that volume and thickness of bamboo fiber composites are larger, but lighter than the bamboo pulp composite. On bamboo fiber composites, interfacial bonding with the matrix resin is less perfect than composite bamboo pulp, because the content of alpha cellulose is relatively lower (Figure 3), so that the resin portion accumulates and polymerizes on the surface of the fiber, causing the composite is much thicker. Therefore, the volume of bamboo fiber composite is larger, although the pulp or bamboo fibers and resins used have the same weight component. Volume of bamboo fiber composite is greater, then the porosity becomes greater as well. Porosity causes the air trapped in the composite (void). The void can be caused by uneven pressure, resin which evaporates, the air trapped in the resin during the mixing, or mixing is not homogeneous.

Sample and Composite Microstructures

Sample and the microstructures of composite are presented in Figure 5 and 6. From Figure 5, visually known that bamboo fiber composite looks denser and darker than the bamboo pulp composite. Besides, from Figure 6, can be seen that there are two components forming composites, i.e. epoxy resin and fiber or bamboo pulp which in this case serves as a composite reinforcement. From that figure are visible also the pores or the presence of air cavities (voids) between the fiber or pulp. The voids are the air trapped in the composite. Voids in the composite material can be caused by uneven pressure, resin which evaporates, and the air trapped in the resin at the time of uneven agitation/mixing. Through these pores the incoming sound waves vibrate the air molecules in the pores, so that the composite can function as a sound absorber material. Besides that, the bamboo fiber composite specimens looks more compact than pulp composite, which will affect to the strength of the composite [34, 35].

Figure 5. Composite of Bamboo Fiber (left) and Bamboo Pulp (right)

Bamboo Fiber Bamboo Pulp Bamboo Fiber Bamboo Pulp Figure 6. Microstructure of Composite (SEM, 15 and 350 times magnification)

Functional Groups Analysis

Bamboo fiber is a cellulose fiber, and its chemical composition contains mostly alpha cellulose [30 in 6]. Cellulose chain is a crystalline structure that is supported by the covalent bonds between the chemical elements. The hydrogen groups on epoxy resin polymer binds to the active group on the cellulose, i.e.

-OH group and the CH2OH forming hydrogen bonds. The longer the chain of the cellulose molecules, the chemical bond with the polymer resin will be many more, so that the composite will be more solid. In addition, macro porous and micro porous areas will be filled by chemical bonds. The results of functional groups analysis is presented in Figure 7 and 8.

Bamboo Fiber

Cellulose consists of the elements C, H and O, which forms the molecular formula (C6H10O5)n. The molecular bond is a very strong hydrogen bonding. The functional group of the cellulose chain is a hydroxyl group (-OH), and these groups can interact with one another with a group -O, -N, and -S, forming hydrogen bonds. The hydroxyl group causes the cellulose surface is hydrophilic. Cellulose chain has a -H group at both ends and the tip –C1 have reducing properties. Cellulose chain structure is stabilized by strong hydrogen bonds along the chain. Chemically, cellulose is a polysaccharide compound with a high molecular weight, regular structure which is a linear polymer consisting of repeat units of b- D – glucopyranose. Characteristics of cellulose appear among others, the crystalline and amorphous structures and the formation of micro-fibrils, which eventually became cellulose fibers. The FTIR spectra of bamboo fiber is presented in Figure 8.a, while the cellulose absorption wave numbers presented in Table 3. [36]. From FTIR spectra of bamboo fiber, it is known that these fibers are cellulose, indicated bythe peak at wave number 3417 cm-1 and 2900 cm-1, which showed a group -OH and -CH. Absorption at wave number 1600 cm-1 is a carbonyl group of the lignin. Bond C = C aromatic symmetrical stretching absorption detected at wave number 1506 cm-1. The absorption at wave number 1429 cm-1 indicate the presence of asymmetric bending CH- group. Group - CH is also indicated in the absorption wave number 1375 cm-1. Nonsymmetrical bond in phase ring detected at absorption wave number 1111 cm-1. In addition, C-O group detected at wave number 1056 cm-1.

Table 3. FTIR Spectra of Cellulose

Wave number(cm-1) Bond stretching 669 OH out of phase bending 899 Nonsymmetrical out-phase ring 1040 C – O 1070 skeletal vibration C – O 1108 nonsymmetrical in phase ring 1159 Nonsymmetrical bridge C – O – C 1374 CH Bending 1420 CH2 symmetric Bending

Epoxy Resin

Epoxy resin (ethylene oxide) is a thermosetting resin which are widely used as adhesives, coatings, and matrices in polymer composites, because of low viscosity, has good insulation properties of the end product even at high temperatures and resistant to heat and chemicals. There are two main groups, namely glycidyl epoxies and non - glycidyl epoxies resin (aliphatic epoxy). The absence of aromatic rings in the epoxy aliphatic cause a decrease in viscosity and resistant to UV rays, making it suitable for outdoor applications. The most common epoxy monomer groups are diglycidyl ether of biphenyl A (DGEBA) and 3,4 – epoxy cyclohexyl - 3’4’ - epoxy cyclohexane carboxylate (ECC) [37], as presented in Figure 7. Characterization of epoxy involves more locations oxyren ribbon ring. There are lots of epoxy resin with a different structure, different degrees of polymerization and others. IR spectroscopy can be used to characterize the properties of epoxy and Figure 7.b. shows the FTIR spectra for HDGEBA and DGEBA epoxy. The results of FTIR analysis for the epoxy resin used in this study is shown in Figure 8.b. From this FTIR analysis, it appears that the uptake for the FTIR spectra similar to DGEBA epoxy.

Figure 7.a. Epoxy Structure, (a) DGEBA, (b) ECC Figure 7.b. FTIR Spectra of HDGEBA and DGEBA Epoxy

Bamboo Fiber Composite

The reaction between epoxy and hydroxyl groups is the reaction of an acid or base catalysis; but the whole of research in the field of wood is a base catalysis, i.e.

Wood – OH + R – CH (–O–) CH2 à Wood –O–CH2–CH(OH) –R [37]

a. Bamboo fiber b. Epoxy c. Composite x : Wave number (cm-1) and y : Transmittance (%) Figure 8. FTIR Spectra of Bamboo Fiber, Epoxy and Composite

Figure 8.c is an FTIR analysis of the test results of bamboo fiber/epoxy composite. By comparing the picture to Figure 10.a. and 10.b. (FTIR analysis of bamboo fiber and epoxy), it is known that the FTIR spectra of the composite is a combination of the spectra of bamboo fiber and epoxy, which is indicated by the peak at the same wave number.

Sound Absorption Coefficient

Standard human auditory response to the sound of the audio frequency is at range of about 20 - 20,000 Hz. Sound generally consists of many frequencies, namely low, middle, and medium frequency components. Standard frequency that can be chosen as an important representative in the environment acoustic was 125 , 250, 500, 1000, 2000, and 4000 Hz or 128 , 256 , 512 , 1024, 2048, and 4096 Hz. The sound absorber is a material that can absorb sound energy from a sound source [17, 38, 39, 40, 41]. To determine the ability of composite results of this study to absorb sound, then be tested using Impedance Tube at a frequency of 1000 Hz - 6300 Hz [24], as shown in Figure 9. Furthermore, Figure 10. shows sound absorption coeficient of bamboo fiber and pulp (Kraft Process) composites compare to wood and wall. From Figure 9 it is known that the absorption coefficient of bamboo pulp composites tend to rise along with rising frequency, i.e. up to 3150 Hz - 5000 Hz , then decreases; whereas for bamboo fiber composites tend to rise along with rising frequency, ie to 2500 Hz, then decreases. It found that the bamboo fiber composites provide the largest absorption coefficient in the frequency range between 3150 Hz - 4000 Hz, which is 0.83 to 0.80; while absorption coefficient of bamboo pulp composite in the same frequency range is lower, i.e. 0. 29. From the test results of the sound absorption coefficient obtained an average coefficient of absorption at the standard frequency (1000 Hz - 4000 Hz ) and high frequency (5000 Hz - 6300 Hz). It is known that composites with bamboo fiber reinforcement on standards frequency provide sound absorption coefficient is relatively high with maximum condition α = 0.97 at a frequency of 2500 Hz (frequency range based on the ability of the sound system or speakers commonly used is up to 2800 Hz). As well at the high frequency, composite of bamboo fiber and pulp provide maximum conditions with α = 0.77 and 0.28 at the frequency of 5000 Hz . Thus the composite have met the minimum standard sound absorption coefficients, i.e. α = 0.25 the reference frequency (5000 Hz) based on ISO 1 654: 1997 [17]. Bamboo fiber composite is much thicker, so the volume of that composite is larger than bamboo pulp composite (Table 2). Therefore, the porosity becomes greater as well. Porosity causes the air trapped in the composite (void), and the amount of the void volume indicates that the porosity of bamboo fiber composites is greater than bamboo pulp composites, so that the absorption coefficient of the composite is higher. In addition for a porous material, sound absorption capability depends on the volume and thickness, the greater the volume and the thicker the material, the higher the sound absorption

coefficients, so that the composite of bamboo fiber, in both standard and high - frequency has a suitable sound absorbers more than bamboo pulp composites. From the literature it is known that the sound absorption coefficient of glasswool on sound frequency between 250 Hz and 2000 Hz on average is between 0.4 to 0.8 (thickness 15 mm to 100 mm); while the coefficient of sound absorption on wood, tile and wall at the sound frequency between 125 Hz to with 4000 Hz , the average row between 0.06 to 0.15 ; 0.4 to 0.8; and 0.3 to 0.7 [42, 43, 44]. Therefore known that sound absorption coefficient (α) of bamboo fiber composites, with a thickness of about 22 mm is relatively the same as glass wool at 2000 Hz, but when compared to the sound absorption coefficient of the wood and the wall (Figure 10), it can be said that the composite has a higher ability to absorb a sound, especially bamboo fiber composites.

Bamboo fiber Bamboo pulp (Kraft process) 1 Wood Wall 0,8 0.8

0,6 0.6

alpha 0,4 0.4

0,2 alpha

0 0.2 1000 1250 1600 2000 2500 3150 4000 5000 6300 Frequency, Hz 0 Bamboo fiber Bamboo pulp (Kraft process) 1000 2000 3000 Frequency, Hz

Figure 10.Sound Absorption Coeficient (α) of Bamboo Figure 9. Sound Absorption Coeficient (α) of Bamboo Fiber and Pulp (Kraft Process) Composites Compare to Fiber and Pulp (Kraft Process) Composites Wood and Wall

In the future it’s expected that bamboo fiber and bamboo pulp are used as a substitute for wood in manufactured wood industry as sound absorber material; because can comply with the applicable standards, i.e. α = 0.25 at the reference frequency (5000 Hz), based on ISO 11 654: 1997 [17]. However, the quality of bamboo fiber composite is higher than bamboo pulp composite, because it can reduce noise up to 77% at the reference frequency (5000 Hz) and 97% at 2500 Hz. Furthermore, from the subsequent research [45] was known that the bamboo fiber composite has high densities, while the physical properties (water content, water absorption, changes in the length and thickness, tensile firmness and flexural rigidity) can conply with the applicable standards for fiberboard (High Density Fiber Board T2 45 Type) [46]. In addition, as a composite, the value - added products derived from bamboo will increase and can reduce the consumption of wood, which the availability is limited. Moreover, it can reduce the use of synthetic fibers and resin, making it more environmentally friendly.

Conclusion

Composite of bamboo fiber and pulp can be used as sound absorber material, because can compy with the minimum standard sound absorption coefficients {α = 0.25 the reference frequency (5000 Hz)}. The quality of bamboo fiber composite is higher than bamboo pulp composite, because it can reduce noise up to 77% at the reference frequency (5000 Hz) and 97% at 2500 Hz. So this study has been successfully to manufacture composite for sound absorber material from bamboo fiber, and obtained the environmentally friendly products, because it can reduce the use of synthetic fibers and resins. Additionally, the physical properties of bamboo fiber composite can comply with the applicable standards as fiberboard (SNI 01 – 4449 - 2006).

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A REVIEW: RECENT RESEARCH IN PAPER PACKAGING FOR FOOD

Qanytah a b, Khaswar Syamsu c, Farah Fahma c, Gustan Pari d 1 a Graduate Program of Agroindustrial Technology, Bogor Agricultural University b Indonesian Center for Agricultural Postharvest Research and Development, Bogor c Department of Agro-industrial Technology, Bogor Agricultural University d Forest Products Research and Development Center, Ministry of Environment and Forestry [email protected]

ABSTRACT

Packaging is an important application of paper materials. About 50% of all paper produced is used for packaging. In the recent years, many new food-packaging concepts have been introduce. The recent effort is transformed paper into varies and excellent modern packaging choice in food industry. There are a range of innovations that can enhance performance with regard to consumers’ valued product characteristics and packaging attributes. These include security packaging, smart or intelligent packaging, and active packaging. The main objective of this paper is to provide a review on recent research in paper packaging for food. The material using for paper packaging, method and system for incorporation materials, structure design of paper packaging and its application have discussed and compared.

Keywords: intelligent paper, packaging, material, structure design

Introduction

Packaging is an important application of paper materials. Packaging has many important functions, such as protection, convenience, reusability, production reality, and carrying printed information and graphics. Packaging protected the packaged foods from hazards such as contamination in the distribution environment, facilitating transportation and storing of foods. About 50% of all paper produced is used for packaging (Datamonitor, 2008). The largest share of global packaging was accounted by paper and board packaging, with sales of $165 billion in 2003, equating to 39% of the market (World Packaging Organisation, 2008). Paper and paperboard also represents the largest proportion by weight of packaging material used. The food and beverage industry is the largest user of packaging generally. Paper has reported to be the most widely used material in packaging applications owing to its characteristics of printability, recyclability, and biodegradability. Currently, paper and paperboard production is increasing every year, packaging paper and paperboard account for more than 50% of total paper and paperboard. Per capita paper consumption has become an international standard measure of a country’s economic development and an important symbol of social civilization. Unfortunately, paper properties such as hygroscopic and porous, its barrier properties against water-vapor, gases and aromas are poor. Paper packaging materials made from cellulose fibers produced from virgin wood, non-wood fiber, agricultural residue, recycled fiber, or combination of those materials, which usually have the biodegradable and recyclable characteristics. The paper often combined with polymers such as plastics and aluminum or metal foils to form laminates for packaging of specific products and for their good barriers properties. Unfortunately, this obtained material losses its biodegradation and recyclability characteristics due to the addition of that component. In the recent years, many new food-packaging concepts have been introduced. The recent effort of the cellulose industry to improve its products has transformed paper into varies and excellent modern packaging choice in food industry. However, paper are permeable to gases, moisture, oils and fats. Consequently, these materials often require treatments such as coatings and laminations. These processes may involve specific materials, plastics and barrier materials, such as aluminum foil, to extend their packaging applications and the shelf life of the products they contain. The development of paper packaging need to be encouraged by improvements in technical performance and influenced

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 169 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 by a number of factors. There are a range of innovations that can enhance performance with regard to consumers’ valued product characteristics and packaging attributes. These include security packaging, smart or intelligent packaging, and active packaging. Security packaging can be achieved by using a paper with a characteristic feature, such as the presence of special fibers, and similar techniques are the subject of continuous development. Intelligent or smart packaging refers to packaging that senses and informs. Development of intelligent/smart packaging is being accelerated by rapid innovation in enabling technologies such as nano-coatings and nano-codes. The main objective of this paper is to provide a review on recent research in paper packaging for food. The material using for paper packaging, method and system for incorporation materials, structure design of paper packaging and its application have discussed and compared.

Trend in Food Packaging

The packaging sector is an important global industry, representing about 2% of the Gross National Product (GNP) of the developed countries. Modern food packaging function not only have a passive role in protecting and marketing the product. It has an active role in processing, preservation and in retaining the safety and quality of foods throughout the distribution chain. Indeed, packaging development has changed the preservation methods used for food products. Food packaging developed strongly during recent years, mainly due to increased demands on product safety, shelf-life extension, cost-efficiency, environmental issues, and consumer convenience. Packaging technologies have been evolve. They have great commercial potential to ensure the quality and safety of food with fewer or no additives and preservatives, thus reducing food wastage, food poisoning and allergic reactions. Intelligent packaging can also monitor product quality and trace a product’s history through the critical points in the food supply chain. An intelligent product quality control system thus enables more efficient production, higher product quality and a reduced number of complaints from retailers and consumers. Intelligent packaging will also give the food industry the means to carry out in-house quality control required by food regulators. The food packaging evolution shown in Figure 1.

Figure 1. Active food packaging systems, concepts and application matrix (Imran et al., 2010).

The definition of active and intelligent packaging according to theActipak project are: 1. Active packaging changes the condition of the packed food to extend shelf life or to improve safety or sensory properties, while maintaining the quality of the packaged food; 2. Intelligent packaging systems monitor the condition of packaged foods to give information about the quality of the packaged food during transport and storage.

According to Figure 1, active packaging techniques for preservation and improving quality and safety of foods can be divided into three categories; absorbers (i.e. scavengers), releasing systems, and other systems. Absorbing (scavenging) systems remove undesired compounds such as oxygen, carbon dioxide, ethylene, excessive water, taints and other specific compounds. Releasing systems actively add or emit compounds to the packaged food or into the head-space of the package such as carbon dioxide, antioxidants, and preservatives. Other systems may have miscellaneous tasks, such as self-heating, self- cooling, and anti microbial/preservation. The system to produce active packaging include: edible films, addition of sachet, incorporation/dispersion, and coating.

Material for Paper Packaging

The majority of paper packaging produced and used in many countries today is made from wood fiber. The ingredients for papermaking include hardwood and/or softwood, wood chips, sawmill residues, water, and chemicals. The rapidly growing demand for paper in the last few years not been fully met by the substitute products introduced lately. The possible solution to this problem is the use of non-wood plants include agricultural waste, which was contain high amounts of cellulose fiber, which could be potentially use to produce paper. Some substantial non-wood plant fibers including agricultural fibers such as: a) seed fibers (cotton, cotton linter); bast fibers (flax, hemps, kenaf, jute, rosella); c) leaf fibers (pineapple, sisal, abaca, banana stalk, switch grass, elephant grass); d) agricultural residues (rice straw, corn cobs and stalks, oil palm fruit bunch, coconut coir) e) bamboo; f) others (bacterial cellulose, algae). Non-wood plant fibers that are currently used or potential to use in the paper industry and its characteristic as shown in Table 1. On the other hand, paper packaging often combined with polymers or metal foils to form laminates for packaging of specific products. Polymers or metal also become problems with increasing pressure to reduce waste going to landfill. In the last decade, environmental issues have become increasingly important, triggering the use of bio-based packaging materials as an alternative to materials produced from nonrenewable resources. Such bio-based packaging materials include naturally occurring proteins, cellulose, starches and other polysaccharides Starch is a kind of important natural polymer with lots of usages and has been widely used in many industry fields such as papermaking. One of newly modified product from starch is starch polyacrylamide graft copolymer. It application in paper packaging material have been extensively reviewed by Liu et al. (2011). Liu et al (2011) studied the preparation of starch polyacrylamide copolymer and its effects on treating wastewater and paper performance. The increasing of dosage of synthesized St-PAM copolymer resulted the basic weight increased, but decreased the tear strength and the fold endurance. The tensile strength and breaking length increased firstly and then decreased. Regarding these research results, there is no points that explained the future application of the paper packaging produced in this study. The use of natural fibers instead of traditional reinforcement materials provides several advantages. Scientist have been developing a number of novel materials based on cellulose nanofibers including nano composite. The properties of cellulosic fibers influenced by many factors like internal fiber structure, chemical composition, micro-fibril angle and cell dimensions which differ from different parts ofa plant as well as from different plants. The mechanical properties of natural fibers also depend on their cellulose type because each type of cellulose has its own crystalline organization, which can determine the mechanical properties. As the properties of natural fiber will also influenced the suitable methods to isolate nanocellulose, a further research was needed. There are some advantage of nanocellulose material such as natural and renewable, biodegradable, reduced carbon footprint, recyclable, reusable, compostable, biocompatible, have high surface area, high

Table 1. Non-wood plant fiber and its characteristic

Non wood plant No Characteristic material Average fiber length is 1.7 mm (0.8-2.8 mm), and width is 0.02 mm (0.01- Sugarcane bagasse 0.034 mm). Fibers are thick wall (Ilvessalo-Pfaffli, 1995). It can used to make 1. (Saccharum printing & writing paper, bristol board, tissue paper, glassine, greaseproof officinarum) paper, duplex and triplex paper.

Average fiber length of 1.5 mm (0.5-2.9 mm) and width of 0.018 mm (0.014- Corn stalks (Zea 2. 0.024 mm). Typical fibers are narrow, thick wall and have blunt or pointed ends mays) [4] (Ilvessalo Pfaffli, 1995).

Cotton stalks Average fiber length of 0.6-0.8 mm and an average fiber diameter of 0.02-0.03 3. (Goossypium) mm (Ilvessalo Pfaffli, 1995).

It has high silica content. Average fiber length is 1.4 mm and width is 0.009 Rice straw (Oryza mm (Ilvessalo-Pfaffli, 1995). It can used to make printing and writing paper, 4. sativa) glassine and greaseproof paper, duplex and triplex paper, corrugating medium, straw board and “B” grade wrapping paper.

Average length of 1.4 mm (0.4-3.2 mm) and width of 0.015 mm (0.08-0.034 mm). Typically, fibers are narrow, thick-wall and have a blunt or pointed ends Wheat straw (Ilvessalo-Pfaffli, 1995). 5. (Triticum aestivum) It can be used to make printing and writing paper, glassine and greaseproof paper, duplex and triplex paper, corrugating medium, strawboard and “B” grade wrapping paper

It grows from sea level to the snow line, fastest growing plants available for pulp. Fiber length varies from species to species. In some species it also varies Bamboo from bottom to top and, in some cases, it varies with intermodal length. Average 6. (Dendrocalamus fiber length is 2.7-4.0 mm and diameter is 0.015 mm (Ilvessalo-Pfaffli, 1995). strictus) It can used to make printing and writing paper, bristol board, duplex and triplex paper, linerboard, wrapping and bag paper, multiwall sack and newsprint substitute.

Under normal conditions, the first harvest completed from 18-24 months after Abaca (Manila planting. Subsequent harvests completed at 3-4 month intervals. Average fiber 7. hemp) (Musa length of 6.0 mm and it has an average fiber diameter of 0.024 mm. It can used textilis) to make specialty papers like superfine, lightweight, bond, ledger, currency and security paper, tea bags, filters, linerboards, wrapping and paper bag.

The fiber length of milling runs is approximately 3-7 mm; first cuts are 5-7 mm 8. Cotton linters and second cuts are 3-5 mm. The average fiber diameter is 0.03 mm. It can used to make high-grade bond ledger book and writing paper. 9. Sago pith fiber The fiber length2,03 - 2,37 mm 10. Water-hyacinth Cellulose content about 65.41% (Joedodibroto, 1983).

172 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 strength and modulus, light weight, dimensional stability, thermal stability, high optical transparency, high thermal conductivity, and low oxygen permeability. Regarding its suitable character as pulp and paper production, some study conduct to investigate its application on pulp and paper. Mihranyan et al. (2012) produce nanocellulose from Cladophora alga mixing with Tween-80 coating to produce paper composite. It results showed that mechanical properties of Polimer Polypyrrole/PPy– Nanocellulose paper was improved, and nanocellulose fiber coating with PPy increased bigger pore and resulted composite with open surface area, and lighter paper. Composite electroactivity character depends on its total porosity. Kajanto and Kosonen (2012) research on paper production using 2 types of nanocellulose (type AS or KS) with dosage level of nanocellulose (0%, 1%) resulting the increasing of paper mechanical properties, even in low dosssage. The 2 types of nanocellulose give the same result. Taipale et al. (2010) study on addition of 6% nanosellulose in paper where the pulp raw material have long fiber and bleach. It showed that paper Scott Bond (+ 55%) increased and tensile index increased (up to + 15 Nm/g). The consumer demands for safe, high quality and extended shelf life foods, driving for innovation in food packaging. As result of this requirement, there were the development idea of new concept that some active interactions between the package and the product may have positive effects. Antimicrobial packaging (AM) technology is an innovative concept to extend the lag phase and/or reduce the growth rate of the microorganisms. The development of antimicrobial films that Quintero et al. (2012) study was the active antimicrobial substances in directly incorporated in the packaging material. Antimicrobial substances incorporated into packaging materials can control contamination by reducing the growth rate and maximum growth population and/or extending the lag phase of the target microorganism or by inactivating microorganisms by contact. According to Quintero et al. (2012), the preparation method of the films produced a huge effect on the antimicrobial and other properties of the films. Optical properties changed depending on the organoclay and the antimicrobial compound used. The mechanical properties of the nanocomposites improved when Cloisite 30B used. Thermal degradation temperature and transition temperature decreased in films containing organoclay and antimicrobial compounds because of a plasticizer effect. The antimicrobial showed strong inhibitor effects against S.cerevisiae, L.innocua and E.coli, obtaining a reduction in the antimicrobial activity of at least 2.0 log CFU/mL.

Methods and System for Incorporation Material

Paper is often associated with other materials, such as plastic material and aluminum, for their good barrier properties that can be advantageously combine with paper stiffness. Paper could coated with some polymer such as ethyl vinyl alcohol (EVOH) or polyolefins, but the addition of synthetic polymer layer caused the paper packaging loses its biodegradation and recyclability characteristics. Naturally, renewable biopolymers have been the focus of much research in recent years because of their potential use as edible and biodegradable films and barrier coating for food packaging. Such biodegradable coatings have the potential to replace current synthetic paper coatings. Agriculturally derived alternatives to synthetic paper coatings provide an opportunity to strengthen the agricultural economy and reduce importation of petroleum and its derivatives. Active packaging has become one of the major areas of research in food packaging. Antimicrobial packaging is of great importance because it could be a potential alternatives solution to extend the shelf life and assure the innocuousness and preservation of food products. Some research of different types of component and biopolymers investigated as paper coating material presented in Table 2. Natural coating have been the focus of much research in recent years due to their potential use as edible and biodegradable films and coating for food packaging. Tabel 2 showed that natural component can be used as barrier coating on paper packaging materials, such as Activated Carbon, Polystyrene/ Silver, Wheat Gluten, Active paraffin formulation with essential oil, and Chitosan. The different coating material have different character and different purposes.

Activated Carbon is used as ethylene absorbers for produce packaging. Ethylene absorbers can be

Table 2. Different types of component and biopolymers as paper coating material

No Coating Paper Material Results Refference

1. Activated Carbon Rice Straw • Increase in the AC content implies Sothornvit (AC) using a decrease in thickness, increase the and Sampoom glucomannan smoothness and grammage puang (2012) (GC) as binder • Increase in the AC content decrease tensile index, burst index, folding endurance, and tear index • The potential application of AC-rice straw papers would be as a separate bag or wrapper or as a laminate inside carton to extend the shelf life of agricultural products that are sensitive to ethylene (banana, mango, tomato, and apple) 2. Polystyrene (PS) Waste paper from • Paper dipping in PS solution and silver Nassar and nanocomposite newsprint paper nanoparticles improve tensile strength. Youssef extracted from When silver nanoparticles first added to (2012) rice straw then the pulp during making paper sheet before dissolved by coating by PS, tensile strength decreased. toluene solvent. • Silver nanoparticles would be the The solution then promising applicants as new antimicrobial added by silver nano particle.

3. Wheat Gluten Paper made from • UTP displayed a higher level of protein Guillaume et (WG) bleached pulp penetration than TP al (2010) with 2 kinds of • The coating of paper by WG solution treatment: resulted in a significant reduction in oil • Surface coated wettability with calcium • Coating paper with WG reduced in water carbonate and vapor permeability starch (TP) • WG coating led to significant gas • Untreated permeability paper (UTP) 4. Active paraffin Kraft Paper • Active paper manufactured with essential Lafuente et al formulation con- oil has activity against A. alternate, where (2010) taining essential solid paraffin coating incorporate with oil from: cinna- active agent have better activity than mon leaf oil, bark paraffin emulsion. cinnamon oil, • Active paraffin-based paper packaging is oregano, and clove very useful approach to extend the cherry tomato shelf life. 5. Chitosan Kraft Paper Coated chitosan on paper matrix have a good Pichavant et fat barrier that could be a potential process to al (2005) develop paper-based packaging material to pet food application. 6. Microfibrillated Base paper • Tensile index and burst index increased Li et al (2014) Cellulose (MFC) firstly and then decreased with the increase with different of NaClO amount. amount of NaClO • The folding endurance of coated paper and air permeability was increased by increasing the NaClO.

174 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 particularly useful in produce warehouses where ethylene gas, a natural plant growth regulator, can rapidly accumulate. During storage, high concentrations of ethylene can lead to accelerating respiration rate and subsequent senescence. Use of ethylene absorbers can significantly extend shelf life, thereby reducing waste in the supply chain and deriving economic benefit for suppliers and retailers. These absorbers can be embedded into paper bags or corrugated fiberboard transit packaging used for produce storage and transport. They can also be incorporated as sachets into retail packs of produce to extend produce shelf life for the benefit of the retailer. Packaging containing anti-microbial coatings and treatments are increasingly being used to extend the shelf life of a wide range of perishable food. The preservative effect of the agent results in significant reductions in food spoilage and infections caused by microbial growth. According to those studies, we understand that antimicrobial component has specific activity against specific microbial. There are increasing concerns globally about non-biodegradable plastics, or plastics-based packaging pollution. Some research also have been extensively reviewed regarding the properties, technology, functionalities, and potential uses of biopolymer films and coatings which done by Kester and Fennema (1986), Anker (1996), Guilbert et al. (1997), Krochta (2002), and Khwaldia et al. (2004).

Paper Packaging Application and Design

Companies continually seek to deliver a better user experience to differentiate their brands and enhance consumer appeal, minimize costs and enhance supply chain performance, and improve the environmental credentials of their products and services. A main challenge for industry is to optimize design of the packaging system. This involves striving to create packaging that balanced in terms of providing product protection and preservation, is cost-effective, creates maximum consumer appeal and at the same time takes into account environmental responsibility (Nampak, 2010). Considering the contrast between the need of standardization and the request of diversification, today materials and technologies represent an opportunity for new structural and functional solution, they have the power of suggestion for packaging designers. The work done followed this evolution of design: products are becoming dynamic, smart, interactive, and emotional. The project focused on the functionality of packaging and future steps will be addressed to the communication and emotional aspects of the developed packaging. Companies design and purchase packaging made by different materials that ensure given performance and that made using the most varied techniques, according to the type of contents to be preserved, protected and transported. It has considered that packaging has its present form by way of continuously following the evolutionary paths of the materials and packaging technologies. The materials have evolved considerably, modifying the possibility of use and broadening their own range of applications to new segments, inventing new solutions, stealing secrets from other sectors and thus transferring them from one material to another in a continuous shift of technological progress. Many package style and structural designs are possible and often specific. Structure design of paper packaging plays an important role in designing packaging. The biodegradable and recyclable characteristics of paper material make paper packaging have very broad prospects of development. Structure design of package containers based on the fundamental functions such as protection, convenience, and reusability and production reality. In modem package design, the structure has become a bond between new materials and new technologies; it is an important part to make packages as close as possible to perfect. This paper review the research of Xiao and Huang (2010) on structure design of paper packaging. In structuring design for papers packaging there are some consideration such as the cost of paper packaging material, the efficiency paper needs, the paper and packaging utilization. Xiao and Huang (2010) described the principle in designing package such as: a) functional principles, b) adaptation principles, c) humanity principles, d) ecological principles, e) simple principles, f) aesthetic principles, and g) innovation principles. In this research, of Xiao and Huang (2010) analyzed the example of inkstone packaging using the computation methods on stacking capacity, the material using for paper production, and the molding process. The invention and development of new instruments and new technologies on the subsystem will

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 175 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 resulting a variety of advanced equipment and instruments used in design and production of packaging structure. The automation present challenges in paper packaging and its subsequent reconfiguration to meet the variety of packs. Dai and Caldwell (2010) studied the principle of multi station-based operation, reconfiguration and the corresponding technologies for paper and paperboard packaging and developed robotic tooling and its mechanisms. Through motion analysis, the reconfiguration of paper and board packaging will understood. Then, the robotic finger designed as reconfigurable tools for folding and tucking the paper material. Using robotic tooling for reconfiguration in paper-and-board packaging the package design for both fast food and confectionary market ware produced. Dai and Caldwell (2010) stated that the technology on configurability and adaptability of finger-type tooling mechanisms can be used to meet the demand of variety and innovation in food handling and packaging and leads to free or rapid changeover in the technology. Convenience features, which enhance pack usability, particularly with regard to ergonomics and open ability, represent another important trend. With the ageing population in many advanced economies, packaging designs that facilitate quick identification of product, provide good legibility, offer ease of opening and use will gain favor with discriminating older consumers. Pack usability is also important to many of today’s younger consumers who may have higher expectations regarding convenience. Consumers are less tolerant of brands that do not fully consider their needs and, increasingly, will switch to brands that do. Ease of opening of food packaging is a high priority for many consumers, particularly the elderly, the visually impaired and those with disabling conditions such as arthritis, who often have difficulty opening cans, bottles and plastic packs. Paper and paperboard-based packaging with ease-of-tear open or pull-open features may offer convenient solutions. For example, paper-based composite cans and retortable paperboard-based cartons with their easy pack opening features present an alternative option to the metal can. An example of a disruptive innovation offering ease of opening and reseal ability of packages for dried product is the Zipbox® (w ww.zipbox.net) from the US. This is a liner less paperboard carton combined with a heat seal attached flexible film header containing a Double Zip zipper profile. Zipbox ® claims other benefits for consumers include product freshness and improved ease of pouring. Smart or intelligent packaging can serve to monitor quality and prevent product wastage, thereby saving resources. Conventional ‘use by’ and ‘best before’ date labelling are relatively crude measures, which often result in products being thrown away unnecessarily. It is expected that labels incorporating devices – such as combined temperature and time indicators (TTIs), freshness indicators, chillness and produce ripeness indicators – for use with paper and paperboard packaging, will become a widespread feature within the retail marketplace. These labels are sensitive to changes in the internal condition of the pack. It will effect a visible color change to alert or inform the consumer or user. This technique also be employed to indicate package tampering. For example, tamper proof labels are available for hermetically sealed gas flushed or vacuum packs which, if exposed to the atmosphere, either though accident or malicious intent, can effect an oxidative color change of the label. Paper-based active packaging containing anti-microbial coatings and treatments are increasingly being used to extend the shelf life of a wide range of perishable food, including baby food, fresh produce, cheese, snacks and cold meats. For example, odorless and taste neutral antimicrobial agents can be released onto the exposed surfaces of food where microbial contamination is most likely to occur. The preservative effect of the agent results in significant reductions in food spoilage and infections caused by microbial growth. Recent development is paper coated with silver nanoparticles (killer paper) which, reportedly, could provide an alternative to common food preservation methods such as radiation, heat treatment and low temperature storage. There are also packages where a paperboard-based complete side wall is heat sealed during injection molding to a plastic framework of minimal weight. A similar package has been developed where the sidewall with a glued side seam is attached to the rim such that it is easily removed from the plastic frame for separate recycling after the container has been used. There is a wide range of tamper evident packaging features available for paper and paperboard packaging, ranging from simple traditional paper security seals to holographic labels and other more sophisticated designs and technologies. Security packaging is an ongoing development area and there are several possible methods to achieve anti-

176 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 counterfeit and tamper evidence. This can be achieved by using a paper or paperboard with a characteristic feature, such as the presence of special fibers, and similar techniques are the subject of continuous development. Other methods are achieved by using special printing techniques, such as using inks that are only readable under specific lighting or using colors that change under specific conditions, for example UV light identifiable QR codes and printed security marks, together with forensic and track- and-trace systems.

Conclusion

Natural component used as barrier coating on paper packaging materials, such as Activated Carbon, Polystyrene/Silver, Wheat Gluten, Active paraffin formulation with essential oil, and Chitosan. The different coating materials have different character and different purposes. In structuring design for papers packaging there are some consideration such as the cost of paper packaging material, the efficiency paper needs, the paper and packaging utilization. The automation present challenges in paper packaging and its subsequent reconfiguration to meet the variety of packs.

Refferences

1. Anker M. 1996. Edible and biodegradable films and coatings for food packaging: a literature review. Goteborg, Sweden: SIC. 2. Barlow CY and Morgan DC. 2013. Polymer film packaging for food: An environmental assessment. Resources, Conservation and Recycling 78 (2013) 74-80. 3. Dai JS and Caldwell DG. 2010. Origami-based robotic paper-and-board packaging for food industry. Trends in Food Science & Technology 21 (2010) 153-157. 4. Datamonitor. 2008. ‘Global Paper and Paperboard – Industry Profile’, June 2008. Available from: http://www.datamonitor.com/. [Accessed Februari 2016]. 5. Guillaume C, Pinte J, Gontard N, and Gastaldi E. 2010. Wheat gluten-coated papers for bio-based food packaging: Structure, surface and transfer properties. Food Research International 43 (2010) 1395-1401. 6. Guilbert S, Cuq B, Gontard N. 1997. Recent innovations in edible and/or biodegradable packaging materials. Food Additives Contam 14:741–51. 7. Imran M, Revol-Junelles AM, Martyn A, Tehrany EA, Jacquot M, Linder M, and Desobry SE. 2010. Active Food Packaging Evolution: Transformation from Micro- to Nanotechnology. Journal of Food Science and Nutrition, 50:9, 799-821. 8. Kajanto I and Kosonen M. 2012. The Potential Use Of Micro- And Nanofibrillated Cellulose As A Reinforcing Element In Paper. Journal of Science & Technology for Forest Products and Processes: VOL.2, NO.6, 2012 9. Kester JJ, Fennema OR. 1986. Edible films and coatings: a review. Food Technol. 40(12):47– 59 10. Khwaldia K, Perez C, Banon S, Desobry S, Hardy J. 2004. Milk proteins for edible films and coatings. Crit Rev Food Sci Nutr 44:239–51. 11. Khwaldia K, Tehrany EA, and Desobry S. 2010. Biopolymer coating on paper packaging materials. Comprehensive reviews in food science and food safety vol. 9, 2010, 82-91. 12. Krochta JM. 2002. Proteins as raw materials for films andcoatings:definitions,current status, and opportunities. In: Gennadios A, editor. Protein-based films and coatings. Boca Raton, Fla.; London; New York; Washington, D.C.: CRC Press. p 1–32. 13. Lafuente AR, Nerin C, and Battle R. 2010. Active paraffin-based paper packaging for extending the shelf life of cherry tomatoes. J.Agric.Food Chem. 2010, 58, 6780-6786. 14. Li L, Yunzhi C, Zhengjian Z. 2014. Preparation of the microfibrillated cellulose and its application in the food packaging paper. Applied Mechanics and Materials Vol 469 (2014) pp 87-90. 15. Liu QX, Xu WC, and Li JL. 2011. Preparation of starch polyacrylamide graft copolymer and its application in paper packaging material. Material Science Forum Vols. 663-665 (2011) pp 1268-1272. 16. Mihranyan A, Esmaeili M, Razaq A, Alexeichik D, Lindstrom T. 2012. Influence of the nanocellulose raw material characteristics on the electrochemical and mechanical properties of conductive paper

electrodes. J Mater Sci (2012) 47:4463–4472 DOI 10.1007/s10853-012-6305-6. 17. Nampak. 2010. ‘Sustainable Packaging, Annual Report 2010’, p. 46, sustainability report. Available from: http://www.nampak.com/DynamicData/AnnualReport/Current/ Sustainability%20report.pdf [Accessed October 2012]. 18. Nassar MA and Youssef AM. 2012. Mechanical and antibacterial properties of recycled carton paper coated by PS/Ag nanocomposites for packaging. Carbohydrate Polymers 89 (2012) 269-274. 19. Pichavant FH, Sebe G, Pardon P, and Coma V. 2005. Fat resistance properties of chitosan-based paper packaging for food applications. Carbohydrate Polymers 61 (2005) 259-265. 20. Quintero RI, Rodriguez F, Bruna J, Guarda A, and Galotto MJ. 2012. Cellulose acetate butyrate nanocomposites with antimicrobial properties for food packaging. Packaging Technology and Science (2012). 21. Sothornvit R and Sampoompuang C. 2012. Rice straw paper incorporated with activated carbon as an ethylene scavenger in a paper-making process. International Journal of Food Science and Technology 2012, 47, 511-517. 22. Taipale T, Osterberg M, Nykanen A, Ruokolainen J, and Laine J. “Effect of Microfibrillated Cellulose and Fines on the Drainage of Kraft Pulp Suspension and Paper Strength,” Cellulose 17(5):1005- 1020 (2010). 23. World Packaging Organisation. 2008. Market Statistics and Future Trends in Global Packaging, p. 11. Available from: h ttp://www.worldpackaging.org/publications/ documents/market- statistics.pdf. [Accessed Februari 2016]. 24. Xiao Y and Huang Y. 2010. Comparison of integrated and split design in structure design of paper package. DOI 978-1-4244-7974-0/10/$26.00 @2010 IEEE.

STUDY OF KINETICS AND THERMODYNAMICS ADSORPTION Cu2+ ION BY SYNTHETIC ZEOLITE FROM COAL FLY ASH

Ahmad Zakaria 1, Wittri Djasmasari, Henny Rochaeni, Yustinus Purwamargapratalaa 2 aAKA Bogor, Bogor 16154, Indonesia aPSTBM-BATAN, Tangerang Selatan, 15314, Indonesia [email protected] [email protected]

ABSTRACT

The aim of this research was to define the order of kinetics model and thermodynamic parameters such as free energy, entropy and enthalpy of adsorption process of metal ion Cu2+ by synthetic zeolite from coal fly ash and the effect of the presence of coexisting ion against of the efficiency of Cu2+adsorption. Experiment using synthetic zeolite as adsorbent and it was carried out at pH adsorbat, contact time and adsorbent concentration optimum that were obtained in the previous study. Kinetics experiment was performed at various contact time 5, 15, 30, 45, 60, 75 and 90 minutes while the thermodinamyc parameters studies was done at temperature 27, 32, 37 and 42 oC. The influence of coexisting ion Mn2+ and Pb2+ to the adsorption process was examined here. The kinetics data were evaluated using a pseudo first-order and a pseudo second-order Lagergren equation. The results revealed that the kinetic data correlated well with the pseudo second-order kinetics model. Thermodynamic studies indicated that the adsorption process was spontaneous and accompanied by an increase in entropy and decrease in Gibbs energy. The coexisting ions Pb(II) or Mn(II) decreased the adsorption capacity of synthetic zeolite in the Cu2+ adsorption, but increased the total adsorption capacity.

Keywords : Kinetics model, Synthetic zeolite, Coal fly ash, Coexisting Ions, Gibbs energy

Introduction

Industrial development in various countries also led to increased industrial pollution significantly, Hence the growing problem of industrial waste . This resulted in the treatment of industrial waste treatment into global topics. Heavy metals such as copper are examples of contaminants that have the potential to destroy the system of human physiology and other biological systems when passing tolerance level. Metals such as copper are produced by industrial metal plating, alloy, steel, dyes, electrical wiring, insecticides, pipelines, and paint (Sarkar et al., 2010). Therefore the government through Kep-51/ MENLH/10/1995 establishing effluent standards for industrial class 1 copper metal content of less than 2 mg/L and for the plating industry under 0.6 mg/L. The presence of Cu ions in industrial waste is usually accompanied by other heavy metal ions. In the plating industry wastes, heavy metal ions Cu is the fifth largest concentration after metals Fe, and Cr, Sn, and Zn, followed by the metal ions with smaller concentrations, namely Ni, Mn, Pb, Cd, and Ag (Venkatiswaran et al., 2007). Some treatment methods for treating heavy metal ions in industrial effluents have been reported in the literature (Sarkar et al., 2010, Gupta & Bhattacharayya 2008, Fan et al., 2008). Among these methods are neutralization, precipitation, ion exchange, biosorption and adsorption. For low metal ion concentration, the adsorption process is the recommended method for taking the metal ion. The process of adsorption involves intermolecular attractive forces, ion exchange, and chemical bonding. Synthetic zeolite derived from coal fly ash is one of the materials that can be used to adsorb heavy metal ions and has the ability to adsorb heavy metal ions is greater than the fly ash (Zakaria et al., 2012). Reaction of synthetic zeolite is similar to the condition of the earth’s crust. The synthesis is done by making the reactants into a gel and then placed in autoclave at temperature range 70oC-150oC. (Sutarno, 2009). Synthetic zeolite were used for the study came from the coal fly ash of power plant

Suralaya (Zakaria et al., 2011). The aim of this research was to define the order of kinetics model and thermodynamic parameters such as free energy, entropy and enthalpy of adsorption process of metal ion Cu2+ by synthetic zeolite from coal fly ash and the effect of the presence of coexisting ion agains of the efficiency of Cu2+ adsorption.

Materials and Methods

Materials and Equipment

The materials needed consist of test materials and chemicals. Test materials used are synthetic zeolite from coal fly ash, while chemicals used consisting of NaOH, HCl, H2SO4, CuSO4, MnCl2,,

Pb(NO3)2, (all quality materials from Merck). The tools used in this experiment are: Atomic Absorption Spectrophotometer, Water bath with temperature control, Oven, shaker, sieve size of 40 mesh, pH meter, balance of 0.1 mg accuracy, whatman filter paper 42, pipette,50 mL volumetric pipette, funnel, flask 50 mL and 100 mL glass and other tools.

Determination of Reaction Kinetics

This experiment was performed after optimization experiments has done. The results obtained experimental optimization of adsorbate pH 4 and adsorbent concentration at 50 mg /100 mL (The stages of this experiment has been carried out by Zakaria et al, 2012). The experiments were performed by varying the reaction time as the independent variable and the other two as variables remain. A number of 50 mL of adsorbate solution with a concentration of 80 mg/L (pH optimum) is added to the synthetic zeolite (optimum weight) in 100 mL erlenmeyer glass. Erlenmeyer glass then agitated with a shaker at 150 rpm for a 5, 15, 30, 45, 60, 75, and 90 minutes. Each variation of a certain time, the sample was filtered and the filtrate was measured using the AAS to determine the concentration of Cu (II) in solution. From these experiments it is known that reaction order information matches the adsorption system by looking at the value of the correlation coefficienton each order of reaction.

Determination of Thermodynamic Parameters

Thermodynamic parameters are determined by varying the temperature of the experiment, ie 27, 32, 37 and 42 oC and the other variables are constant. This experiment was done by a number of 50 mL of adsorbate solution (pH optimum) with a concentration of 80 mg/L added into 100 mL erlenmeyer glass already containing synthetic zeolite (optimum weights) and then agitated for the optimum time. After the sample filtered, and then the filtrate was measured using the AAS to determine the concentration of Cu (II) in solution.

Adsorption Experiment for Binary Metal Systems

This experiment performed binary adsorption system, in example by adding a number of metal ions Mn or Pb adsorbate in the solution of Cu (II). So it is known relationships adsorption capacity of Cu (II) with the presence of Mn or Pb metal ions in a solution of the system as well as comparison of the strength of the interaction of Mn2+ and Pb2+ on the adsorbent. Experiments done by making a solution of adsorbate containing 80 mg/L Cu (II), the combined concentration of 80 mg/L Cu (II) with 25 mg/L Pb (II), and the combined concentration of 80 mg/L Cu (II) with 25 mg/L Mn (II). Then the erlenmeyer shaken during the optimum time, then the sample was filtered and the filtrate was measured using the AAS.

Calculation

The amount of heavy metal adsorbed by adsorben fly ash was calculated using the following equation :

...... (1)

Co is the initial concentration (mgL-1), Ce is the final concentration in the solution phase equilibrium (mgL-1), Qe is adsorption capacity or the concentration of adsorbate on the adsorbent at equilibrium (mgg-1), m is adsorbent mass and V is volume of adsorbate.

Result and Discussion

Effect of Contact Time

Adsorption kinetics describes the solute retrieval speed by the adsorbent during the adsorption reaction time. This parameter is important because it determines the efficiency of the adsorption process. Effect of contact time on the adsorption capacity can be seen in Figure 1,. In the Figure 1, it can be seen the increasing adsorption capacity of the adsorbent aligned with the contact time and in the 75th minute equilibrium has occurred. The time needed for equilibrium depends once the adsorbate and the adsorbent used and the interaction of both. Gupta and Bhattacharyya (2008) have reported the equilibrium time of 180 minutes for adsorbates of Pb (II) and Ni (II) with kaolin adsorbent and montmorilonite.

Figure 1. Effect of contact time on the adsorption capacity of Cu2+

Increased speed of adsorption occurs at the beginning of the contact time, but after almost all sides actively interact with metal ions, the adsorption rate decreases. So there is no significant increase in the adsorption capacity as the active adsorbent was saturated, so the adsorption rate is only dependent on the migration of metal ions in the liquid phase to the surface of the complex adsorbent - adsorbate (Yu et al., 2000).

Figure 2. Relationship adsorption capacity versus contact time for 1st order kinetics

The first order kinetics equation models and second-order false done by plotting t against log (qe-qt) versus t and t/qt as Lagergren equation (Figure 2), so that the known value of the adsorption rate constant (k), the optimum adsorption capacity prediction (qe) and coefficient ditermination. In this experiment used adsorbate concentration of Cu2+ 80 mg.L-1.

Figure 3. Relationship adsorption capacity versus contact time for 2nd order kinetics.

Coefficientditermination for the pseudo first-order analysis is smaller than the second-order false. Predictive value of adsorption capacity compared to the experimental value of the optimum adsorption capacity have error reaches -70.5% (Table 1). So that the pseudo first-order kinetics equation is less suitable to be applied as a model for the adsorption kinetics of synthetic zeolite adsorbent. Therefore, continued evaluation using pseudo-second-order equation. Data results of the cofficient ditermination (R2) > 0.99 (figure 3 andTable 1), while the validity test error obtained adsorption capacity of synthetic zeolite is 1.91%. This suggests that the kinetic parameters of adsorbent satisfy pseudo second-order equation because it has a high degree of accuracy in predicting the optimum adsorption capacity experiments.

Table 1 Comparison of first-order rate constant and the pseudo second-order and predictions and experimental qe values

Pseudo second-order kinetics parameters C0 qe (mg/g) Adsorbent (mg % K1 qe 2 K2g/mg qe % 2 -1 experiment -1 R R L ) (minutes ) (cal) error mnts (cal) error Synthetic zeolite from 80 44.2 0.062 13.04 -70.5 0.9369 0.0130 45.04 1.91 0.9998 coal fly ash

Effect of Temperature

Adsorption of copper ions increases with increasing temperature of 300-315 K experiment (Figure 4). The increase in the adsorption capacity due to the higher temperatures that occur from activation of the active surface of the adsorbent, increased metal ion kinetic energy, and the formation of smaller metal ions due to the reduction of the effects of hydration, so that it may penetrate the deeper layers of pores (Fan et al., 2008)

Figure 4. Effect of temperature on the adsorption capacity (qe) of Cu2 + by synthetic zeolite at pH 4

Energy enthalpy ( H0) synthetic zeolite adsorption-adsorbate concentration of 80 mgL-1 was 62 KJ mol-1 (Table 2) are endothermic. Some studies have been reported of them by Fan et al. 2008 for the adsorbent and adsorbate Penicillium simplicissium Cd (II), Zn (II) and Pb (II), as well as Barnidele et al. (2010) with the Bulgarian zeolite and adsorbate Cu (II). In Table 2, the change in entropy of adsorption energies are all positive values. From these data it can be concluded that an increase in the degree of irregularity in the adsorbent-adsorbate system, so the metal ions adsorbed on the adsorbent are more disordered (Kubilay et al., 2007). This phenomenon in the adsorption system is very beneficial because it can increase the stability of the adsorbent-adsorbate complex.

Table 2 Thermodynamic parameters of adsorption of Cu2 + by coal fly ash

Thermodynamic parameters Adsorbat Temperature Adsorbent 0 0 0 Cu2+ (mg L-1) (oC) G H S (Kj mol-1) (Kj mol-1) (J mol-1) 27 -2.200 Synthetic 32 -3.270 80 zeolite 37 -4.340 42 -5.410 62 214

Value of the Gibbs free energy of adsorption systems is negative in all experimental temperature conditions (see Table 2). This proves the formation of spontaneous adsorption system. The calculation of the free energy at temperature of 27, 32, 37 and 42, the value of which tends to be negative, indicates that the spontaneous adsorption process at higher temperatures. The increase in temperature causes the adsorption process easier due to increased metal ion kinetic energy making it easier for the metal ion adsorbed on the pore deeper layers.

Figure 5. Plot Van’t Hoff adsorption of Cu2 + 80 mg L-1 by synthetic zeolite from coal fly ash.

Values of thermodynamic parameters of adsorption of Cu2 + by coal fly ash adsorbent, obtained from the calculation of the slope and intercept of linear equations and Van’t Hoff plot (Figure 5).

Effect of Co Ions

Heavy metal ions Mn and Pb is a metal ion that is often found in industrial effluents with metals Cu. The presence of these ions commonly found in industrial waste plating, iron, and steel. Therefore, please note the effect of co metal ions on the adsorption capacity of Cu (II). In this experiment, adsorbate Cu (II) is made from salt sulfate and applied to a binary system consisting of two types of ions in solution adsorbate, ie metal ions Cu2 + with Mn2 + and Cu2 + and Pb2 +. Efficiency and adsorption capacity of Cu2 + ions was influenced by Mn2 + and Pb2 +. The presence of these ions in a solution of copper adsorbate can decrease the efficiency and capacity of the copper adsorption. (Table 3). This is due to the competition between the metal ions of Cu, Mn and Pb in getting the site active adsorbent to adsorbent-adsorbate complexes formed.

Table 3 Effect of co ions on the adsorption efficiency of Cu2 + by zeolite synthetic adsorbent

Initial concentration Adsorption efficiency Adsorption capacity (mg g-1) Adsorbent (mg L-1) (%) Cu Pb Mn Cu Pb Mn Total Cu Pb Mn - 80 0 0 25.78 - 25.78 96.97 - - Zeolite 80 25 0 25.40 - 33.70 95.64 100 - synthetic 8.300 80 0 25 25.16 3.081 28.24 94.56 - 38.06 -

The presence of Pb or Mn ions with copper ions can simultaneously reduce the adsorption capacity of Cu (II) by synthetic zeolite adsorbent, but can improve overall adsorption capacity, so the benefit of heavy metal ion adsorption process. This phenomenon is due to a shift in the equilibrium towards the formation of adsorbent-adsorbate complex with increasing concentration of the adsorbate (Gufta & Bhattacharayya 2008). The mechanism of adsorption of metal ions was also due to the precipitation of metal hydroxides on the surface of the adsorbent (Hui et al., 2005). As supporting data, the value of Ksp -14 -16 -19 2 + (Mn (OH)2, Pb (OH)2 and Cu (OH)2 in a row is 4 x 10 , 3 x 10 , and 2 x 10 . So Pb is faster settles over Mn ions (II), thus the Pb ions adsorbed on the adsorbent surface is greater and causes increasing the efficiency of adsorption (Zakaria et al., 2014).

Conclusion

Adsorption kinetics is determined as the pseudo second-order. Adsorption reactions tend to be spontaneous and endothermic. The presence of Mn or Pb ions decreases the efficiency of adsorption of Cu2 + but increase the total capacity of adsorption.

Acknowledgement

The authors would like to thanks The Director Polytechnic of AKA Bogor.

References

1. Fan T, Liu Y, Feng B, Zeng G, Yang C, Zhou M, Zhou H, Tan Z, Wang X. 2008. Biosorption of cadmium(II), zinc(II), and lead(II) by penicillium simplicissium: Isoteherm, kinetics and thermodynamics. Journal of Hazardous Materials 160: 655-661 Gupta SS, Bhattacharayya GK. 2008. Immobilization of Pb(II), Cd(II), Ni(II) ions on kaolinite and montmorillonite surfaces from aqueos medium. Journal of Enviromental Management 87: 46-58. 2. Gupta SS, Bhattacharayya GK. 2008. Immobilization of Pb(II), Cd(II), Ni(II) ions on kaolinite and montmorillonite surfaces from aqueos medium. Journal of Enviromental Management 87: 46-58. 3. Hui KS, Chao CYH, Kot SC. 2005. Removal of mixed heavy metal ions in wastewater by zeolite 4A and residual products from recycled coal fly ash. Journal of Hazardous Materials B 127: 89-101. 4. Kubilay RS, Gurkan A, Savran T, Sahan. 2007. Removal of Cu(II), Zn(II) and Co(II) ions from aqueous solution by adsorption onto natural bentonite. Adsorption. 13:41-51. 5. Mazari Magazine. 2009. Abu terbang batubara sebagai adsorben. (terhubung berkala). http:// mazarimagazine.com/2009/06/ abu-terbang batubara-sebagai adsorben. (15 Februari 2009). 6. [MenLH] Menteri Negara dan Lingkungan Hidup. 1995. Keputusan Menteri Negara dan Lingkungan Hidup No.Kep-51/Menlh/10/1995 tentang Baku Mutu Limbah Cair Kegiatan Industri. 7. Sarkar B, Xi Y, Megharaj M, Krishnamurti GSR, Rajarathnam D, Naidu R. 2010. Remediation of hexavalent chromium through adsorption by bentonite based Arquad 2HT-75 organoclays. Journal of Hazardous Materials. 183: 87-97. 8. Sutarno. 2009. Sintesis, karakterisasi, dan aplikasi MCM-41. Di dalam: Aryanto Y, editor. Material canggih; Rekayasa material berbasis sumber daya alam silika-alumina. Kelompok Minat Kimia Material Universitas Gajah Mada. 2009. hlm 83-116. 9. Ventkatiswaran P, Vellaichanny S, Palanivelu K. 2007. Speciation of heavy metals in electroplating industry sludge and wastewater residue using inductively coupled plasma. International Journal Environ Sci. Tech. 4(4): 497-504. 10. Yu B, Zhang Y, Shukla A, Shukla SS, Dorris KL. 2000. The removal of heavy metal from aqueous solution by sawdust adsorption-removal of copper. Journal of Hazardous Materials B 80: 33-42. 11. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Yustinus Purwamargapratala. 2012. Adsorpsi Cu(II) Menggu-nakan Zeolit Sintetis dari Abu Terbang Batu Bara. Prosiding Pertemuan Ilmiah IPTEK BAHAN 2012. PT BIN-BATAN. 12. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Yustinus Purwamargapratala. 2011. Karakterisasi Zeolit Sintetis dari Abu terbang Batu Bara dengan Difraksi Sinar –X. Prosiding Seminar Nasional Hamburan Neutron dan sinar X ke-8 . PT BIN-BATAN 13. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Wittri Djasmasari. 2014. Study of Kinetics and Thermodynamics as well as The Effect of the Presence of Co Ions in Influencing adsorption Cu2+ ion by coal fly ash adsorbent. Proceeding ASEAN COSAT 2014. LIPI Press

SYNTHESIS Li4Ti5O12-Sn ANODE MATERIALS AS LITHIUM BATTERY WITH ULTRASONOMETRY

Yustinus Purwamargapratala a 1, Jadigia Ginting a 2, Mardianto b 3 a PSTBM-BATAN, Tangerang Selatan, 15314, Indonesia b University of Lampung, Lampung, Indonesia 1 [email protected] 2 [email protected] 3 [email protected]

ABSTRACT

Synthesis of Li4Ti5O12-Sn Anode Materials As Lithium Battery With Ultrasonometry. The research of synthesis Li4Ti5O12 has been realisized using ultrasonic method that was aimed to know the influence of the addition Sn to the conductivity and the materials structure of lithium titanate. Synthetic materials used were LiOH and TiO2, while as additives used Sn with percentages of 0, 5%, 10%, 15% and 20%. Lithium hydroxide, titanium dioxide, and Sn were mixed into the media aquabidest and stirred for two hours at a rate of 300 rpm. Then reacted with ultrasonic for two hours, filtered and washed with distilled water and then rinsed with acetone. Drying was carried out over night at room temperature, compacted with hydraulic press at a pressure of 4000 psi and pellets formed were sintered in the furnace at 800 °C for two hours. Characterization was performed using LCR meter to measure the conductivity of the material, X-ray diffraction (XRD) to determine the crystal structure, optical microscopy to determine the morphology of materials with SEM-EDS and to know the composition of the material. XRD characterization results showed that between five samples Li4Ti5O12 formed , the highest intensity at the q : o -6 angle 2 35,6 . Li4Ti5O12 have solid particles with the conductivity optimum 6.57658 x 10 S/cm with Sn addition of 5 %.

Keywords: Li4Ti5O12, anode, lithium batteries, ultrasonic

Introduction

Battery is a device that can convert the chemical energy as an active material with its electrical energy known by the electrochemical process in oxidation and reduction changement. The battery consists of three parts, namely the anode, cathode and electrolyte. The anode is defined as the electrode where the oxidation tacking place (negative electrode) and the cathode is the reduction positive electrode processing. Battery anodes used in lithium batteries are generally composed by graphite. The advantages of graphite which has high capacity and also has real limitations not useful for high discharge rates force to litiation form dendritic anode coating and susceptible to the occurrence of a short circuit in the battery and cause an explosive in terms of the safety. Therefore were formation other materials that have a high enough voltage difference against Li/Li and ensuring the formation of the phenomenon litiasion on the electrode surface [1]. One that has been useful is the LTO material developmet with is lithium titanate ceramic material.

Li4Ti5O12 are ceramic lithium-titanium oxide, better known as lithium titanate having spinel structure in a face-centered cubic in space groups . The main properties of the ceramic material is the ability of the structure not material that change the shape during a Li+ ion insertion. Kingo Ariyoshi et al [2], reported in their observation that very precision using synchroton XRD to measure the change in the crystal lattice that are very small, at the 0002 A and 0006 A discharge lattice shrinkage in subsequent discharge process. Lithium titanate is one of the most promizing anode material for lithium batteries despite having a lower specification capacity of graphite 175 mAhg-1 meanwhile graphite has a capacity of 372 mAhg-1

[3]. Lithium titanate (Li4Ti5O12, called LTO in battery industry) is a good anode material for applications

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 187 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 that have battery power capability and long life cycle. LTO superiority lies in its power density and chemical stability, but the battery LTO-based batteries have a higher voltage: 2.5 V compare to LiCoO2 [4] and 1.9 V compare to LFP [5]. Lower operating voltage brings significant advantages in terms of security. These batteries can also be recharged quickly. Data show that the battery can be safely charged at higher rate of 10o C, and can be charged in less than 10 minutes. LTO-based batteries also have operating temperature range wider and replenishment efficiencies exceeding 98%. Energy density is lower compared to other lithium ion batteries, but still higher than the lead-acid (accu) and NiCd batteries [6]. In various studies, some addition to simply synthesized with only LiOH and TiO either, many researchers are adding additives into lithium titananat. Various additives were added: chromium (Cr) [7], silicon (Si) [8], magnesium (Mg) [9], graphene [10], aluminum (Al) [11], and carbon (C) [12].

This research will be focused the synthesis Li4Ti5O12 with variations addition of tin (Sn) as an additive to find its effect to increase the conductivity and its material structures. This research is the development of Li4Ti5O12 research that has been done before[13]. Use of Sn and ultrasonometri process is expected to produce composite particles LTO-Sn with a homogeneous and increase the conductivity LTO. It is necessary to optimalise of the concentration of Sn added in to composite formation LTO-Sn.

Materials and Methods

Tools and Materials

The tools used in the study is a spatula, micro balance, measuring cups, glass beaker, magnetic stirrer hotplate, ultrasonic, vacuum filter, compacting, furnace, X-ray diffraction (XRD), impedance capasitance resistance (LCR) meter, optical microscopy and scanning microscope electron - energy dispersive spectrometer (SEM-EDS). While the materials used are aquabidest, lithium hydroxide, titanium dioxide, SnO and acetone.

Experimental Methods

Lithium hydroxide was mixed with 60 mL aquabidest and stirred for 30 minutes with a magnetic stirrer was then added titanium dioxide, stirred for 15 minutes and then added SnO, stirring was continued for 15 minutes. Addition of SnO varied to obtain various samples with Sn concentrations: 0%, 5%, 10%, 15% and 20% that. Samples formed suspension was treated by ultrasonic for 2 hours at a frequency of 50 Hz and then filtered using a vacuum filter and washed with acetone, powdering results were dried for 15 hours at room temperature. The powder samples was compacted with 4000 psi for 1 minute to form pellets. The fifth sample in the form of pellets sintered in a furnace at a temperature of 800 °C for two hours. Characterization is done by XRD (X-ray diffractometer) to determine the phase of the sample, the conductivity was measured with LCR meter and the morphological observation with an optical microscope and SEM- EDS (Scanning Electron Microscope Energy Dispersive Spectroscopy).

Results and Discussion

The results of the sample characterization using X-ray diffraction, is shown in Fig. 1. a-e, and analyzed by standard material Li4Ti5O12 for diffraction patterns of PCPDFWIN 79-0911. The results of the analysis by X-ray diffraction showed that the samples after ultrasonometri LiOH and TiO2 and continued with heat process can produce Li4Ti5O12. Ultrasonometry intended to produce a homogeneous particle distribution with a small grain size. It was very helpful in optimizing the calcination process. Fig. 1 shows that the addition of 5% Sn causes diffraction peaks appear at 2q = 17,36o which is a characteristic Sn peak. This means that the LTO-Sn composite formation can be done on the addition of 5% Sn. The addition of Sn exceed 10% can result a new phase at 2q : 18,37o; 35,60o; 43,27o; 62,85o;

82,33o and indicated as SnO. This shows that there is an excess of SnO which can no longer useful interact with Li4Ti5O12.

Fig 1. X-ray diffraction pattern of the sample with additives Li4Ti5O12-Sn: a.0 %Sn, b.5% Sn, c.10% Sn, d.15% Sn, and e.20% Sn.

Observations using optical microscopy showed the morphology of the distribution Sn in the sample. Sn particles in the sample with concentration of 5% Sn seemed to spread more homogeneous than samples with higher concentrations of Sn. This shows that the use of Sn to 5% effective as an additive. This is confirmed by the measurement results of EDS (energy dispersive spectrometer) in the range of 0-20 keV and counting rate of 2449 cps, as shown in Fig. 2, it appears the Sn peak.

Fig. 2. Results of EDS measurements of samples with Sn addition of 5%

SEM observation and the results shown in Fig. 3. Distribution Sn Li4Ti5O12 sample will affect the value of the ionic conductivity of the sample. More smoothed distribution of Sn on a material, the conductivity increases. This is because the ions will flow evenly throughout the surface of the material so that the conductivity of the material become better. Inversely unclear distribution of Sn in the material, then the value of the conductivity of the material will be decreases. This is because the ions will only flow through dots or lines formed in some parts of the sample and not entire of the sample traversed by the ions.

(a) (b) (c)

(d) (e)

Fig 3. Observation of morphology of samples SEM(a) 0% Sn (b) 5% Sn; (c) 10% Sn; (d) 15% Sn; (e) Sn 20%

LCR meter measurement results the sample Li4Ti5O12-Sn of Sn 0%, 5%, 10%, 15% and 20% obtained conductivity values as shown in Table 1.

Table 1. Values Li4Ti5O12 conductivity by percentage Sn

Sn conductivity F range No (%) (S/m) (Hz) 1. 0 2.6121 x 10-5 4000 – 8000 2. 5 6.57658 x 10-6 2000 – 6000 3. 10 3.31894 x 10-5 2000 – 6000 4. 15 3.03389 x 10-6 100 – 500 5. 20 8.41395 x 10-7 500 - 900

Conductivity value of Li4Ti5O12 fluctuation or changes indeterminate on each additional Sn. Optimum conductivity value is Li4Ti5O12 happened with the addition of Sn by 5% while the value of the lowest conductivity of Li4Ti5O12, is addition of 20% Sn. Value Li4Ti5O12 influenced by the distribution of Sn in the sample. More equitable distribution of Sn in the sample will give higher conductivity value will be higher. Nor vice versa, the uneven distribution of Sn in the sample, then making conductivity become lower as well. This can be observed that looking the distribution of Sn using optical microscopy showed the distribution of samples Li4Ti5O12-Sn good on the addition of 5% Sn.

Conclusion

We are successfully performed the synthesis and the characterization of Li4Ti5O12-Sn using LiOH, o TiO2 and Sn as additive with ultrasonometry techniques and sintering at a temperature of 800 C for two hours. XRD characterization results showed that from the five samples, formation of Li4Ti5O12 o phase takes place with the highest intensity at 35,60 . Li4Ti5O12 formed are solid particles with optimum conductivity value is 6.57658x10-6 S.cm-1 with 5% Sn addition.

Acknowledgement

The author would like to thank all those who have helped in this research, in particular to the Head of Advanced Materials Science And Technology.

References

1. Subhan, Achmad dan Bambang Prihandoko. “Pembuatan Komposit Anoda Li4Ti5O12 dan Soda Lime Silica.” Jurnal Ilmu Pengetahuan Dan Teknologi Telaah Volume 29. Pusat Penelitian Fisika LIPI: Serpong, Tangerang Selatan. 2011.

2. Kingo Ariyoshi, Ryoji Yamato, Tsutomu Ohzuku. “Zero-strain Insertion Mechanism of Li[Li1/3Ti5/3O4] for Advanced Lithium-Ion (Shuttlecock) Batteries”, Electrochimica Acta 51 (2005) 1125-1129. 2005.

3. Jin, Yun-Ho, et. al. “Facile Synthesis Of Nano Li4Ti5O12 For High Rate Li-Ion Battery Anodes.” A Springer Open Journal Of Nanoscale Research Letters. 2012. 4. Tian, B.B., H. F. Xiang., L. Zhang, Z. Li., H. H. Wang. “Niobium Doped Lithium Titanate As a High Rate Anode Material For Li-Ion Batteries”. Electrochim. Acta 55. 5453-5458. 2010. 5. Yang, S. B., X. L. Feng, K. Mullen. “Graphene-Base Titanium Nanosheets With High Surface Area For Fast Lithium Storage.” Sandwich Like. Adv. Mater 13. 3575-3579. 2011.

6. Priyono, Slamet dan Bambang Prihandoko. “Studi Awal Substitusi TiO2 Lokal Pada Sintesis Li4Ti5O12 Dengan Metode Metalurgi Serbuk.” Prosiding Simposium Nasional Inovasi dan Pembelajaran Sains 2015 (SNIPS 2015) Bandung. 2015. 7. Li, Song-Ying, et. al. “Electrochemical Properties Of Citric Acid-Assisted Combustion Synthesis

Of Li4Ti5O12 Adopting Cr By The Solid-State Reaction Process.” Ionics, DOI 10.1007/s11581-014- 1329-3. 2014

8. Chen, Chunhui, Richa Agrawal dan Chunlei Wang. “High Performance Li4Ti5O12/Si Composite Anodes For Li-Ion Batteries.” Journal Of Nanomaterials. Department of Mechanical and Materials Engineering, Florida International University, Miami. 2015 9. Shenouda, Atef Y. dan K. R. Murali. “Electrochemical Properties Of Doped Lithium Titanate Compounds And Their Performance in Lithium Rechargeable Batteries.” Journal Of Powder Source 176. 332-339. 2007.

10. Shi, Ying, Wen, Lei dan Hui-Ming Cheng. “Nanosized Li4Ti5O12/Graphene Hybrid Material With Low Polarization For High Rate Lithium Ion Batteries.” Journal Of Powder Source 196. 8610-8617. 2011. 11. Lin, Jeng-Yu, et. al. “Sol-Gel Synthesis Of Alumunium Doped Lithium Titanate Anode Material For Lithium Ion Batteries.” Journal Of Electrochemica Acta 87. 126-132. 2013.

12. Li, Baohua, et. al. “Synthesis And Characterization of Long Life Li4Ti5O12/C Composite Using

Amorphous TiO2 Nanoparticles.” International Journal Electrochemical Science Vol. 6. 3210-3223. 2011.

13. Purwamargapratala Yustinus dan Jadigia Ginting. “Li4Ti5O12 Synthesis As a Battery Anode Materials With Solid State Reaction Method”. Proceeding of 2nd Nuclear Energy Technology Seminar, Denpasar. 2015.

MODIFIED OPERATION OF A LABORATORY REFINER FOR OBTAINING DRIED THERMOMECHANICAL PULP FROM NON- WOOD FIBERS

Lilik Tri Mulyantaraa b 1, Roni Maryanab, Vu Thang Dob, Atanu Kumar Dasbc, Hiroshi Ohib2, Keiichi Nakamatad aCenter of Agricultural Engineering Research and Development, Ministry of Agriculture in Indonesia, bUniversity of Tsukuba, 1-1-1 Tennodai, Tsukuba Ibaraki 305-8572, Japan, cCurrent affiliation: PT. Indah Kiat Pulp & Paper Tbk. Perawang Mill, Indonesia dHokuetsu Kishu Paper Co., Ltd., 3-2-2 Hongoku-cho Nihonbashi, Chuo-ku Tokyo 103-0021, Japan [email protected] [email protected]

ABSTRACT

A process for the production of thermomechanical pulp (TMP) from non-wood fibrous materials has not been industrialized. On the other hand, there is a requirement for the production of dried TMP from non-wood fibers for the preparation of medium density fiberboard (MDF board) as an alternative to wood and as a possible method of treatment of agricultural wastes. Dried fibers are required to produce high quality MDF board. Sugarcane (Saccharum officinarum) bagasse (SB) and empty fruit bunch (EFB) of oil palm (Elaeis guineensis) are non-wood fibrous materials that are easily available in Indonesia, and have the potential to be developed as fibers for use in materials of MDF board. This research is aimed at modifying the operation of a laboratory pressurized TMP refiner to obtain dried fibers from non-wood fiber sources for fabricating MDF materials under suitable conditions. An approximate solid content of 80% of oil palm EFB dried fibers were obtained by this modified method. These fibers then could be fully dried to obtain a solid content of 90%. On observing the results from fiber fractionation and the length of these dried fibers, it was found that the oil palm EFB dried fibers were comparable to mixed light hardwoods fibers produced in an industrial MDF board process.

Keywords: Thermomechanical pulp, oil palm empty fruit bunch, medium density fiberboard, fiber fractionation, fiber length

Introduction

The pulp yield of approximately 90% obtained in the mechanical refining process is one of the advantages of using empty fruit bunch (EFB) of oil palm (Elaeis guineensis) as a raw material in the pulp and paper industry1). In the refining process of thermomechanical pulp (TMP), individual fibers are separated by mechanical forces and then substantially developed to meet their papermaking properties2). Usually, higher temperatures can have a better softening effect on fibers, leading to easier initial fiber separation and fibrillation3), which leads to better single fiber properties4). The ideal refining process removes the middle lamella and outer layers from the single fiber (cell) wall to produce fibers and fines with good bonding potential3). It is possible to preserve the fiber length with softening by increasing the temperature5). Refining pressure had a significant effect on the mechanical properties of medium density fiberboard (MDF board).6, 7) The increment of steam pressure in refining significantly improved the mechanical properties of MDF board fabricated from oil palm trunk8). In Japan, one of the refining equipment used for TMP is a laboratory pressurized refiner (model: BRP45-300SS) manufactured by Kumagai Riki Kogyo Co., LTD. (Nerima, Tokyo), and it mainly comprises three parts: machine, processing, and outlet. The machine of TMP refiner includes a main electric motor that has a maximum disk rotation of 3000 rpm. The processing part consists of a pressurized hopper (material input and heater), a screw conveyor (material feeder), a gearbox (for the speed reduction ratio), a disk-clearance (plate gap) adjustment, a belt-pulley (for transmission), and a single disk refiner (consisting of a rotor and stator of 300 mm diameter) with a certain pattern (Disk pattern J in this study). The outlet part includes a pulp container (blow tank) (Fig. 1) 1, 9, 10). © 2016 Published by Center for Pulp and Paper through 2nd REPTech 193 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Fig. 1 Technical drawing of a TMP refiner

In this study, the TMP refiner was equipped with a steam boiler (model: SU-200) supplied by MIURA Co., LTD. (Matsuyama, Ehime) that provides a maximum steam pressure of 0.98 MPa. Additionally, the pulp blow tank can be connected to a conical bottom joint, an on-off blow valve, a blowing pipe, and a pulp blow box to fabricate dried fibers for use in the manufacturing of MDF board. The pulp blow box had a length of 72 cm, width of 60 cm, and height of 58 cm with four 60 mesh (250 µm opening) stainless steel wire sides. A process that produces TMP from non-wood fibrous materials such as sugarcaneSaccharum ( officinarum) bagasse (SB) and EFB of oil palm has not been industrialized. On the other hand, there is a requirement for the manufacture of dried TMP from these non-wood fibers for the preparation of MDF board, which can be an alternative to wood, and a possible method of treatment of agricultural wastes. Dried fibers are required to produce high quality MDF board. SB and oil palm EFB are non-wood fibrous materials that are easily available in Indonesia, and have the potential to be developed as fibers for use in MDF board. This research was aimed at modifying the operation of a laboratory pressurized TMP refiner to obtain dried fibers from SB and oil palm EFB for fabricating MDF materials under suitable conditions.

Experimental

Material Preparation

In this study, SB and oil palm EFB were obtained from PT. Madukismo in Yogyakarta, Indonesia and PT. Perkebunan Nusantara VIII in Bogor, West Java, Indonesia, respectively. SB was manually washed twice and dried in direct sunlight. The moisture level after drying was approximately 8–10%. The dried SB was cut into 0.5–2.0 cm size pieces using a shredding machine, while the oil palm EFB was cut into 0.5–4.0 cm size pieces by a laboratory disk mill. A chemical (6 g of NaOH: 2% dosage based on materials) was added to water and the solution was then mixed with the oil palm EFB. The advantages of using the chemical for oil palm EFB has been explained in a previous study 11)

Operating Procedure of TMP Refiner

The TMP refiner was kept under pressurized conditions, where the pressure of the steam was adjusted to 0.7 MPa at 165oC. The disk clearance was set at 0.10 mm, which was recommended in a

194 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 previous study1) where the oil palm EFB was refined at 0.10-0.20 mm clearance, and the obtained fibers were characterized by fractionation. After retaining for 20 min in the pressurized hopper, a screw feeder was started and at the same time, the pulp blow valve with a conical bottom joint was immediately opened. Refining, which included the finishing of all materials was completed in 3 min, the screw feeder was then stopped, and the blow valve was closed. The disk temperature was recorded at 1 min intervals.

Final Drying of Obtained Pulp

Finally, the obtained pulp was dried by blowing a warm air into the pulp blow box from its bottom wire side for 180 min for oil palm EFB and 360 min for SB using a commercial warm-air drier (Mitsubishi Electric AD-X80). The flow rate and temperature of the drier were approximately 20 L/min and 60– 65°C, respectively. After separating the pulp into two parts in the pulp blow box, the solid content of pulp was determined. The drying duration was confirmed as the solid content of the pulp in one part had reached 90–92%.

Evaluation of Pulp Properties

The properties of the fibers can be classified by the fractionation methods using dried fibers and wet fibers12). In this study, fiber fractionation was done according to the condition of the dried fibers. Three screens with 850, 355, and 180 µm opening (20, 45, and 80 mesh, respectively) were used for this method. Ten grams (oven-dried weight) of refined fibers was charged into the upper screen (850 µm opening) with 30 stainless steel balls (12.5 mm diameter) to disperse the fibers and to send them smoothly to the subsequent screens during shaking for 2 min. The four fractions were named as “on 850 µm opening”, ‘355–850 µm opening”, “180–355 µm opening”, and “pass 180 µm opening”. The refined fibers of SB and oil palm EFB were compared to the refined fibers of MLH obtained from the industrial process of Hokushin Co., Ltd. Additionally, the three fractions except the longest fraction (“on 850 µm opening”) dispersed in water, and the fiber length and width of each fraction was determined by a Lorentzen–Wettre fiber tester CODE 912.

Results and Discussion

Solid Content of Obtained Pulp

The SB and oil palm EFB fibers obtained in the pulp blow box were divided into two parts depending on the difference between average solid contents, and named as first grade (higher solid contents) and second grade (lower solid contents). The separation should occur as follows: After the pulp blow valve was opened and the pressurized steam blew the refined fibers through the pulp blow pipe to the blow box, the flocks of refined fibers hit the stainless steel wall of the pulp blow box, which was on the opposite side of the pulp blow pipe. Then, the flocks of fibers that separated from the steam turned toward to the wall at the other side of the pulp blow box to become individually separated fibers, which resulted in sufficiently dried fibers. The first and second grade oil palm EFB fibers had a solid content of 81.4–86.8% and 46.6–53.4%, respectively (Table 1). The first and second grade SB fibers had a solid content of 55.6% and 50.2%, respectively. These fibers can be used for MDF board preparation after obtaining a solid content of more than 90%.

Table 1 Solid content and weight ratios of the first and second grade fibers

Liquid to EFB ratio Solid content (%) Weight (%) No. Materials (L/kg) 1st grade 2nd grade 1st grade 2nd grade 1 EFB 0.1 86.8 53.4 70 30 2 EFB 4.0 81.4 49.9 60 40 3 EFB-2% NaOH 4.0 81.9 46.6 73 27 4 SB 0.1 55.6 50.2 67 32

Characterization of Fiber Fractionation

The results of the fractionation of the dried fibers showed that the ratios of the “355–850 µm opening” fractions for oil palm EFB and SB refined fibers were almost the same as that of MLH fibers (Fig. 2). The ratio of the coarse “on 850 µm opening” fraction for oil palm EFB fibers without water was slightly higher than those of other oil palm EFB and SB conditions. The reason for this observation could be that impregnation with water softens the lignin prior to refining13, 14). The result of fiber fractionation shows that oil palm EFB fibers impregnated with water prior to refining had the lowest ratio of the coarse fraction.

Fig. 2 Fractionation of dried fibers

Next, the fiber length of each classified fraction was determined by a Lorentzen–Wettre fiber tester. Table 2 shows that the fiber length of the “355–850 µm opening” fraction for oil palm EFB fibers impregnated with water was longer than those of the oil palm EFB fibers without water and oil palm EFB fibers with alkaline solution (2% NaOH). Additionally, the fiber lengths of these fractions of all oil palm EFB fibers were shorter than that of MLH refined fibers.

Table 2 Comparison of mean fiber length and width of EFB laboratory refined fibers and mill MLH fibers

Opening 355–850 µm Opening 180–355 µm Opening 180 µm pass No. Materials Length Width Length Width Length Width (µm) (µm) (µm) (µm) (µm) (µm) 1 EFB-without water 767 31.9 493 28.9 425 29.2 2 EFB-with water 893 30.5 537 26.9 368 26.6 3 EFB-2% NaOH 826 31.5 694 29.5 462 28.2 4 SB-without water 1055 39.0 591 38.8 473 37.0 5 MLH mill fibers 1134 28.6 788 28.5 596 30.8 a Determined using a Lorentzen-Wettre fiber tester CODE 912.

Conclusions

This research is aimed at modifying the operation of a laboratory pressurized TMP refiner to obtain dried fibers from non-wood materials such as SB and oil palm EFB for fabricating MDF materials under suitable conditions. A solid content of approximately 80% of oil palm EFB dried fibers and approximately 55% of SB dried fibers were obtained by this modified method for the production of MDF materials. These fibers could be fully dried to a solid content of 90–92% for fabricating MDF materials. According to the results from fiber fractionation and the measurement of the fiber length of

196 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 these dried fibers, the SB and oil palm EFB dried fibers were comparable to the mixed light hardwoods fibers produced in an industrial MDF board process.

Acknowledgements

The authors are grateful for the assistance offered by Dr. Hideaki Takahashi, Hokushin Co., Ltd.

References

1. Harsono, Mulyantara LT, Rizaluddin AT, Nakagawa-izumi A, Ohi H, Nakamata K (2015) Properties of fibers prepared from oil palm empty fruit bunch for use as corrugating medium and fiberboard. Jpn TAPPI J 69: 1349–1359̶̶̶̶ 2. Gorski D, Hill J, Engstrand P, Johansson L (2010) Review: Reduction of energy consumption in TMP refining through mechanical pre-treatment of wood chips. Nord Pulp Paper Res J 25 (2):156– 161 3. Li B, Li H, Zha Q, Bandekar R, Alsaggaf A, Ni Y (2011) Review: Effects of wood quality and refining process on TMP pulp and paper quality. Bioresources 6:3569–3584 4. Muhic D (2010) Improved energy efficiency in double disc chip refining, Thesis, Mid Sweden University, SE-851 70 Sundsvall, Sweden 5. Kure KA, Sabourin MJ, Dahlqvist G, Helle T (1999) Adjusting refining by changing refiner plate design and rotational speed-effect on structural fibre properties. J Pulp Pap Sci 26:J346–352 6. Xing C, Deng J, Zhang SY, Riedl B, Cloutier A (2006) Properties of MDF from black spruce tops as affected by thermomechanical refining conditions. Holz Roh Werkst 64:507–512 7. Aisyah HA, Paridah MT, Sahri MH, Astimar AA, Anwar UMK (2012) Influence of thermomechanical pulping production parameters on properties of medium density fiberboard made from kenaf bast. J Appl Sci 12:575-580 8. Ibrahim Z, Aziz AA, Ramli, R, Mokhtar A, Lee SJ (2013) Effect of refining parameters on medium density fiberboard (MDF) properties from oil palm trunk (Elaeis guineensis), Open J of Compos Mater 3:127–131 9. Han G, Umemura K, Zhang M, Honda T, Kawai S (2001) Development of high-performance UF- bonded reed and wheat straw medium-density fiberboard. J Wood Sci 47:350–355 10. Kamijo Y, Sugino M, Miyanishi T (2015) Fiber morphologies and sheet properties of hardwood thermomechanical pulp. Jpn TAPPI J 69:1125–1133 11. Mulyantara LT, Harsono H, Maryana R, Ohi H (2016) Properties of thermomechanical pulps from sugarcane bagasse and oil palm empty fruit bunch as non-wood materials. Proceedings of 83rd Pulp Pap. Res. Conf. Jpn TAPPI, 22–23 June, Tokyo, pp 119–122 12. Benthien JT, Bahnisch C, Heldner S, Ohlmeyer M (2014) Effect of fiber size distribution on medium- density fiberboard properties caused by varied steaming time and temperature of defibrillation process, Wood Fiber Sci 46 (2):1–11 13. Back EL, Salmen L (1982) Glass transition of woods component hold implications for molding and pulping processes. TAPPI 65(7):107–110 14. Illikainen M (2008) Mechanism of thermomechanical pulp refining, Thesis, Faculty of Technology, Dept. of Process and Environmental Engineering, University of Oulu, Finland

BRIGHTNESS STABILITY OF DISSOLVING PULPS: EFFECT OF THE BLEACHING SEQUENCE

Jordan Perrin1, Dominique Lachenal, Christine Chirat Grenoble INP-Pagora, 461 Rue de la papeterie, 38402 St Martin d’Hères, France 1jordan.perrin@grenoble –inp.org

ABSTRACT

The factors governing the brightness reversion of dissolving pulps under heat exposure have been investigated. Carbonyl groups (CO) were intentionally introduced on fully bleached pulp by oxidation. They were clearly responsible for a loss of brightness stability. These groups were partly eliminated by an alkaline extraction stage (E), which improved brightness stability. However, an alkaline peroxide stage (P) was more efficient than E to decrease brightness reversion, but without any additional CO loss. Moreover, an unbleached dissolving pulp was bleached in the laboratory with ECF and TCF (ozone based) sequences to the same brightness. The CO content was about the same in both cases and at a very low level. The ECF bleached pulp showed substantial lower brightness stability than the TCF pulp. These results suggest that the chemistry of chromophores present in the unbleached pulp also govern brightness stability. In situ detection of phenolic chromophores in bleached dissolving pulp was performed by EPR spectroscopy and UV Raman. Their content depended on the bleaching sequence, which may be related to brightness reversion differences.

Keywords: brightness reversion; dissolving pulp; carbonyl groups; UV Raman spectroscopy; EPR spectroscopy; ECF and TCF bleaching

Introduction

The mechanism of brightness reversion of bleached chemical pulps under heat exposure is still not fully understood. Several factors were claimed to play a key role in brightness reversion. Among them, hexenuronic acid groups (HexA) [1,2], carbonyl groups [3,4] or residual lignin [5] are the more often cited. However these factors could not explain the origin of some contradictory conclusions on the respective brightness stability of ECF and TCF bleached pulps [6]. It was shown that peroxide treatment is more effective than chlorine dioxide stage to improve the brightness stability of a bleached pulp [7]. The purpose of this study was to try to understand better the ageing of dissolving pulps by combining the analysis of their oxidized functional groups (CO and carboxyl (COOH) groups), EPR spectroscopy and UV Raman spectroscopy measurements, and their behaviour upon heat exposure.

Experimental

A bleached commercial eucalyptus dissolving pulp (4.5% hemicellulose, DP 690) and its unbleached counterpart (kappa number 2.7) were used in this study. The bleached pulp was oxidized by sodium hypochlorite (0.5% and 2% on pulp) under acidic conditions (pH 4.7) to generate oxidized groups

(mostly CO) [3]. These steps are referenced as H0.5% and H2%. E (1% NaOH, 10% consistency, 80°C for

1h) and P (as E with 0.8% H2O2 added) stages were performed on the oxidized pulp. The unbleached pulp was bleached according to D(Eop)DP (ECF) and (ZEo)(ZEo)(ZP) (TCF) sequences. Ozone stages (Z) were run at high consistency (around 38%) and pH 2.5. Alkaline extraction stage was reinforced with 2 bars of oxygen (Eo). D(Eop)DP was performed at 10% consistency. First chlorine dioxide (D) stage was carried out at 60°C for 60 min and the second at 75°C for 80 min. (Eop) and P were run at 80°C for 70 and 60 min respectively. The chemical charges were chosen to reach 89+% final brightness. Pulp brightness was measured according to the ISO 2470 standard. Ageing of pulp was carried out in an oven for 24h at 105°C. Brightness reversion is expressed by the post color number (PCN). Pulp viscosity was measured according to ISO 5351 and the values converted into DPv [8]. After oxidation

DPv was also measured after borohydride reduction to prevent cellulose depolymerization during the viscosity measurement (reduced DPv). Carbonyl and carboxyl content were determined by CCOA and FDAM (measuring uronic groups) methods respectively [9,10]. EPR spectroscopy was performed on a Bruker EMX Plus spectrometer equipped with a ER-4102ST Bruker cavity at 9.4GHz at ambient temperature on finely ground pulp. UV Raman was performed on handsheets with Renishaw 1000 UV Raman spectrometer, connected to a Leica DMLM microscope and an Innova 90C FreD frequency- doubled Ar+ ion laser. The excitation wavelength of the laser was 244 nm; power output, 10 mW; and measuring transmittance, 25%. The spectra were normalized to cellulose peak at 1094 cm−1.

Results and Discussion

Impact of Oxidation on Yellowing

The oxidation of the commercial bleached eucalyptus dissolving pulp by sodium hypochlorite creates carbonyl and to a lesser extent carboxyl groups on the pulp carbohydrates (Table 1). Figure 1 represents the carbonyl content against the molecular mass. Both formation of carbonyl groups and cellulose depolymerization are observed. Post color number (PCN) values indicate that pulp oxidation causes a decrease in brightness stability.

Table 1 Effect of hypochlorite oxidation on stability CO and COOH contents and brightness stability of bleached dissolving pulp

Euca TCF H0.5% H2% Brightness (%ISO) 89.0 91.2 92.1 PCN 0.18 0.50 1.34 DPv 690 560 230 Reduced DPv nd 620 300 CO (µmol/g) 5.1 16.2 67.6 COOH (µmol/g) 13.6 13.0 22.4

The oxidized pulps were treated with E and P stages. Figure 1 and Table 2 reveal that carbonyl groups are substantially decreased during the alkaline extraction. Conversely uronic carboxyl groups content is not reduced. As expected, a parallel decrease of the PCN and CO content is observed. It is interesting to notice that the PCN is decreased further in P compared to E, whereas the CO (and COOH) content does not differ significantly. Therefore, the beneficial effect of H2O2 on brightness stability would be also due to other factors than carbohydrate CO (and COOH) content. This effect would be related to the chemistry of H2O2 with some pulp chromophores [11]. This chemistry would be likely the one responsible for the brightness improvement observed during P bleaching.

Table 2 Effect of E and P stages on the characteristics of oxidized bleached dissolving pulp (2% hypochlorite)

H2% E treated P treated Brightness (%ISO) 92.1 90.9 93.2 PCN 1.34 0.87 0.75 DPv 230 190 170 CO (µmol/g) 67.6 44.4 45.9 COOH (µmol/g) 22.4 25.1 27.9

Fig. 1. Effect of E and P stages on Mw and CO distribution of oxidized bleached dissolving pulp (2% hypochlorite)

Influence of The Bleaching Sequence on The Brightness Stability of Bleached Dissolving Pulp

The unbleached dissolving pulp was bleached in the laboratory with both D(Eop)DP (ECF) and (ZEo)(ZEo)(ZP) (TCF) sequences. Table 3 gives the main properties of these pulps, before and after the final P stage. Final brightness is the same whether the pulp is bleached with chlorine dioxide- or ozone-based sequences. The cellulose is slightly more depolymerized after the TCF sequence, indicating that the pulp carbohydrates have been slightly more oxidized. However DP is quite acceptable for viscose applications. Unexpectedly, the ECF pulp has lower brightness stability than the TCF pulp. The difference is especially high before the last P stage. The final peroxide stage reduces the gap, but the TCF pulp remains superior. If carbonyls are considered in parallel, it is shown that here the pulp with the higher content in CO has the better brightness stability, which again indicates that the CO content is not the only factor acting on brightness stability.

Table 3 Effect of ECF and TCF bleaching on the characteristics of dissolving pulp before and after the last P stage

(ZEo)(ZEo)Z (ZEo)(ZEo)(ZP) D(Eop)D D(Eop)DP Brightness (%ISO) 88.5 89.8 88.8 89.6 PCN 0.46 0.3 0.71 0.38 DPv 660 620 770 740 CO (µmol/g) nd 6.5 nd 4.2 nd: not determined

Study of The Formation of Phenolic Structures by Alkaline Treatment of Oxidized Cellulose

EPR spectroscopy is a very sensitive method to observe organic radicals. Lignin samples generally exhibits an intense band which corresponds to stabilized semiquinone radicals [12]. This band is found also in unbleached pulp and is still visible in fully bleached pulps [13]. These radicals must belong to extended conjugated phenolic structures. Whether or not these structures, when present in kraft pulps, originate from wood lignin is uncertain since the cooking of fully bleached pulp under kraft conditions leads to a more intense EPR signal for the cooked carbohydrates, suggesting that the carbohydrates themselves may form such phenolic structures [13].

After an alkaline extraction applied on an oxidized pulp (H2%, see above) we observed that the brightness was decreased. During the alkaline extraction, some carbonyl groups disappeared. If β-elimination is the most considered reaction to explain the carbonyl removal, it cannot be responsible for the yellowing of the cellulose. EPR spectroscopy was used for detection of radicals in pulps. Figure 2 shows that an oxidized fully bleached pulp (H) has a low intensity signal, which might be due to residual phenolic structures. After

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 201 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 the alkaline extraction (HE), the intensity of the signal is strongly increased, meaning that some stable radicals similar to those observed in lignin are formed.

Fig. 2. EPR spectrum of hypochlorite oxidized pulp (H) before and after alkaline extraction (E)

Fig. 3. Raman spectrum of hypochlorite oxidized pulp (H) before and after alkaline extraction (E)

UV Raman spectra of these pulp were recorded (Figure 3).The curves are normalized taking the 100 cm-1band (cellulose) as internal standard The phenol and the conjugated double bonds (quinones) bands are observed at ~1600 cm-1 and ~1650 cm-1 respectively. Differences between signals are easier to -1 visualize by drawing the difference spectra ( Δ after – before E) between 1400 and 1800 cm . (Figure 4). The increase of the peaks at 1605 and 1645cm-1 during the alkaline extraction (HE-H) confirms the parallel formation of both phenols and quinones in alkaline conditions. These lignin-like structures are formed by degradation of oxidized cellulose. However, during a peroxide stage, neither phenolic structures nor quinones stay in the pulp since the difference in raman spectra is close to zero. This explains the better brightness after P. The formation of phenolic structures and quinones from oxidized cellulose under alkaline conditions is in accordance with previous work by Vikkula and al. [14] who proposed a cyclisation mechanism leading to both phenols and quinones from carboxymethyl cellulose.

Fig. 4. Difference in Raman spectrum of hypochlorite oxidized pulp (H) before and after alkaline extraction (E)

Study of the occurrence of phenolic and quinone structures in ECF and TCF bleached dissolving pulp

The two D(Eop)DP (ECF) and (ZEo)(ZEo)(ZP) (TCF) bleached dissolving pulps were analysed by UV Raman spectroscopy (Figure 5) . It is shown that the ECF bleached pulp contains more phenolic structures and quinones than the TCF bleached pulp. The origin of these structures may be either residual lignin or modified carbohydrates (cooked carbohydrates and E treated oxidized carbohydrates are prone to form phenolic structures and quinones as discussed previously). The relative inefficiency of chlorine dioxide to get rid of quinones has already been observed [6]. Moreover quinones are formed when lignin reacts with chlorine dioxide [6]. The presence of quinones in greater quantity in the ECF pulp would be one reason for its lower brightness stability.

Fig. 5. UV Raman spectrum of (ZEo)(ZEo)(ZP) and D(Eop)DP bleached pulps

Conclusions

1. Carbonyl groups introduced in fully bleached dissolving pulp by oxidation increase their brightness reversion upon heat exposure. E stage performed after oxidation dramatically decreases the CO content and improves the brightness stability. 2. The addition of hydrogen peroxide in E (P stage) does not improve the carbonyl removal further. However, it has a positive impact on brightness and brightness stability. 3. Ozone-based TCF sequences give a pulp with better brightness stability than conventional ECF. 4. Brightness reversion would be impacted not only by the oxidation state of the carbohydrates but also by the chemical structure of some residual chromophores, which, according to UV Raman spectroscopy would be more quinonic after ECF bleaching. 5. Some lignin-like structures (phenols and quinones) are formed from oxidized cellulose during alkaline extraction. At the same time the CO content of cellulose is reduced. These two effects would

have an opposite influence on brightness stability, which may complicate the picture. Adding H2O2 has a positive effect on brightness stability likely because it destroys quinones.

Acknowledgements

The authors would like to thank Pr Antje Potthast for welcoming one of us at BOKU University to run the CCOA and FDAM experiments, and COST FP1205 for funding this stay, and Pr Tapani Vuorinen for UV Raman analysis.

References

1. T. Liitiä and T. Tamminen, in 3rd Int. Conf. Eucalyptus Pulp (ICEP), Belo Horizonte, Brazil (2007). 2. V. L. Silva, A. G. Lino, R. A. Ribeiro, J. L. Colodette, A. Forsström, and E. Wackerberg, BioResources 6, 4801 (2011). 3. M. Lewin, Macromol. Symp. 118, 715 (1997).

4. Z. Zhou, A.-S. Jääskeläinen, I. Adorjan, A. Potthast, P. Kosma, and T. Vuorinen, Holzforschung 65, 289 (2011). 5. O. Sevastyanova, On the Importance of Oxidizable Structures in Bleached Kraft Pulps, KTH, 2005. 6. H. U. Suess, Pulp Bleaching Today (De Gruyter, 2010). 7. H. U. Suess and C. L. Filho, in ABTCP (2003), pp. 1–12. 8. H. Sihtola, Comparison and Conversion of Viscosity and DP-Values Determinated by Different Methods (Keskuslaboratorio, 1963). 9. R. Bohrn, A. Potthast, S. Schiehser, T. Rosenau, H. Sixta, and P. Kosma, Biomacromolecules 7, 1743 (2006). 10. J. Röhrling, A. Potthast, T. Rosenau, T. Lange, G. Ebner, H. Sixta, and P. Kosma, Biomacromolecules 3, 959 (2002). 11. T. Hosoya and T. Rosenau, J. Org. Chem. 78, 3176 (2013). 12. C. Bährle, T. U. Nick, M. Bennati, G. Jeschke, and F. Vogel, J. Phys. Chem. A 119, 6475 (2015). 13. D. Cardona-barrau, C. Matéo, D. Lachenal, and C. Chirat, Holzforschung 57, 171 (2003). 14. A. Vikkula, J. Valkama, and T. Vuorinen, Cellulose 13, 593 (2006).

BUILDING INNOVATION TECHNOLOGY CONCEPT IN PRINTING INDUSTRY INTO PRINTING EDUCATION

Muhammad Nurwahidina1, Untung Basukia, Ponadia, Adi Susantob aJurusan Teknik Grafika, Politeknik Negeri Media Kreatif bManagement Informatika, Universitas STIKUBANK [email protected]

ABSTRACT

Printing Industry today enter in Information Technology era. The opportunity in Indonesia printing industry market is high. It should be become Indonesia Government concern in Creative Industry. In order to achieve this goals, we recommends : upgrading the lecture on this major by sending study abroad in linear major, standarization ASEAN curriculum in this major (Graphic Arts and Imaging Printing), creating many entrepreneurs which has specification on this industry, creating many young peoples, innovative, and creative, getting support from Indonesia Government on this creative industry, tend to innovative, creative and technology based, no more labor based with conventional models, and enhancing International network, academic and industry.

Keywords : innovation technology concept, printing industry, printing education

Introduction

Printing Education was developed very well since 15 years ago in Thailand. The paradigm was changed totally by yearly development. Thailand Printing Industry today enter in Information Technology era. Challenges in this industry also tight in printing quality competition. Since the academic and industry have same vision and mission under Government and Printing Association, all printing company in Thailand become one unity with one achievement. SMEs also change the mindset from labor based in Innovation based. The differences also significantly from processing aspect become product aspect. Processing aspect today was replaced by technology, no need many labor worker working in this area. Automatization in production will be decrease labor cost and make the production optimal in cost value. The consequences of technology implementation is standarization in education field. Western country reduce the use of labor in production and replace by automatiatization in the each aspect. They need the labor as manage and leader the change and innovation. Making concept of system that delivered on production result is important rather than have so many labors with operators job on processing field. Technology and Innovation will make so many short cut that the processing will be maximize. Learning from Thai Printing Industry, everything was changed, Old Model was dissappear and change to innovative and customized product. In Education Sector, Printing Course Major also changed. They no longer teach as old models but they drive the student become creative and innovative, thinks to be SMEs business.

Based on chart above, source: PIRA International Ltd 2010. The opportunities in printing industry sector drive into creative and innovative industry already. Thailand was developing this concept and make preparation for 15 years, from education and lead industry to enter that Global Market. The basic that they developed in Printing Industry, made the basic education stronger. Thailand Government give facility to send many lecture study abroad. Creativity and Innovation couldn’t based on experience only. It must walking together, experience and education. How Thailand’s government upgrade this industry? The answer is by prepared all human resources from education side. Academic drive the industry.The government facilitated by sending all human resources (lecture, staff and student). Today all industries in Thailand growth and owned by native. All was developed by native, no more foreign. It happen because Thai Education also strong building the basic. Indonesia must learn how to empowerment human resource by good education. Figuring newest trend in printing industry is innovation, creativity and technology must walking together and support among each other. We cannot avoid the development tehnology to each industrial sectors. Many companies in Thailand reduce their labor and change into technology investment. Their consideration faster, effective in time, effeciency in cost and reduce human resource problem. It tend to academic must produce matched human resource that industry need. Printing Indutsry also support many new SMEs (Small Medium Entreprise) into Innovative, Techonology, and Creative Concept in order to capture trend. Today in printing industry established art design in packaging, flexible packaging, digital printing, large format (Offset) and Media Transforming Digital Communication.

Conventional Printing not able for next 5 years. United States Media Association give the future picture, because of technology no more newsprint anymore. Publishing and Infographic move to Digital. Offsett only large format and paper packaging, others will be flexo and gravure. Information channel also move into technology too. Business world move to digital and social media. This movement give direct impact to print media and publishing industry. Others ASEAN Country beside Thailand, Singapore and Malaysia also move into Digital way. Indonesia still on transitionn progress. The figure show to us Print Media Business today. We cannot imagine the prospect of future print media and book publishing since information technology influenced this industry. This changes tend to us become innovative, creative and have own market. Printing Industry also got impact directly from this technology revolution. Printing Company will survive if they have their own product and unique, innovative and creative. One of printing house in Thailand, they was old, since 1974 and fourth biggest printing industry in Thailand. Sritong Name Plate Company, this company basic is screen printing but they produce specific product and have R&D department for make many innovations in their main product. This Company is the example of printing company who has specific product based on research and development. They produce name plate that only them capable to made it. This company have strong R&D and specific product that always innovate. From That company we learn if education is a must. No bargain and no other options. Printing Industries never dies, innovation will be a challenge to this industry, technology aplication and upgrade human resources become big consideration to keep this industry survive. Thailand success with this industry revolution, all sectors was supported among each sectors. At Saraburi Province that Research and Development Departement that belong of Chulalongkorn University shown to us. How

important education in Industry today. We cannot avoid that development since technology growth very fast. Indonesia must develop on education sector first before develop in product. Today many printing houses in Thailand leave Labor Aspect models, they no need to hire so many inappropriate human resources. They replaced by technologies and hire smart and matched person in field.

Indonesia Today

Indonesia industry especially printing industry, today we call it Creative Industry still need more development in many aspects. The opportunity in Indonesia printing industry market is high. It should be become Indonesia Government concern in Creative Industry. Many young and productive ages (Golden Ages) in Indonesia still unemployement. Creative Industry give challenge and opportunity on it. Firstly upgrade the quality of education and influence them become innovator and creator in this industry. It need new breakthrough, revolution breakthrough to change their mindset become entrepreneur in this industry. Although our workshop and research in Thailand just for one week, it give us clearly vision about the real opportunity into this industry by building strong match education. Engineering, Scientist, Informatics Technologis much more needed compare by Economic and Social Major. Stage of transition development show to us Indonesian need fast and new breakthrough into Innovation and Technology era. The opportunity still strong, based on demography and the industrial capacity. Labor concern model should be leave and change to Innovation model which Information Technology Based. International market tend to that era, all customize no mass production anymore. The concept driven to us become more creative. Skill worker must be created from education side.

Thai industries developed and create so many native skill worker, in the past around 5 years ago, many foreign skill worker work in local company, today no longer foreign skill worker, all become native worker. Comparing with Indonesia, the industry still dominant with foreign skill worker, it happen because the quality education didn’t follow what the Industry need today. Now become Academic concern how to boost the quality of Indonesian skill worker. Polimedia and UNISBANK develop networking with many foreign student in order to boost the quality of Indonesian Human Resource possible have same standard with foreign worker in ASEAN. This is big home work for all Indonesian University and Polytechnic.

The figure show to us, trend of Indonesia market, in 2009 – 2010 education component increase significant and give contribution to Indonesia Competitiveness. However it occuring new problem, Indonesia lack of engineering and science skill lecture on it. This is become big homework for Indonesia Minister of Education and Indonesia Government. Now Minister of Technology Research who responsible with University level of education stimulate many lectures and university to develop research and they support fund for research and study abroad. Suggest many university make collaboration with foreign univesity for research, study, and curriculum standarization. The industry growth significantly but inbalance with human resource. For the industry better they pay foreign human resource to run their business rather than using local worker and still send to them training etc. This our Industry faces. After we go to Thailand, train with Chulalongkorn University and go to industry, now we realize how important education is. We lack engineering and scientist, Indonesia has so many economic and social graduates but rare in specific engineering and science. In Thailand today engineering and science become big concern in education also industry. They prepare this area since 15 years ago to make balance in human resource and education standard. It also happen at other country at ASEAN beside Indonesia, they changes to create engineering and scientist in order to produce many skill worker in order to support innovation and information technology changes. The figure above based in Indonesian Statistic Data 2013, shown Creative Industry Sector and positioning. Printing include in industri kreatif (Creative Industry) figure. It support Indonesia income. Indonesian Creative become Indonesian government concern since President Joko Widodo. Indonesia is a country in Southeast Asia, situated at the equator, and located between Asia and Australia as well as between the Pacific and Indian Ocean. It sits between two continents and two oceans. Comprising of 17,508 islands, Indonesia is the largest archipelago country in the world. With a population of 222 million people in 2006, Indonesia is also the fourth most populous country in the world. It ranked

44th of 139 countries on the Global Competitiveness Index, a survey conducted by one of the leading institutions based in Europe. A number of materials can become the elements of the competitiveness, including institutions, infrastructure, macro economy, health, education, market efficiency, technological readiness, business, and innovation.In 2005 the country only sat at 69th position, and in 2002 it was at 54th position.

181 Figure 1. Indonesia Demographic Condition Source: Indonesian Coordinating Ministry for the Economy (2010). Currently Indonesia is not considered as advanced industrial countries in the world because there are still many problems in developing its industry, one of which is the number of new entrepreneurs in Indonesia. Only as many as 440 thousand entrepreneurs or approximately 0.2% of the total Indonesian people who are entrepreneurs, compared with advanced industrial countries like the United States (20%), Japan (18%), and the UK (18%). Even among developing countries, the rate of entrepreneurs in Indonesia is still considered low, for example Singapore (10%), China (5%), and India (5%). This is a dilemma because entrepreneurs have a major contribution in the development of industry.

Indonesian Income Growth One interesting findings in the Global Competitiveness Report 2010- 2011 was the fact that the competitiveness of developed countries and developing movement towards 182 a single point. The World Economic Forum released a progress report each year of competitiveness which is based on a survey on business leaders and the latest economic indicators show the importance in Indonesia’s competitiveness globally. Its rank climbed 10 levels to rank 44 of 139 countries. This is mainly due to an increase in macroeconomic indicators, health, and basic education, according to the report. The quality of overall infrastructure has increased from 96 to 90. The protection of intellectual property rights (IPRs) has increased from 67 to 58; the national savings rate has increased from 40 to 16, the effectiveness of antimonopoly policy has risen from 35 to 30, and the impact of taxation has ascended from 22 to 17. Meanwhile, business sophistication index has also increased, including the number of local suppliers, from 50 to 43, while the distribution value chain has decreased, from 35 to 26; the control of international distribution has declined, from 39 to 33, and the sophistication of the production process has also dropped, from 60 to 52. The ranking was based on a comprehensive survey on each the state. Indonesia was behind Portugal (46th), Italy (48th), India (51st), South Africa (54th), Brazil (58th), Turkey (61st), Russia (63rd), Mexico (66th), Egypt (81st), Greece (83rd), and Argentina (87th). Among ASEAN countries, Indonesia was ranked the fifth after Singapore (3rd), Malaysia (26th), Brunei Darussalam (28th), Thailand (38th), Vietnam (59th), Philippines (85th), and Cambodia (109th). Thailand’s economy depends on labor-intensive manufacturing sector for decades, but now the country is in a stage of development of creative industries driven by 177 knowledge and information. Knowledge-based economy is considered as the basis for the development of creative economy. Thailand has sought to enhance its role in international trade with a more proactive and have shifted the focus to the knowledge and creativity-based production with the aim to add more value to his country. Thailand considers knowledge management as an important factor to promote economic development, in addition to managing the infrastructure and services, develop knowledge and technology, and promoting R&D and innovation to commercialization. Software, animation, and games industry in Thailand is still small compared with other types of creative industries. Software market in Thailand was worth THB 67 billion in 2010, while animation and games respectively were worthTHB 10 billion and THB 12 billion. The industry currently does not make a significant contribution to the GDP of the country, because they face problems related to financial supports, target markets, and human resources. However, it is believed that the software, animation, and games will play an important role in the future for the creative economy, because they are considered a real cluster in each type of industry and creativity of Thailand. In addition, the Software Industry Promotion Agency under the jurisdiction of the Ministry of Information and Communications Technology has been spearheading a national scheme to support industries ranging from financial support, marketing, and professional training programs. Currently, the

210 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 government announced the creative economy as a national agenda. Thus the industry is still growing, even during the global economic recession. The needs of creative economy, public and private partnerships, international cooperation, government stability, government policies, and strong private sector will make the animation softwareand games become the main export products nationwide. Thailand was ranked 17 of top 20 exporters of creative goods in 2005. Although not recognized as a major exporter in this field, Thailand is developing itself to become one of the significant exporters of creative goods and services. According to the Thailand governmenteconomic and social development plan as well as increased creativity is considered as part of measures for economic restructuring. Comparing between Indonesia and Thailand Creative Industry, at this chapter printing and graphic art industry, Indonesia below Thailand. Thailand has well prepared on it. The contribution Indonesia Creative sub sector is mainly vary, the chart below shown each sector contribution on it. Printing Industry at Indonesia also give contribution on In Indonesian GDP. Now our concern and mind set should be changed on it. The industry still give high opportunity on it. Now depend on us how to utilize that opportunity.

Conclusions

This paper give us very clearly about Thailand Creative Industry especially related with our course major, Graphic Arts and Imaging Printing. In order to change from labor based to innovation and technology based. Our priority is listed. Education is important, without enough and standard education, all just flew like a dream. Concerning in education field, engineering, science, chemical and information technology next 10 years willl be rare. Since today try to concerning at that field in order to support creative industry. Social and Business Economic is too many and over produce. Engineering fields become decrease. Now since we workshop from Thailand together with Chulalongkorn University, we realize how important all major in balance. Our home work are,

1. Upgrading the lecture on this major by sending study abroad in linear major This must concern on related field that support the Industry, Today cannot sell the graduated just like is. Now Univesity, polytechnic must concern on what industry would like it? University must provide their product ready to work with industry, not ready to think. Practically based should be higher percentage rather that theoretical based. Giving them the newest curricullum and product. Sending staff and lecture study or training abroad is important. In order to upgrade Indonesian education standarization. Especially related with Creative Industry. Packaging, Publishing, Media and Commercial Printing are part of Creative Industry. © 2016 Published by Center for Pulp and Paper through 2nd REPTech 211 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

2. Standarization ASEAN curriculum in this major (Graphic Arts and Imaging Printing). Curriculum is the basic and guidance what kind product that University give to them. Our major is Graphic Arts and Imaging Printing. It means we cannot give them old models, Today all informatic technology based, mostly all continent tend to teach IT based. What is the trend and future trend. Technology always develop and growth past. IT era must the newest. Standarization is needed for curriculum among university in ASEAN. After the curricullum has been same with others, hopefully the quality of skill workers also standard. In the future ASEAN Country Industry under Native control, not foreign.

3. Creating many young peoples, innovative, and creative. SMEs in creative industry, especially in Printing still have high opportunity and chance. Compare with other major, printing still favorable, studying printing can give chance in SMEs, for example, material supplier, consultant, printing house, digital printing, product design, etc. University must prepare them not only have high grade also entrepreneurship too. This tend to them more innovative and creative. Customatization order much more favorable compare with mass production in small quantity job order. In the Future, SMEs become regenerate and the industry still running on.

4. Creating many entrepreneurs which has specification on this industry Related with poin number 3, entrepreneurs will be support the industry life cycle, the industry will always regeneration and develop. Without any SMEs or young entrepeneur the industry possible going down. Based on Indonesia experience when economuc crisis 1998, almost all big companies colaps, only SMEs survive at support the Indonesia economic running. Innovation and Creativity is needed. Now how the education can support and effort? Giving them the best education.

5. Tend to innovative, creative and technology based, no more labor based with conventional models. Innovation, creativity, IT based become consideration for industry. Labor based was leave it no more hire so many labor in one company in order to bost production capacity with high operational cost. Many companies tend to reduce the operational cost by efficiency and effectivity concept. Single mass producion product, today cannot give warranty for future. Today customization product push the company produce many product variations, especially in paper packaging and flexible packaging. Unique product was favorable, seems like product design with art touch. Thailand printing industries mostly innovation and technology based. They investing technology and hire smart skill workers, multitalent skill worker. Reducing the operational cost but the company income increased by produce specific and special product. For example Sritong Nameplate Company, Ltd. Their product only them can produce with export quality. Research and Develepment Department now needed in industry. Building R&D Department need smart and skill worker who has research based soul. This is push the education to build it in together with industry. Chulalongkorn University has suceed on it.

6. Getting support from Indonesia Government on this creative industry. Government concern and support is the key of success in any industries, without their support and concern is impossible the industry can growth. Getting Government attention should be from Education and Industry synergy and working together. Thailand Government can mix between Education and Industry with their printing association in the middle and make communication bridge among 3 parties. Thai Gasma have important role in this. Now after we did workshop in Thailand it become our case sample how to optimize Indonesian Printing Association (PPGI) seems like THAI-GASMA in order to get pay attention from Indonesian Government stronger.

7. Enhancing International network, academic and industry. Networking also have very important key roles in the development, not only the education, also industry and trade sectors. Academic (Education) need international network for standarization and upgrade their human resource and curricullum. Industry and Trade sector need to enhance International network in order to get International concern and market for local product, knowing

international standard and needed. Education side possible make MOU with foreign university who have high grade in education. UNISBANK and POLIMEDIA developing the cooperation with CHULA in many aspect, especially in Imaging Printing which become our concern. Industry also developing G to G cooperation and with association. Without any international netwok, the industry could be stuck without any information for outside.

References

1. Simatupang, T. M., S. Rustiadi and D. B. M. Situmorang (2012), ‘Enhancing the Competitiveness of the Creative Services Sectors in Indonesia’ in Tullao, T. S. and H. H. Lim (eds.), Developing ASEAN Economic Community (AEC) into A Global Services Hub, ERIA Research Project Report 2011-1, Jakarta: ERIA, pp.173-270. 2. Hermantoro, Hengky, “Creative Industry in Indonesia” in The Malaysia Intelectual Property Cooperation, My IPO, Kuala Lumpur 12-13 December 2013. 3. http://www.slideshare.net/imultimedia/creative-industry-in-indonesia, “Creative Industry in Indonesia” 4. Ministry of Cordinator and Economic Affairs, “A challenge for Indonesia”, 2013 5. PIRA International LTD, “Global Retail – Ready Packaging Consumption, 2010.

UTILIZATION OF PAPER MILL REJECTS WASTE AS A RAW MATERIAL OF COMPOSITE PARTICLE BOARD (CPB)

Yusup Setiawan 1, Aep Surachman, Kristaufan Joko Pramono, Sri Purwati, Henggar Hardiani Center for Pulp and Paper (CPP) Jl. Raya Dayeuhkolot No. 132 Bandung-Indonesia 1 [email protected]

ABSTRACT

Rejects waste of paper mill using recycled paper as a raw material contain fiber of 50.75% and HDPE plastic of 49.25%. It can be utilized as a raw material on the preparation of composite particle board (CPB) as a cheap building material. The CPB was prepared by mixing from rejects waste with either Maleic Anhydride (MA) or HDPE plastic pellet. Addition of MA or HDPE plastic pellet into rejects waste was varied in the dose of 2.5% to 10% and 2.44% to 9.09%, respectively. CPB was molded in hot 2 press machine at the constant pressing pressure of 25 kgf/cm with the varying the temperature of 150, 165 and 180oC for 5, 10 and 15 minutes, respectively. CPB was analyzed for physical properties such as density, moisture content, thickness swelling, and water absorption, and mechanichal property such as internal bond according to Indonesian quality standard for particle board (SNI 03-2105-2006) and Japan Industrial Standard (JIS A 5908-2003). Heavy metal content of CPB such as Chromium (Cr), Cadmium (Cd), Copper (Cu) and Lead (Pb) was also analyzed. Results indicates that CPB had the density of 0.80 - 0.91 gram/cm3, the moisture content of lower than 2%, the thickness swelling of 0.19 – 11.16%, and the 2 internal bond of 2.43 – 3.79 kgf/cm . These physical and mechanical properties of CPB have complied with the Indonesian quality standard and Japan Industrial Standard. CPB had very low content of heavy metal (< 0.08 mg/L) so that it is safe for environment.

Keywords: paper mill; reject waste; hot press; composite particle boards

Introduction

Composites particle board (CPB) is composites containing a wood component in particle form and a polymer matrix from thermosets or thermoplastics materials. The most often used polymers for CPB are polypropylene (PP), polyethylene (PE) and polyvinyl chloride (PVC) (Yadav, 2015). There is a tendency of waste recycling and using it for producing the CPB, recently. Use of renewable materials for manufacturing CPB could contribute the solution of raw material shortage for the particle board industry (Ghalehno and Nazerian, 2011; Muruganandam, 2016). Environmentally friendly or green building materials are becoming more widely used in industrial production practices. These materials are nontoxic and are made from renewable or recyclable resources (Anderson et al., 2005; Atuanya et al., 2015). CPB has been manufactured from different types of raw materials in the form of small particles which is impregnated with resins as binders. It is also reinforced with heat and pressure during molding (Youngquist, 1999; Muruganandam, 2016). The plastic polymers act as a matrix in binding of wood powders or other natural powders. The reinforcement of wood powders is the main key in providing high strength and stiffness as well as resistance to bending of composites product (Bhaskar et al., 2012). Some literature reported that CPB can be made from many materials such as bark, sawdust (Poges et al., 1981), wheat straw (Cheng et al., 2004), waste wood chips (Wang et al., 2007), recycle paper (Nourbakhsh and Ashori, 2010), bamboo waste (Laemlaksakul, 2010), kenaf particles (Juliana and Paridah, 2011), mixture of baggase and industrial wood particles (Tabarsa, 2011), rosella stalks (Ghalehno and Nazerian, 2011), baggase and industrial wood particles (Dahmardehghalehno and Bayatkashkoli, 2013). CPB have many desirable properties such as high density, high surface hardness, abrasion resistance, high durability, etc. Composites particle board can be manufactured in different sizes, shapes, thickness and densities and it can be utilized for housing, industries and in commercial buildings as partition walls, window entryway boards, table tops, board sheets (Kavitha et al., 2015 ; www.espace.library.uq.edu.au/, 2016.).

In the paper industry using recycle paper as raw materials, reject waste is generated from the decomposition of the fiber in the amount of 5 – 10% paper production (Setiawan et al., 2014). Now a day, reject waste is generally discarded as a land fill. Haynes et al. (2009) reported that reject waste component is consisted of 45% plastic, 21% paper, 10% metal, and 24% other materials. According to Setiawan et al. (2014) composition reject waste after metal separation is 50.75% fibers and 49.25% plastics, where the plastic components is more than 99% HDPE plastic type (Setiawan and Surachman, 2015). These fibers and plastics component in reject waste of paper industry has potency to be utilized as a raw material for manufacturing of CPB. The objective of study is to investigate the properties of the CPB made from reject waste of paper industry. The quality of CPB resulted is compared with the quality standard of particle board. Heavy metal content in water soaking of CPB is also analyzed and studied.

Materials and Methods

Materials

Reject waste with a moisture content of 40 - 50% was taken from a paper mill’s production process of corrugating medium and kraft liner paper made from recycled paper. The reject waste was dried in the sun to heat it up, resulting in a moisture content of less than 10%. Maleic Anhydride (MA) was used as a coupling agent and High Density Polyethylene (HDPE) plastic pellets with the length of 2-3 mm and a diameter of 1-1.5 mm as a matrix additional.

Methods

The dried reject waste was shredded with a knife of shredding machine. The shredding machine has a holes screen of around 4 mm for the output of the shredding results. Shredded reject waste (250 to 500 g) or mixture of shredded reject waste with either MA (2.5 to 10 wt%) or HDPE plastic pellets (2.44 to 9.09 wt%) was inserted into iron molds having a size of 20 cm length, 20 cm width and 1 cm thickness which is based stainless steel plate and teflon sheet. Materials was flattened and given the pressure to become solid. Then the material in a mold was covered with teflon sheet and stainless steel plate. It was then inserted into the hot press machine. In the hot press machine, the material was heated o o o 2 at each temperature of 150 C, 165 C and 180 C at a pressure of 25 kgf/cm for 5, 10 and 15 minutes, respectively. After completion of hot compression, the composite particle board resulted was removed from the hot press machine and cooled at room temperature. The composite particle board resulted was test for physical properties including density, moisture content, thickness swelling and water absorption, and testing of the mechanical properties was internal bond. Density of CPB was calculated by equation 1.

Density (g/cm3) = Wa/Va (1)

Wa = air dried weight

Va = air dried volume

Moisture content of CPB was calculated by equation 2. Moisture content (%) = (Wa - Wo/Wo )*100 (2)

Wa = air dried weight

Wo = Oven dried weight of the particle board

Water absorption test was done by immersed of specimen in distilled water in a glass vessel at room temperature of 25◦C. Water absorption of CPB was calculated by equation 3.

Water absorption (%) = (Wf– Wi/Wi)*100 (3)

Wf = final weight

Wi = initial weight

Thickness swelling test was done by immersed of specimen in distilled water at room temperature of 25◦C. Thickness swelling of CPB was calculated by equation 4.

Thickness swelling (%) = (Tf - Ti/Ti)*100 (4)

Ti = initial thickness

Tf = final thickness

Internal bond test is a mechanical test performed on packaging materials to determine the maximum load that can be applied to a material before it ruptures or tears. Tensile testing machine is used to calculate the tensile strength. The sample was placed on the machine and anchored at both ends. As the machine was pumped manually, both tensioned ends were stretched till it failed. Failure occurred by splitting. The internal bond was calculated by equation 5.

δt = Wt*b*t (5) δt = Tensile stress (N/mm²),

Wt = Failure tensile load (N) b = Breadth of the specimen (mm) t = Thickness of the specimen (mm)

All testing procedure of CPB is according to the Indonesian National Standard, SNI 03-2105-2006 (Anonymous, 2006) or Japan Industrial Standard, JIS A 5908-2003 (Anonymous, 2003). Heavy metal such as Chromium (Cr), Cadmium (Cd), Copper (Cu) and Lead (Pb) concentrations in the soaking water of composite particle board for soaking time of 120 hours was also analyzed by atomic absorption spectroscopy (AAS) methods.

Results and Discussion

In this study, the effect of press time, raw material weight and press temperature, MA addition, HDPE plastic pellet addition to the CPB properties, and heavy metal concentration in water soaking was described as the following.

Effect of Press Time to CPB Qualities

The quality of CPB made from 250 g of reject waste in varying of press time of 5, 10, and 15 minutes is shown in Table 1. This table shows that CPB made by different press time does not indicates significant differences in their density (0.82 – 0.83 g/cm3). All of CPB has low moisture content (0.88 – 2.01%). Press time affect to the thickness swelling and water absorption of CPB. The lowest of thickness swelling and water absorption of CPB at 2 hrs and 4 hrs water immerssion is made by press time of 10 minutes. This value of thickness swelling affect to the internal bond properties of CPB as indicated 2 in Table 1. The highest of internal bond properties of CPB (3.73 kgf/cm ) was made at press time of 10 minutes. Internal bond strength is one of the properties which have lot of significance to determine the maximum load that can be applied to a material before it ruptures or tears (Muruganandam, 2016). Comparing to the quality standard of particle board, the quality of CPB made from reject waste has complied with Indonesian and Japan standard, except CPB made by press time of 5 minutes.

Effect of Reject Waste Weight and Press Temperature to CPB Qualities

The quality of CPB made from reject waste in varying of reject waste weight of 250 g, 375 g, 500 g, and varying of press temperature of 165oC and 180oC at 10 minutes of press time is shown in Table 2.

Table 1. Effect of press time to CPB qualities

Testing results Moisture Thickness Water Internal No Sample code Density swelling (%) absorption (%) 3 content Bond (g/cm ) 2 (%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm ) 1 R-250-165-5 0.82 1.12 9.12 11.44 43.65 50.74 1.06 2 R-250-165-10 0.83 2.01 5.07 6.08 22.42 28.01 3.73 3 R-250-165-15 0.83 0.88 7.97 9.21 42.02 45.87 2.92 SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5 JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

Table 2. Effect of reject waste weight and press temperature to CPB qualities

Testing results Moisture Thickness Water absorption Internal No Sample code Density 3 content swelling (%) (%) Bond (g/cm ) 2 (%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm ) 1 R-250-165-10 0.83 2.01 5.07 6.08 22.42 28.01 3.73 2 R-375-165-10 1.00 0.90 16.38 16.38 12.69 20.16 2.55 3 R-500-165-10 1.03 0.41 7.13 8.16 6.03 12.38 2.44 4 R-250-180-10 0.90 1.38 6.43 7.30 25.90 28.50 2.36 5 R-375-180-10 0.99 1.20 6.11 8.01 12.09 21.01 2.33 6 R-500-180-10 1.01 0.85 5.60 7.35 11.31 21.62 2.22 SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5 JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

The increasing of the weight of reject waste as a raw materials used could be a CPB more compact. It has effect in increasing of the density of CPB. It increased from 0.83 g/cm3 to 1.03 g/cm3 and from 0.90 g/cm3 to 1.01 g/cm3 with the increasing of reject waste weight used (250 – 500 g) in each press temperature of 165oC and 180oC, respectively. On the other hand, it decreased the water absorption properties both for 2 hrs and 24 hrs of water immersion. The decreasing of to the water absorption of CPB was 22.42 % to 6.03% and 28.01% to 12.38%. At press temperature of 180oC, both for 2 hrs and 24 hrs of water immersion, water absorption of CPB decrease from 25.90% to 11.31% and 28.50% to 21.01%, respectively. While effect the increasing of the weight of reject waste as a raw materials used to the internal bond properties of CPB was insignificant. The highest of internal bond properties of CPB 2 2 o o of 3.73 kgf/cm and 2.36 kgf/cm was made of press temperature of 165 C and 180 C, respectively. Comparing to the quality standard of particle board, the physical properties and internal bond of all CPB made from reject waste has complied with Indonesian and Japan standards.

Effect of MA Addition into Reject Waste to CPB Qualities

The quality of CPB made from reject waste of 250 g mixed with the varying of MA concentration of 2.5 – 10 % at press temperature of 165oC and press time of 10 minutes can be seen in Table 3.

Table 3. Effect of MA additional into reject waste to CPB qualities

Testing results Moisture Thickness Water Internal No Sample code Density 3 content swelling (%) absorption (%) Bond (g/cm ) 2 (%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm ) 1 RMA2.5 0.84 1.05 6.11 13.58 16.40 38.37 1.49 2 RMA5 0.82 1.22 2.35 13.51 12.35 19.84 2.43 3 RMA7.5 0.83 0.82 1.57 5.07 8.24 18.63 3.79 4 RMA10 0.81 0.50 1.28 1.47 9.42 21.11 3.38 SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5 JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

The addition of MA as coupling agent into reject waste is intended to homogenize mixture of fiber having hydrophilic property and HDPE plastic having hydrophobic property. CPB made by MA addition of 7.5% gave thickness swelling and water absorption which is lower than of without MA addition as seen in Table 1. In this case, MA has a function as coupling agent in homogenized a mixture of fiber having hydrophilic property and HDPE plastic having hydrophobic property. Internal bond property of CPB is rather high than of without MA addition. This CPB quality has complied with Indonesian and Japan standard.

Effect of HDPE Plastic Pellet Addition into Reject Waste to CPB Qualities

The quality of CPB made from reject waste of 250 g mixed with HDPE plastic pellet of 2.44 – 9.09% at press temperature of 165oC and press time of 10 minutes can be seen in Table 4. The addition of HDPE plastic pellet into reject waste is intended to add binder matrix of fiber contained in reject waste. Results indicated that the quality of CPB is increase for the density. But their thickness swelling, water absorption and the internal bond are not improved well. The possibility of this case is the HDPE plastic pellet which is added too big size so that it is not mix well in rejects waste.

Table 4. Effect of PE additional into reject waste to CPB qualities

Testing results

No Sample code Moisture Thickness Water Internal Density 3 content swelling (%) absorption (%) Bond (g/cm ) 2 (%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm )

1 RPE-2.44 0.91 0.93 10.21 13.87 44.01 47.88 0.89

2 RPE-3.85 0.86 1.03 7.95 13.15 52.72 57.56 1.37 3 RPE-6.98 0.90 0.76 9.43 12.00 40.03 43.56 1.58 4 RPE-9.09 0.83 0.82 8.90 12.63 41.50 44.93 2.70 SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5 JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

Heavy Metal Concentration in Water Soaking of CPB

Concentration of heavy metal for Cr, Cd, Cu and Pb in soaking water of CPB after 120 hours soaking time is shown in Table 5. This table shows that heavy metal for Cr, Cd and Cu is not detectable in CPB. CPB is only contains Pb in the concentration of 0.07 – 0.08 mg/L. Low concentration of heavy metal in CPB might be caused by heavy metal retained in CPB or low heavy metal content in recycled paper used by paper mill. The concentration of heavy metal of CPB is almost similar with © 2016 Published by Center for Pulp and Paper through 2nd REPTech 219 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 glass-fiber reinforced cement (GRC) sold comercially in Indonesia. Comparing to Indonesian Toxicity Characteristic Leaching Procedure (TCLP) standard, it has complied with this standard. Therefore CPB is safe for environment.

Table 5. Heavy metal concentration in water soaking of CPB

Heavy metal concentration (mg/L) No Sample code Cr Cd Cu Pb 1 R-165-15 nd* nd* nd* 0.08 2 RPE-9.09 nd* nd* nd* 0.07 3 GRC nd* nd* nd* 0.08 Indonesian TCLP standard 2.5 0.15 10 0.50 Note : *nd = not detectable

Conclusions

Composite particle board (CPB) can be made from reject waste of paper mill using recycle paper as a raw material at the press temperature of 165 – 180oC and press time of 10 minute having the physical properties (density, thickness swelling) and the mechanic property (internal bond) complied with Indonesian and Japan Industrial standards. Reject waste of paper mill can be utilized as a raw material for CPB as a building material. The addition of MA or HDPE plastic pellets into reject waste is insignificant in improvement of the CPB quality. CPB contains a low of heavy metal content (0.07 – 0.08 mg/L) so that it is safe for environment.

Acknowledgements

I would like to thank to all technician of testing laboratory, Center for Pulp and Paper (CPP) the Ministry of Industry, for their assistance. I would also like to thank to Director of CPP the Ministry of Industry, for his support so that the research project is completed.

References

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Contribution to Greenhouse Gas (GHG). International Journal of Technology (2015) 5: 847-855 8. Haynes, R.D., Malloch, J., Cuddy, K., Nicodimos, E., 2009. Ask the Recycle Mill Gals. Progress in Paper Recycling. Vol. 18, No. 3, p.13-20 9. Anonymous. 2006. SNI 03-2105-2006. Papan Partikel. Badan Standardisasi Nasional. Standar Nasional Indonesia, Jakarta. 10. Anonymous. 2003. JIS A. 5908:2003. Particleboards. Japan International Standard. Japan Standard Association. Tokyo. 11. Youngquist, J.A. 1999. Wood based composites and panel products in wood handbook: wood as an engineered material, Gen. Tech.Rept.FPL-GRT-113.,USDA Forest Serv., Forest Prod, Madison, WI,1999, p.1-31. 12. Ghalehno M.D and Nazerian M. Producing Roselle (Hibiscus Sabdariffa) Particleboard Composites, Ozean J. Appl. Sci., 2011, Vol. 4, No. 1, p. 1–5. 13. Anderson, A., Yung, A, and Tanaka, T. Eco-Friendly Alternatives to Wood-based Particleboard, January, 2005. 14. Poges S, Thomas D, Close G, and Court C., United States Patent 191, 1981. 15. Cheng, E., Sun, X., and Karr, G. S. Adhesive properties of modified soybean powders in wheat straw particle board, Compost. Part A Appl. Sci. Manuf., 2004, Vol. 35, p. 297–302. 16. Wang, S.Y., Yang, T.H, Lin, L.T, Lin, C.J, and Tsai, M.J. Properties of low-formaldehyde-emission particleboard made from recycled wood-waste chips sprayed with PMDI/PF resin, Build. Environ. 2007, Vol. 42, No. 7, p. 2472–2479. 17. Nourbakhsh, A. and Ashori, A. Particleboard made from recycle paper treated with maleic anhydride. Waste Manag. Res.2010. Vol. 28, No. 1, p. 51–55. 18. Laemlaksakul, V. Physical and mechanical properties of particleboard from bamboo waste, WorldAcad. Sci. Eng. Technol., 2010, Vol. 64, No. 4, p. 561–565. 19. Juliana, A.H and Paridah, M. T. Evaluation of basic properties of kenaf (hibiscus cannabinus l) particles as raw material for, 18th Int. Conf. Compos. Mater. 2011, Vol. 36, p. 1–6. 20. Tabarsa, T. Producing Particleboard Using of Mixture of Bagasse and Industrial Wood Particles, Key Eng. Mater. 2011, Vol. 471–472, p. 31–36. 21. Dahmardehghalehno, M. and Bayatkashkoli, A. Experimental particleboard from bagasse and industrial wood particles, Int. J. Agric. Crop Sci., 2013, Vol. 5, No. 15, p. 1626–1631. 22. Kavitha, M. S, Hariharan, S. and Natarajan, R. The physico-mechanical property of particle board from coconut coir reinforced with municipal solid waste, International Journal of ChemTech Research, 2015, Vol. 8, No. 2, p. 760–767.

STUDY FOR CHARACTERIZATION AND DRYING SLUDGE OF PAPER MILL: ITS POTENTIAL AS ENERGY SOURCE

Sari Farah Dinaa1, Himsar Ambaritab2, Yanto Lawic3, Siti Masriani Rambea aCenter for Research and Standardization Industry Medan, Jl. Sisingamangaraja no. 24 Medan-20217, Indonesia bDepartment of Mechanical Engineering, University of North Sumatera, Jl. Almamater, Kampus USU Medan-20155, Indonesia cPT. Evergreen International Paper, Jl. Dalu 10 A-B, Tanjung Morawa-20362, Indonesia [email protected], [email protected] [email protected] [email protected]

ABSTRACT

Paper mill produces large amounts of sludge containing primarily fines of cellulose fibers that still has a calorific value. To utilize it as a source for energy substitutions, then the moisture content should be lowered. This study is a preliminary study to look at the potential use of sludge as an energy source. Study was conducted to characterizes and define the drying kinetics of sludge on laboratory scale. Sludge comes from the paper mill that using old corrugated container as raw material for kraft liner making. Samples was taken directly from the final disposal after belt press with average water content of 60%. Characterization includes on-waste, ultimate and proximate analysis. Drying of sludge using an oven with temperatures varying of 100°C and 120°C until the moisture content of 10% was achieved. The sample is weighed every thirty minutes until a constant weight is achieved. Based on drying kinetics model (MR vs. time) which have been obtained then conducted to determine the calorific value on a wide range of moisture content (60, 50, 40, 30, 20 and 10%). The entire experiment was performed in triplicate. The results showed that the higher the temperature, the shorter the drying time. Results of on-waste analysis is to meet the requirements of quality standards, according to Kep 04/BAPEDAL/ IX/1995 and PP No.85 of 1999, except for the parameters Co, Mo and Ni for not testing. The results of proximate and ultimate analysis showed value of fixed carbon and total sulfur are respectively of 46.79 % and 0.13 %. Both variations in temperature show the same pattern kinetic model that is polynomial order two with the effective diffusivity values respectively 5.071x10-10 m2/sec at 100 °C and 7.607x 10-10 m2/sec at 120°C. The lower the water content, the higher the calorific value.

Keywords: sludge, properties, drying kinetics, caloric value

Introduction

The paper mill is one of the industries that produce waste, both in liquid or solid form which is quite large. Solid waste management as WWTP sludge (sludge) and the ash (bottom and fly ash) until now only for landfilling or as a filler in the manufacture of building materials such as brick, concrete wall panels and normal [1,2,3]. Sludge has been the most difficult thing for handled in the paper mill waste treatment. The main cause is not due to its toxic content but the physical form which requires more extensive landfill. So, it would lead to higher costs in the future and may even be banned entirely in some areas [4]. As the waste derived from biomass, sludge has also been used to fertilize farmland, mixed materials in the manufacture of bricks and cement [5,6].

Tabel 1. Sources and Types of Solid Waste Paper Mill’s

No Sources of Waste Types 1 Stock Prep. unit Wet sludge and plastic - Primary sludge (output of physico-chemical processes) 2 Waste water treatment - Secondary sludge (output of biological processes) 3 Power plant bottom ash dan fly ash

Utilization of sludge as a biomass based fuels are currently being carried out abroad, especially in European countries. The advantage of the use of sludge is organic matter content there is renewable, therefore do not contribute to CO2 emissions. However, if the sludge with high moisture content directly burned in the generating unit can reduce boiler efficiency [7]. Solid waste generated from paper mills is varied in terms of type and amount, depending on the raw material used, stock preparation and paper machine performances. Based on the source. Based on the original source, the solid waste coming from paper mills without deinking process derived from three sources, as presented in Table 1. Based on government regulation, PP No. 18 of 1999 and its amendments No 85 of 1999, contains a statement of the type of solid waste paper mill which is characterized as toxic and hazardous materials. It is presented in Table 2. Based on these regulations indicate that only solid waste from pulp and paper mills that are contaminated with ink (deinking unit) and ash (fly ash and bottom ash) from the burning of coal and waste incineration process are classified as toxic and hazardous material.

Table 2. List of Toxic and Hazardous Waste from Specific Source in Pulp and Paper Industry [8]

Types of Industries and Waste Code Source of Pollution Description Activities Activities related to Waste water treatment plant Sludge from wastewater or sludge the ink, including a WWTP which process D.212 contaminated with ink deinking process in effluent originating from paper mills deinking process Fly ash and bottom ash (with Power plants that use Combustion of coal for contaminant above the quality D.223 coal as fuel power generation standard of toxic and hazardous waste) The operation of waste Waste incineration process - Fly ash and bottom ash D.241 incinerator - Flue gas residue

Solid waste characterization test to identify the level of its toxic and hazardous, can be determined through several tests such as: toxicity characteristic leaching procedure) and LD50 (lethal dose fifty) test as well as on-waste test (total maximum levels of waste). Results of previous studies proving WWTP sludge solid waste according to PP 85 1999 is not identified as toxic and hazard waste [8]. Direct combustion of sludge has been carried out for the purposes of energy recovery, but this study did not involve the feasibility study of burning sludge when its moisture content is still high. However, under controlled conditions it can be used as a sustainable fuel for co-generation [9]. Pellets are made from a mixture of sludge (50.75%) and reject plastic (49.25%) of liner-medium paper mills with a water content of <10% has shown the potential of 5-50% as coal substitution. The trial results indicate no finding of slagging and fouling in the boiler [10]. The essential requirements in order for a material can be used as fuel is the calorific value. The results of previous studies are presented in Table 3 shown that calorific value of biomass and fossil are largely determined by carbon, hydrogen and moisture contents [11]. One of the disadvantage that have been considered in the use of sludge as fuel for the boiler is the high moisture content (50-60 %). It takes large amounts of energy to evaporate bound and free moisture contained in the sludge. If the sludge with high moisture content inserted into boiler directly, it would have significant on decreasing of efficiency boiler as shown in Figure 1.

Table 3. Comparison of Some Boiler Fuel Properties [11]

Fir wood waste Sludge of Natural Coal Pulp and Oil No. 6 Gas Bituminous Bark Ranting Paper Moisture Content, % wet 40-60 45-55 50-70 0 3-8 0,05-2 basis Caloric value (HHV) - Dry basis, GJ/ton 19-21 19-25 9-19 52-55 28-33 - Wet basis, GJ/ton at % 10 40-44 11 (50%) 6 (65%) 0 - MC (50%)

Bulk Density, kg/m3 (wet 290- 920- 260-320 500-900 0,7 720-880 basis) 380 1020

Element Analysis - Carbon 55 51 25-50 74-75 76-86 86-90 - Hydrogen 5,8 5,8 3-6 23-25 3.5-5 9.5-12 - Oxygen 39 43 19-38 - 3-11 - - Nitrogen 0.1 0.1 2-5 0-3 0.8-1.2 - - Sulfur 0.1 0.02 0.05-0.5 - 1-3 0.7-3.5 - An-organic 3 0,1 3-50 - 4-10 0.01-0.5

CO2 emissions, kg CO2/GJ 0 0 0 50 82-94 74 Boiler Efficiency 180 - Flue gas temperature, °C 180 180 180 250 250 40- - Excess air, % 55-65 60-120 10 20 10 100 - Efficiency, % 68-62 60-30 83 83 84 70-55 Theoritical Combustion Temperature, Temperature, Combustion Theoritical

70 1750 60 1500 50 , Boiler Efficiency, %

fuel Boiler Efficiciency 40 Sp. Steam Generation Combustion Temperature 1250 30

20 1000

750 0 C 20 24 28 32 36 40 44 48 52 56 60 64 68 Steam Generation,Steam t/bdt Moisture Content of Sludge, %

Fig. 1 Effect of Sludge Moisture Content on Boiler Performance [11]

One of kraft liner-medium paper mills in North Sumatera province dispose of sludge 28 tonnes/day at a moisture content of 55-60% only as landfilling application. Laboratory-scale studies have been conducted to characterize the sludge through on-waste, ultimate and proximate analysis, determine the effect of moisture content to the calorific value, profile of kinetics drying. These researches also calculates the energy required for drying sludge. Technical and economic studies also were conducted to look the potential of sludge as coal substitution at power plant unit.

Material and Method

Samples Preparation

Samples used were derived from solid waste paper mills (sludge) which is using old corrugated containers (OCC) as a raw material. Sludge is taken from belt press which is often referred as primary sludge. Firstly, the initial moisture content of sample is determined using the oven method. Based on the calculation of the initial moisture content is then performed experiments.

Figure 2. Primary Sludge

Procedures

On-Waste Analysis

Testing parameters for on-waste analysis includes Pb, Cu, Cd, Cr, Zn, Sn, Se, CN, F, Hg and As. The tests were conducted in the instrument laboratory of Center for Research and Standardization Industry Medan using atomic absorption spectophotometric test method (SNI 06-6989-2004).

Proximate and Ultimate Analysis

Ultimate and proximate analysis were conducted in the laboratory of Mineral Technology Bandung (TEKMIRA) using ASTM D3176-2015 test method.

Drying Procedure

150 grams of wet sludge are weighed to be dried in oven. Temperatures of drying were varied 100 and 120°C. Decreased weight of the sample was measured by an analytical balance every 30 minutes. To avoid heat loss during weighing, then it is done immediately. The drying process is stopped until they reached a constant weight (equilibrium). During drying, the time required and the power consumed is measured and recorded. The data obtained are in triplicate.

Drying Characteristics

Drying characteristics of sludge were expressed through the determination of moisture reduction rate profile and effective diffusivity. It will be discussed in the form of moisture content versus time curve. Non-dimensional moisture content (MR) was used and defined as

(M − M ) MR = t e (1) (Mi − M e )

Where M, Me and Mi are moisture content at t time, moisture content at equilibrium and moisture content at initial condition, respectively. The effective diffusivity Deff is determined by using the analytical

226 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 solutions of Fick’s second law in slab geometry, with the assumptions of moisture migration being by diffusion, unidimensional moisture movement, neglible shrinkage, constant diffusion coefficients and temperature was as follows [14]

 2 2  M 8 ∞ 1 (2.n −1) .π .Deff .t MR = = ∑ .exp−  (2) 2 2 = −   M 0 π n 1(2.n 1)  4L 

2 Where Deff is the effective diffusivity coefficient (m /s); L is the half thickness of the slab (m) and n is the positive integer. For long drying period the above equation can be simplified, by taking the natural logarithm of both sides [12]:

2 8  π .D .t  Ln MR = ln −  eff  (3) 2  2  π  4.L 

By plotting ln MR versus time, the slope of the line will be the constant of the above linear equation. Thus, the effective diffusivity can be calculated using the following equation:

 4.L2  D = slope x   (4) eff  2   π 

The Potential of Sludge Utilization as Coal Substituent

The study on the potential of sludge utilization is calculated based on the calorific value ratio of sludge to coal (sub-bituminous)

Energy requirements for drying of sludge is calculated by the following equation:

Q = {(ms . C p ) + ((mw. C p ) )}.* (T f − Ti ) + mev . λ (5) s sludge w water

Where ms, mw and mev respectively are mass of dry sludge, water is not evaporated, water evaporated.

Cpsludge and Cpwater are heat capacity of sludge and water in kJ/kg.°C. Tf and Ti are temperature of final and initial in °C. l is latent heat of evaporation in kJ/kg.

Results and Discussion

On-Waste Analysis

According to a decree of Kep 04/Bapedal/IX/1995 and Government Regulation PP No.85 of 1999 there are 14 (fourteen) parameters are set to determine whether the industrial solid waste can be categorized as toxic and hazardous waste or not. In this study, there are 3 (three) parameters which can not be tested (Co, Mo and Ni). Test results of on-waste analysis as presented in Table 4 shows that sludge of paper mills which is use OCC as raw materials are fulfil the standard quality for B. Therefore, it can be said that 79% of test data (11 of 14 parameters) is not categorized as toxic and hazardous material.

Analysis Proximate and Ultimate

The results of proximate and ultimate analysis of sludge is done by varying the moisture content of 60%, 50%, 40%, 30%, 20%, and 10% can be seen in Table 5. The moisture content is inversely proportional to the fixed carbon, volatile matter, nitrogen, carbon and sulphur contents. Ash, oxygen, © 2016 Published by Center for Pulp and Paper through 2nd REPTech 227 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Tablel 4. Result of On-Waste Analysis

Quality Standards, mg/kg Results, mg/ Parameter A B kg Pb 3000 300 11,40 Cu 1000 100 36,00 Cd 50 5 0,50 Cr 2500 250 1,16 Zn 5000 500 90,90

Tablel 4. Result of On-Waste Analysis (continued)

Quality Standards, mg/kg Parameter Results, mg/kg A B Sn 500 50 5,23 Hg 20 2 0,37 As 300 30 <0,02 Co 500 50 *) Mo 400 40 *) Ni 1000 100 *) Se 100 10 1,11 CN 500 50 0,18 F 4500 450 <0,012 note: *) not tested and hydrogen tend to be proportional to the decrease in moisture content. Compared with the data in Table 3, the sulfur content of the sludge is much lower than the levels of sulfur contained in coal. At the time of the burning of coal in the boiler, sulfur contained in the coal will be turned into SO2 and SO3 which pollute the air. In addition, sulfur is also trigger corrosion on boiler heating surfaces. Therefore, the total sulfur steam coal is expected to not more than 1%.

Table 5. Test Result of Analysis Proximate and Ultimate

Sample Code Analysis/Parameter Unit A B C D E F Proximate - Moisture content 61.15 49.34 39.64 28.96 19.28 11.72 % in dried sample 11.18 11.47 11.52 10.94 9.10 8.20 % - Ash content 22.37 28.48 31.48 35.64 34.95 33.29 % - Volatile matter 5.30 10.71 17.36 24.46 36.67 46.79 % - Fixed Carbon

Ultimate - Carbon 14.28 16.12 18.51 21.57 25.98 29.42 % - Hydrogen 7.70 7.62 7.54 7.46 7.37 7.29 % - Nitrogen 0.42 0.45 0.49 0.53 0.57 0.61 % - Total Sulphur 0.11 0.11 0.12 0.12 0.12 0.13 %

Drying Characteristics

Kinetic model used is the empirical equation model was built using experimental data of weight loss of samples versus time. In this study, both temperature and concentration of water inside sludge were assumpted are uniform and only a function of time. So, the rate of decreasing of moisture content are the one-dimensional case and their solution is expressed as non-dimensional value ratio which is formulated by Eqs. (1). Results of drying sludge equation models with variations on temperature of 100°C and 120°C were shown in Figure 5 and Figure 6, respectively. The effect of temperatures shows that the higher drying temperature need the shorter time for evaporation. The results of the curves fitting for both of drying temperature variations provide the same model that is second-order polynomial

1.2

0.8

0.6 MR y = 2E-06x2 - 0.0048x + 1 0.4 R² = 0.9917

0.2

0 0 50 100 150 200 250 Waktu Pengeringan, menit

Figure 5. Moisture Ratio versus DryingTime for 100°C

1.2

0.8

0.6

y = 9E-06x2 - 0.0077x + 1 Moisture Ratio0.4 R² = 0.9959

0.2

0 0 20 40 60 80 100 120 140 160 Waktu Pengeringan, menit

Figure 6. Moisture Ratio versus DryingTime for 120°C

Effective Diffusivity (Deff)

Effective diffusivity (Deff) is an overall mass transport property of moist which includes liquid diffusion, vapor diffusion, hydrodynamic flow and other possible mass transfer mechanism. Deff is one of the important parameter used to evaluate drying and by using Eqs. (3) and (4) it was calculated. By plotting the data ln MR and the drying time (seconds) as shown in Figure 7 and Figure 8, obtained a model of linear equations with constant k = 0.0002 (at 100°C) and 0.0003 (at 120°C). This constant k then substituted into Eqs. (5). By inserting a half thick slabs of sludge that is 0.0025 m, the effective

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 229 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 diffusivity values obtained sludge drying ie 5.0712x10-10 m2/sec (at 100°C) and 7.607x10-10 m2/sec (at 120°C). These values are in the range of previous research conducted by Zen et al to dry the sludge using superheated steam 120-280°C method of thin layers with thickness variation of 2-10 mm, ie 2.52.10-10 – 3.32. 10-9 m2/sec.

0 0 2000 4000 6000 8000 10000 12000 14000 -0.5

-1

-1.5 Ln MR -2 y = -0.0002x + 0.2885 R² = 0.9385 -2.5

-3 Drying Time, sec

Figure 7. Ln MR Versus Drying Time at 100oC

0 0 2000 4000 6000 8000 10000 -0.5

-1 y = -0.0003x + 0.3024 -1.5 R² = 0.9245 Ln MR -2

-2.5

-3 Drying Time, sec

Figure 8. Ln MR Versus Drying Time at 120oC

The Potential of Sludge Utilization as Coal Substituent

As we know that under controlled conditions, sludge can be used as a sustainable fuel for cogeneration. However, high moisture content (average 60-65%) cause of this renewable energy sources has become inefficient when burned directly. Based on the relationship between the moisture content of the sludge to its calorific value as presented in Table 5 shows that the maximum moisture content is allowed to get the highest calorific value is 15%. And then used as the base for calculating the potential of sludge utilization as coal substituent as presented in Table 6

Table 6. Data Sludge and Coal

No Parameter Unit Value 1 Initial Weight of Wet Sludge ton 28.00 2 Initial Moisture Content % 65 3 Final Moisture Content (After Drying) % 15 4 Weight of Sludge After Drying (15% MC) ton 11.53 5 Caloric Value of Sludge (15% MC) kkal/kg 2468.49 6 Caloric Value of Coal kkal/kg 5113.38

From the data as presented in Table 6 shows that savings of coal can be done when utilizing the sludge by moisture content up to 15% is as follows:

 2486.49  Coal Substituent =   * 11.53  5113.38  = 5.606 tons/day

Potential savings = 5.606 ton x US$43.88/ton = US$ 246/day or US$75,800/year

By using the Eq. (5), total energy required to dry the sludge of moisture content of 65% to 15% are 211,1 kJ/kg sludge (at 100°C) and 218.3 kJ/kg sludge (at 120°C).

Conclusions

Test results of on-waste analysis shows that sludge of paper mills which is use OCC as raw materials are fulfil the standard quality for B. The sulfur content of the sludge is much lower than the levels of sulfur contained in coal fuel. The moisture content is inversely proportional to the fixed carbon, volatile matter, nitrogen, carbon and sulfur contents. The effect of temperatures shows that the higher drying temperature need the shorter time for evaporation. The results of the curves fitting for both of drying temperature (100°C and 120°C) variations provide the same model that is second-order polynomial. Effective diffusivity values obtained sludge drying ie 5.0712x10-10 m2/sec (at 100°C) and 7.607x10-10 m2/sec (at 120°C). These values are already in the range of previous research. Saving potential of coal if substituted with dried sludge (15% MC) is a 5.606 ton/day. Total energy required to dry the sludge of moisture content of 65% to 15% are 211,1 kJ/kg sludge (at 100°C) and 218.3 kJ/kg sludge (at 120°C).

References

1. Angelina E.L., Sondang D.P., Penggunaan Limbah Bubur Kertas dan Fly Ash pada Batako, Konferensi Nasional Teknik Sipil 7 (KoNTekS 7) Universitas Sebelas Maret (UNS) Surakarta, 2013, 24 – 26. 2. Aan Fauzi, Ferry Indraharja, Pemanfaatan Limbah Sludge Kertas PT. Adiprima Suraprinta pada Pembuatan Panel Dinding, ISBN No. 978-979-18342-0-9. 3. Dewi Rara W.S., Pembuatan Beton Normal dengan Fly Ash Menggunakan Mix Desain yang Dimodifikasi, Skripsi Jurusan T. Sipil, Fak. Teknik Universitas Jember, 2013. 4. Johan G., Hannu P., Papermaking Science and Technology, Book 19, Environmental Control, Finnish Paper Engineers Association and TAPPI, 1998. 5. Ribeiro P., Antonio A., Luis QA., Victor C., Recycling pulp mill sludge to improve soil fertility using GIS tools, Resources, Conservation and Recycling, 54 (2010): 1303-1311. 6. Cernec F., Zule J., Moze A., Ivanus A., Chemical and microbiological stability of waste sludge from paper industry intended for brick production. Waste Management & Research, 2005, 23(2): 106- 112. 7. Dan Gavrilescu, Energy from Biomass in Pulp and Paper Mills, Environmental Engineering and Management Journal, 2008, Vol. 7, No. 5, pp: 537-546. 8. Purwati S., Rina S. Soetopo, Setiadji, Yusup S., Potensi dan Alternatif Pemanfaatan Limbah Padat Industri Pulp dan Kertas, Berita Selulosa, 2006, Volume 41, No. 2, page: 68-79. 9. Kraft, D.L., Orender, H.C., Considerations for using sludge as a fuel, Tappi, 1993, Vol. 76, (3): pp. 175- 183. 10. Yusup S., Sri Purwati, Aep S., Reza B.I.W., Henggar H., Pelet Reject Industri Kertas Sebagai Bahan Bakar Boiler, Jurnal Selulosa, 2014, Vol. 4, No. 2: 57 – 64. 11. Agra Simons, Energy Cost Reduction in the Pulp and Paper Industry, A Monograph, 1st edition, Pulp and Paper Research Institute of Canada, ISBN0-919578-15-2, 1999,

12. Clement A. D., Assidjo N. E., Kouame P., Yao K.B., Mathematical Modelling of Sun Drying Kinetics of Thin Layer Cocoa (Theobroma Cacao) Beans, Journal of Applied Sciences Research, 2009, 5 (9): 1110 – 1116, 13. Doymaz, I., Drying characteristics and kinetics of okra, Journal of Food Engineering, 2005, 69: 275 – 279. 14. Zhang Xukun, Yao Bin, Wu Qi, Luo Jun, Xu Gang, Xu Jianguo, Analysis of effective diffusivity of sludge in superheated steam drying based on Fourier number method and optimization method, Transactions of the Chinese Society of Agricultural Engineering, 2015, Vol. 31 Issue 6: 230-237. 15. Jolanta L., Jaroslaw G., Effect of Incineration Temperature on The Mobility of Heavy Metals in Sewage Sludge Ash, Environtment Protection Engineering, 2012, Vol. 38, No. 3, p:31- 44.

CYAN-MAGENTA-YELLOW (CMY) CONVERSION MODEL ON DIGITAL COLOR PROOF PRINTER

Wiwi Prastiwinarti 1, Noorbaity 2 Politeknik Negeri Jakarta, Jalan Prof. Dr. G.A. Siwabessy, Kampus UI, Depok 16425, Indonesia 1 [email protected] 2 [email protected]

ABSTRACT

In the context of print quality, gray color data is very important. We propose a method based on polynomial modelling to calculate the gray color data of different lightness. The standard color target ECI2002 CMYK for ICC profile is firstly printed out, and the corresponding CIELAB are obtained by a spectrodensitometer with color sensors. Secondly, the polynomial regression method is used to determine the relationship between these two color space, in which the given CIELAB color’s then CMY value is calculated. At last, as there are solving errors within the polynomial modeling, a new color target is developed to find the real gray color based on the relationship and the final relationship between CIEL* and CMY are obtained. The obtained results demonstrate that the proposed polynomial modelling method works remarkably well with the average color error is 3.18DE which is below the printing error threshold, and indicates polynomial regression modeling is suitable for gray color calculations.

Keywords : polynomial modelling; CIEL*a*b; Color space; colorymetri.

Introduction

Color is very important for printing quality. Color and quality control starts with color management in prepress, an important step before any real printing actually takes places. Gray Component Replacement (GCR) process in prepress is used to reduce the process color of cyan (C), magenta (M) , and yellow (Y), and replaces them with an equal amount of black (K) ink. Theoretically the substitution of chromatic inks (Cyan, Magenta, Yellow) with a black one can easily performed, improper settings of GCR level can cause significant color difference in the image, because black ink cannot replace the colorfulness of chromatic ink. Therefore, it is very important to determine the relationship between the CMY and K because the black ink has no chroma, the issue turn into finding the same lightness between the K color and the combination of C, M, and Y. For CMYK printers, during the process of calculating gray color data, the CIEL* can be selected to link the CMY and K where the combination of C, M, Y colors and the K color correspond to CIEL* value. CIELAB color space is often used to connect the device color space. In the process of conversion between CIELAB and CMY color, the color target has to be used which includes many color patches (Fashandi, 2010). The color target in this research is EC12002 CMYK for ICC profile which has 1485 color patches. Target of this research is employed for gathering sample data and then ten gray colors with different CIELAB values are used for calculating CMY values, to test the conversion error the calculated CMY values may present come chroma after printing, then a new gray color target is created to modify the CMY values to get the real gray color. Converting color process from CMY to CIELAB can be defined as characterization (Lee dan Lee, 2013), the contrary process if often called calibration (Yang et al., 2012), focus of this research is calibration. The commonly used calibration algorithm are 3D interpolation (Pekkucuksen and Altunbasak, 2013; Liu et.al., 2013; Srivastava et al., 2010), polynomial regression (Hong et al., 2001; Nussbaum et al., 2011), neural network (Kang and Anderson, 1992; Hwang et al., 2013), The research of Sun Bangyong (2014) is propose the polynomial regression model to calculate gray color data with the same lightness and the color target is IT8.7/3 which has 928 color patches on a copper paper 120 gsm on HP Indigo 5500 printer, and the result is the average error 2.65DE. This research propose similar model, polynomial regression model to calculate the gray color data with different lightness, but with 1485 color patches, and the color target is ECI2002 CMYK for ICC profile , the experiment of this research use semiglossy paper 44 inch - 190 gsm on Epson Stylus

9700 digital color proof Printer. A digital proof is a color prepress proofing method where a job is printed from the digital file using inkjet, color laser, dye sublimation, or thermal wax print technologies to give a good approximation of what the final printed piece will look like. The digital proof is generally less expensive than other prepress proofs.

Polynomial Regression Model

During the printer calibration process, firstly the standard color target ECI2002 CMYK for ICC profile which has 1485 color patches is printed out. Within 1485 color patches, most of color patches are not gray, it is hard to find the CMY patches which contain none chroma information. The color target ECI2002 CMYK has 1485 color patches, within 1485 color patches there are 528 patches; their CIELAB value can be measured by Spectrodensitometer XRite 530. The relationship between CMY dan CIELAB can be modelled as :

CL( *, a *, b *)=++++aa01 L * a 2 a * a 3 b * a 4 L * a * + a 5 a * b * + a 6 L * b *

ML( *, a *, b *)=++++ββ01 L * β 2 a * β 3 b * β 4 L * a * + β 5 a * b * + β 6 L * b * (1)

YL( *, a *, b *)=++++γγ01 L * γ 2 a * γ 3 b * γ 4 L * a * + γ 5 a * b * + γ 6 L * b *

Where the coefficients n-koefisien a , β ,γ are determined, the CMY value can be calculated. The calculation of polynomial regression coefficients are usually based on the least squares method, which minimizes the variance of the unbiased estimators of the coefficient, under the the condition of the Gauss-Markov theorem. The coefficient of equation (1) can be calculated as below

U= ( VVT )(−1 VP ) (2)

where U is coefficient matrix, P is sample data CMY matrix, and V is sample data CIELAB matriz.

Experimental Results

Firstly, the color target ECI2002 CMYK for ICC profile is printed out on a 190 gsmsemiglossy paper 44 inch by Epson Stylus 9700 printer, a kind of digital color proof printer, and then the spectrodens X-rite 530 is used to measure CIELAB values. Within the measured results for 526 CMY sample data, the maximal CIEL* value is 91 and the minimal CIEL* value is 24. Between these two CIEL* value, another ten CIELAB are selected to calculate the CMY values which form gray colors. Secondly, the polynomial regression method is used to determine the relationship between CMY and CIELAB, and the ten gray colors CMY and CIELAB values are obtained bellow.

No L a b C M Y 1 24 0 0 64 62 98 2 32 0 0 57 61 76 3 39 0 0 52 60 59 4 46 0 0 47 57 43 5 54 0 0 42 53 30 6 61 0 0 38 47 21 7 68 0 0 34 41 14 8 76 0 0 32 29 23 9 84 0 0 29 23 10 10 91 0 0 28 13 12

At last, as there are solving error within the polynomial regression model, the directly calculated gray color data may be inconsistent with the actual gray data. For example within the second gray color data in Table 1, the calculated CMY is (57,61,76) for the CIELAB value (32,0,0) but when this CMY color is printed out, the CIELAB values is (30, -1,0). Therefore a new testing target similar to GrayFinder19 is developed according the color data in table 1. Figure 1 show the ten group of low chroma patches are arranged, and the center patch’s CMY value is from the data of table 1. Taking the first group for example, the CMY of center patch is (57,61,76), and all the C value of patches remains unchanged, while the M value of the left patches are 61-1, 61-2, 61-3, respectively, and the M values of the right patches are 61+1, 61+2, 61+3; similarly the Y value of the upper patches are 76+1, 76+2, 76+3. And the Y value of the underneath patches are 76-1, 76-2, 76-3. When the gray color target is printed out and measured, the real gray color with CIEa*= 0 and CIEb* = 0 can be found. Finally, Table 2 show CIEL* and CMY value of the real gray colors. With the gray color data in table 2, the relationship between CIEL* and CMY are determined, any given lightness gray color’ CMY can be simulated. The third-degree polynomial is used to calculate CMY value :

2 3 C(L) = α0 - α1L* - α2 L* + α3 L*

2 3 M(L) = -β0 + β1L* - β2 L* + β3 L* (3)

2 3 Y(L) = γ0 - γ1L* + γ2 L* - γ3 L*

From equation (3), the gray color data curves for lightness L* from 24 to 91 are described from the curve in figure2. To know the accuracy of the obtained gray color data, twenty testing patches were selected to calculate the color errors. Twenty CIELAB gray color data were randomly selected between L= 24 and L =91 (CIEa*=0 and CIEb*=0). For the given CIEL values, CMY values are calculated according to equation (3); These CMY values are printed out dan measured, and the new CIELAB values obtained. The two groups of CIELAB are compared using color difference formula, and the average error is 3.18DE and the maximal error 6.42DE. This experiment result is acceptable, because for most of the printing process the average error threshold is 5DE, the polynomial regression model is suitable for gray color calculations.

Figure 1. the gray target used to find the real gray color

Table 2. Gray Colors by Reprinting dan Measuring

C M Y L a b 64 65 96 28 0 0 57 63 74 29 0 0 52 61 60 42 0 0 47 55 45 44 0 0 42 55 32 55 0 0 38 45 23 58 0 0 34 40 16 63 0 0 32 35 10 72 0 0 29 25 12 80 0 0 28 14 14 93 0 0

Figure 2. The Gray color Data Curves

Conclusions

The proposed polynomial regression model for calculating gray color data is essential for color reproduction in printing process. If the CMY color data is not accurate, the gray image will show some chroma in the highlights. Mid-tones, or shadow. In this experiment, the accuracy of gray color data is acceptable.

Acknowledgements

This research is supported by Politeknik Negeri Jakarta and Printing Technology Department Politeknik Negeri Jakarta. I gratefully acknowledge Mr Abdillah for his supporting of this research. Also, I appreciate Ms. Noorbaity for her patient and sharing her great experience in Mathematics.

References

1. [1] Bangyong Sun. Calculating Cyan-Magenta-Yellow-Black (CMYK) Printer Gray Component Data Based On Polynomial Modelling. Academic Journal. 2014. Vol. 9 No. 9. Pp 352-356 2. [2] Fashandi H, Amirshahi SH, Tehran MA. Evaluation of Scanner Capability for Measuring The Color of Fabrics with Different Textures in Different Setups. Fibers Polym. 2010. 11(5) :767-774

3. Hong GW, Luo MR. Rhodes PA. A study of Digital Camera Colorimetric Characterization based on Polynomial modeling. Color Res. Appl. 2001. 26(1):76-84. 4. Nussbaum P. Regression Based Characterzation of Color Measurement Instruments in Printing Application. In: Conference on Color Imging XVI – Displaying, Processing, Hardcopy and applications, Proceedings of SPIE. San Francisco, CA.2011. 7866:78661R. 5. Srivastava S. color management Using Three Dimensional Look-Up Tables. Jurnal Imaging Science Technology. 2010. Vol. 54. No.3. 2010. pp 030402. http://dx.doi.org/10.2352/J.ImagingSci. Technol.54.3.030402. 6. J. Morovic. Digital Color Imaging Handbook. Chapter 10 : Gamut Mapping. CRC Press, ISBN: 084930900X: Ed. by G. Sharma.2002.

THE INFLUENCE OF DENSITY TROPICAL HARDWOOD TO FIBERS, CHEMICAL AND PULP QUALITY

Wawan Kartiwa Haroen Center for Pulp and Paper, Bandung [email protected]

ABSTRACT

Basic density of the wood is one of factors to be considered in industry pulp, because the basic density will affect the production capacity and the quality of pulp produced. Observation and study tropical hardwood basic density between 0.30 to 0.98 on 21 species plants , 121 test sample interval is classified into 7 classes basic density. In the group of density to analyze the relationships between basic density haradwood to fiber morphology, chemical of wood, pulp quality and physical properties pulp sheets. The analysis shows the Basic density of tropical hardwoods will affect the cell wall thickness fiber, lignin content of wood, pulp yield, residual alkaline pulping, Kappa Number, tear strength and folding indurace of pulp sheet. From its study produced 12 models of statistical equations and regression coefficients of the gravity of tropical hardwood fiber morphology, chemical content, pulp quality and physical properties of resulting pulp sheet. This equation model can be used as a simulation tool to make a selection of hard-wood pulp as raw material with a specific gravity used, the specific terms and conditions.

Keywords : Basic density,Fiber morfology,Quality pulp,Regression

Introduction

The use of wood as raw material for pulp in Indonesia started around 1970, when the natural forest resources began to be utilized optimally to support foreign exchange. 1960s pulp material using agricultural waste and plantation in line with the founding of the paper industry in Indonesia. Since the time of the Dutch paper mill was associated potential of the area, a famous West Java rice farming area and produce rice straw waste. Built a paper mill with raw material rice straw in Padalarang. East Java lot of growing crops and sugar cane bagasse waste, built a paper mill Leces. Technological developments of the 20th century, built kraft paper pulp mill in Aceh, make a raw material from pine wood. 21th Century paper pulp industry in Indonesia 90% uses wood from natural forests or crops. The government regulation on timber extraction permits tropical forests including age, type and location resulting pulp quality varied. The use of wood for pulp approximately 4.5 to 5.0 m3 solid wood, it’s means the pulp mill designed to produce 1,000 tonnes/day equivalent is required logs 4,500-5,000 m3/day, or an area forest to cut 20-22 ha/day record in-growth trees 225 m3/ha. (Kartiwa, 1998). Consumption wood pulp as the raw material resulting in high utilization of wood various types to maximum. The problem resulted pulp fluctuation quality and the possibility of quality is decline. Factors that may effect the quality of pulp including basic Basic density, according to Brown (1994), Cassey (1980) basic densityof wood for pulp preferably have basic densityless than 0.8. The basic density make effect to the pulping process, especially use of chemicals pulping. To improve basic densityof wood that is associated and quality products ahir, conducted a study and analysis of quality basic densitywood pulp, chemical fibers and wood basic densityusing a secondary data FAO has a variation basic density0.30-0.98. Analysis using statistical regression correlation. The study has results obtained are expected to predict the quality of sulphate pulp tropical hardwood with a different basic density types.

Basic Density of Wood

The basic density of wood is a comparison between wood basic density to basic water at 4°C. (Cassey 1980; Kocureck 1987; Kellomaki 1998) or basic densityof wood is heavy computation value divided by volume.Basic densitywood types are necessary to calculate the cost transportation, predicting of strength, and durability properties of wood as construction. The higher the basic densityof the wood wood strength better and have expensive prices for construction materials. Full peripheral in the pulp industry that does not come into force, because the basic densityof the wood for pulp to be mild to moderate range of 0.35 to 0.65 (Parhan 1983, P3HH. 1989; Dulsalam, 2014). The basic densityof the plant influenced by age of plant, plantation area and genetics. Basic densitywill cause differences to cellwall thicknes, fiber dimention and type of vessel. The basic densityhardwood have effect to chips quality and current energy consumtion of chipper machine. Variation of basic densitymake a chips uniformity and consumme of energy chipper machine. (Kelomaki 1998, Tappi 2005). Differences in the manufacture of pulp densitu of wood required higher cooking chemicals, slower penetration of chemicals to chips. The basic densityis important economic benefit element for selection a raw material pulp. Because the wood for pulp purchased by volume but the product pulp are sold on basis weight so that the basic density becoming one of decisive parameter. Basic densitywood pulp results are directly related to volume unity, the relationship caused by wood as a raw materials. High basic densityof the wood that will produce hard milled pulp properties, bulky paper sheet, tensile strength, folding indurance and bursting strength very low but tear strength is high. The wood basic densitymay effect which the height position of stem, tree age, structure wood , genetics, fiber dimensions, and extractive substances.

Table 1. Characteristic of wood pulp

Pulp quality Good Medium Poor Colour of wood White-yellow Brown-Dark Dark Basic Basic density < 0,50 0,50-0,60 0,60 Fiber length, mm > 1,6 0,9-1,6 < 0,90 Holoseluloce,% > 66 60-65 < 60 Lignin,% < 55 25-30 30 Extractives, % < 5 5-7 >7

Sulfate Pulp

Pulp sulphate or kraft process invented by C.F Dahl (Germany) where he added sodium sulfate ( salt cake ) into the recovery furnace as a substitute chemicals are lost during the process operations soda . Commercially started in 1885 in Sweden ( Scott & Abbolt 1995; FAO ) . Paper from pulp sulfate has the physical strength and excellent fiber formation , so that the sulphate pulp process until now still survive and leading technology to produce pulp in the world.

Hardwood Pulp

All kinds of plants have the cellulose fibers and can be used for pulping. But in the election process to consider the technical and economic factors (Kartiwa, 1998). Technical factors include the basic Basic density, and the nature of the plant. This is to obtain optimal pulp quality at an economical cost.

Tabel 2. Classification basic density

Very light Light Medium Heavy Specific grafity < 250 251-450 451-800 >800 Densiy 0,25 0,26-0,45 0,451-0,80 >0,80 Pulp Type Mechanis Mechanis/ Chemical Chemical Chemical

Wood tropical hard-wood and a wide variety of more than 400 types (Vademecum, 1976; Atlas Wood Indonesia 2005). Wood selected commercially for pulp material has been maintained and cultivated to sustain the industry. But to consider the utilization of wood has not been known as an alternative to wood pulp. Timber of mixed tropical forests, consisting of more than two types of wood will have different properties. As the diversity of basic Basic density, chemical content varies can result in pulp quality is not standard. The issue needed to aspire wood selection stage with the kind of future variations are not too wide. The results of the study and approach through a statistical simulation can contribute to pulp producers in analyzing the influence of the basic densityof the wood to be used.

Experiments

Materials

Data sample of basic densitytropical hardwood obtained were used in this study from FAO (1979 ), which is processed and grouped into seven groups of basic densityfrom 0:30 until 0.98 . Wood samples taken at random many 21 species of plants consists of species Sterculia sp , Alba sp , Sclerolobium sp , Poeteria sp , Drypetes sp , Bombax sp , Peltogyne sp , Perebea sp , Caryocarpus sp , Peoroma sp , Diospyros sp , Heyronima sp , Simarouba sp , Sapium sp , ap Duroira , Manilkara sp , Pterocarpus . Each wood species that enter into a class of basic densityare taken randomly 5 wood samples to represent a class of its basic Basic density

Methods

Data hardwood that has a basic densityof 0.98 0:30 until processed according to share class with a difference of 0.9 for each class. Data are grouped into seven classes specified intervals with statistics, class time interval calculation result type is composed of 0:30 to 0:39; 0,40-0.49; 0:50 to 0:59; 0.60-0.69; 0.7-0.79; 0.80-0.89 and 0.90-0.99. Each class is represented by the sample interval timber as much as 5 random sample that represents the basic densityof the wood. Sample was selected in the group 7 class was analyzed statistically to parameter morphology fiber length, wall thickness of the fiber, the content of extractives, lignin content, yield sulphate pulp, residual alkali cooking, Kappa Number (maturity pulp), the index is torn, the bursting index , folding endurance and long break up , Data processed © 2016 Published by Center for Pulp and Paper through 2nd REPTech 241 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 grouped and analyzed to determine the relationship between the basic densityof the wood on several parameters of fiber morphology, chemical and pulp quality. Processing data using regression analysis to determine the strength and influence indicated by the value R2 regression, as well as the model equation y = ax + b. Observations and analysis are divided into three groups, consisting of groups 1 to the basic densityof the fiber length, fiber wall thickness, extractive and lignin. Group 2 for the basic densityof the yield pulp, pulp maturity (KN), active and residual alkali content of extractives in the pulp. Group 3 for the relationship of basic densityon the physical properties of pulp sheets.

Results and Discussions

Based on the data in Table 4 for the observation of the 21 species of tropical hardwood timber that is grouped into seven classes basic densityinterval showed the following results. Long fibers that have a range of 1.13-1.83 mm fiber length, based on the classification of fibers according to Klemm (Cassey.1980) its fibers included into the medium. to long term (> 1.6 mm) with an overall length of 1:44 mm. While the cell wall thickness of 0.25-18.75 μ between classified into fiber wall thin to thick. The classification of the wood fiber that has a quality class II and III of wood as a raw material has the properties of basic densitypulp in mild to severe, thin to thick-walled fiber, the fiber has a lumen of small to medium. Physical properties of the resulting pulp sheet has tear strength, bursting strength good or moderate. (Vademecum 1979).

Basic Density to Fiber Morphology

The basic densityof wood to fiber length shows the results showed not correlated and not significantly. The value shown by R2 = 0.113 (11.3 %) were small with the equation Y = 0.035x + 1.298. This means that the higher the basic densityof the fiber length is formed not in line with increasing fiber length . But it turns out the fiber wall thickness can be influenced by the basic densityof the wood that is significantly in line with the value of R2 = 0.728 (72.8 % ) were great with the equation Y = 0.813x + 2055 . This shows that the basic densityof the wood will effect each other against the wall thickness of the fiber or the fiber wall thickness can be influenced by past timber species. This statement is in accordance with the 1980 Cassey that wood basic densitycan be influenced by type of wood cell wall thickness (Figure 1). In his study , we attempt to use basic densityan easyily measurable parameter, to correlate the effect of fiber properties to asses their value for pulp.

Fig 1. Relationship of basic density to fiber morfology

The graphic in Figure 1 shows that the higher the basic densityof the wood , the walls of plant fibers will be more thick, while length of the fiber is not much influenced wood basic Basic density.

Simulation and prediction how the direction changes wood basic density to fiber wall thickness of plant can be formulated with a model equation Y = 0.813x + 2055 . The simulations showed that wood basic densitycan be effect the thickness of cellwall fiber , so that the wood basic densityof light wood would be predicted to have thin cellwall fiber is expected to be easier pulping and fibrilation.

Basic Density to Chemical

Wood basic densityof chemically analyzed in the study only analyzes for lignin and extractives , according to Cassey 1980, Kocurec 1987 , Sixta , Herbert.2006 have is strongly related. Study showed that high levels of lignin will be influenced by increasing basic densityand contribute to strong with a high coefficient of regression equation Y = 1.130x + 21.92

Fig 2. Relationship of wood basic density between wood chemical

The content of wood extractives observed no significant effect on the high or low densities of wood , see Figure 2 and Table 1. Mean levels extractif can not be predicted by looking at the high or low basic densityof wood , that is value of R2 = 0.002 ( 0.2% ) is very small and the relationship equation Y = - 0.004x + 3.047. Lignin content between 22.10-39.40% on average 27.04%, wood has a medium to high lignin content (Vademecum 1976), whereas the levels of extractive between 1:09 to 11:41% on average 3:07%. Based on 21 types of hardwood pulp qualifies as material. Period of wood for pulp raw material past its kind arranged to have densities of less than 0.80, with a fiber length of more than 0.9 mm, less than 33% lignin and ektraktif less than 5%. Such criteria may be considered for use as raw material for pulp, but the pulping process used cooking excess chemicals required to achieve the same maturity pulp. (Attachment 1). Extractive high in wood poses problems in pulping and stains on the pulp. Obstacles like these are often found in mixed hardwood densities vary, so the quality of the pulp is not standard, it needs to be studied in-depth because it is still a matter of discussion to resolve it.

Basic Density to Pulp Quality

Effect of wood basic densityon yield parameters analyzed pulping, residual alkali and Kapa Number pulp. The results showed the yield pulp between 41.60-56.24% (average 48.67%) for a wood type 0.3 (low) will produce high-yield pulp with a Kappa Number of active low and residual alkali cooking low. Means that the low densities that will be easy to pulping and produces good quality pulp (Cassey 1980, Kocurec 1987, Sixta, Herbert.2006). Cooking with active Alkali 15%, Sulfiditas 25% is good enough as indicated by the level of maturity pulp by Kappa Number is low for a particular type.

Fig 3. Relationship of wood basic density to chemical pulp

The basic densityof wood against bursting index does not show a real relationship, the higher the basic densityof bursting index has not changed much strength with the regression coefficients 2R = 0.313 for the equation Y = - 0.031x + 0885. figure 3. The analysis result is predictable and suggested the use of wood for pulp cultivated in monoculture and its basic densityis less than 0.70 or flakes of wood pulp, the raw material cultivated wood basic densityvariation of less than 0.70. With predict for prediction and the results of the study are expected to be able to keep the pulp quality and share the quality standards.

Table 3: Wood basic density to physical properties of pulp ,(freenes 400 mL CSF

Basic Basic Bursting index Tearing index Folding Double folds density (mN/kg) (Nm2/kg indurace (m) (times) 0.3 0.81 1.69 7800 46 0.4 0.84 1.68 7200 56 0.5 0.78 1.98 6733 54 0.6 0.86 2.06 8033 39 0.7 0.79 2.10 6766 31 0.8 0.50 1.74 4866 18 0.9 0.74 1.62 5666 13

Table 3 shows the higher of wood basic density can be effect the folding indurace, bursting index, tearing index and double folds of sheet pulp. The higher wood basic density used in the manufacture pulp, can be produce low-quality of pulp with the physical pulp properties decreased with the higher basic densityof wood. As shown in the group wood basic density0.6-0.70 and 0.80-0.90 physical quality of pulp decreased with increasing the basic densityof wood. The basic densityof wood against bursting index can not show any real felationship to high or low wood basic densitywith the value of regression R2 = 0.313 (31.3%) to the equation Y = 0.031x + 0885. According Cassey 1980, Kocurec 1987; Heikkurinen , 1999 . suggests that , on a sheet of pulp cell wall fiber can affect the tearing strength towards the side wall of the fiber . So that the paper sheet will be stronger when holding force on the cell walls of fiber

Figure 4. Relationship of wood basic density to pulp quality

The results of the observations and analysis contained regression suitability as proposed Parham et.all, 1983. The basic density of the wood need to be considered for selection as wood pulp material, because it can effect the physical strength pulp. The relationship can be seen in Figure 3 and Table 2. Effect of the basic densityof the hard-tropical wood fiber, chemical, pulp pulping and quality sheets, can be tested by using the approach of the equation in Table 3. This equation can be a tool as an initial study.The basic densityof wood can determine the yield and Kappa Number sulphate pulp with the way the relationship is the regression coefficient 2R = 0.317 with the equation Y = 1.603x + 26 290 with a tendency to influence each other . This condition can be used as a starting point for predicting the wood to be used .

Tabel 3 . Regression and corelation coeffisients basic density wood

Equation R-squared

Fiber length., mm Y = 0.035x + 1.298 R2 = 0.113

Cellwall thickness, µ Y = 0.813x + 2.055 R2 = 0.727 Yield pulp, % Y = - 0.482x + 50.225 R2 = 0.496 Residual alkaline, % Y = 0.461x + 2.362 R2= 0.693 Lignin, % Y = 1.130x + 21.92 R2 = 0.768 Wood extractives , % Y = - 0.004x + 3.047 R2 = 0.002 Kappa Number Y = 1.603x + 26.290 R2 = 0.317 Pulp extractives, % Y = - 0.004x + 3.047 R2= 0.001 Tear index, Nm2/kg Y = 0.093x + 1.605 R2 = 0.880 Bursting index.,mN/kg Y = - 0.031x + 0.885 R2 = 0.313 Folding indurance, times Y = - 6.785x + 65.571 R2 = 0.771 Tensile strength, m Y = - 394.18x + 8300 R2 = 0.567

Table 4. The basic densityof wood to fiber, chemical and pulp quality

Interval Tear Basic Fiber Cellwall Yield Residual Wood Pulp Bursting Bright basic Lignin index Basic length thickness pulp alkaline extractive extractive index ness Basic (%) K N (mN/ density (mm) (µ) (%) (g/l) (%) (%) (Nm2/kg) (%GE) density kg) 0.3 0.3-0.39 1.49 3.83 50.37 3.20 24.10 2.28 27.00 0.40 0.81 1.69 26.33 0.4 0.4-0.49 1.20 3.00 47.70 3.73 24.23 3.80 32.60 0.80 0.84 1.51 29.17 0.5 0.5-0.59 1.26 4.00 49.17 3.47 23.77 2.64 22.83 0.39 0.78 1.98 29.00 0.6 0.6-0.69 1.64 5.58 47.78 3.07 25.00 2.79 38.23 0.54 0.86 2.06 22.98 0.7 0.7-0.79 1.27 4.67 49.22 4.27 28.77 4.84 38.97 0.46 0.79 2.10 22.16 0.8 0.8-0.89 1.83 8.67 46.42 6.00 30.40 3.06 31.03 0.37 0.64 1.74 23.33 0.9 0.9-0.99 1.40 7.42 47.03 5.73 28.87 2.10 37.63 0.55 0.55 1.62 20.17

Note: Sulfate pulping AA: 15 %, Sulfiditas : 25% , Suhu 170o C, Ratio 1:4 , Freeness 400 mL Csf, Wood Basic density 0.30-0.98. Source: FAO been processed.

Conclusions

Observation to 21 types of tropical hardwood have a basic density 0.30-0.98 to relationship with the nature and quality fiber as raw material for pulp obtained the following results : • Cell wall thickness fiber will be increase in line with the increased wood basic density, but basic density is not a lot influence to morfology long or short fiber. Lignin content in wood is influenced greatly to wood basic ic density, more higher wood basic density make a high levels of lignin on wood. • The basic density timber make effects the quality of sulfate pulping,the higher basic densityof wood will be produce a low yield of pulp with a higher Kappa Number (KN). • Wood basic densityof tropical timber forest will be effect the quality of sulfate pulping process,more higher basic densityof wood will be produce low yield of pulp and Kappa Number (KN) is high. Wood basic densityof tropical hardwood less than 0.70 will be produce quality pulp is good, especially the tear and tensile strength .

References

1. Ahmed, A.Myers.G.C.Abu Bakr, S.Packaging grade kraftpulp fromsmall-diameter soft-wood, Proceedings,Tappi Press,Atlanta,Geogia,USA. 2. Arry Widianto. Pengaruh teknik silvikkultur terhadap kualitas kayu. Forpro.Vol.4.No.1.Edisi juni 2015. Hal.6-10. 3. Axen.R.R. Kraft pulping – economic benefits from screening wood chips by thicknes. 4. Brown,H.P; A.J. Panshin; C.C. Forsaith. Texbook of Wood Tech.Vol.1. Mc.Graw-Hill Book.Co.Inc. 4th.Ed.New York. 1994. 5. Cassey,J.P. Pulp and Paper Chemistry and Chemical Tech.Vol.1,3rd ed..Jhon Willey and son.New York. 1980. 6. David E White; Charles Courcheme; T.Mc.Donough; Laurie Schndeck; Gerry Petter; Jim Raches & Gopal. Effect of laboratory pine wood & pulp properties on sheet characteristic.Tappi Journal 2011. February .pp.36-41 7. Dinwoodi,J.M. The relationships between fibre morfology and paper properties.a Review of literature Tappi.J.46.8. 8. Dmitri Gorski;Atti Luukonen;Marc Sabourin & James Olson. Two stage low-consistensy refining of mechanical pulp. Appita Journal. 2012. Vol.65.No.3.Juli-September 2012. 9. Dulsalam. Keteknikandan pemanenn hasil hutan.Sintesis RPI 2011-014. Puslitbang keteknikan dan pengolahan hutan, Bogor. 2014. p.145 246 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

10. Dwiyanto,Wahyu ; Sri Nugroho Marsoem. Tinjauan hasil-hasil penelitian faktor alam yang mmpengaruhi sifat fisik dan mekanis kayu Indonesia. Jurnal Ilmu dan Teknologi Kayu Tropis. Vol.6.N0.2.Juli 2008.hal.85-100 11. Earl.I.W Ramsedell . The practical aplication of statisical analysis in the industrial process. Tappi Press p.39-48 12. FAO. Pulping and paper making properties of fast-growing plantation wood species. Rorestry industries division forestry departement. 1976. 13. FAO. Evaluation of mixed Tropical Hardwoods for Pulp and Paper Manufacture. FAO of the United Nations . Rome. 1976. 14. Gindl,W.Grabner,Mwimmer, R. The influence of temperature on latewood lignin content in treeline Norway spruce compared with maximum Basic density ring width Tree. 2000. 15. Heikkurinen, Annikki; Mikael Lucander; Jari Sirvio and Antero Varhimo. Effect of spruce wood and fiber properties on pulp quality under varying defibration condition.Tappi Intern.Mechanical Pulping Conference. The Westin Galleria.Tapp Press. 1999. 16. Holik,Hebert . Handbook of Paper and Board. Wiley-Vch Verlag GmbH & Co.KgaA. 2006. 17. Kaitang Hu, Yonghao Ni, Yayun Zhou and Xuejun Zou.Substitution of hardwoodbkraft with aspen high-yield in lightweight coated wood-free papers. Tappi Journal vo.5.No.5.p.20 18. Kang, K.Y. Zang, S.Y. Manfield, SD. The effect of initials spacing on wood Spesific. grafity, fibre and pulp properties in Jack pine. Holzforchung 2004 (58):455-463

THE EFFECTS OF ALKALINE PRE-IMPREGNATION PRIOR SODA- ANTHRAQUINONE PULPING ON OIL PALM EMPTY FRUIT BUNCH FIBRE

Chong Yin Hui, Ng Shi Teng, Leh Cheu Peng a 1 aBioresource, Paper and Coatings Technology, School of Industrial Technology, Universiti Sains Malaysia, 11800 Minden, Pulau Pinang 1 [email protected]

ABSTRACT

Oil palm empty fruit bunch (EFB) fibre was used as the raw material in this study to investigate the effect of alkaline pre-impregnation prior to the common soda-anthraquinone (AQ) pulping. The effect of three independent variables of alkaline pre-impregnation, namely reaction temperature, time and alkaline charge, on the soda-AQ pulp and handsheet properties were examined and compared. The alkaline charge applied on the pre-impregnation and pulping was totalled up as 25% based on the oven- dry weight of material. The results obtained showed that the application of alkaline pre-impregnation would increase the pulp yields and paper properties significantly in comparison to the unpre-impregnated one; even though the effects on the pulp properties such as pulp viscosity and kappa number were trivial. It was suspected that the increase of handsheet mechanical properties was due to the retention of a large part of hemicellulose which could contribute to a higher pulp yield, better hydrogen bonding but a lower average pulp viscosity due to its low degree of polymerization. Among the independent variables, the reaction temperature contributed the most influence on the mechanical properties of handsheet. This study found out that without the additional use of alkaline charge, the application of a low alkaline charge pre-impregnation at mild elevated temperature (50-65°C) followed by a normal pulping was capable of improving the handsheet mechanical properties of the resultant pulp. Nevertheless, it showed less impact on pulp properties.

Keywords: Alkaline pre-impregnation; soda-AQ pulping; mechanical properties, oil palm empty fruit bunch

Introduction

Various chemical pretreatments prior to an ordinary pulping have been reported for the enhancement of pulping efficiency [1-3]. According to Brannvall and Backstorm [2], using a high effective alkali (2M) impregnation on mixed softwood chips at 130°C for 30 min could increase the subsequent kraft pulping yield up to 2% due to the higher retention of cellulose and hemicellulose. On the other hand, Bykova and co-workers [3] found that pre-treating pine wood chips with model green liquor (at a ratio 0.7:1 of liquor to wood) followed by kraft pulping showed that the residual lignin content decreased from 4.4% to 3.0% without causing any impact on pulp viscosity in comparison to the conventional kraft pulping. It was suggested that the diffusion and chemical redistribution on the biomass were the reasons for improving the rate of delignification [3-4]. On the other hand, Ang and co-workers [1] reported that the implementation of alkaline pre- impregnation on kenaf bast fibre at room temperature for 15 hours followed by soda-anthraquinone pulping showed higher pulp yield and handsheets’ strength properties than the conventional single-stage soda-AQ pulping did. The beneficial effects of the alkaline pre-treatment (recycled black liquor) prior to a conventional kraft pulping on the pulp and handsheet properties were also reported by Tripathi and co-workers [5]. It was reported that the screened yield, pulp viscosity, tensile, tear, and burst index of mixed hardwood pulp were improved by 2.1%, 1.8 cP., 8.5%, 30.8%, and 35.7%, respectively, as compared to the normal kraft pulping. The findings indicated that the application of a two-stage pulping process could enhance the removal of lignin from the biomass while minimize the loss of carbohydrates, especially hemicellulose [1,5-6] through the alkaline hydrolysis and dissolution [1,4-5].

Since late 1970s, biomass residues generated from palm oil industry have attracted interest from local and overseas researchers for converting them into value added fibrous materials, which include pulp for papermaking, cellulose derivation, composites and so on [7,8,9,10]. Fibre from oil palm empty fruit bunch (EFB) has been widely investigated for the production of papermaking or even dissolving pulp due to its: i. Economical feasibility as it is a process waste from palm oil factories with relatively lower cost in comparison to fibre crops; ii. Chemical suitability as it contains relatively high in carbohydrates and low in lignin contents; and iii. Environmental sustainability as it is annually renewable and will not involve additional logging activity [8-11]. According to some research studies, EFB soda and kraft AQ pulps were suitable for paper production and their resultant paper properties were comparable to paper produced from commercial hardwood pulps [9, 11]. However, due to its relatively shorter fibre length (<1.0mm), the paper from EFB pulps demonstrated relatively lower strength [9, 12]. In order to further improve the properties pulp and paper produced from oil palm EFB fibre, in this study, the modified pulping method (alkaline pre-impregnation followed by soda-AQ pulping) was employed to produce papermaking pulp from EFB fibre. Different from previous studies, instead of room temperature with prolonged impregnation time, mild elevated impregnation temperatures (50- 65°C) were used and the treatment time was shortened to 2 to 4 hours. Besides that, the effect of alkaline charge of pre-impregnation on the pulp and handsheet properties was also investigated.

Experimental

Materials

The oil palm empty fruit brunch (EFB) was supplied by United Palm Oil Sdn. Bhd, Nibong Tebal, Penang, Malaysia. The EFB fibrous strands were first soaked overnight in filtered tap water and then washed to remove contaminants. After that, the washed EFB fibrous strands were air dried for a week and kept in a plastic bag for further use.

Methods

Alkaline Pre-Impregnation and Soda-Anthraquinone (AQ) Pulp Preparation

Alkaline pre-impregnation and soda-AQ pulping of EFB fibre strands were carried out by using a 4 litre stationary stainless steel digester (made by NAC Autoclave Co. Ltd., Japan). The pre-impregnation was conducted with the fixed liquor to material ratio of 7:1 and different combinations of alkali charge (on the oven dry basic of EFB), temperature and time as listed in Table 1. All fibres were ensured immersing by the cooking liquor in the reaction digester for attaining a homogenous impregnation effect. Immediately after the alkaline pre-impregnation was done, 0.1% (on the oven dry basic of material) of anthraquinone and a higher concentration of sodium hydroxide solution were added to the liquor- material mixture in the digester to top up the alkali charge to 25% without washing. The ratio of liquor to material of the subsequent pulping process was increased to 8: 1. The digester was then heated within 90 min to the fixed cooking temperature of 160°C with a tolerance of 3 degree Celsius and maintained at the temperature for 120 min. The overall pulping conditions were shown in Table1. After the completion of pulping, the collected soda-AQ EFB pulp was defiberized together with spent liquor in a hydro-pulper for 10 min and washed thoroughly with filtered tap water in a stainless steel mesh filter. The pulp was further disintegrated mechanically in a three bladed disintegrator for 1 minute at a pulp consistency of 2.0% and then screened by Somerville flat-plate screen fitted with 0.15mm slits. The screened pulp was then spin-dried and kept in at 4°C. The weight and moisture content of the spin- dried pulp were determined in order to calculate the screened yield of the pulp.

Table 1: Alkaline pre-impregnation and soda-anthraquinone pulping conditions for EFB

Alkaline pre-impregnation Soda pulping Tem- Alka- Total Alkaline Tem- pe-rature, Time, h line Charge (L:W) charge (NaOH) pe-rature, Time, h (L:W) AQ, % °C (NaOH), % topped up, % °C AP1 50 2 5 1:7 20 160 2 1:8 0.1 AP2 50 2 8 1:7 17 160 2 1:8 0.1 AP3 50 4 5 1:7 20 160 2 1:8 0.1 AP4 50 4 8 1:7 17 160 2 1:8 0.1 AP5 65 2 5 1:7 20 160 2 1:8 0.1 AP6 65 2 8 1:7 17 160 2 1:8 0.1 AP7 65 4 5 1:7 20 160 2 1:8 0.1 AP8 65 4 8 1:7 17 160 2 1:8 0.1 Handsheet making

The handsheet making was conducted by using TAPPI T205 sp-02 – Formation Handsheet for Physical Tests of Pulp.

Pulp and Paper properties

The pulp and handsheet properties were analyzed according to Technical Association of the Pulp and Paper Industry (TAPPI) Standard—T236 (2013) to find the kappa number and T230 (2008) to determine pulp viscosity while the physical properties and brightness of handsheet were determined based on T220 (2010) and T525 (2012), respectively.

Result and Discussion

Effect of Alkaline Pre-Impregnation Variables on Screened Pulp Yield

As shown by Fig. 1, the screened pulp yield of all the alkaline pre-impregnated-soda-AQ pulping was relatively higher in comparison to the ordinary soda-AQ pulping. It was noted that the yield resulted from the pre-impregnation with 8% alkali charge were relatively higher as compared to their counterpart with 5% alkali charge. According to Ang and co-workers (2010), the increase of pulp yield by adopting an mild alkaline impregnation prior to a conventional pulping process was basically due to the total alkali involved during the pulping process at elevated temperature (160°C) was basically lower than the one without pre-impregnation. This phenomenon was probably due to, during the pre-impregnation, part of the alkali was impregnated into fibre and caused some lignin extraction or dissolution [1,2,5]. Thus, even though the remaining alkali charge was topped up for the subsequent pulping process, the alkali charge during the pulping was actually lower than 25% as compared to single pulp process. As well recognized that the alkali charge mainly affected the degradation and dissolution of lignin as well as carbohydrates during pulping, hence, the increase of screened pulp yield indicated that the dissolution of biomass was reduced. Moreover, when the alkali charge used during impregnation was higher, the remaining alkali charge topped up for pulping became lower and therefore, the degradation and dissolution of the biomass, especially carbohydrates, were moderated. Among all the pre-impregnations, conditions with 8% alkali charge treated at 65oC for 2 hours (AP6) and at 50oC for 4 hour (AP4) gave relatively higher screened yields of 54.0% and 53.8%, respectively.

Fig. 1. Effect of alkaline pre-impregnation variables on total yield of oil palm EFB soda-AQ pulps. * the percentage of alkaline charge (NaOH) applied during the alkaline pre-impregnation process.

Effect of Alkaline Pre-Impregnation Variables on Kappa Number

With the fixed soda-AQ pulping condition, all pulps produced by the impregnation incorporated pulping approach demonstrated, albeit small, relatively lower kappa number (12.3-13.2) than that produced by the control single pulping (13.9) as shown in Fig. 2. Nevertheless, the most noteworthy reduction of kappa number was shown by impregnation conditions of 8% alkali charge for 2 hours (AP2) and 5% alkali charge for 4 hours (AP3) heated at 50°C. The further increase of reaction time and/or temperature of AP2 and alkali charge and/or reaction temperature of AP3 did not exhibited any beneficial effect on kappa number reduction. This results designated that moderate pre-impregnation conditions was sufficient for effective reduction in kappa number as it could help for better chemical impregnation and lignin dissolution. It was believed that as more severe pre-impregnation conditions were applied such as higher impregnation temperature, they would increase the rate of alkali penetration and consequently, affected the delignification rate adversely during the pulping process since the alkali charge remained was lowered. Nevertheless, the effect of alkaline pre-impregnation on EFB fibre was different from that on kenaf bast fibre [1] as the later attained a higher kappa number when the soda-AQ pulping was incorporated with alkaline impregnation. It was suggested that the different effect might due to the variation of biomass and also the condition of pre-impregnation applied.

Fig. 2. Effect of alkaline pre-impregnation variables on kappa number of oil palm EFB soda-AQ pulps. * refer to percentage of alkaline charge (NaOH) were applied during the alkaline pre-impregnation process.

Effect of Alkaline Pre-Impregnation Variables on Pulp Viscosity

In comparison to the control soda-AQ pulps (26.2 cP.), the pulp viscosity of all the impregnated- soda-AQ pulps was relatively lower (21.4-25.6 cP.) (Fig. 3). As mentioned earlier in sections 3.1, the adoption of alkaline impregnation might moderate the degradation and dissolution of the carbohydrates of biomass during the subsequent pulping stage and resulted in a higher pulp yield. Hence, it was believed that the decrease of pulp viscosity might not due to extended degradation of cellulose, but the retention of a larger part of hemicellulose. This is because the degree of polymerization (DP) of the amorphous hemicellulose was much lower than that of cellulose, thus, when the amount of hemicellulose retained in the pulp was increased, the average pulp viscosity was decreased relatively [1]. Nevertheless, among all the impregnation conditions, the changes of the three reaction variables did not show signification variation on pulp viscosity.

Fig. 3. Effect of alkaline pre-impregnation variables on pulp viscosity of oil palm soda-AQ pulps. * refer to percentage of alkaline charge (NaOH) were applied during the alkaline pre-impregnation process.

Effect of Alkaline Pre-Impregnation Variables on Handsheet’s Properties

As mentioned earlier, the effect of alkaline pre-impregnation on soda-AQ pulp properties was rather small; however, the handsheet properties of the resultant soda-AQ pulp showed a significant improvement, especially the tensile index as presented in Table 2. The implementation of impregnation allowed higher retention of hemicellulose, at the same time, lessened the cellulose degradation during the pulping process. These beneficial effects consequently improved the handsheet properties as the presence of hemicellulose would provide better inter-fibre bonding via carboxylic groups’ hydrogen bonds while less cellulose degradation would retain pulp with higher fibre strength. Moreover, the formation of fibre-fibre bonding in the pre-impregnated soda-AQ pulps were also improved due to better lignin removal, which increased the flexibility and hydrophilicity of fibres. Excluding the tensile index of AP1 and AP5, the pulps impregnated at higher temperature (65°C) showed higher strength properties in comparison to their counterpart impregnated at lower temperature. On the other hand, a prolonged reaction time and/or high concentration did not cause any negative impact on all the three strength properties. This indicated that fibre strength of all the pulps was still retained strong due to negligible cellulose degradation. Nevertheless, the changes of the three impregnation variables did not exhibited consistent effect on the handsheet properties. For instance, even though AP1 yielded handsheet with the highest tensile index, (20.1 Nm/g), its tearing and burst indexes showed least improvement. Among all the impregnation conditions, handsheet of AP7 showed good improvement in all tensile (19.0Nm/g), tearing (7.0 mN.m2/g) and burst (3.8 kPa.m2/g) indexes. In order to further verify the reason which caused positive effect on handsheet properties, further investigation on the chemical composition and water retention of each impregnated pulp was recommended.

Table 2.Handsheet’s properties of oil palm EFB soda-AQ pulps with and without alkaline impregnation.

Alkaline pre-impregnation Response Alkali Tensile Tearing Burst Temperature, Time, Brightness, charge, Index, Index, Index, kPa. °C h % % Nm/g mN.m2/g m2/g Control 16.9 ± 0.2 6.0 ± 0.3 3.2 ± 0.3 42.4 ± 0.4 AP1 50 2 5 20.1 ± 0.6 6.0 ± 0.3 3.5 ± 0.3 43.6 ± 0.3 AP2 50 2 8 18.0 ± 0.4 6.2 ± 0.3 3.7 ± 0.3 46.5 ± 0.3 AP3 50 4 5 18.3 ± 0.9 6.8± 0.4 3.5 ± 0.3 44.5 ± 0.3 AP4 50 4 8 15.3 ± 0.8 6.9 ± 0.2 3.5 ± 0.3 43.1 ± 0.5 AP5 65 2 5 17.0 ± 0.6 6.9± 0.2 3.8 ± 0.2 44.5 ± 0.3 AP6 65 2 8 19.3 ± 0.2 6.9 ± 0.4 3.8 ± 0.3 45.5 ± 0.3 AP7 65 4 5 19.9 ± 0.3 7.0 ± 0.4 3.8 ± 0.3 43.4 ± 0.3 AP8 65 4 8 19.1 ± 0.9 7.5 ± 0.5 3.7 ± 0.2 44.6 ± 0.3

The effect of alkaline impregnation on pulp brightness was also investigated. As shown in Table 2, the alkaline pre-impregnated soda-AQ pulps resulted in a small increment of pulp brightness from 42.4% up to 46.5%. The improvement of the pulp brightness was most probably due to increment of the rate of delignification as a slightly higher kappa number reduction was observed for all the pre-impregnated soda-AQ pulps [1]. Moreover, the pulp (AP2) with the highest brightness was also exhibited the lowest kappa number. Besides that, the increase of pulp brightness might be also caused by lesser alkaline darkening effect as the alkali charge during the pulping was reduced. Among all the impregnation conditions, the pulp which had undergone the impregnation with 5% alkali charge treated at 65oC for 4 hours (AP7) produced handsheet with highest mechanical properties in average and moderate high pulp yield and low kappa number. On the other hand, if highest screen yield was taken into account, impregnation with 8% alkali charge treated at 65oC for 2 hours (AP6) was considered as the optimum impregnation condition and it also gave beneficial effect on brightness and rather high handsheet mechanical properties.

Conclusion

The application of an alkaline pre-impregnation prior to soda-AQ pulping on oil palm EFB fibres showed significant beneficial effects on the pulp yield and handsheet mechanical properties. However, it showed less impact on delignification and pulp viscosity. Among the independent variables, the reaction temperature gave the most influence to the handsheet’s mechanical properties. Nevertheless, further research is required to identify the optimum condition of the subsequent pulping process and pulp properties after the alkaline impregnation.

Acknowledgment

References

1. Ang LS, Leh CP, and Lee CC. Effects of alkaline pre-impregnation and pulping on Malaysia cultivated kenaf (Hibiscus cannabinus). BioResources 2010; 5(3), 1446-1462. 2. Brännvall E and Bäckström M. Improved impregnation efficiency and pulp yield of softwood kraft pulp by high effective alkali charge in the impregnation stage. Holzforschung 2016; 70(11): 1031- 1037 3. Bykova T, Klevinska V, and Treimanis A. Effect of green liquor pretreatment on pine wood components behaviour during kraft pulping. Holzforschung 1997; 51(5):439 4. Ban W, Lucia, LA. Enhancing kraft pulping through unconventional, higher sulfide-containing pretreatment liquors–A review, TAPPI J 2003; 2(3): 1-26. 5. Tripathi S, Sharma N, Bhardwaj NK, and Varadhan R. Improvement in kraft pulp yield and strength properties of paper by black liquor pre-treatment of chips. Bio-Resources 2016; 5(1): 3-14 6. Lönnberg B. Pre-impregnation of wood chips for alkaline delignification.Cellulose Chem. Technol. 2016; 50 (5-6), 675-680 7. Dungani R, Karina M, Subyakto, Sulaeman A, Dede H and Hadiyane A. Agricultural waste fibers towards sustainability and advanced utilization: A review. Asian J Plant Sci 2016; 15(1-2): 42-55. 8. Rushdan I, Latifah J, Hoi WK, and Mohd Nor MY. Commercial-scale production of soda pulp and medium paper from oil palm empty fruit bunches. J Trop ForSci 2007; 19, 121-126. 9. Law KN and Wan Rosli WD. Oil Palm fibers as papermaking material: potentials and challenges. Bio-Resources 2001; 6(1), 901-917. 10. Ng SH, Ghazali A, and Leh CP. Anthraquinone-aided hydrogen peroxide reinforced oxygen delignification of oil palm (Elaeis guineensis) EFB pulp: A two-level factorial design. J Cell ChemTechnol 2011; 45(1-2):77-87 11. Tanaka R and Wan Rosli WD. Production of pulp from oil palm empty fruit bunches by environmentally-friendly methods. Lignocellulose’99 - 2nd Colloqium on Potential Utilization of Starch and Lignocellulosic Material for Value Added Application.USM, Penang. 1999; pp 36-42 12. Sahari J, Shah MKM, Nuratiqah MN and. Rao MM. Developing and prototyping of empty fruit bunch high density board. J. Adv. Res. Des. 2014; 3(1), 1-8

POTENTIAL AND PROSPECTS OF RENEWABLE ENERGY RESOURCES IN PULP AND PAPER INDUSTRY

Syamsudin Center for Pulp and Paper, Jl. Raya Dayeuhkolot 132, Bandung 40258, Indonesia [email protected]

ABSTRACT

The energy conservation and increased concern for the environment has become a priority in the Indonesian industrial development. To ensure the sustainability of industrial development, it is require a savings and diversification of energy as well as greater attention to the development of renewable energy resources that are cheaper and safer. This paper reviews the potential and prospect of renewable energy resources in pulp and paper industry. The pulp and paper industry have some energy-rich biomass resources. These resources are produced in all stages of the pulping and papermaking process: wood preparation, pulp and paper manufacture, chemical recovery, recycled paper processing, and wastewater treatment. The energy-rich biomass resulting from the pulp industry including bark falling from the debarking drum, sawdust coming from the slasher deck, wood waste from wood yard, pins and fines from chip screening, knots from deknotting, foul condensate, black liquor from digester, and sludge from wastewater treatment. The energy-rich rejects resulting from the paper industry including fiber bundles, plastics, foils and polystyrene, deinking and non-deinking sludge from wastewater treatment. The new renewable energy with higher energy density could be produced by turpentine decantation; steam stripping of foul condensates; pelletization of wood residue and paper reject; hydrothermal treatment of sludge; torrefaction, pyrolysis and gasification of biomass; and fermentation and anaerobic digestion of sludge. The renewable energy products are turpentine, stripper off gas (SOG), methanol, hydrated sludge, biomass pellet, torrified biomass, bio-oil, syngas, biogas and bioethanol.

Keywords: Renewable energy; pulp and paper; biomass; reject.

Introduction

Currently, Indonesia’s dependence on fossil fuels for domestic consumption is still high at 96% (petroleum 48%, gas 18% and coal 30%) of the total consumption. In the last ten years (2003-2013), the final energy consumption in Indonesia has increased from 79 million TOE to 134 million TOE or grown by an average of 5.5% per year [1]. On the other hand, Indonesia face of declining fossil energy reserves and can not balance with the discovery of new reserves. Indonesia has petroleum reserves in 2013 about 7.55 billion barrels (MMSTB) with potential reserves about 3.85 billion barrels and proven reserves about 3.69 billion barrels [1]. Total reserves of natural gas in 2012 about 150.39 TSCF with proven reserves about 101.54 TSCF and potential reserves about 48.85 TSCF [1]. The coal reserves in 2013 about 28.97 billion tons, while coal resources about 119.82 billion tons [1]. Assuming there is no discovery of new reserves, based on the ratio of R/P (Reserve/Production) in 2014, the petroleum will run out in 12 years, natural gas in 37 years and coal in 70 years [2]. Expected future trends in energy development will shift from fossil-based energy into renewable energy. This is based on the fact that fossil energy resource cannot be renewed so that eventually will run out, whereas Indonesia has significant renewable energy resources [2]. To ensure the security of energy supply, the government had issued Regulation No. 79/2014 on National Energy Policy with the target of achieving the role of new and renewable energy at least 23% by 2025 and 31% by 2050 [3]. The Indonesian Ministry of Industry has developed an industrial policy through RIPIN 2015-2035 with respect to some aspects which have the characteristics and relevance that is strong enough with the national industrial development, such as energy shortages and increased concern for the environment. Energy shortages have been felt, and to ensure the sustainability of industrial development, it is required a policy of energy savings and diversification as well as greater attention to the development of renewable energy resources which are cheaper and safer. In addition, to

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 257 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 ensure the sustainability of the industrial sector in the future, the development of green industries need to be given higher priority through eco-products regulation, use of renewable energy and environmentally friendly, as well as hazardous materials. Mitigation of climate change and energy security are two of the driving forces for increased biomass energy utilization. Green industry is industry that prioritizes the efficiency and effectiveness of the resources usage in a sustainable manner in its production process. Limited reserves of fossil fuels have encourages the pulp and paper industries to conserve and diversify the renewable energy alternatives that are more environmentally friendly and cheaper. The pulp and paper mills have a large energy potential because they process a massive amount of lignocellulosic material which contain varying amounts of cellulose, hemicellulose, lignin and a minor amount of extractives [4]. These resources are produced in all stages of the pulping and papermaking process, i.e wood preparation, pulp and paper manufacture, chemical recovery, recycled paper processing, and wastewater treatment [5]. Pulp mill is an intensive energy industry, but they should be able to fulfill the energy it self through energy conservation technology integration of various biomass in the processes. Currently, the pulp mill fulfill their energy needs by burning the heavy black liquor in the recovery boiler and bark and other wood waste in the power boilers.

Renewable Energy Resources in the Pulp Mills

The main types of renewable energy resources generated from pulp mills could be classified as biomass rejects, foul condensate, black liquor and watewater treatment sludge.

Biomass Rejects in Pulp Mills

The energy-rich biomass resulting from the pulp industry including bark from the debarking drum, sawdust from the slasher deck, wood waste from wood yard, pins and fines from chip screening, black liquor from digester and sludge from wastewater treatment (Table 1) [5]. Rejects generated at pulp mill are knots from deknotting and pulp rejects from fine screening. Bark represents up to 300 kg/t of pulp and shares 60-90% from wood wastes in a pulp mill and have heat of combustion around 20 MJ/kg (dry basis) [6]. Pins and fines represent 50-100 kg/t o.d. pulp. Knots represent 2-6% on unscreened pulp or 25-70 kg/t of pulp [5] and pulp reject from fine screening represent 30 kg/t o.d. pulp.

Table 1. Generation of biomass waste in a Kraft mill [5]

No. Waste Yield (kg/t o.d. pulp) 1. Sawdust from the slasher deck 10 – 30 2. Bark from the debarking drum 100 – 300 3. Pins and fines from chip screening 50 – 100 4. Wood waste from woodyard 0 – 20 5. Knots from deknotting 25 – 70

Foul Condensates

The energy-rich biomass also come from foul condensate. Chemical pulp mills, including kraft mills generate considerable amounts of condensates during pulp-making process. The condensate streams of concern include the condensates of the multiple effect evaporator, the overflow of the blow heat accumulator, condensates from the digester system, the underflow from the turpentine decanter and condensates from non-condensable gas (NCG) system. Condensate contains several volatile compounds (VOCs), total reduced sulfur (TRS) compounds, and traces of black liquor. The VOCs include methanol, ethanol, acetone and terpenes. Methanol is the major VOC in kraft pulp mill. The main TRS compounds are hydrogen sulphide (H2S), methyl mercaptan (CH3SH), dimethyl sulphide (CH3SCH3) and dimethyl disulphide (CH3SSCH3) [7]. The TRS is formed as the sulphide and hydrogen sulphide ions react with lignin and the methoxyl groups of lignin fragment. Methanol is formed when the hydroxyl reacts with a

258 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 lignin methoxyl group. Typical pollutant loads and heat combustion of pollutant component from foul condensate from Kraft mill are presented in Table 2 and Table 3.

Table 2. Typical pollutant loads in foul condensate from Kraft mill [8]

Total flow MeOH Turpentine TRS Source (kg/tonne) (kg/tonne) (kg/tonne) (kg/tonne) Batch digester mill (softwood): Digester accumulator overflow 1125 4.0 0.50 0.20 Turpentine decanter underflow 250 1.5 0.50 0.15 Total evaporator condensate 7000 4.2 0.25 1.00 Continuous digester mill (softwood): Turpentine decanter underflow 450 2.5 0.50 0.12 Total evaporator condensate 8000 7.5 0.50 1.20

Table 3. Heat combustion of pollutant component from foul condensate [8]

No. Pollutant Net Heat of Combustion (kcal/kg) 1. MeOH 5037

2. H2S 3647

3. CH3SH 6229

4. CH3SCH3 7371

5. CH3SSCH3 5638

Black Liquor

Black liquor, spent cooking liquor, is the raw material for the recovery cycle that contains organics from the wood and all of the inorganic chemicals used for delignification [9]. The organic compounds in the black liquor about 55% and inorganic compounds about 45% [9] with typical higher heating values 13-15.5 MJ/kg of solid black liquor, depending on wood species and pulp yield [5]. The organic compounds in the black liquor consists of a compound formed from the sodium salt of lignin, resin and fatty acids, acid from carbohydrates, and other organic compounds contained in the wood. The inorganic compounds include sodium carbonate, sodium thiosulfate, sodium sulfide, and sodium hydrosulfide. A pulp mill generates 1.7–1.8 tonnes dry solids of black liquor per tonne of pulp [10].

Wastewater Treatment Sludge

Wastewater treatment process generates sludge cake, which is consists of primary sludge generated in primary clarifier and biological sludge generated in the secondary clarifier. The primary sludge consist of high fiber concentration and inorganic substances while the secondary sludge consist of mostly organic debris from biological process and inorganic materials from the nutrients to enhance biological treatment processes. The primary sludge can be dewatered relatively easier. Primary sludge can be dried until moisture content about 70% by a belt press, or until 50% with a screw press [11]. Compared with the primary sludge, the secondary sludge is very difficult to dewater. The presence of intracellular water causes secondary sludge more difficult to be dried by conventional mechanical dewatering. The mechanical dewatering can only reduce the moisture content to about 85%. These sludges are generally blended together, a polymer added and dewatered together to a 25–40 % dry solid content [12]. The calorific value of pulp mill sludge about 20-24 MJ/kg (dry and ash-free basis) [13]. Total generation of sludge cake per ton of product varies, depending on the production processes and the wastewater treatment processes. Kraft pulp mill generate sludge cake about 58 kg/ton of product, sulfite pulp mill about 102 kg/ton of product and deinking pulp mill about 234 kg/ton of product [13].

Renewable Energy Resources in the Paper Mills

Wastes from paper industry are mostly combustible. The main types of solid waste generated from paper mills could be classified as rejects from recovered paper, deinking sludges, primary sludges generated in the clarification of process water by kidney treatments and secondary sludges from the clarifier of the biological units of the wastewater treatment [14].

Rejects in Paper Mills

The paper-recycling process of paper mills generates reject waste in the region of 5-25% of its raw material, depending on the recovered fiber quality and process used in the mill [5]. The rejects from recovered paper composed by impurities such as lumps of fibres, staples and metals, sand, glass and plastics, and paper constituents as fillers, sizing agents and other chemicals [14]. The two major categories of rejects are coarse and fine rejects. Coarse reject has its origin in recovered paper pulping and de-trashing, as well as coarse screening. Coarse rejects differentiate into heavy and light coarse rejects. The heavy coarse rejects consist of metal, stones, not disintegrated paper or wet strength paper, wires, etc. The light coarse rejects consist of fiber bundles, plastics pieces, foils, polystyrene, etc. Fine reject comes from process stages like cleaning, fine screening and from the approach flow. Fine rejects differentiate into heavy and light fine reject. The heavy fine rejects mainly consist of sand, glass, staples and other metallic office waste, discharged from cleaners, as well as from the heavy junk traps of combined screening/cleaning equipment. The light fine rejects from slot screening or light weight cleaning contain fiber broke, spin-ups, stickies, wax, filler etc. [5]. The components of reject waste are largely comprised of 51% fibers and 49% plastic [15]. The wet reject material can have a moisture content in excess of 70% [16]. The light coarse reject has the highest possible caloric value of >11 MJ/kg [5]. One of the limitations of solid waste for energy is bulky and high moisture content which is difficult to be stored, transported and utilized [17].

Deinking Sludge

Deinking sludge is generated in the mills producing recycled fibre from recycled paper. Deinking sludge refers to the float or scum that is evolved from the air flotation process used to remove inks and dyes from the recycled paper fibres [18]. The sludge on a dry mass basis can vary from 20% in a newsprint mill to 40 % in a tissue mill. Total suspended solids in the deinking sludge can be categorized into organic matter (such as short fibres or fines) and inorganic matter (such as kaolin, clay, calcium carbonate, titanium dioxide that are resulting from coating materials, ink particles, deinking additives, dyes, other pigment based contaminant and other chemicals used for paper production) [12]. De-inking sludge has a high moisture content in the range 35-60% [19] with typical gross heating value (HHV) of 6-7 MJ/kg on a dry basis [18] and high ash content in the range of 45-65% depending on the quality of the fibre initially brought into the mill [16].

Wastewater Treatment Sludge

Balwaik and Raut [20] have reported that about 300 kg of sludge is produced for each ton of recycled paper. The primary sludge consists of mostly fines of cellulose fibers and papermaking fillers (such as kaolinitic clay and/or calcium carbonate) and it is relatively easy to dewater. The secondary sludges consists of a high microbial protein content, make it difficult to dewater. The secondary sludge volumes are lower than those corresponding to the primary sludge, since most of the heavy, fibrous or inorganic solids are removed in the primary clarifier. The secondary sludges are often need to be mixed with primary sludge or other filtration aids to permit adequate dewatering [12]. When compared with coal, paper sludge has very high levels of moisture and volatile matter, but low fixed carbon content (Table 4). Due to the high ash content and low caloric value of paper sludge, it is necessary to improve the combustion chamber temperature to enable the co-combustion of sludge with other fuel, to sustain the combustion stability and reduce the emission of toxicants [21].

Table 4. Proximate, ultimate and heating value of biomass waste from pulp and paper mill

Pulp sludge Pulp reject Black Recycled paper Paper reject No. Analysis Knot Coal [22] [22] liquor sludge [15] 1. Proximate analysis (adb) a. MC 9.08 9.42 13.74 28.0 4.83 3.93 12.21

b. VM 57.53 68.16 60.30 29.5 42.60 81.93 41.86

c. FC 8.72 17.00 18.81 8.5 4.96 6.98 39.18

d. Ash 24.67 5.42 7.15 34.0 47.61 7.10 6.75 2. Ultimate analysis (adb) a. C 31.21 39.43 40.12 44.5 23.09 n.a 55.78

b. H 5.10 6.50 6.02 4.3 2.73 n.a 6.32

c. O 37.33 47.79 45.73 44.7 25.81 n.a 30.24

d. N 1.29 0.35 0.18 0.1 0.49 n.a 0.69

e. S 0.40 0.51 0.80 6.4 0.27 n.a 0.22 3. LHV, cal/g 2931 3656 3691 3119 850 7002 5360

Production of Renewable Energy in the Pulp dan Paper Mills

The renewable energy with higher energy density could be produced by steam stripping of foul condensates from digesters and evaporators, pelletization of wood residue and paper reject; hydrothermal treatment and hydrothermal liquefaction of sludge; torrefaction, pyrolysis and gasification of biomass; and fermentation and anaerobic digestion of sludge (see Figure 1). The renewable energy products are turpentine, stripper off gas (SOG), methanol, hydrated sludge, biomass pellet, torrified biomass, bio-oil, syngas, bioethanol and biogas.

Fig. 1. The kraft pulp mill and the alternative technologies for biofuels production [4]

Physical Conversion-Based Technologies

Turpentine Decantation

Turpentine is obtained in quantity when pulping resinous woods such as pine. Turpentine is recovered primarily from the digester relief gases. The gases are conducted to a cyclone separator where liquor carryover is removed, then to a condenser where the steam and turpentine are condensed. Condensate from the condenser is then decanted to separate the turpentine. The condensed turpentine is immiscible and will float on the condensed water permitting separation and transfer to storage. Turpentine then overflows to turpentine storage while the water underflow is combined with other contaminated condensate streams for steam stripping [23].

Stripping of Foul Condensates

The major foul condensate treatment methods include air stripping and steam stripping. Air stripping requires an air to condensate ratio of 3-5% weight for TRS and 16-20% weight for BOD. Steam stripping is the dominant condensate treatment. Steam stripping requires a steam to condensate ratio of 3-5% weight for TRS and 15-20% weight for BOD. In the steam stripping for BOD, the top of the stripper becomes a distillation column to concentrate the methanol [8]. Up to 95% of the methanol can be removed from the foul condensate and captured in the overhead vapours from the steam stripping process [24]. The TRS compound, turpentine and methanol are concentrated in the stripper-off gases (SOG). The stripper-off gases (SOG) can be transported as a gas, or condensed and transported as a liquid and used to replace fossil fuel in lime kiln, recovery boiler, power boiler or incinerator. Concentrated steam stripper condensates consist primarily of methanol which can be burned as a fuel. A combination of treatments that include air stripping, steam stripping, distillation and reverse osmosis is described to obtain purified biomethanol suitable for sale or use on site (Figure 2) [7].

Fig. 2. Process and system of producing purified methanol at pulp mills [7].

Pelletization

Attempts to overcome the poor handling properties of biomass, i.e. its low bulk density and inhomogeneous structure, have resulted in an increasing interest in biomass densification technologies, such as pelletization [25]. Pelletization is the process of compressing or molding a material into the shape

262 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 of a pellet. Fuel pellets are more uniform in shape, size, energy content, and moisture than the paper mill residues, making them easier to transport, store, convey and need smaller storage space. Their high energy density means they have more energy by volume than paper mill residues [26]. Residues from the log debarking process in sawmills, wood composite mills, and pulp and paper mills can be used for pellet. Lehtikangas [27] investigated the quality properties of pelletised sawdust, logging residues and bark, and concluded that bark and logging residues are suitable raw materials for pellets production, especially if the ash content is controlled. Setiawan and Surachman [15] investigated reject waste pellets of paper mills as fuel and their contribution to greenhouse gas. The reject waste pellets had a high calorific value (7002 cal/g) and low ash (6.70%) and sulphur contents (0.15%). Utilization of 10% reject mixed with 90% coal as boiler fuel could reduce CO2 gas as greenhouse gas (GHG) emissions by about 9%. In order to improve the combustion characteristics of sludge, the most popular method is to mix the sludge with auxiliary fuel (coal, refuse, sawdust etc), desulfurizer and binder to produce solid fuel.

Thermal Conversion-Based Technologies

Hydrothermal Treatment

About 80% of water content of biosludge is recognized as bound water which cannot be separated by conventional dewatering devices such as centrifuge or filter press due to high strength binding between water molecules and sludge solids surface [28] and the potential presence of biologically active organisms or compounds [29]. The hydrothermal treatment process can convert waste to value- added resources such as coal-like solid fuel or organic fertilizer. The hydrothermal treatment (HTT) is similar to hydrothermal carbonization (HTC) and hydrothermal liquefaction (HTL) in term of using a subcritical water condition as a medium (Table 5). Water under high temperature and pressure that is close to the critical point (374°C and 22.1 MPa), called subcritical water (SW), has the dielectric constant similar to that of organic solvent dichloromethane (methylene chloride) make the SW is good medium for dissolving organic compounds [30]. Differences of hydrothermal treatment, hydrothermal carbonization and hydrothermal liquefaction are presented in Table 5. Drying the feedstock is not needed in the hydrothermal process, which makes it especially suitable for naturally wet biomass. The hydrothermal process occurred in aqueous medium which involves complex sequences of reactions including solvolysis, dehydration, decarboxylation, and hydrogenation of functional groups [31].

Table 5. Typical operating parameters of hydrothermal treatment, hydrothermal carbonization, hydrothermal liquefaction [30]

No. Process T range P range RT Objective 1. Hydrothermal treatment 160–240°C Pressure where the 15–90 min upgrade waste materials (HTT) water in the liquid state 2. Hydrothermal 160–350°C 4–12 h biochar and bio crude oil carbonization (HTC) production (usually 180–220°C) 3. Hydrothermal liquefaction 300–400oC 10–25 MPa 0.2–1.0 h biochar and bio crude oil (HTL) production

Areeprasert et al. [32] investigate the solid fuel production from paper sludge employing hydrothermal treatment (HTT) under subcritical hydrothermal conditions and evaluated fuel property, water removal performance, mass distribution, and energy balance of the process. The produced solid fuel had higher heating value, comparable H/C and O/C atomic ratios with that of coal, water reduction after dewatering of raw and treated paper sludge was 5.4% and 19.1%, respectively, and the recovered energy was significantly higher than the energy input. Areeprasert et al. [33] investigated the combustion characteristics of the hydrothermally treated paper sludge and found that the activation energy of the treated paper sludge was lower than the original material in range of 113–147 kJ/mol. Treatments of o secondary pulp/paper sludge in water at 250–380 C for 15–120 min in the presence of N2 atmosphere

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 263 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 resulted in yields of water-soluble oils at 20–45 wt% and yields of heavy oils at 15–25 wt%, with higher heating values of 10–15 and 435 MJ/kg, respectively [34].

Torrefaction

Torrefaction or mild-pyrolysis is a thermochemical treatment method for the conversion of biomass by an operating within temperature range of 200-300oC under atmospheric conditions in absence of oxygen and characterised by low particle heating rates (< 50 °C/min) and relatively long residence time (typically 1 hour) [35]. Torrefaction is based on the removal of oxygen (decreasing O/C ratio) from biomass which aims to produce a fuel with increased energy density by decomposing the reactive hemicellulose fraction [36]. During torrefaction the biomass polymers, especially hemicelluloses, are degraded mainly by depolymerization, demethoxylation, bond cleavage and condensation reactions [37]. A typical mass and energy balance of torrefaction is 70% of the mass is retained as a solid product containing 90% of the initial energy content; 30% of the mass is converted into torrefaction gases (i.e. the volatile organic compounds released as flue gas), containing only 10% of the energy content of the biomass [35]. In addition to densifying energy content, torrefaction also reduces the hydroscopic property of biomass, making the biomass absorb less moisture when stored [4]. Reckamp et al. [38] investigated the potential of paper mill sludge as a biomass feedstock for bio-oil and biochar production through acid hydrolysis and torrefaction pretreatments to alter the physicochemical properties. In combination with pelletization, the aim is to produce a durable biobased fuel pellet of high energy density, with a high degree of homogeneity and hydrophobic characteristics [39]. Table 6 provides an overviewof the properties of TOP pellets in comparison with wood, torrefied biomass and conventional wood pellets. Compared to non-torrefied pellets TOP pellets show better hydrophobic behavior, strength and higher density [36]. A number of studies have shown that torrefaction increases the efficiency of biomass combustion ([40], [41]) and gasification [42] processes.

Table 6. Properties of wood, torrefied biomass, wood pellets and TOP pellets [35]

Torrefied Wood pellets TOP pellets Parameter Unit Wood biomass low high low high Moisture content % wt. 35% 3% 10% 7% 5% 1% Calorific value (LHV) as received MJ/kg 10.5 19.9 15.6 16.2 19.9 21.6 dry MJ/kg 17.7 20.4 17.7 17.7 20.4 22.7 Mass density (bulk) kg/m3 550 230 500 650 750 850 Energy density (bulk) GJ/m3 5.8 4.6 7.8 10.5 14.9 18.4

Pyrolysis

Pyrolysis is thermal decomposition of organic components in biomass starts at 350°C–550°C and goes up to 700°C–800°C in the absence of air/oxygen by releasing volatile matter from biomass [43]. The process is very complex and consists of both simultaneous and successive reactions when organic material is heated in a non-reactive atmosphere. The long chains of carbon, hydrogen and oxygen compounds in biomass break down into smaller molecules in the form of gases, condensable vapours (tars and oils) and solid charcoal [44]. Pyrolysis has attracted more interest in producing liquid fuel product because of its advantages in storage, transport and versatility in application such as combustion engines, boilers, turbines, etc. [44]. Based on the operating condition, pyrolysis can be classified into slow, fast and flash pyrolysis (Table 7).

Table 7. Typical operating parameters and products for pyrolysis process [44]

Pyrolysis Solid Residence Heating Particle Product Yield (%) Temp. (K) Process Time (s) Rate (K/s) Size (mm) Bio-oil Char Gas Slow 450–550 0.1–1 5–50 550–950 30 35 35 Fast 0.5–10 10–200 <1 850–1250 50 20 30 Flash <0.5 >1000 <0.2 1050–1300 75 12 13

Slow pyrolysis has been used to enhance char production, while fast and flash pyrolysis can maximize the conversion of biomass into liquid (bio-oil) products. Char can be directly used as fuel for combustion or gasification. Bio-oil can be directly used as fuel for combustion or further processed into fuels and chemicals derivation uses some methods such as catalytic cracking with zeolite, hydrogenation, steam reforming, emulsification, and other metods [31]. Liquid bio-oil is composed of hundreds of chemical constituents from various chemical groups, primarily anhydrosugars, phenols, furans, ketones, aldehydes, and carboxylic acids, whose compositions affect the physicochemical properties of bio-oil [38]. Strezov and Evans [45] investigated the products of paper sludge pyrolysis to determine their properties and potential energy value. The bio-oils collected at 500°C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500°C had a calorific value of 13.3 MJ/kg. Venderbosch and Prins [46] collected the representative values for wood-derived pyrolysis oil properties and listed in Table 8.

Table 8. Typical properties of wood derived crude bio-oil [46]

Physical property Pyrolysis conditions Water content (%) 15–30 Temperature (K) 750–825 pH 2.8–3.8 Particle size (µm) 200–2000 Density (kg/m3) 10500–1250 Moisture (%) 2–12 Elemental analysis (% db): Cellulose (%) 45–55 C 55–65 Ash (%) 0.5–3 H 5–7 Yields (%): N 0.1–0.4 Organic liquid 60–75 S 0.00–0.05 Water 10–15 O Balance Char 10–15 Ash 0.01–0.30 Gas 10–20 HHV (MJ/kg) 16–19

Gasification

Gasification is a thermochemical conversion of solid fuels with the gasification agent to produce a fuel gas called producer gas. The gasification agent can be air (21% O2 and 79% mol N2), O2-enriched air, pure oxygen, steam, CO2 or a mixture of such compounds ([47], [48]). Gasification product contains mainly H2, CO and CH4 (generally less), as well as other gases such as CO2, H2O, N2, and some heavy hydrocarbons (tar) ([48], [49]). The producer gas can be processed into a gaseous fuel as a fuel or synthesis gas for the production of chemicals ([50], [51]). The performance of the gasification process is affected by several operating parameters such as biomass type, moisture content, reactor configuration, gasification agent, temperature, pressure, steam/biomass ratio, oxygen/biomass ratio and others [52]. The gasification process is usually can be represented by the equations below.

C + O2 → CO2 combustion

C(s) + H2O(g) Û CO(g) + H2(g) heterogeneous water shift

C(s) + CO2(g) Û 2CO(g) Boudouard reaction

C(s) + 2H2Û CH4 metanation

CO + H2O(g)Û CO2 + H2 homogeneous water shift

Black liquor gasification can be an alternative of recovery boiler in the recovery cycle of the pulp mill to produce electricity, chemicals or fuels such as DME (dimethyl ether), synthetic natural gas, methanol, hydrogen or synthetic diesel [9]. Black liquor gasification technologies are distinguished in two major classes; (1) Low temperature gasification, and (2) High temperature gasification. Low temperature gasifier operates at 600–850oC, below the melting point of inorganics, thus avoiding smelt-water explosions while high temperature gasification units generally operate in the 900–1000oC range, and produce a molten smelt [53]. Black liquor gasification can also be integrated with combined-cycle technology, i.e black liquor gasification combined-cycle (BLGCC), which has potential to produce significantly more electricity or the syngas can be used for synthesis of bio-methanol and bio-DME (dimethyl ether). Table 9 compares potential electricity or fuel production from various studies.

Table 9. Bio-refinery performance estimates based on BLG studies e.g. BLGCC and BLG for biofuel production. Fuel values are based on lower heating values (LHV)

Parameter BLGCC BLG for biofuel production

Reference Larson et Eriksson Ekbom et al. Andersson Larson et al. (2006) Naqvi al. and Harvey and Harvey et al. (2003) (2003) (2004) (2006) (2010) Product Electricity Electricity MeOH DME H2 DME FTL MA CH4

Pulp production, ADt/ 1600 2000 2000 2000 2000 1600 1600 1600 1000

day BLS flow, tDS/day 2724 3420 3420 3420 3420 2724 2724 2724 1700

BLS flow, MW 350.7 487 487 487 487 350 350 350 243.5

Biomass import, MW 27.1 21.3 129 125 123.5 77.4 102 89.2 107

Electricity, MW 15.2 86.5 -45.9 -48.7 -56.7 -99.6 12.4 8.2 1.1

Import/Export (-/+) Fuel production, MW - - 272 275 261 168 112 60 240.2 Sources: Larson et al. (2003), Eriksson and Harvey (2004), Ekbom et al. (2003), Andersson and Harvey (2006), Larson et al. (2006), and Naqvi et al. (2010) at [9].

Syamsudin et al. [54] has simulated the gasification of kraft pulp sludge and found that the product gas have a heating value about 11 MJ/Nm3 and co-combustion of this gas for lime kiln in a kraft pulp milll could reduce the natural gas consumption about 18% .

Biological Conversion-Based Technologies

Anaerobic Digestion

Anaerobic digestion involves a series of processes in which microorganisms break down organic matter in the absence of oxygen via hydrolysis, acidogenesis (fermentation), acetogenesis, and methanogenesis [55]. Anaerobic digestion has some advantages, such as a significant reduction of the biomass (30–70%) and the production of biogas consists of about 50–80% of the energy carrier methane. Anaerobic digestion has been widely applied for primary and secondary sludge from pulp and paper mills. The pulp and paper sludge contains proteins (22-52%), lignin (20-58%), carbohydrates (0-23%), lipids (2-10%), and

266 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 cellulose (2-8%) [56]. Yunqin et al. [57] studied the alkali pretreatment to enhance biogas production in the anaerobic digestion of pulp and paper sludge and got results that alkali/NaOH pretreatment could be an effective method for improving methane yield with pulp and paper sludge with the highest methane 3 yield under optimal pretreatment condition was 0.32 m CH4/kg VS removal, 183.5% of the control. Lin et al. [58] studied anaerobic co-digestion of pulp and paper sludge and monosodium glutamate waste liquor and demonstrated that the accumulative methane yield attained to 200 mL/g volatile solid (VS) added and the peak value of methane daily production was 0.5 m3/(m3.d) with methane reaching up to 80% of the total biogas composition. Soetopo et al. [59] investigated the paper mill sludge treatment with a two-stage anaerobic digestion (hydrolysis-acidogenesis and methanogenesis) and showed that the process could produce biogas approximately 130 mL/L sludge or 0.16 L/g COD reduction with methane gas level of 69–79% and reduced COD up to 78–82%. Anaerobic digestion also has been successfully used for various pulp and paper mill streams (Table 10).

Table 10. Composition and anaerobic digestibility of various pulp and paper mill streams [60]

COD concentration Methane generation Type of wastewater COD removal rates (%) (g/L) (m3/kg COD removed) TMP 2.0 – 7.2 50 – 70 0.30 – 0.40 TMP-chip washing 5.6 83 0.32 CTMP 6.0 – 10.4 45 – 66 0.18 – 0.31 Sulfite pulping effluent 6.2 – 48 29 – 38 0.14 – 0.30 Kraft evaporator condensates 0.6 – 6.5 70 – 99 0.29 – 0.35 Recycled paper mill 0.6 – 15 58 – 86 0.24 – 0.40

effluent

Fermentation

The production of ethanol from lignocellulosic biomass generally involves four steps: feedstock pretreatment, enzymatic saccharification, fermentation, and product recovery [61]. The cellulosic and hemicellulosic sugars obtained through acid and enzymatic hydrolysis can efficiently be used for ethanol fermentation either by separate hydrolysis and fermentation (SHF) or simultaneous saccharification and fermentation (SSF). Some studies available related to fermentation of paper sludge for ethanol production by SHF and SSF, most of these studies used Saccharomyces cerevisiae (Tabel 12). The high lignocellulosic content of the paper sludge (Tabel 11) offers an opportunity as a feedstock for production of ethanol. Polysaccharides present in the sludge are highly accessible to enzymatic hydrolysis due to the physical and chemical processing undertook during pulp and paper manufacturing [62]. Compared to other cellulosic feedstocks, paper sludge have negative feedstock cost, no requirement for pre-treatment to be made amenable to enzymatic hydrolysis, and integration of processes into a preexisting industrial infrastructure at a mill.

Table 11. Typical composition of dry paper sludge [63]

No. Component Amount (g/g dry paper sludge) 1. Total sugar 0.66 Glucan 0.44

Mannan 0.02

Xylan 0.07

2. Other sugars 0.13 3. Clay 0.30 4. Others 0.04

Sebastiao et al. [64] studied the life cycle assessment of advanced bioethanol production from pulp and paper sludge. Two optimisation scenarios were evaluated: (1) using a reduced HCl amount in the neutralisation stage and (2) co-fermentation of xylose and glucose, for maximal ethanol yield. Both scenarios displayed significant environmental impact improvements. Chenet al. [65] studied economic evaluation of the conversion of industrial paper sludge to ethanol, and concluded that the most profitable case was fractionated virgin sludge (from a virgin paper mill) to ethanol with a net present value (NPV) of US$ 11.4 million, internal rate of return (IRR) of 28%, payback period of 4.4 years and minimum ethanol revenue (MER) of US$ 0.32 per liter.

Table 12. Some studies related to fermentation of pulp and paper sludge for ethanol production

No. Material Process Result References 1. Paper sludge SHF with cellulase and S. cere- The ethanol yield was 190 g/kg of dry pa- [66] visiae GIM-2 per sludge (overall conversion of 56.3% of the available carbohydrates on the initial substrate) 2. Paper sludge SSF with a cellulase produced Ethanol yield was 23% (g ethanol/g PSOM) [63] from paper sludge by the hyper- (two times higher than that obtained by cellulase producer, Acremonium SHF). Paper sludge is a good raw material cellulolyticus C-1 for sacchari- for bioethanol production fication, andSaccharomyces cerevisiae TJ14 for ethanol production. 3. Pulp and paper SSF with Saccharomyces cere- Highest ethanol yield of 42.5 g/L [58] sludge visiae CICC 1001 at pH 6.0, 6% of total solid 4. Paper sludge SSCF batch experiments with Conversions of paper sludge to ethanol of [62] solids concentration of 178 g/L 51 % with a maximum ethanol concentration of 19 g/L.

Conclusion

The pulp and paper mills have a large energy potential and prospects of renewable energy resources. These resources are produced in all stages of the pulping and papermaking process. Energy-rich biomass in pulp mill includes bark, sawdust, wood waste, pins, fines, knots, foul condensates, black liquor, and sludge. Energy-rich rejects in paper mill includes fiber bundles, plastics, foils and polystyrene, deinking and non-deinking sludge. The renewable energy with higher energy density could be produced by turpentine decantation, steam stripping, pelletization, hydrothermal treatment, torrefaction, pyrolysis, gasification, fermentation and anaerobic digestion. The renewable energy products are turpentine, stripper off gas (SOG), methanol, hydrated sludge, biomass pellet, torrified biomass, bio-oil, syngas, biogasand bioethanol. Some technologies are already operating commercially such as steam stripping, gasification and anaerobic digestion, but some technologies are still being improved such as fermentation.

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RECYCLING OF USED BEVERAGES CARTONS AS AN ENVIRONMENTAL EDUCATION PROGRAM

Ligia Santosa 1, Andri Taufick Rizaluddin Center for Pulp and Paper, Ministry of Industry, Republic of Indonesia Jl Raya Dayeuhkolot No.132 Bandung, INDONESIA 1 [email protected]

ABSTRACT

Recycling is a good solution to give some added values to solid waste so that it can become new alternative source for available raw material. The world demand of beverages cardboard has increased by 9,1% in 2015 to $35,8 billion worth (Tetra pak contributed for $11,9 billion). With mainly consist of 74% fiber in every used beverages cardboard (UBC), recovery process of UBC secondary pulp fiber has promising potential source for raw material of pulp. Although it is difficult to be degraded naturally, previous researches on the processing of UBC shows that this solid waste can be recycled in order to obtain secondary fiber and poly aluminum. The objective of this research is to study the recovering process of secondary pulp from aseptic packages through the repulping process, separating it from the poly aluminum, producing paper liner from the secondary pulp, and then testing it properties according to Indonesian National Standard for SNI 8053.1.2014. The results showed that the recycling process can recover 30-32% of secondary fiber. The test result of paper liner properties showed that it proceed all Indonesian National Standard for paper liner. The study is part of the introduction and provision of information recycling of aseptic packages as an environmental education program for high school students. They are the main consumers of products UBC. The students were invited to see the direct practice of recycling in CPP consists of fifty-two students representing schools from Bandung and two students from the college.

Keywords : recycling, used beverages cartons (UBC), secondary fiber, poly aluminium, paper liner, wastewater treatment, environmental educations

Introduction

Food and beverages product critically needs some type of packaging for product labeling, transportation, protection, and preservation. The focus of food and product packaging was initially more into protection and preservation of the product. Growing concern about the environment, combined with the desire to increase product quality and value-added, has led to increasing analysis of packaging’s environmental impact [1]. (UBC) is a type of packaging which is made of up to seven layers, which are composed of mainly 74% fiber, 21% polyethylene and 4% aluminium foil (alufoil). As made up from seven materials and designed to preserve beverages from decayed, UBC is hard to be degraded naturally. After being used, UBC is often perceived as waste by consumers. Although has 74% fiber content, UBC is categorized as reject and unwanted in paper mills that uses waste paper as raw material. The problem is mainly because of the difficulties of separating fiber with other composition [2][3]. Many brand has begun to differentiate themselves by adopting packaging materials and systems that are identified as more “environmentally-responsible”. As a producer and one brand of UBC, Tetra Pak has a responsibility to solve this UBC problem. Recycling is the process of collecting and processing materials that would otherwise be thrown away as trash and turning them into new products. It has many benefits, such as reduces the ampunt of waste sent to landfills and combustion facilities; conserves natural resources such as timber, water, and minerals; saves energy; reduces greenhouse gas emissions that contribute to global climate change; helps sustain the environment for future generations; and helps create new well-paying jobs in the recycling and manufacturing industries [4]. Recycling is one of a good solution to increase a positive added-value of a solid waste both economically and environmentally which also give a positive image

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 273 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 of the producer to the community. Many researches has been done to quantify the environmental impact of packaging to the industry in order to reduce cost and improve performance. Tetra Pak was the one that initiated the development of the tetrahedron shaped package. Tetra Pak offers packaging equipment for liquid products, and provide a range of processing and packaging technologies for use with a broad array of products, from ice cream and cheese to fruit, vegetables and pet food. Tetra Pak also has policies to reducing the environmental impact of its operations and to enhancing the environmental performance or its products abd solutions [5]. In the year of 2015, Tetra pak had successfully sold 184 billion of its packages. With the increasing of the world demand for 9,1% per year to $35,8 billion worth product (Tetra pak contributed for $11,9 billion), and mainly contained 74% fiber in every UBC, the recovering process of UBC into secondary pulp fiber is a potential source for raw material of pulp [6][7]. Center for Pulp and Paper, in cooperation with PT. Tetra Pak Indonesia, has been established join research cooperation to recycle UBC since laboratory scale experiment in 2004. Previous study showed that secondary fiber pulp [8] and polyalum [2] were successfully recycled from some of used beverages cardboards (UBC) PT.Tetra Pak Indonesia. The repulping process was aimed to defiberizing and to separate polyalum and the slurry contained recycled secondary fiber pulp which was separated at the rotary drum screening process (Fig.1). Theoritically, all aseptic packages as one of UBC type also has a potential to be recycled and recover their secondary pulp and polyalum. The objective of this research is to study the possibility of one type of aseptic packages from one of beverages packaging industry in Indonesia, to be recycled into secondary pulp and to test its quality according to Indonesian National Standard for as packaging paper liner (SNI 8053.1.2014). The result of this research would also be benefecial for further study of UBC utilization and recycling process.

Methodology

The material used in this study were UBC of aseptic packages from one of beverages packaging industry in Indonesia. In the preparation process, the UBC were emptied, separated from the straw and then flattened. The repulping process of the UBC was devided into several steps, which are raw material disintegration, filteritation and pulp sheet formation. UBC was placed in a hydropulper, mixed and formed into slurry with the additon of water. Polyethilene and aluminum layers were separated and recovered in a rotary drum filter screen. The slurry which has been separated with polyethilene and aluminum layers were transferred into headbox and then repulped into pulp sheets in the wire. The repulping process of recycled secondary fiber pulp was showed at figure 1. Pulp from the sheet forming process was collected and tested.

Figure 1. Repulping process of aseptic packaging of UBC

Fiber type of the recycled pulp from the sheet forming was tested in the parameters of kappa number, fiber type, coarseness, freeness, tensile strength, breaking length and density, based on SNI 0494: 2008, SNI ISO 16065-2:2010, SNI ISO 5267-2: 2010, SNI ISO 1924-2: 2010, and SNI ISO 534: 2011. The wastewater quality from the mill was tested in the parameters of BOD, COD, TSS and pH, based on SNI 06-6989.2-2004 (Chemical Oxygen Demand/COD), SNI 06.6989.3-2004 (Total Suspended Solid/TSS), and Standard Methods 2005 (Biological Oxygen Demand/BOD). All test results were being tested in the Center for Pulp and Paper Bandung. The recycled pulp from the process in the figure 1, was then undergone paper liner production process in the third party institution. The paper liner production process was showed in the figure 2. Stock preparation to mix furnace consisting fiber, filler and chemical additive. The variations used were with beating processes of 360 mL CSF at 105 gsm, 360 mL CSF at 200 gsm, 300 mL CSF at 60 gsm, and 400 mL CSF at 60 gsm. The processes were then continued with web forming in the cylinder mold, pressing, drying, finishing and converting. The paper liner sheets produced from the third party institution were then being tested in the parameters of gramature, Cobb, pH, tensile, tear, burst, stiffness, holding endurance and porosity.

Figure 2. Paper liner production process

Result

In the repulping process (Figure 1), polyalum and polyethilene was separated from the slurry with the drum screen, and the slurry which fulled with secondary fiber was then made into wet pulp. From a total of 74% fiber content from UBC around 40% was succesfully recycled into wet pulp, the result showed a 30-32% secondary fiber rendement in average. The recycled fiber in the wet pulp showed a good clean quality pulp without any unwanted aluminum or polyethilene. The characterization of the wet pulp was showed at Table 1.

Table 1. Wet pulp characterization from repulping processof UBC

Moisture Breaking Kappa Coarseness Freeness Tensile Density Content Fiber type length number (µg/m) (CSF) (kN/m) (g/cm3) (%) (m) 69.59 38.54 Medium-Short 123 600 5.32 5711 0.65

The wastewater quality from the repulping process was also studied to understand furthermore about the recycling life process of UBC. The results were showed in Table 2.

Table 3. Effluent wastewater quality from the repulping process

Parameter Unit Effluent quality Effluent standard [9]

TSS ppm 227,5 100 COD ppm 551,69 200 BOD ppm 308,2 100 pH - 6,82 Neutral

The effluent wastewater qualities from the repulping process are all below Indonesian effluent standard according to Indonesian Ministry of Environmental law, except for pH. It means that the mill implementation of repulping process will need a wastewater treatment installation to decrease their wastewater pollutants. The pulp from recycling process was then processed in the third party to be produced into paper liner. The process of repulping will have some progressive deterioration effects to fiber properties compared with original pulp fiber [10]. To assure the fiber quality, the paper liner product from the recycled pulp of UBC was characterized and the result data was compared with Indonesian standard SNI 8053.1.2014 [11] of paper liner, which was showed at Tabel 3. It were showed that paper liner product sheets were proceed most of the parameters for Indonesian standard of paper liner, with the exception of beating process 360 mL CSF at 200 gsm with slightly outside the limit, but still showed a potential value.

Table 3. Characterization of paper liner from recycle pulp of UBC

Gramature Cobb Tensile Tear Burst Stiffness Holding Porosity Parameter pH (gr/m2) (gr/m2) (Nm/g) (mNm2/g) (kN/g) (gf.cm) endurance (mL/min) 360 mL MD 71.7 MD 5.1 MD 10.6 MD 13.0 CSF 109.6 45.3 6.67 2.03 282 CD 17.3 CD 7.7 CD 2.7 CD 4.0 105 gsm 360 mL MD 61.4 MD 7.9 MD 39.5 MD 14.0 CSF 189.5 70.8 6.67 1.96 CD 21.6 CD 8.8 CD 13.8 CD 5.0 200 gsm 300 mL CSF 55 8.8 7.8 5.70 237 60 gsm 400 mL CSF 69 10.8 7.5 5.85 60 gsm SNI (Indo- nesian Stan- 125 Max 80 Min 2 Max 1500 dard) [11]

This study also included a socialization of the recycling information of the aseptic packages as an environmental education program to high schoool and college students as the main consumer of UBC products. Representatives from fifty two schools in Bandung area and two colleges, Telkom University Bandung and Akademi Teknologi Industri Padang, were invited to study the UBC recycle program in the Center for Pulp and Paper Bandung. The students were showed the raw materials of UBC, repulping process of aseptic packaging of UBC from hydropulper up to the pulp sheet product, and also the separated process of aluminium foil.

(a) (b) Figure 3. Students from schools in Bandung were showed the hydropulper (a) and thickning (b) equipment

Conclusion

Pulp fiber from used beverages cardboard has some potentials to be recycled into product of liner paper. It were showed that paper liner product sheets were proceed most of the parameters for Indonesian standard of paper liner, especially for beating process 360 mL CSF at 105 gsm which were proceed all of the parameters for Indonesian standard. However there is still need some improvement and room for progress. Environmental education program about recycling of UBC was also already conducted, around 50s schools from around Bandung were invited to the recycle center, two colleges (Telkom University Bandung and Akademi Teknologi Industri Padang) were also invited.

Acknowledgement

We would like to thank all those who have helped make this research a success. We would like to thank Miss Mignonne Akiyama and Mr. Reza Andreanto from PT. Tetra Pak, and also we would like to thank Mr. Davin and Mr. Avey from PT. Indolakto for all the cooperation during this research.

Refferences

1. United Nation Environmental Proramme (UNEP) and The Society of Environmental Toxicology and Chemistry (SETAC), An Analysis of Life Cycle Assessment in Packaging for Food & Beverage Applications, http://www.lifecycleinitiative.org/wp-content/uploads/2013/11/ food_packaging_11.11.13_ web. pdf, 2013 (accesed 14 December 2016). 2. Santosa, L., Utilization of Alufoil Waste from Aseptic Packaging Recycling Process for Coagulant Production, Proceeding of Reptech 2012, 2013, p. 176-180. 3. Santosa, L., Pembuatan Pulp Daur Ulang Sampah Kemasan Kertas dari Sampah TPS dan Sampah TPA Wilayah Bandung di Pusat Inovasi Daur Ulang BBPK, Prosiding Seminar Pembangunan Jawa Barat, 12-13 Juni 2012, p. 249-255 4. Environmental Protection Agency, https://www.epa.gov/recycle, 2016 (accessed December 14th 2016, updated November 15th 2016). 5. Tetra Pak, http://www.tetrapak.com/id, 2016 (accessed December 15th 2016). 6. Tetra Pak, http://www.tetrapak.com/about/facts-figures, April 2016 (accessed January 25th 2017). 7. Freedonia, http://www.freedoniagroup.com/industry-study/world-aseptic-packaging-2859.htm, 2017 (accessed January 25th 2017). 8. Santosa, L., Recycling Prospect of Long Fibers Separated from Used Aseptic Beverage Carton (in Indonesian language), Proceeding of Reptech 2009, p. 56-60. 9. Ministry of Environment of Indonesia. PerMenLH No. 5/2014, http://jdih.menlh.go.id/, 2014 (Accessed November 14th 2015).

10. Spangenberg, R.J., Secondary Fiber Recycling, TAPPI Press, Atlanta, Georgia, 1993, p. 7-19. 11. National Standardization Agency of Indonesia (BSN), SNI 8053.1.2014, http://sisni.bsn.go.id/index. php?/sni_main/sni/detail_sni_eng/22348, 2017 (Accessed January 25th 2017)

UTILISATION OF OIL PALM BIOMASS: EXAMPLES OF LABORATORY-SCALE AND FEASIBILITY STUDIES

Tanaka Ryohei Research Planning and Coordination Department, Forestry and Forest Products Research Institute, Tsukuba, Japan [email protected]

ABSTRACT

For utilising woody biomass from palm oil industries, laboratory-scale research studies have been carried out under the collaboration between Japanese and Malaysian institutions. To utilise these research achievements, it is necessary to establish an integrated system for the biomass usages. A feasibility study toward setting up the system shows the necessity of involvement of rural development and reduction of environmental impacts. To fill these requirements, a firm blue-print by presenting a model system may be necessary for the biomass utilisation.

Keywords: oil palm, biomass, pulp, paper, composites, feasibility, utilization, integrated, model

Introduction

It is well recognised that the utilisation of oil palm biomass is one of the most important issues at palm oil producing countries for reducing wastes from the oil production, which may lead the industry sustainable and environment-friendly. Toward this purpose, there are many individual research studies have been carried out for utilisation technologies at laboratories in various institutions such as universities, research organisations and private sectors. Although there are quite number of excellent achievements in the technological development, it is not easy to be applied in commercial scale for creating new products from oil palm biomass. In order to make further progress on this matter, we have carried out a feasibility study for setting up an integrated system on oil palm biomass utilisation in Malaysia. The study was under the programme of ‘Dispatch of Science & Technology Researchers’ implemented through the collaboration between Japan Society for the Promotion of Science (JSPS) and Japan International Cooperation Agency (JICA). There are two practical activities in this study; one is to create a researchers’ network between Japanese and Malaysian research institutions, and another one is to carry out basic experimental studies for the production of board materials and woody composites from oil palm biomass such as trunks and empty fruit bunches (EFB). The programme was designated for two years from 2010 to 2012 and the study was carried out through occasional visits to related institutions in Malaysia. In this paper, our achievements on the utilisation technologies are introduced at first, which are mainly laboratory-scale research studies, including the preparation of various types of pulp and paper and bio-composites. Secondly, the feasibility study under the JSPS-JICA programme is summarised, which includes networking scientific research works and rural developments. Finally, an ideal system for utilising biomass from palm oil industries will be proposed from outputs of this study.

Lab-Scale Research Studies

Collaborative research studies on the utilisation of oil palm biomass between the Japanese and Malaysian institutions have been carried out continuously for more than 15 years. Here we would like to introduce some achievements of laboratory-scale research studies from the collaboration.

Production of Various Types of Pulp from EFB

Preparation of various types of pulp has been studied to make EFB useful as a raw material for related industries.

Figure 1. EFB pulps

It was found that EFB chemical pulps can be bleached by various chlorine-free processes to obtain a commercial level of brightness with paper quality comparable to hardwood kraft pulp (Figure 1, left) [1,2]. The combination of acid pre-hydrolysis, soda-anthraquinone (AQ) pulping and chlorine-free bleaching processes was found to be effective for producing dissolving pulp from EFB (Figure 1, right) [2,3].

Preparation of EFB-Glycerol Composites

Studies on the utilisation of oil palm empty fruit bunches (EFB) and glycerol from biodiesel fuel (BDF) waste have been carried out for the development of lignocellulose-based polyurethane (PU) composites. To produce the PU composites, the BDF-by-product glycerol and EFB mixture needs to be pressed at a high temperature as shown in Figure 2. It is essential to use an isocyanate compound as a cross-linker, but it is possible to reduce its amount to a certain level while still retaining the mechanical strength of the composite. For EFB fibres, it is necessary to clean their surfaces, but an organic solvent is not required, water with detergent is good enough. The content of EFB can be increased to 70~80% of the whole composite without serious loss of mechanical strength [4,5].

Figure 2. Preparation of an EFB-glycerol composite

Feasibility Study for Setting Up the Utilisation System

Main purpose of the feasibility study under the JSPS-JICA programme is to set up an integrated system on oil palm biomass utilisation in Malaysia. Our activities were to create a network between institutions for research studies and for practical involvements and to propose an ideal system for the setting-up. The study was carried out when the Japanese members visited Malaysia more than ten times between 2010 and 2012, each time 1~4 weeks. The Malaysian counterpart was School of Industrial Technology, Universiti Sains Malaysia (USM) and meetings were held occasionally either in Penang or in Kuala Lumpur with JICA, SIRIM and FELCRA. Besides the meetings, we visited oil palm plantation sites belonging to FELCRA and exchanged opinions and ideas with the staff and workers (Figure 3). We also attended international and domestic conferences organised by FRIM, MPOB, USM and JIRCAS. These occasions were quite important to obtain the latest information in research and development for oil palm biomass and to exchange ideas with experienced scientists from various research areas. Factory visits were other important activities for the study to know recent situation of the biomass usages. The visit includes pulp and paper mills using EFB, plywood factories for OPT and palm oil mills.

Figure 3. Oil palm plantation sites

Through the study, two things have become clear for the establishment of the system: (1) technological progress should be made in combined with rural development at regions depending on palm oil industries; (2) environmental impacts should be reduced by balanced usages of oil palm biomass. Considering these requirements, we tried to build up an ideal system for the integrated utilisation. Figure 4 shows a flow chart of research and development, which must be necessary to be carried out for establishing the system.

Figure 4. The concept of an integrated utilisation system for oil palm biomass

The Category (1) ‘Evaluation’ includes life cycle assessment (LCA) and economic feasibility. LCA must be conducted from material and energy balances for the production of a certain product using a raw material of oil palm biomass. It is also important to determine the cost performance during the production. In this category, the establishment of methods for the LCA and the cost evaluation will be main purposes of the study. For the production of biomass-origin products, it is necessary to have the initial stage of raw material treatment, i.e. the collection, transportation and processing of oil palm biomass. The processing includes the conversion of the biomass wastes to easy-handling materials such as EFB shredded fibres. For these purposes, the Category (2) ‘Raw material processing’ section includes the development of a new-type of biomass processing centre by designing and locating a pilot plant. Research studies on the production of value-added products are continuation of currently on-going studies at various institutions (the Category (3) ‘Value-added products’). The most important thing in each study is to make a clear goal and to set a time limit in basic approaches. Then the research work © 2016 Published by Center for Pulp and Paper through 2nd REPTech 281 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 makes progress towards its application in cooperation with a related industry. When all categories are brought together, it will demonstrate a production trial and evaluation test as a model system of the biomass utilisation, which is shown as ‘Showcase’ in Figure 4. Once these model systems are set up, it must be a turn of related industries such as wood boards, panels, energy and pulp / paper. The role of research and development for the establishment of biomass utilisation system is to connect between individual academic research studies and industries. At this point, the most important thing is that the industrial progress involves rural development of oil palm related areas. If the industry is only beneficial to present palm oil industries, there is no progress in the development toward sustainability including environmental issues. To be a ‘Win-Win’ situation for both economy and environment related to palm oil industry, it is necessary to utilise the biomass from oil palm properly and to show it is beneficial for the economy of local societies.

Conclusions

Palm oil is an excellent agricultural product for us, human beings. We are utilising natural plants efficiently such as palm oil. However, when we intensively plant a useful crop or tree, it is no longer ‘natural’. For oil palm, we are only using its oil and do not care its residues. This is not properly ‘natural’. For proper nature, a metabolic system should work for all plants and creatures. However, an oil palm plantation is man-made, so that it is necessary for us to keep its metabolism working. It means that we should utilise not only palm oil but also woody biomass from the palm efficiently for keeping the plant metabolism.In this study, our research studies have been introduced and the integrated system has been proposed for the utilisation of oil palm woody biomass. We hope our achievement will be a starting point for sustainable palm oil industries.

Acknowledgement

Parts of this study have been carried out as an international collaborative research project of Japan International Research Center for Agricultural Sciences (JIRCAS) and the programme of ‘Dispatch of Science & Technology Researchers’ implemented through the collaboration between Japan Society for the Promotion of Science (JSPS) and Japan International Cooperation Agency (JICA).

References

Tanaka R., Wan Rosli W.D., Magara K., Ikeda T. and Hosoya S., (2004), “Chlorine-free bleaching of kraft pulp from oil palm empty fruit bunches”; Japan Agricultural Research Quarterly (JARQ), 38, 275-279. Tanaka R., Leh C.P. and Wan Rosli W.D., (2013), “Utilisation of empty fruit bunches (EFB) for the production of various types of pulp”; JIRCAS Working Report, 80, 21-25. Wan Rosli W.D., Leh C.P., Zainuddin Z. and Tanaka R., (2004), “Effects of pre-hydrolysis on the production of dissolving pulp from empty fruit bunches”; Journal of Tropical Forest Science, 16, 343-349. Tanaka R., Tay G.S., Rozman H.D., Sugimoto T. and Hatakeyama H., (2012), “Fundamental studies on polyurethane (PU) composites containing oil palm fibres and glycerol-based polyols”; JIRCAS Working Report, 73, 39-42. Tanaka R., Sugimoto T., Tay G.S., Rozman H.D., Hirose S. and Hatakeyama H., (2013), “Utilisation of empty fruit bunches (EFB) and glycerol for the development of lignocellulose-based composites”; JIRCAS Working Report, 80, 34-41.

RESEARCH ON THE PREPARATION AND ACTIVITY TEST THREE TYPES OF DRY SORBENT FOR FLUE GAS DESULFURIZATION

Herri Susanto1, Muhammad Arif Susetyo, David Bahrin Department of Chemical Engineering Institut Teknologi Bandung, Bandung 40132 Indonesia [email protected]

ABSTRACT

Increasing the use of low quality coal particularly with a high sulfur content in power plants will bring about an increase in SO2 emission. The standard emission for SO2 in flue gas set by the Ministry of Life and Environment, Regulation no. 21/2008 is 600-1000 mg/Nm3 depending on the power plant type and year of starting operation. It is common industrial knowledge that coal fired power plant fueled with coal having a sulfur content of more than 0.35% will exceed this limit. A commercially proven Wet Limestone Forced Oxidation method is popular for flue gas desulfurization (FGD). However, this technology is difficult to be retrofitted in the existing power plants, formerly installed without FGD. One of the preferable methods to be retrofitted in the existing power plant is dry sorbent FGD. In this method, dry sorbent is injected in the duct of flue gas leaving the furnace. Experimental and theoretical studies have been conducted to evaluate the effectivity of Ca(OH)2 and NaHCO3 as dry sorbents, at various particle sizes, adsorption temperature and gas flow rate. After about 1.5 hours of utilization,

NaHCO3 conversions were in the range of 20-90% and the conversions of SO2 were in the range of 10-

67%. NaHCO3 sorbent was found more effective than Ca(OH)2. Although it is much more expensive than the later. These two chemicals are available in the local market. A regenerable sorbent, CuO/g-Al2O3 has been successfully prepared in our laboratory. In this chemical adsorption, CuO reacts with SO2 and

O2 (available in flue gas) to become CuSO4. In the following desorption process, spent sorbent CuSO4 decompose to CuO and SO3. In addition to the advantage in regenerability, this adsorption-desorption process produces SO3 which may be further converted to H2SO4. Sorbent CuO/g-Al2O3 was prepared using the dry impregnation method and five type of sorbent with different Cu contents were studied: 5Cu (actual content of 4.92%), 8Cu (7.68%), 15Cu (14.13%), 22Cu (20.80%) dan 27Cu (25.80%). Among these five types, sorbent 8Cu was the best with respects to the specific pore area and the uniformity of distributed of Cu on g-Al2O2 and the adsorption capacity. Sorbent 8Cu had the highest adsorption capacity, i.e. 0.98 mol of SO2 per mol of Cu (close to the stoichiometric of 1/1), moreover the reaction of the sorbent support, g-Al2O3 with SO2 could be neglected.

Keywords: flue gas desulfurization, dry injection, calcium carbonate, sodium bicarbonate, regenerable sorbent, impregnation method, absorption capacity, fixed bed tubular reactor

Introduction

Combustion of coal with sulfur content in the range of 0.4-0.6 weight of coal (as received) will produce SO2 emission that is more than the standard. The standard of SO2 emission were regulated by

Ministry of Environment, Republic of Indonesia through regulation No. 21/2008, which limits the SO2 3 emission in flue gas of CFPP (coal fired power plant) maximum is 750 mg/Nm , at 7% O2 content (dry basis). Until recently, only 2 CFPP (3860 MW, 2016) in Indonesia utilized flue gas desulfurization (FGD) process where total capacity of CFPP is 23,344.5 MW utilized limestone forced oxidation (LSFO) and sea water FGD. The first of FGD technology are applied in Indonesia is LSFO FGD in CFPP of Tanjung Jati B with the capacity of 4 x 660 MW, located at Jepara-Central Java and the second is SW FGD in CFPP of Paiton II with capacity is 2 x 610 MW that is located at East Java. The FGD technology that has been applied in Indonesia could be classified as wet process. Disadvantages of wet FGD process are: (1) requirement of large water volume; (2) production of liquid and solid waste; (3) flue gas reheating requirement before release to atmosphere; (3) the high pressure drop of flue gas and (4) wide area

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 283 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 requirement [1, 2]. All of the implemented FGD technology has been imported from other country, so the development research of FGD technology especially dry process of FGD is very important for the future use.

Dry process of FGD using calcium hydroxide (Ca(OH)2) and sodium bicarbonate (NaHCO3) sorbent and regenerable CuO/g-Al2O3 sorbent are preferable to be used in CFPP. Ca(OH)2 is a commercial sorbent that has been widely applied to FGD process. Ca(OH)2 sorbent is not literally dry but may contain small amount of water to increase their SO2 adsorption capacity. Different from NaHCO3 sorbent, water will be decomposed from sorbent and released to environment. NaHCO3 sorbent have some advantages such as having the high of SO2 adsorption capacity (380 mg SO2/g NaHCO3), more stable when stored under longer period at room temperature, the side product (Na2SO4) has economic value (reduce desulfurization cost), can be applied at low temperature (170-425°C) which is suitable with flue gas temperature of CFPP and easy application on existing CFPP as there are not much change in the furnace-boiler configuration of CFPP [3, 4].

Injection of Ca(OH)2 and NaHCO3 sorbent can be done in the duct before or after air preheater of CFPP [3, 4]. This technology was called dry sorbent injection (DSI) FGD. The main difference between DSI FGD with LSFO FGD and SW FGD is the absence of an absorber column, where the desulfurization reaction is conducted in the flue gas stream within the flue gas duct [3]. Reaction occuring in desulfurization process for Ca(OH)2 sorbent experiments is shown by the following equation.

Ca(OH)2(s) + SO2(g) + ½ O2(g) + H2O(g) à CaSO4.2H2O(s) (1)

For NaHCO3 sorbent, the first reaction is thermal decomposition of sodium bicarbonate into sodium carbonate and the second reaction is desulfurization reaction such as shown on the following equation.

2NaHCO3(s) + heat à Na2CO3(s) + H2O(g) + CO2(g) (2)

Na2CO3(s) + SO2(g) + ½ O2(g) à Na2SO4(s) + CO2(g) (3)

Reaction (1) and (2) began to take place at temperature of 150°C. Reaction (3) is very effective for SO2 adsorption until 425°C. Above 425°C, sintering or agglomeration of Na2CO3 will occur, and effectiveness of desulfurization reaction is reduced significantly [3]. Reaction temperature chosen for the experiment must be suitable or compatible with the temperature profile in the flue gas duct of CFPP, in which the temperature is in the range of 350-400°C (area between economizer and Air-Preheater) and 140-160°C (area after air preheater) [3]. Another for flue gas desulphurization of coal fired power plant is using regenerable sorbent, CuO/g-

Al2O3. The use of CuO/g-Al2O3 sorbent is advantageous in the way that it can be regenerated without a significant decrease of adsorption capacity [2, 5, 6, 7, 8, 10]. This sorbent can chemically adsorb SO2 and O2 in flue gas following this reaction.

CuO(s) + SO2(g) + O2(g) à CuSO4(s) (4)

This reaction take place effectively at temperature in the range of 300 to 450°C. The spent sorbent is regenerated using a reducing gas such as H2, CH4 or NH3 or using thermal decomposition.

CuSO4(s) + 2H2(g) à Cu(s) + SO2 (g) + 2H2O(g) (5)

CuSO4(s) + 4H2(g) à CuS(s) + 4 H2O(g) (6)

CuSO4(s) + ½ CH4(g) « Cu(s) + SO2(g) + ½ CO2(g) + H2O(g) (7)

CuSO4(s) + hot air à CuO(s) + SO3(s) (thermal decomposition) (8)

Regeneration with thermal decomposition is more preferable because it does not require any addition reducing gas. Adsorbed SO3 is then converted into H2SO4. Unfortunately, thermal decomposition method may reduce durability of CuO/g-Al2O3 sorbent to heat [9, 11].

Experimental studies on the adsorption capacity of Ca(OH)2, NaHCO3 and CuO/g-Al2O3 are presented in this paper. Effectivity of these three sorbents are compared one to the other.

Experiments

NaHCO3 99% pure was obtained from the local market is more than 99% pure. Preparation of sorbent involves only size reduction with the particle size distribution. The reaction temperature was in the range of 150-525°C. Initial weight of sorbent used for every experiments was 0.5 gram. Desulfurization experiments was conducted semi continuously in tubular tube (fixed bed) reactor. Measurements of SO2 concentration were done using flue gas analyzer PCA-3 Bacharach at the interval of 1 minutes. The 3 inlet SO2 concentration was 2500 mg/Nm in the air with gas flowrate was 1.209 L/min as the results of optimization between contact time (0.062 second/cm sorbent). Reynolds number of gas flowrate was 134, which was classified as a laminar flow. Reactor pressure was set to be atmospheric. Two parameters may be used to indicate the success of desulfurization experiments. The first was SO2 conversion or mass fraction of SO2 absorbed or reacted with Ca(OH)2 and NaHCO3.

(9)

The second was conversion of sorbent or sorbent mass fraction that reacted with SO2 during experiments as shown on the following equation.

(10)

As source of active phases CuO, Cu(NO3)2.3H2O solution was successfully impregnated to the support 2 g-Al2O3. This support has spesific surface area, pore volume and average pore diameter of 218.43 m /g, 3 0.46 cm /g and 8.33 nm respectively. Five types of CuO/g-Al2O3 sorbents were obtained: 5Cu (intended Cu concentration of 5%, actual of 4.92%), 8Cu (7.68%), 15Cu (14.13%), 22Cu (20.80%) and 27Cu

(25.80%). Drying and calcination conditions of CuO/g-Al2O3 sorbent is the same as previously done by Yuono et al., 2015 [8]. The average pore diameter and pore volume of sorbent have been analyzed using Nitrogen Adsorption-Desorption with Barrett-Joyner-Halenda model. The specific surface area has analyzed using Brunauer-Emmet-Teller method (Nova 3200e Quanta Chrome). Crystallinity phase of the support and the sorbent has analyzed by X-Ray Diffraction (Bruker D8 Advance).

Activity test of CuO/g-Al2O3 sorbent at various of copper content were conducted at 300, 350, 400 and 450°C for 60 minutes each. The SO2 concentration in the feed gas was in the range of 18,400-

21,000 ppmv in the air. The best CuO/g-Al2O3 sorbent obtained from experiments was further used on the adsorption-regeneration process. Regeneration of the spent CuO/g-Al2O3 sorbent using thermal decomposition technique using air as carrier gas were done at 500, 600 and 700°C. Both of the adsorption and regeneration experiments were carried out with a gas flow rates in the range of 1.4 – 1.8 mL/sec for 60 minutes. The initial weight of the sorbent utilized on every experiments were about 1.0 gram.

The amount of SO2 adsorbed by sorbent was measured from the difference of the SO2 amount between inlet and outlet gas to/from the reactor. The amount of SO2 was measured by titration method using NaOH solution (0.1M) with the reaction such as shown on our previous study [8]. The schematic diagram of the experimental set up for sorbent activity test is show on Figure 1.

6 2

1 4 7 Waste gas

Measurement of SO2 concentration

1. Mixing tank 3. Sorbent 5. Temperature controller 7. Compressor 2. Manometer 4. Furnace 6. flowmeter

Figure 1. Experimental set up

Results And Discussion

Performance of SO2 Adsorption using Ca(OH)2 and NaHCO3 sorbent experiments

Typical raw data acquired from the experiment is as described in the Figure 2. SO2 in the gas was 3 reduced until the value is about 500 – 800 mg/Nm . The difference of SO2 concentration in gas flow between the inlet and outlet reactor was the SO2 absorbed or react with the sorbent.

Figure 2. Typical progress of desulfurization

SO2 adsorption using Ca(OH)2 was found very low (Figure 3). This process required H2O in the feed gas to increase SO2 and Ca(OH)2 conversion. SO2 adsorption experiments using NaHCO3 sorbent at various of particle size has shown that SO2 conversion where is sorbent conversion is highest with particle size of 37-74 micron or 200-400 mesh (Figure 4). If the particle size is smaller than 37 micron, desulfurization effectiveness was very low which was due to ineffective contact between gas and sorbent.

Figure 3. Effect of SO2 concentration on desulfurization effectiveness

Figure 4. Effect of particle size on desulfurization effectiveness

Since the effectiveness of Ca(OH)2 was very low, further experiment was focused on the used of

NaHCO3 sorbent. The best adsorption condition was found at a temperature of 425°C, giving conversions of both SO2 and NaHCO3 of about 50% (Figure 5). Probably NaHCO3 sorbent underwent decomposition at 400°C to 425°C, so it became very active at 425°C. While at temperature above 425°C, NaHCO3 underwent agglomeration resulting in the reduction of effectiveness.

Figure 5. Effect on reaction temperature on desulfurization effectiveness

Regenerable CuO/g-Al2O3 Sorbent Experiments

The specific surface area and pore volume of the sorbent significantly decreased with increasing the copper content (Figure 6) but the average pore diameter of the sorbent tends to be constant (Figure 7). This phenomenon was due due to CuO layer cover the smaller sized pores of the sorbent so that the average pore diameter was not significantly reduced [12]. Among five types of sorbent, 5Cu was the best with respects to the specific pore area and the uniformity of distributed of Cu on g-Al2O2 [12]. In our previous studies, in XRD analysis, the increase of copper content will increase the peak of CuO that showed copper was not cover uniform on the surface of the support and tend to made agglomeration on the pore of sorbent [12]. In the chemisorption, uniform CuO cover on the surface of the support was desirable because only the top layer of CuO can react with SO2.

SO2 adsorption capacity of sorbent decreased with increase in copper content such as shown on Figure

8. This phenomenon has caused by excessive amount of CuO (reactant) but for the sum of SO2 inlet reactor tends to be constant. The high copper content may cause the formation of CuO multilayer on the sorbent [12]. SO2 adsorption capacity of sorbent will increase with the increase in reaction temperature

(Figure 8). However, at higher temperature, penetration of SO2 increases and the reaction takes place in the pore of the CuO/g-Al2O3 sorbent [13].

Figure 6. Specific surface area and pore volume of the g-Al2O3 support and CuO/g-Al2O3 sorbent

Figure 7. Average pore diameter of the g-Al2O3 support and CuO/g-Al2O3 sorbent

Figure 8. SO2 adsorption capacity of the CuO/g-Al2O3 sorbent

5Cu sorbent was more effective in adsorbing SO2 as compared to other sorbent such as shown on

Figure 8. In ideal condition, SO2 that adsorbed or reacted with CuO was reacted in a stoichiometric proportion. For 1 gram of 5Cu sorbent, the maximum amount of SO2 that can react with CuO is 49.6 mg or 0.78 mmol. The SO2 adsorption capacity of 5Cu was above the stoichiometric amount especially at 400 and 450°C. These might be attributed to the possible simultaneous reaction between SO2 and the g-Al2O3 support through catalytic reaction since copper did not cover completely the g-Al2O3 support [11, 13]. Activity test of three types of dry sorbent for flue gas desulfurization were done successfully with the best of SO2 adsorption capacity which found on the NaHCO3 sorbent was about 259.73 mg SO2/g sorbent. If compared with CuO/g-Al2O3 sorbent with the high value was 74.18 mg SO2/g sorbent, these value is very high. However the use of CuO/g-Al2O3 sorbent is more advantageous because this sorbent can be regenerated and used repeatedly. In our previous studies shows that regeneration of CuO/g-Al2O3 sorbent using hot air at temperature of 600°C were not significant reduced SO2 adsorption capacity of sorbent [8, 12].

Conclusions

Based on the experiment data, the optimum temperature with regard to effectiveness of NaHCO3 sorbent in desulfurization adsorption process is 425°C. Particle size of NaHCO3 that results in maximum effectiveness in desulfurization process is between 37-74 micron or 200-400 mesh. Ca(OH)2 sorbent were not effective to adsorb SO2 because water vapor was not enough available in the desulfurization process.

The best of SO2 adsorption capacity owned by NaHCO3 sorbent with the value was about 259.73 mg

SO2/g sorbent. The use of CuO/g-Al2O3 sorbent is more advantageous because can be regenerated and used repeatedly.

Acknowledgment

These studies is a part of master and doctoral research in Chemical Engineering and Mechanical Engineering Graduate Program of Institut Teknologi Bandung. This research are financially supported by PT. Pupuk Sriwidjaja Palembang, PT. Perusahaan Listrik Negara (Persero) and Hibah Kompetisi 2016-Ministry of Research, Technology and Higher Education Republic of Indonesia. Participation in this seminar was financially supported by Hibah Kompetisi 2016, Ministry of Research, Technology and Higher Education Republic of Indonesia.

References

1. A. Dehghani and H. Bridjanian, “Flue gas desulfurization methods to conserve the environment,” Petroleum and Coal, vol. 52, 2010, pp. 220-226.

2. Y. Mathieu, L. Tzanis, M. Soulard, J. Patarin, M. Vierling and M. Moliere, “Adsorption of SOx by oxide materials: A review,” Fuel Processing Technology, vol. 114, 2013, pp. 81-100. 3. M. A. Susetyo, T. Hardianto, D. Bahrin, and H. Susanto, “Modelling of dry reagent for dry flue gas desulfurization,” Proceeding of International Seminar on Chemical Engineering in Conjuction with Seminar Teknik Kimia Soehadi Reksowardojo, Bandung, October 2016. 4. M. A. Susetyo, T. Hardianto, D. Bahrin, and H. Susanto, “Dry flue gas desulfurization for power generation,” Proceeding of Seminar Nasional Tahunan Teknik Mesin XV (SNTTM XV), Bandung, October 2016.

5. V.S. Gavaskar and J. Abbasian, “Dry regenerable metal oxide sorbents for SO2 removal from flue gas. 1. Development and evaluation of copper oxide sorbents,” Industrial and Engineering Chemistry Research, vol. 45, 2006, pp. 5859-5869. 6. S.G. Deng and Y.S. Lin, “Synthesis, stability, and sulfation properties of sol-gel-derived regenerative sorbents for flue gas desulfurization,” Industrial and Engineering Chemistry Research, vol. 35, 1996, pp. 1429-1437. 7. Z.M. Wang and Y.S. Lin, “Sol-gel-derived alumina-supported copper oxide sorbent for flue gas desulfurization,” Industrial and Engineering Chemistry Research, vol. 37, 1998, pp. 4675-4681.

8. Yuono, D. Bahrin and H. Susanto, “Preparation and characterization of CuO/γ-Al2O3 for adsorption

of SO2 in flue gas,” Modern Applied Science, vol. 9, 2015, pp. 107-113. 9. K.S. Yoo, S.M. Jeong, S.D. Kim and S.B. Park, ”Regeneration of sulfated alumina support in CuO/

g-Al2O3 sorbent by hydrogen,” Industrial and Engineering Chemistry Research, vol. 35, 1996, pp. 1543-1549.

10. C. Macken, B.K. Hodnett and G. Paparatto, “Testing of the CuO/Al2O3 catalyst-sorbent in extended

operation for the simultaneous removal of NOx and SO2 from flue gases,” Industrial and Engineering Chemistry Research, vol. 39, 2000, pp.3868-3874. 11. D. Bahrin, Subagjo and. H. Susanto, “Effect of regeneration temperature on particle characteristics

and extent of regeneration of saturated SO2-adsorption of CuO/g-Al2O3 sorbent,” Procedia Chemistry, vol. 16, 2015, pp. 723-727. 12. D. Bahrin, Subagjo and H. Susanto, “Preparation, characterization, adsorption and regeneration

test of CuO/g-Al2O3 adsorbent for SO2 removal from flue gas in coal-fired steam power plant,” Proceeding of Regional Symposium on Chemical Engineering (RSCE), 2016, pp. 47-52.

13. D. Bahrin, Subagjo and H. Susanto, “Kinetic study on the SO2 adsorption using CuO/g-Al2O3 sorbent,” Bulletin of Chemical Reaction Engineering & Catalysis, vol.11, 2016, pp.93-99.

PULPING OF OIL PALM TRUNK USING ENVIRONMENTALLY FRIENDLY PROCESS

Wieke Pratiwia1, Andoyo Sugihartob2, Susi Sugestyb aCenter for Material and Technical Product, Jalan Sangkuriang 14, Bandung 40135, Indonesia bCenter for Pulp and Paper, Jalan Raya Dayeuhkolot 132, Bandung 40258, Indonesia [email protected] [email protected]

ABSTRACT

Oil Palm Trunk (OPT) is a non-wood cellulosic raw material which is not yet widely utilized in pulping and papermaking. Research on the utilization of abundant Oil Palm Trunk (OPT) for pulp using Environmentally Friendly Process was carried out successfully. Two types of OPT were used in this research, i.e: from Sabah (Malaysia) and Lebak (West Java Province). Pulping was carried out using the kraft and the soda anthraquinone processes by varying the active alkali in the range of 13-17%. Then bleaching of pulp was carried out using the Elemental Chlorine Free (ECF) process. Before pulping the raw material was subjected to chipping and depithing as pretreatment. Analysis of raw material covered physical and chemical properties, and also fiber morphology.Fiber from Sabah OPT and Lebak OPT could be classified into the moderate fiber length with the length in the range of 1.05-1.37 mm. OPT were very bulky as shown by the chips pile density of 102.16 kg/m3 for undepithed Sabah OPT, and 62.91 kg/m3 for depithed one. The physical properties of OPT pulps were comparable to that of pulp from Acacia mangium which was commonly used as raw material for pulp. With respect to the bleachability and physical properties, pulping of Lebak OPT using kraft or soda-anthraquinone process with active alkali of 15% were considered as optimum condition. Depithing on Sabah OPT with high pith content could increase physical properties of pulp. ECF bleaching with ODEoDnD sequence on pulps from Sabah OPT gave satisfactory results with respect to the physical properties. Since Sabah OPT had a high pith content, the yields of bleached pulp were relatively low, i.e. in the range of 24.67- 26.73%. However, the physical properties of the bleached pulps from undepithed or depithed Sabah OPT were higher compared to those of the LBKP as that specifiedin SNI.

Keywords: depithing, kappa number, Elemental Chlorine Free, bleached pulp, physical properties, Leaf Bleached Kraft Pulp (LBKP)

Introduction

Indonesia is a palm oil exporting country with an ever increasing value, from 4.11 million tonnes in 2000 became 20.58 tonnes in 2013 [1]. The increase in production of palm oil, the more waste is generated. The waste or residue of oil palm plantations consist of leaves from pruning activities, palm stems from replantations programs, as well as empty fruit bunches, kernel shell and fiber from oil processing mill. Fiber and palm kernel shell are utilized as fuel in steam power plant in palm oil mills. The leaves and trunks are usually left in the field [8], which may cause various problems if it is not managed properly. Oil Palm Trunk (OPT) is a type of waste from oil palm plantations, which is usually left in the field to rot and may untidy place and hamper movement of the worker [4, 6, 8]. Currently, oil palm plantation residue is available in quite considerable quantities due to the high expansion rate of oil palm plantation. The area of oil palm plantation in Indonesia increased significantly from 4.2 million hectares in the year of 2000 became 10.5 million hectares in 2013. In 2014, the total area of oil palm plantations in Indonesia was approximately 11 million hectares [1]. During harvesting, every hectare of palm plantation yields over 70 tonnes of dry trunk as biomass waste [2] As a source of lignocellulosic material, OPT is less expensive compared to wood. Utilizing OPT as a raw material to produce value-added products will not only reduce the overall costs of pulp production,

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 291 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 but will also increase economic return of oil palm plantation [7]. OPT is a non-wood cellulosic raw material which is not yet widely utilized in pulping and papermaking. Due to the limited characteristic of fibers, an attempt has been made to utilize OPT as a substitute for wood fiber in pulping. Research on the possibility of OPT as a raw material for pulp using environmentally friendly process is reported in this paper. Pulping was carried out using the kraft and the soda anthraquinone processes. Then bleaching of pulp was carried out using the Elemental Chlorine Free (ECF) process. Evaluation of pulp handsheets was done to observe the quality of pulp. Before pulping the raw material was subjected to chipping and depithing as pretreatment. Analysis of raw material covered physical and chemical properties, and also fiber morphology.

Materials and Method

Raw Materials

Oil Palm Trunk used in this experiment were originally from Sabah (Malaysia) and Lebak (Pandeglang, West Java Province). The OPT from Sabah was received in the form of 20 disks cut from 5 different oil- palm trees. Each tree was cut into four parts of the trunk, i.e: Bottom (B), Middle Bottom (MB), Middle Top (MT) and TOP (T), with the diameter in the range of 35-45 cm and thickness of 5-8 cm. While raw material from Lebak was received as its original condition.

Method of Experiment

Pulping was conducted in two methods, i.e.: the Kraft process for Sabah OPT, and the Kraft and the Soda AQ processes for Lebak OPT (see Figure 1). Bleaching was conducted in the ODEoDnD sequence which was an elemental chlorine free (ECF) as one of the environmentally friendly processes. Determination of physical and optical properties were applied on bleached pulp and unbleached pulp..

Preparation of Feedstocks

All types of raw material were chipped to get feedstock for pulping. Sabah OPT was prepared in two kinds of feedstocks: undepithed and depithed, then called as SU and SD respectively (see Figure 1). The SD feedstock was obtained from mixing of equal portions of depithed fibers, i.e. 25% each of B, MB, MT and T Sabah OPT. So, the effect of the absence of pith in feedstocks could be evaluated. Preparation of feedstock from Lebak was only for undepithed materials which was consisted of Bottom, Middle and Top parts of trunk.

Analysis of Morphological, Physical and Chemical Properties of Raw Material

Analysis of morphological, physical and chemical properties of raw materials were conducted according to the Indonesian National Standard (SNI). The chemical analysis of depithed and undepithed feedstocks included lignin, holocellulose, alpha cellulose, ash, extractives, and pentosan contents. The solubility in 1% NaOH, cold water and hot water were also determined according to SNI.

Pulping and Bleaching a. Pulping

The kraft (sulfate) and the soda anthraquinone processes were used by varying the active alkali of 13%, 15% and 17% (see Table 1). The kraft process was used for feedstock of undepithed and depithed Sabah OPT (SU and SD, see Figure 1). The kraft and the soda anthraquinone processes were used for undepithed OPT from Lebak (LU, Figure 1). Pulping processes were conducted in a three liter rotating digesters circulated in heated air.

Figure 1. Procedure of experiment

Table 1. Pulping Conditions of Oil-Palm Trunk

No Process Variable Kraft Soda AQ*

1. Active alkali (% as Na2O) 13 ; 15 ; 17 13 ; 15 ; 17

2. Sulfidity (% as Na2O) 25 - 3. Anthraquinone (AQ), % - 0.1 4. Liquor ratio 1 : 4 1 : 4 5. Maximum temperature (oC) 170 170 6. Time to reach maximum temperature (hours) 2 2 7. Time at maximum temperature (hours) 1.5 1.5 * only for Lebak OPT

Pulp was then washed and screened prior to the determinations of the screen yield and Kappa number (KN). b. Bleaching of Pulp

Elemental Chlorine Free bleaching process using five stages of ODEoDnD sequence (see Table 2) was applied to pulp obtained from Sabah OPT.

Evaluation on Unbleached and Bleached Pulps

The unbleached and bleached pulps from Sabah (SU-UKP and SU-BKP, and SD-UKP and SD-BKP) were beated separately in a Niagara Beater. The results were made into pulp handsheets and tested for their physical and optical properties acccording to the Indonesian National Standard (SNI). The freeness of pulp was tested using Schopper Riegler (SR) Freeness Tester. Pulp from Lebak OPT was treated in the same way as those for Sabah OPT. The freeness of the pulp from Lebak OPT was tested using Canadian Standard Freeness Tester.

Results and Discussion

Properties of Feedstocks

The undepithed Sabah OPT (SU), of course consisted of fibers and pith. The fiber contents of the

Table 2. The Bleaching Process Conditions of SU-UKP and SD-UKP

Chlorine- Extraction- Chlorine-dioxide and Chlorine Oxygen Process dioxide Oxygen neutralization Stage -dioxide No. Stage Variables Stage Stage (Dn) Stage (O) (D) (Eo) D n (D)

1. O2 , pressure in atm 6 – 6 – – –

2. MgSO4, % 0.5 – – – – –

3. ClO2, as active chlorine – 0.22 KN – – – –

4. ClO2, % – – – 1 – 0.5

5. H2SO4, % – 0.4 – – – 0.35 6. NaOH, % – – 2 0.35 0.2 – 7. Consistency, % 10 10 10 10 10 10 8. Temperature, oC 100 70 70 75 75 75 9. Time, minutes 60 60 60 120 10 150 Note : In the Dn-Stage, Chlorine Dioxide stage was followed by neutralization without any washing in between

Bottom, Middle Bottom, Middle Top and Top parts of Sabah OPT were 59.68%, 55.48%, 62.50% and 50.64% respectively (see Table 3). Meaning that more than 50% of the raw material might be utilized as the feedstock for pulping. On the other hand, pith consisted of parenchyma cell, which had to be removed before pulping since it might cause a much chemical consumption for pulping [3].

Physical and Morphological Properties of Feedstock

The physical and morphological properties of feedstock are shown in Table 3. Fiber from Sabah OPT and Lebak OPT could be classified into the moderate fiber length with the length in the range of 1.05- 1.37 mm. OPT were very bulky as shown by the chips pile density of 102.16 kg/m3 for undepithed Sabah OPT, and 62.91 kg/m3 for depithed one. These values are lower compared to chips pile density of Acacia mangium (133-162 kg/m3) and chips pile density of pine (177-244 kg/m3) [4]. The higher the chips pile density, the higher the digester capacity. Fiber content of Lebak OPT (an average of 87.88%) was significantly higher than that of Sabah OPT (an average of 57.07%). This difference was understandable as they originated from two different places and possibly two difference variety. Based on the morphological and physical properties of fiber, oil palm trunk had a potency to be used as a raw material for pulp such as Acacia mangium which is commonly used for pulp.

Chemical Composition of Feedstock

Chemical composition of undepithed Sabah OPT and depithed Sabah OPT are presented in Table 4. In addition, the chemical composition of Acacia mangium of three years age from Indonesia is also presented. As previously mentioned, data for SU and SD (Sabah OPT) were obtained from the mixtures of equal portions of B, MB, MT and T parts (see Figure 1). As expected, depithing could reduce the lignin content in feedstock, so a reduction in chemicals for pulping might be expected too. Significant reductions were also observed in ash and silicate contents. A significant increase in holocellulose content was obtained from 68.68% to 79.67% for SU and SD respectively, even the later was higher than that of Acacia mangium (73.61%). Although the alpha cellulose content of SD was still lower than that of Acacia mangium (42.18% vs 46.11%), it increased already from its original value of 33.21%. Moreover, contents of all other impurities such as extractives and soluble compounds decreased significantly. Thus the depithing operation was an effective pretreatment for OPT.

Table 3. The Physical and Morphological Properties of Raw Material

Sabah Lebak Acacia No. Parameters Middle Middle Mangium Bottom Top Bottom Middle Top Bottom Top [11] 1. Fiber length (L), mm Minimum 0.50 0.40 0.37 0.40 0.49 0.38 0.38 0.43 Maximum 2.42 2.85 2.91 2.76 2.19 2.17 2.01 1.28 Average 1.36 1.22 1.37 1.33 1.24 1.09 1.05 0.79 2. Fiber diameter (D), mm 37.34 36.22 29.79 29.61 27.21 23.04 17.83 13.90 3. Lumen (l), mm 25.88 25.99 22.42 22.37 6.20 5.37 3.90 9.51 4. Cell wall thickness (w), mm 7.73 5.11 3.68 3.62 10.51 8.84 6.97 2.20 5. Runkel Ratio (2w/l) 0.44 0.39 0.33 0.32 3.39 3.29 3.57 0.46 6. Fiber content, % 59.68 55.48 62.50 50.64 85.62 85.60 89.11 - 7. Pith content, % 40.32 44.52 37.50 49.36 14.38 14.40 10.89 - 8. Density, kg/m3 244 219 214 197 - - - 407 9. Chips pile density, kg/m3 147.36 Undepithed OPT 102.16 - - - Depithed OPT 62.91 - - -

Table 4. Chemical Composition of Oil-Palm Trunk

Sabah OPT Lebak OPT, Undepithed Acacia No. Parameters Undepithed, Average Bottom Middle Top mangium SU LU 1. Lignin, % 25.34 22.62 21.62 24.08 22.77 26.41 2. Holocellulose, % 68.68 72.95 70.88 67.26 70.36 73.61 3. Alpha cellulose, % 33.21 41.87 40.18 37.28 39.78 46.11 4. Pentosan, % 25.01 23.55 23.79 23.18 23.51 20.76 5. Extractives, % 2.03 2.10 2.04 3.51 2.55 3.28 6. Ash, % 4.69 2.18 3.11 6.47 3.92 0.32 7. Silicate, % 2.32 1.02 1.69 4.52 2.41 - 8. Solubility in 1 % NaOH, % 31.79 18.56 21.61 25.82 22.00 13.68 Cold water, % 9.97 4.50 6.34 8.32 6.39 2.10 Hot water, % 10.12 6.10 7.29 8.59 7.33 3.33

The undepithed Lebak OPT had uniform compositions of main components: lignin, holocellulose, alpha cellulose and pentosan (presented in Table 4). However, the alpha cellulose content of Lebak OPT was lower than that of Acacia mangium (46.11%). Significant differences were observed in the ash contents of undepithed Lebak OPT, i.e: 2.18%, 3.11% and 6.47% respectively for bottom, middle and top parts of trunk. These increases in ash content from the bottom to the top of trunk might related to the fact that ash content in empty fruit bunches was very high (up to 6.68%) [3]. Similarly, the silicate contents were also increased 1.02%, 1.69% and 4.52% from the bottom to the top of trunk. These two properties had to be considered in designing chipper and other equipments for feedstock preparation.

Pulping

Pulping conditions were employed in order to obtain the bleachable grade pulps with Kappa number of about 14-20. Kappa number is a measure of degree of delignification indicating how far the delignification occurs. This means that the lower Kappa number the lower bleaching chemical charge.

The screened yield tended to decrease with the increase of active alkali, both for SU (undepithed Sabah OPT) and SD (depithed one). The screened yield based on the original raw material of SD pulps were much lower (28.67 – 31.37%) compared to those of SU pulps (43.23 – 46.84%) due to the depithing process with a depithing yield of 57.07% (avg).

Table 5. Results of Sabah OPT Kraft Pulping (at Sulfidity of 25%)

* * # Active Alkali Total Yield ) Screened Yield ) Kappa Number No Samples ) (%) (%) (%) KN 1. 13/SU-UKP 13 50.36 46.84 80.55 2. 15/ SU-UKP 15 44.61 43.49 47.04 3. 17/ SU-UKP 17 43.93 43.23 24.07 4. 13/ SD-UKP 13 32.89 31.37 50.40 5. 15/ SD-UKP 15 29.95 29.54 18.42 6. 17/ SD-UKP 17 28.87 28.67 14.12

Note: #) see Legend in Figure 1; *) based on the original raw material

Results of Sabah OPT kraft pulping are shown in Table 5. To obtain pulp with about the same KN, undepithed Sabah OPT required more active alkali as shown in samples of 15/SU-UKP and 13/SD-UKP to obtain KN of 47.04 and 50.40 respectively. On the other hand, a same pulping condition would give a higher KN from undepithed than that of depithed (compare KN for 13/SU-UKP vs 13/SD-UKP; 15/ SU-UKP vs 15/SD-UKP and 17/SU-UKP vs 17/SD-UKP). Based on the value of KN, pulps from pulping with active alkali of 15% and 17% (15/SD-UKP and 17/SD-UKP) could be classified as bleachable grade pulps. While from undepithed feedstocks, only pulp from 17/SU-UKP was bleachable grade. Eventhough, the other pulps might be bleached, but they required more chemicals. By considering the screened yield and Kappa number (KN), the optimum condition for Lebak OPT (see Table 6) was pulping with the active alkali of 15%, both for kraft or soda anthraquinone (SA) processes. Pulp obtained from the kraft pulping with this condition had the screened yield of 37.43% and KN of 20.83, while that from the SA pulping had the screened yield of 38.95% and KN of 17.38. Pulps with these value of KN met the requirement for further bleaching process. In term of screened yield and Kappa number, the soda anthraquinone process gave better results compared to that of the kraft process. Therefore, it could be concluded that the environmentally friendly soda-anthraquinone process was suitable for pulping of OPT.

Table 6. Results of Lebak OPT Kraft and Soda-Anthraquinone Pulpings

* * # Active Alkali Total Yield ) Screened Yield ) Kappa No Samples ) (%) (%) (%) Number (KN) 1. 13/LU-UKP 13 45.96 43.08 45.10 2. 15/LU-UKP 15 38.35 37.43 20.83 3. 17/ LU-UKP 17 36.51 36.29 16.52 4. 13/ LU-USP 13 41.76 39.57 28.23 5. 15/ LU-USP 15 39.70 38.95 17.38 6. 17/ LU-USP 17 37.06 36.88 13.38 Note: #) see Legend in Figure 1 ; *) based on the original raw material

Bleaching of Pulp

Elemental Chlorine Free (ECF) bleaching process was applied to Sabah undepithed and depithed (SU and SD) pulps by using five stages bleaching process i.e. ODEoDnD sequence. The bleaching sequence was intended to reduce organochlorine compounds in the bleaching effluent, as indicated in some reports that chlorine dioxide can be used as a substitution for chlorine. The use of oxygen delignification (the first stage) was aimed to remove a substantial fraction of the lignin in unbleached pulp [9]. Results of bleaching of Sabah OPT pulp is presented in Table 7. Bleaching of pulps from undepithed Sabah OPT (SU-UKP, see Figure 1) yielded in bleached pulps (SU-BKP) with yields in the range of 24.67-26.73%, brightness in the range of 73.10-78.00 %GE, and dirt content in the range of 20.65-31.00 mm2/m2 (as presented in Table 7). While bleaching of SD pulp gave lower yields of about 26%, brightness in the range of 76.00-79.20% GE, and dirt in the range of 23.50-58.00 mm2/m2.

Table 7. Results of Bleaching of Sabah OPT Pulp

*) **) # Kappa Number, KN Yield Brightness Dirt No. Samples ) (%) (%GE) (mm2/m2) Brownstock O2 1. 13/SU-BKP 80.55 68.26 26.73 78.00 22.90 2. 15/SU- BKP 47.04 32.32 24.82 75.50 31.00 3. 17/SU- BKP 24.07 14.46 24.67 73.10 20.65 4. 13/SD- BKP 50.40 37.28 26.49 79.20 23.50 5. 15/SD- BKP 18.42 12.35 27.03 76.60 58.00 6. 17/SD- BKP 14.12 9.52 26.08 76.00 33.00

Notes: #) see Legend in Figure 1 *) based on the original raw material ; **) determined at initial freeness

In general, yield based on the original raw material are lower than 30%. The low yield possibly due to decomposition of the raw material begins. These could also be seen at the results of chemical components analysis, i.e. the soluble component in 1% NaOH, in hot water and in cold water were higher than those of wood. Particularly for depithed bleached pulps, the low yield might also be due to the low depithing yield, i.e. an average of 57.07%.

Evaluation of Physical Properties

Pulp made from Sabah OPT

The physical properties of pulps made from Sabah OPT at the freeness of 40oSR are presented in Table 8. Pulping of undepithed Sabah OPT using 15% and 17% active alkali gave pulp with significantly higher tensile index than those of pulping using 13% active alkali (compare: 15/SU-UKP and 17/SU-UKP vs 13/SU-UKP). But for depithed Sabah OPT, there was no significant differences in resulted from pulping with various active alkali (13/SD-UKP, 15/SD-UKP, and 17/SD-UKP). These tensile index of pulps made from Sabah OPT were much lower than that of Acacia mangium unbleached pulp. The burst index of all unbleached pulps from Sabah OPT (undepithed SU-UKP and and depithed SD-UKP) did not change with the active alkali of pulping, and they were in the range of 3.5 to 5.7 MN/ kg (Table 8). The burst index of all SU-UKP and SD-UKP were significantly lower than that ofAcacia mangium. While the tear index of all pulp from Sabah OPT apparently did not change with preparation of feedstock (either SU or SD) and the active alkali of pulping (either 13, 15 or 17%). Moreover, they were closer to that of Acacia mangium (7.12 Nm2/kg), and much better than that of Leaf Bleached Kraft Pulp specified in SNI 6107:2015 (5.50 Nm2/kg).

Table 8. Tearing, Bursting and Tensile Strength of Sabah OPT Pulp at Freeness of 40oSR

Tear Index, (Nm2/kg) Burst Index, (MN/kg) Tensile Index, (Nm/g) No. Samples#) unbleached bleached unbleached bleached unbleached bleached (-UKP) (-BKP) (-UKP) (-BKP) (-UKP) (-BKP) 1. 13/SU- 7.56 8.62 4.19 4.68 47.23 51.15 2. 15/SU- 6.50 7.92 3.53 5.00 53.74 53.08 3. 17/SU- 7.77 9.10 3.86 4.49 50.40 50.56 4. 13/SD- 7.00 8.76 4.81 4.68 64.25 51.25 5. 15/SD- 7.75 9.15 5.13 4.79 59.39 58.06 6. 17/SD- 7.05 8.41 5.67 4.82 64.00 56.07 7. Acacia mangium 7.38 7.12 7.10 5.24 93.00 49.20 pulp [5]

8. Leaf Bleached 5.50 2.50 45.00 Kraft Pulp [10] Note: #) see Legend in Figure 1

In general, the tear index of pulps from Sabah OPT could be improved by bleaching process (as presented in Table 8). Even the tear index of bleached pulp (SU-BKP and SD-BKP) were significantly higher than that of Acacia mangium pulp. The burst index of undepithed pulps were also improved by bleaching process, but they were still lower than that of Acacia mangium pulp. For pulp from depithed feedstocks, no improvement on the burst index were observed. Unlike the tear and burst index, the tensile index of pulps from Sabah OPT (both undepithed and depithed feedstocks) in general decreased due to the bleaching process. Actually, the tensile index of Acacia mangium pulp also decreased significantly due to the bleaching process from 93.00 to 49.20 Nm/g [5]. Since the decreases in tensile index of unbleached pulps from Sabah OPT were small, the tensile index of bleached pulp of Sabah OPT become higher than that of Acacia mangium pulp, and also higher than that of LBKP, 45 Nm/g [10].

Pulp made from Lebak OPT

For Lebak OPT, pulping was applied only to undepithed feedstocks. Results of pulping using kraft and soda-anthraquinone processes were presented already in Table 6 (Section 3.4). Physical properties are presented in Table 9. In general, unbleached pulp of LU (undepithed Lebak OPT) from the kraft pulping had better physical properties than that from the SA process. However, the physical properties of unbleached pulp from Lebak OPT were much lower than that of Acacia mangium pulp, with the exception of the tear index of pulp obtained from the kraft pulping.

Table 9. Tearing, Bursting and Tensile Strength of Unbleached Pulp from Lebak OPT at Freeness of 300 mL CSF

# Tear Index Burst Index Tensile Index No. Sample ) (Nm2/kg ) (MN/kg ) (Nm/g) 1. 13/LU-UKP 8.70 3.30 37.0 2. 15/LU-UKP 9.20 3.60 36.0 3. 17/LU-UKP 6.90 3.70 38.0 4. 13/LU-USP 6.80 3.30 28.0 5. 15/LU-USP 6.70 4.20 35.0 6. 17/LU-USP 7.50 3.40 46.0 7. Acacia mangium pulp [5] 7.38 7.10 93.0 Note: #) see Legend in Figure 1

Conclusions

Possibility of oil palm trunk as a source of fiber for pulp has been studied experimentally. In term of their physical and morphological properties, OPT had the potency to be developed as raw material for paper pulp to substitute for wood fiber. The physical properties of OPT pulps were comparable to that of pulp from Acacia mangium which was commonly used as raw material for pulp. With respect to the bleachability and physical properties, pulping of Lebak OPT using kraft or soda-anthraquinone process with active alkali of 15% were considered as optimum condition. In term of screened yield and Kappa number, the soda anthraquinone process gave better results compared to that of the kraft process. It could be concluded that the environmentally friendly soda-anthraquinone process was suitable for pulping of OPT. Depithing on Sabah OPT with original high pith content could increase physical properties of pulp. ECF bleaching with ODEoDnD sequence on pulps from Sabah OPT gave satisfactory results with respect to the physical properties. Since Sabah OPT had a high pith content, the yield of bleached pulp were relatively low, i.e. in the range of 24.67-26.73%. However, the physical properties of the bleached pulps from undepithed or depithed Sabah OPT were higher compared to those of the LBKP as that specified in SNI.

Acknowledgment

We would like to thank to Sandwell Inc. for the cooperative research on the utilization of oil palm trunk. We also appreciate the discussion with researchers and technical support from technician in the Center for Pulp and Paper.

References

1. Tree Crops Estate Statistics of Indonesia, Palm Oil, 2013-2015. Directorate General of Estate Crops. Jakarta; December 2014 2. Maminski et al. Enhancement of Technical value of Oil Palm (Elaeis guineensis Jacq.) waste trunk through modification with 1,3-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU); 23 July 2016 3. Pratiwi W, Sugiharto A, Sugesty S. Development of Oil Palm Trunk for Paper Pulp. Unpublished Technical Report, Institute for Research and Development of Cellulose Industry; 2001 4. The Utilization of Oil Palm Plantation Residue as Raw Material for Pulp, Unpublished Technical Report, Institute for Research and Development of Cellulose Industry, in cooperation with Sandwell, Inc; 1999 5. Uzair, et.al. Pengaruh Umur Kayu Acacia manginum terhadap Sifat-sifat Pulp untuk Kertas (The Influence of Acacia manginum Wood Ages on the Properties of Paper Pulp). Simposium Selulosa dan Kertas XII (Symposium on Cellulose and Paper XII); 1991 6. Wan Daud WR, Nam Law K. Oil Palm Fibers as Papermaking Material: Potentials and Challenges. BioResources 6(1), 901-917; 2011 7. Sulaiman, O et al. The Potential of Oil Palm Trunk Biomass as an Alternative Source for Compressed Wood, BioResource 7(2), 2688-2706; 2012 8. Joedodibroto R. Palm Plantation Residues as An alternative Source of Cellulose Raw Material for The Pulp and Paper Industry. In: Joedodibroto R. Indonesian Natural Resources for Pulp and Paper, Bandung ; 2000. p. 41-48 9. Dence CW and Reeve DW. Pulp Bleaching: Principles and Practice. Atlanta, TAPPI PRESS; 1996 10. SNI 6107:2015. Leaf Bleached Kraft Pulp (LBKP) 11. ---. Penelitian Pembuatan Pulp dari Kayu Acacia mangium Berbagai Umur (Research on Pulping of Varoius Ages of of Acacia mangium). Unpublished Technical Report; 1995

IMPACT OF THE INTERNET ON CONSUMPTION AND PRODUCTION OF PAPER PRODUCTS

Kristaufan Joko Pramono, John Cameron Economics of Development, International Institute of Social Studies, Erasmus University of Rotterdam, Kortenaerkade 12, The Hague, 2518 AX, The Netherlands

ABSTRACT

One of the interesting features of the Internet is online information. It would likely affect demand for newsprint, and printing and writing paper. Moreover, the advance of the Internet has enabled sellers to expand their market to other countries, influencing demand for packaging paper to protect product from sellers to purchasers. This research applied correlation data analysis methodology to study impact of the Internet to the change of consumption and production of paper products in the world. Digital devices would make people prefer access online news rather than newspapers, reducing newsprint consumption and production level in many countries. Competition among printed and digital books, and traditional marketing and advertising would make insignificant change world’s consumption and production of printing and writing paper in many countries. The impact of Internet would raise the rates of packaging paper use, increasing the production level on average.

Keywords: Internet; newsprint; printing and writing paper; packaging paper

Introduction

The Internet is a great phenomenon and then it could change the people’s habit in finding information from paper-based to electronic screens. Furthermore, it would likely affect the demand for paper products. One of the interesting features of the Internet technology is online information. It could make people easy to access information and read on electronic screens rather than on paper. The emergence of electronic media has reduced the growth of demand for newsprint. In Europe, according to BCG (2010: 8) the electronic media has given the biggest negative impact to newspapers amongst other paper products, reducing the readership about 4.5 percent per year. The emergence of the Internet, in accordance with Lei and Li (2007: 2), has a negative impact on printing and writing paper demand in the United States. It means that paper-based media such as books and magazines would be avoided by their readers because people tend to switch to online information. However, according to Moore and O’Hear (2008: 17), even though the Internet has offered the easiness for people to find information from screens, many people are still more comfortable in readingon hardcopy. They stated that paper-based information has emotional and individual dimension compared to online information. The advance of internet technology could encourage the use of printing and writing paper. Kinsella et al. (2007: 9) have explained that the advance of the internet technology would boost demand for printing paper because paper-based medium is needed in marketing and advertising activities. Moreover, they analysed that growth of advertising on the Internet supports the paper-based advertising; therefore, there will be an upward trend of printing and writing paper demand. Moreover, according to BCG (2007: 8), people will search information of advertisement on the Internet when they are busy but they will look for detailed information on paper-based media. It seems that the Internet has made it easier for business people to expand their market share through paper-based advertising, and then demand for printing and writing paper would increase. Moreover, the advance of the Internet technology has enabled sellers to expand their suppliers to other countries; therefore, buyers could purchase products from different countries. It is because that the Internet has made data transfer easily and fast, and then it could be a foundation in supporting international trade (Meltzer 2013: 1). Furthermore, Lei and Li (2007: 15) has analysed that the emergence of the Internet technology has inspired people to invent e-commerce. Therefore, it encourages people to purchase products from their own home without going the real market or department store. As a result,

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 301 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 demand for packaging paper would increase in response of the growth of trading activities (Kinsella et al. 2007: 9). Furthermore, according to Meltzer (2014: 1), the role of the Internet in business area is that it has generated new platform in which there is interaction between people and information; moreover, the Internet has also facilitated companies to be creative in producing and delivering their products to customers. Social media have introduced an opportunity for people to create information supporting trading activities. Some enterprises have productively utilized the Internet to create platforms to facilitate suppliers and purchasers in the world to make commercial relationships. Additionally, these enterprises build new commercial platforms to support other business areas. Subsequently, enterprises can beneficially use the Internet to support their business by declining expenditures, distributing the products to customers more effectively, and developing new idea of business prospects. According to the INCPEN (2012: 3) explained that the Internet has changed the way customers purchase by offering easy accessibility and time effectiveness; therefore, online commerce is rising worldwide. Most of the enterprises provide business model services of product delivery to customers. Consequently, packaging paper is necessary to fulfil this rapid demand, because the packaging is essential to protect product from sellers to purchasers.

Literature Review

The decline of newsprint consumption rate in some of these advance countries was because newspaper publishers would likely move to online digital formats. The reason of this migration was that newspaper publishers faced the decrease of revenue from advertisements and the decline of an amount of their readership (GA 2014: 2). Moreover, Chiang (2013: 12) explained that the development of digital formats and the advance of the Internet technology have provided consumers different choices of channels in access to information; consequently, paper manufacturers would lose a part of their markets and it diminished demand for newsprint. The advance of internet technology could encourage the use of printing and writing paper. According to Kinsella et al. (2007: 9), the emergence of the Internet based technology would likely increase consumption of printing and writing paper because paper-based medium is necessary to support business activities, especially marketing and advertising. Moreover, their study argued that development of online advertising would also improve traditional advertising; therefore, consumption trend of printing and writing paper would rise. However, Pineault et al. (2008:42) explained that electronic media is one of the sources of information that could compete with paper-based information; furthermore, it could reduce demand for printing and writing paper. In the future, a number of printed transactional files are predicted to be smaller than present situation because consumers would likely choose to accept these files in the digital formats and keep them by means of electronic mail or throughout the Internet. The internet provides the opportunity to inspire an invention that in turn could improve the rate of productivity because, according to Meltzer (2014: 1), it could lower the expenditures of transaction and empower enterprises to allocate available sources efficiently. In addition, every person can learn new knowledge and master new skills from the Internet; therefore, human capital would develop. Furthermore, this condition would enhance the capacity of enterprises and empower them to raise their productivity in international trade competition. Moreover, Meltzer (2014: 1) explained that the advantages of the Internet for economy are not restricted to big global businesses endowed with abundant sources and knowledge to infiltrate international markets. Small and medium businesses could also utilize the features of the Internet to contribute in global commerce. More specifically, the Internet has supported channels to reach international market at inexpensive expenditures; consequently, small and medium businesses have an opportunity to experience the international competition.

Results and Discussion

3.1 Consumption and Production of Newsprint

The Internet technology has delivered significant impact in reducing newsprint circulation in the United States. Figure 1 illustrates a striking decline of newsprint consumption in the United States. From

11.6 million tons in 1996, the consumption level plunged to the level of 4.2 million tons in 2012. For some other countries, there was also small decline of their newsprint consumption levels.

Figure 1 The Highest National Consumption of Newsprint Source: FAOSTAT – Forestry database

Different with the United States and some other countries experiencing newsprint consumption reduction, China has demonstrated the increase of their newsprint consumption rate from 1.2 million tons in 1996 to 3.9 million tons in 2012. Table 1 illustrates the number of kinds of printed newspapers published in China. It indicates that readerships of newspaper in China have demonstrated a growth from 1980 to 2000.

Table 1 Number of Published Newspapers in China between 1980 and 2000

Year Number of Kinds of Printed Newspapers 1980 118 1990 773 1999 2038 2000 2007 Source: CDC, China Data Center, University of Michigan (as cited in Luo 2003: 11)

Figure 2 The Highest National Production of Newsprint Source: FAOSTAT – Forestry database

There was an increase of newsprint production in China. Between 1996 and 2012, the production of newsprint grew from 900 thousand tons to 3.8 million tons. In other words, it increased by 2.9 million tons in 16 years. Even though the production in 1996 was far below the production in Canada, the United States, and Japan, it touched the roughly similar production level of newsprint with those countries in 2009 onwards. On the other hand, the production rates of newsprint in Canada and the United States decreased significantly from 9 million tons to 3.9 million tons (57 per cent decrease) and from 6.3 million tons to 2.9 million tons (54 per cent decrease), respectively.

3.2 Consumption and Production of Printing and Writing Paper

Figure 3 shows trends of consumption of printing and writing paper in some countries. The trends in some countries excluding China were stable. The emergence of the Internet technology did not give significant impacts to consumption of this paper product. On the one hand, the Internet have triggered the emergence of digital devices by which people could access information worldwide; on the other hand, people are more comfortable to read on paper or books.

Figure 3 The Highest National Consumption of Printing and Writing Paper Source: FAOSTAT – Forestry database

The decline of printing and writing paper consumption was largely because of the recession happened in the period of 2006 and 2008. After the recession, the rates of consumption of this paper product were roughly stable. In other words, even though there are features of the Internet that could be utilized via digital devices to access the information, the consumption rates of printing and writing paper remain constant. In China, there was an increase of printing and writing paper consumption between 1996 and 2012. The Internet technology has stimulated schoolchildren to study Chinese; in other words, educational systems in China has been formulated to synchronize objectives between teachers and students; eventually, this condition creates innovation in explaining sophisticated ideas and concepts to the students, and it encourages communications between teachers and students (Yuan and Hao, as cited in Ge and Ruan 2013: 23). With the Internet technology, instructors improve their function and position in education. Ge and Ruan (2013: 23-24) argued that the implementation of the Internet technology in education systems in China not only provides learning environment with technology but, more essentially, also creates new concepts about teaching and studying. The impact of the Internet based technology has surpassed its function as mere supporting instrument in education; it has made a change of concepts about transferring knowledge, encouraged instructors to get rid of old-fashioned instruction style, and inspired them to discover novel strategy in teaching to motivate students in studying.

Table 2 Number of Published Books and Magazines in China between 1980 and 2000

Year Number of Kinds of Printed Books Number of Kinds of Printed Magazines 1980 21621 2191 1990 80224 5751 1999 141831 8187 2000 143376 8725 Source: CDC, China Data Center, University of Michigan (as cited in Luo 2003: 11)

China has increased literacy level of its people. Furthermore, there would be more people in China reading books and magazines; consequently, consumption rates of published books and magazines would also increase. According to Luo (2003: 11), the growth of level of literacy is a strong foundation for enterprises in publishing businesses. Table 2 illustrates the increase of numbers of types of books and magazines published in China. This progress indicates the development of publishing industries in China. The rise of book and magazine circulations would likely give a positive effect to demand for printing and writing paper as a resources material for producing books and magazines. Table 3 indicates that advertising revenues in China increased in both magazines and the Internet. The appearance of the Internet did not reduce revenues from advertising in printed magazine for publisher industries. The growth of advertising revenues in printed magazine was 18.7 per cent on average in the period from 1999 to 2002. For advertising revenues in the Internet, there was more rapid growth of the revenues, that is, more than 100 per cent on average per year on the same period. It means that even though there was an increase of number of people accessing information from the Internet, printed magazines in China has also demonstrated the increase of their readerships.

Table 3 Advertising Revenues in China between 1999 and 2002

Year Magazine Internet 1999 900 90 2000 1130 350 2001 1350 390 2002 1500 490 in million RMB Source: China State Administration of Industry & Commerce and iResearch (as cited in Luo 2003: 12)

As a result, the rise of number of kinds of printed books and magazines in China could increase the need of printing and writing paper as material for producing books and magazines. As illustrated by figure 3 above, consumption rate of printing and writing paper in China has grown rapidly among other countries that showed constant rate of printing and writing paper consumption.

Figure 4 The Highest National Production of Printing and Writing Paper Source: FAOSTAT – Forestry database

The United States, China, and Japan are the greatest producers of printing and writing paper in the world. Between 1996 and 2012, those three countries produced 350 million tons, 238 million tons, and 183 million tons of printing and writing paper, respectively. Hence, the sum of total productions in the United States, China, and Japan equals 771 million tons or it represented 44 per cent of international printing and writing paper production since the production of printing and writing paper in the world was 1.7 billion tons in the same period. The production of printing and writing paper in China increased dramatically. From 1996 to 2012, the production of printing and writing paper rose from 5.6 million tons to 25.3 million tons. In other words, it increased by 19.7 million tons in 16 years. It exceeded the printing and writing paper production in Japan from 2002 onwards and in the United States from 2008 onwards even though the production in China in 1996 was far below the production in the United States and Japan. The production rates in the United States and Japan decreased from 22.5 million tons to 16.1 million tons (28.4 per cent decrease) and from 10.8 million tons to 8.7 million tons (19.7 per cent decrease), respectively. Even though production of printing and writing paper in China increased dramatically, the rate of consumption of this paper product was also increased at roughly the same speed. Therefore, most of its production was aimed to fulfil internal demand.

3.3 Use and Production of Packaging Paper

As an emerging economy, China is developing many economic sectors including manufacture. Figure 5 indicates the quantity of packaging paper needed by China to wrap and deliver its products to customers in different countries. It grew from 14.8 million tons in 1996 to 62 million tons in 2012, more than fourfold. Compared to other countries, China is the largest producer of packaging paper and raising its production quantity. The growth of packaging paper use in China illustrates that developing of Chinese manufacturing sector was remarkable.

Figure 5 The Highest National Use of Packaging Paper Source: FAOSTAT – Forestry database

The United States, China, and Japan are the largest producers of packaging paper in the world. From 1996 to 2012, the total productions of packaging paper in those three countries are 787 million tons, 558 million tons, and 204 million tons, respectively. Therefore, the sum of total productions in the United States, China, and Japan equals 1.55 billion tons or it accounted for 53 per cent of global packaging paper production since the world’s production of packaging paper in that period was 2.9 billion tons. There was a striking growth of packaging paper production in China. Between 1996 and 2012, the production of packaging paper grew from 14.8 million tons to 61.3 million tons. In other words, it increased by 46.5 million tons in 16 years. Even though the production in 1996 was far below the production in the United States, it surpassed the packaging paper production in the United States from

2008 onwards. The production rates in the United States and Japan declined slightly from 47.4 million tons to 45.9 million tons (3.2 per cent decrease) and from 12.3 million tons to 11.3 million tons (8.3 per cent decrease), respectively.

Figure 6 The Highest National Production of Packaging Paper Source: FAOSTAT – Forestry database

Even though China was a second largest producer of packaging paper in the world, this country was not the major exporter of packaging paper product. China is not listed in the top ten of packaging paper exporters. Almost all of its production of packaging paper was used domestically. It could be explained that China is an emerging country that it is boosting many of economy sectors including manufacturing industry. Almost all of products could be built in China with competitive prices; therefore, the products could penetrate markets in many countries. In order to maintain the quality of the products in transportation, the good quality of packaging paper is necessary. As a result, although there was a tremendous production of packaging paper in China, most of them was needed to deliver its own products to global market.

Conclusion

The decline of newsprint consumption rate in these advance countries was because newspaper publishers would likely move to digital formats, and it made a number of newspaper reader move from paper-based news to internet-based news. People have started to change their reading habit from newspaper to electronic screens. The advance of the Internet technology has stimulated this transformation of reading habit. The more advance the technology of internet the more comfortable for people to access information. Moreover, technology of electronic screens would make it easy to access the Internet; consequently, to read news, people would rather choose online newspaper. Furthermore, the change of reading habit could reduce consumption level of newsprint. After the emergence of electronic readers, the world’s production of newsprint declined. Béhar et al. (2010: 2) explained that the emergence of digital era has changed the publishing industries. Initially, there were no a comfortable electronic screens for people to read; subsequently, more people would rather choose printed books, but after the invention of digital devices, many people migrate from printed to digital books. Moreover, Pineault et al. (2008: 42) explained that electronic media is one of the sources of information that could compete with paper-based information. However, the advance of internet technology could also encourage the use of printing and writing paper. According to Béhar et al. (2010: 5), digital era would made people have their own virtual library, and in turn it could inspire them to purchase their printed favourite books. Kinsella et al. (2007: 9) claimed that the development of the Internet technology would raise consumption level of printing and writing paper because paper- based medium is appropriate material to promote business activities such as marketing and advertising. © 2016 Published by Center for Pulp and Paper through 2nd REPTech 307 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Because of this competition, there was no significant change world’s consumption of printing and writing paper. The trends of production of printing and writing paper also showed insignificant change. According to Meltzer (2014: vi), the advantages of the Internet for large companies in advanced countries are limited in maximizing their capacity, business sectors, and services to their market in the world. In other words, there would be some limitation of utilizing the full features of the Internet as a foundation to support the global trade. These restrictions range throughout the whole of business chain supported by the Internet. On the other hand, the Internet offers benefits to support and boost production progress. Firstly, the Internet could advance the level of efficiency in production methods and increase the effectiveness of management procedures throughout business elements. Secondly, invention of methods in business activities, which is the element of productivity improvement, could be supported by the Internet technology. Thirdly, the internet could be utilized as a basis for improving productivity progress in the sector of services. Lastly, Meltzer (2014: 5) argued that the Internet could give a chance for customers to get much information about products that are available locally and globally. Because of these different conditions, some countries experienced the decline of consumption of packaging paper, but some other countries increased their packaging paper consumption. Oversupply in one country could fulfil demand in other countries. Overall, the impact of Internet to consumption of packaging paper was significantly positive.

References

1. Béhar, P., L. Colombani and S. Krishnan (2010) ‘Publishing in the Digital Era: A Bain & Company Study for the Forum d Avignon’. Bain & Company, Inc. 2. BCG (2007) The Prospects for Graphic Paper. Boston: The Boston Consulting Group. 3. BCG (2010) Turning the Page: How the Digital Revolution is Squeezing Demand for Graphic Paper. Boston: The Boston Consulting Group. 4. Chiang, J. (2013) ‘IBISWorld Industry Report 32212: Paper Mills in the US’. IBISWorld Inc. 5. Ge, X. and J. Ruan (2013) ‘Integrating Information and Communication Technologies in Literacy Education in China’. Accessed on August 9, 2014 from http://www.ou.edu /uschina/ICT%20 Chinese%20 Literacy.pdf . 6. INCPEN (2012) Packaging and the Internet: A Guide to Packaging Goods for Multi-Channel Delivery Systems. Reading: The Industry Council for Packaging and the Environment. 7. Kinsella, S., G. Gleason, V. Mills, N. Rycroft, J. Ford, K. Sheehan, and J. Martin (2007) ‘The State of the Paper Industry: Monitoring the Indicators of Environmental Performance’, A collaborative report by the Steering Committee of the Environmental Paper Network. 8. Lei, L. and H. Li (2007) ‘Computer Usage and Demand for Paper/Paperboard Products’, Preliminary Study. Atlanta: Georgia Institute of Technology. 9. Luo, J. (2003) ‘Chinese Newsprint and Printing & Writing Paper Industry’. Accessed on July 31, 2014 from http://www.cpbis.gatech.edu/files/papers/CPBIS-WP-03-04%20Luo_Chinese%20 Newsprint%20 and%20Printing%20Writing%20 Paper%20Industry.pdf. 10. Meltzer, J. (2013) ‘The Internet, Cross-Border Data Flows and International Trade’, Issues in Technology Innovation (22): 1-21. 11. Meltzer, J. (2014) ‘Supporting the Internet as a Platform for International Trade: Opportunities for Small and Medium-Sized Enterprises and Developing Countries’, Global Economy and Development Working Paper No. 69. Washington, DC: Brookings Institution. 12. Moore, G. and J. O’Hear (2008) ‘Paper’s Future Role’, Paper360º April 2008, p. 16-18. 13. Pineault, D., J. Shane, B. Pellows, J. Hamilton, and S. Adoniou (2008) ‘Demand Drivers for Printing Paper’. PaperAge.

RECOVERY OF ACETIC ACID FROM PREHYDROLYSATE FROM A CANADIAN HARDWOOD KRAFT DISSOLVING PULP MILL

Avik Khan a, Laboni Ahsan a, Xingye An a, b, Baobin Wang a, Jing Shen a, b, and Yonghao Ni a 1 a Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick, E3B 5A3, Canada b Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology, Tianjin 300457, China c Key Laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry University, Harbin 150040, China 1 [email protected]

ABSTRACT

The utilization of dissolved organics in prehydrolysate (PHL) to produce value-added chemicals is of interest from the integrated forest biorefinery perspective. This paper presents an overview of research work on the recovery of acetic acid from prehydrolysate collected from a Canadian hardwood kraft dissolving pulp mill. The acetic acid recovery process consisted of: 1) adsorption using activated carbon (AC) or lime mud, to remove lignin, and 2) recovery of acetic acid from the treated PHL (TPHL), by using amine-based resin adsorption or amine-based reactive extraction. The use of an amine-based resin under the conditions studied led to a 98% acetic acid recovery from Model solution (MAA) and 46% from TPHL. For the amine-based reactive extraction, the Trioctyl amine (TOA)/octanol system had 80.48%, 61.84% and 63.53% acetic acid recovery from MAA (1% model acetic acid solution), PHL and treated PHL (TPHL), respectively; subsequently, acetic acid in the organic phase (TOA-octanol) was back extracted using a sodium hydroxide solution, while the solvent (TOA- octanol) was regenerated.

Keywords: Biorefinery, Prehydrolysate, Bio-chemicals, Acetic acid, Resin adsorption, Reactive extraction, Activated carbon treatment, Lime mud treatment

Introduction

The forest product sectors, especially the pulp and paper industry, have made significant contributions to Canadian economic development. The Kraft-based dissolving pulp production technology has received much attention mostly due to growing market demand from Asian countries, and in Canada, a number of mills have converted to the prehydrolysis kraft dissolving pulp productions in recently years. Furthermore, the integrated forest biorefinery concept (van Heiningen, 2006; Li et al., 2010), aiming to produce bioenergy and biomaterials, besides the traditional pulp and paper products, will allow these operation’s processes to have more revenue sources (Fornell & Berntsson, 2012; Huang et al., 2010). Much R&D effort has been devoted to develop effective processes to convert forestry and agricultural biomass into a large spectrum of products; or to recover/separate chemicals from sustainable bioresources, biowastes and biomaterials (Mao et al., 2008; Mateos-Espejel et al., 2013). The prehydrolysate (PHL) of Kraft based dissolving pulp process is an attractive source for the same purpose. In current practice, the liquor is burnt in a recovery boiler. The mostly hemicellulloses containing PHL is not a good source for heat as they have lower heating value than lignin. Therefore, it is desirable to separate/recover the dissolved organics in PHL as value added products. The main components of the PHL, which is from an Eastern Canadian mill operating a hardwood kraft dissolving pulp production, are listed in Table-1 (Shen et al., 2011). In the pre-hydrolysis process, much of the hemicelluloses and some part of lignin are extracted from the wood chips. As shown in Table-1, the total amount of sugar was 50.33 g/L, whereas, acetic acid, lignin and furfural constitute 10.11, 9.22, and 1.43 g/L, respectively. Acetic acid is a bulk industrial chemical that has many applications. The demand for acetic acid is increasing by approximately 3%~4% every year. The global demand for acetic acid in 2010 was 9.5 million tons (Amidon et al., 2008), and it is desirable to produce acetic acid from renewable biomass.

Figure-1 Schematic of the acetic acid recovery processes

In this paper, we have presented an overview of the research work, on the recovery of acetic acid from PHL (from the kraft based hardwood dissolving pulp production process), that was carried out at the University of New Brunswick in Canada. Two different pathways (Figure-1) were adopted to achieve desired results. As shown in Figure-1, the prehydrolysate was first treated using absorbent, such as lime mud (Shen et al., 2011) and activated carbon (Liu et al., 2012), to remove lignin-like material. The resultant treated prehydrolysate (TPHL) was then subjected to 1) amine- based resin adsorption (Ahan et al., 2014; Ahan et al., 2016), or 2) amine-based reactive extraction (Ahsan et al. 2013; Yang et al. 2013a; Yang et al. 2013b), to recover the acetic acid from the treated PHL (TPHL).

Table-1: Chemical compositions of PHL (g/L) (Shen et al., 2011)

Chemicals in PHL after hydrolysis of wood Composition (g/L) Sugar 50.33 Acetic acid 10.11 Lignin 9.22 Furfural 1.43

Experimental

Materials

Acetic acid (purity > 99%) was obtained from Fisher Scientific Canada. Industrial prehydrolysate (PHL) samples were collected from a Kraft-based dissolving pulp mill in eastern Canada. The activated carbon (CR325W-Ultra) samples were obtained from Carbon Resources. The weak base resin Purolite A111S was supplied by Purolite International Ltd. Extractant TOA (98%) and diluent Octanol (99.99%) were obtained from Sigma Aldrich Chemical Co. and Fisher Scientific, respectively.

Methods

Activated Carbon (AC) and Resin Treatment

The PHL was treated with powdered activated carbon (AC) at room temperature for 5 h. The weight ratio of PHL to AC was 20:1, and the shaking speed was 150 rpm. All resins and different volumes of 1% model acetic acid (MAA) solutions and AC treated PHL (TPHL) were taken with different ratios (1:5 to

1: 20) for adsorption study in a thermostatic shaker at 25 °C. Agitation was provided at 150 rpm for 1 hr. The amount of adsorbate on adsorbent and in solution at equilibrium can be represented as:

qe (g/g) = (Co-Ce)V/W------(1)

Xe= Ce*V------(2)

Where Co and Ce (g/L) are the acetic acid concentration at initial and equilibrium, respectively. V(L) is the volume of solution and W(g) is the weight of adsorbent used in the experiment. Regeneration/ desorption was done in a same manner of adsorption with 4% NaOH at 1 to 10 resin to alkali solution mass ratio, 1 hour and 150 rpm of shaking speed.

Extraction Methods

Equal weights of an organic solvent (different ratio mixture of amine and octanol) and an aqueous solution of 1% acetic acid model or PHL or TPHL were charged in Erlenmeyer flasks separately. These were then stirred by magnetic bar at 500 rpm for 30 minutes at 25 °C, followed by centrifuging at 3,000 rpm for about 5 minutes to separate the two phases. Afterwards, back extraction was done adding a different mole ratio of NaOH solution to the organic extracted solvent at various weight phase ratios following the same stirring speed, time, temperature, centrifuging speed used in the extraction stage.

Acetic Acid and Furfural Analysis

The initial and equilibrium acid concentrations of furfural and acetic acid were determined using 1H 1 NMR spectroscopy. All quantitative acetic acid H NMR spectra were recorded at 298 K in H2O:D2O (4:1) using a Varian/Agilent INOVA 300 NMR spectrometer operating at a frequency of 299.838 MHz.

Lignin Analysis

The lignin contents of the original PHL and TPHL were measured based on the UV/vis spectrometric method at a wavelength of 205 nm (Tappi UM 250) (Liu et al., 2012).

Sugar Analysis

The sugar contents in the pre-hydrolysis liquor and the raffinate were determined by using an Ion Chromatography with a Pulse Amperometric Detector and CarboPacTM PA1 column (Dionex-300, Dionex Corporation, Canada).

Results and Discussion

Removal of Lignin from PHL by Adsorption using Activated Carbon or Lime Mud

Activated Carbon Treatment

It is desirable to obtain a high degree of lignin removal to justify the application of PHL in biorefinery applications (Wei et al., 2006). An activated carbon sample, CR325W-Ultra with a high surface area (1350 m2/g), was chosen to carry out the AC treatment. The effects of AC treatment on the removal of lignocelluloses are presented in Table-2 (Ahsan et al., 2016). We can see that the AC treatment decreased the lignin and furfural content in PHL by 81.8% and 60.1%, respectively. Liu et al. (2011) also reported substantial removal of lignocelluloses from PHL due to AC treatment (Liu et al., 2011).

Table-2: Characterization of PHL before and after CR325W-Ultra treatment (Ahsan et al., 2016) or lime mud treatment (Shen et al., 2011)

Activated Carbon Lime Mud Treatment Treatment Component PHL TPHL % Removal PHL TPHL % Removal Lignin (g/L) 10.11 1.85 81.8 9.22 8.18 11.3 Acetic acid (g/L) 10.18 9.82 3.22 10.11 8.16 16.4 Furfural (g/L) 1.48 0.59 60.1 1.43 1.13 21.3 Total sugars (g/L) 59.12 58.69 1.04 50.33 49.93 0.8

Lime mud treatment

Besides activated carbon treatment, lime mud treatment can also be applied to obtain the TPHL. Shen et al. (2011) have recovered dissolved lignocelluloses successfully from the prehydrolysate of the kraft- based dissolving pulp production process by adsorption to lime mud produced in the causticizing plant of the kraft process. The effect of lime mud treatment on the removal of lignocelluloses are presented in Table-2 (Shen et al., 2011). We can see that the lime mud treatment decreased the lignin and furfural content in PHL by 11.3% and 21.3%, respectively.

Recovery of Acetic Acid using Amine- Based Resin Adsorption

At this stage our main objective was to recover acetic acid from the TPHL. Purolite A111S, a weak- base anionic resin with tertiary amine functional groups, was chosen to accomplish the objective. Its (Purolite A111S) polymer structure is based on a polystyrene-divinyl benzene matrix. From Figure-2, we can see that the adsorbent-to-adsorbate ratio had a significant impact on adsorption efficiency. The adsorption of acetic acid was increased with the increase of adsorbent dose. The mass ratio of TPHL or MAA solution to resin was 20:1, 10:1, 5:1, 4:1, and 3.3:1. For TPHL, the maximum adsorption (57%) was observed at a resin-to-TPHL ratio of 3.3. At 10:1 aqueous-to-resin dose, the adsorption capacity reached 98% for 1% MAA, which was 1.5 meq/g of dry resin, but thereafter absorption became slower. Acetic acid adsorption was 46% from 8.17 g/L of TPHL, which was 0.63 meq/g of dry resin only at 10:1 aqueous-to-resin dose. The experimental adsorption capacity of the MAA sample per the manufacturer was close to the original total capacity of the A111S, which is 1.7 meq/g of dry resin. The lower recovery from TPHL may be attributed to the presence of sugars and lignin in addition to acetic acid in the TPHL, which may hinder acetic acid adsorption.

Figure-2: Effect of adsorbent on the adsorption of acetic acid from the TPHL and MAA at 25 °C for 1 hr (Ahsan et al., 2016)

Regeneration of Resin

Regeneration of the resin is critical from an economic perspective. Table-3 shows the amount of acetic acid was desorbed from the resin by using 4% NaOH. Higher alkali concentration removed more acetic acid from the resin, but this condition could have detrimental effect on the properties of resin (Lv et al., 2012). Therefore, a 2%~4% NaOH seems to be the optimized concentration for this purpose. From Table-3, it was clear that desorption increased with increasing temperature. At room temperature, 78% and 66% acetic acid of MAA and TPHL were desorbed as sodium acetate from adsorbed resins, respectively, which increased to 90% and 84% with increasing temperature by 20 °C. The lower desorption for the TPHL was obviously due to presence of lignin and other dissolved organics which were also adsorbed and block the pore of resin.

Table-3: Desorption of acetic acid by 4% NaOH solution at 1: 10 ratios of resin and alkali solution for 1 hr at 150 rpm

Desorption of acetic acid from resin Feed 25 °C 35 °C 45 °C Concentration in Concentration in stock % % % Concentration filtrate filtrate Desorbed Desorbed Desorbed in filtrate (g/L) (g/L) (g/L) MAA 78% 7.02 85% 7.65 90% 8.10 TPHL 66% 2.64 74% 2.96 84% 3.36

Recovery of Acetic Acid by Reactive Extraction

Effect of Amine Concentration

The second approach was to follow the reactive extraction approach using tri-n-octylamine (TOA) as the solvent. Table-4 illustrates the influence of amine to acid stoichiometric ratio on the extraction of acetic acid from the model acetic acid solution. The results presented (in Table-4) are in terms of distribution coefficient (KD), extraction efficiency, and overall loading factor. The reactive liquid-liquid extraction of acetic acid (HA) with TOA (B) gives a reaction complex (BHA) which remains in organic phase and may be represented by:

HAaq + Borg = BHAorg ------(3)

The distribution coefficient, KD, is defined as the ratio of organic acid in the two phases by (Datta et al., 2011):

KD = [HA]org / [HA]aq ------(4)

Table-4 shows that the distribution coefficient, DK value increased with increasing stoichiometric ratio and this shows shifting of acetic acid to organic phase from the aqueous phase. At the stoichiometric ratio of 1, the KD value was 4, where extraction of acetic acid was around 80%. The highest extraction of acetic acid (92%) was achieved at the molar ratio of 3, when KD value was 12. Obviously, more base in solution can separate more acid, which is also supported by other results (Sahin et al., 2009). Diluents has an influence on the formation of acid-amine complexes, and therefore on the values of the distribution coefficient. The formation of an acid-amine complex is promoted by the dipole-dipole interactions between diluent and complex; and/or by the complex-diluent hydrogen bond (Bízek et al., 1993).

Table-4: Effect of TOA concentration on extraction of 1% MAA (organic to aqueous phase weight ratio is 1)

Amine to acetic acid Recovery of acetic acid Overall Loading factor, Distribution co-efficient,

molar ratio (%) [acid]org/ [amine]org KD [acid]org/[acid]aq 3.0 to 1 92.31±0.34 0.32 12.0

1.5 to 1 86.20±0.78 0.60 6.22

1.0 to 1 80.48±0.97 0.84 4.12

0.75 to 1 74.14±0.15 1.03 2.86

0.5 to 1 67.30±0.67 1.41 2.06

0.25 to 1 50.51±0.78 2.07 1.02

0.1 to 1 44.03±0.88 4.20 0.79

It was also observed that the loading ratio increased with decreasing amine concentration. But the total extraction of acetic acid decreased with the decrease of TOA concentration. It was also noticeable that the value of the loading factor was more than 1 when the amine is less than acetic acid in stoichiometric ratio, which was referred as overloading (Tamada et al., 1990). The same trend was also observed by Reisinger (Reisinger & King, 1995) in extraction of acetic acid with Amberlite LA-2 (a secondary amine) where overloading sustained for lower stoichiometric amine concentration. A higher loading factor at <1 stoichiometric ratio can be explained by the formation of acetic acid dimer as shown in Figure-3. It is also evident from Figure-3, that via hydrogen bonding a second acetic acid can be complexed (forming complex II), which is responsible for the loading factor of >1. Noting that the acid-amine complex is stabilized by the hydrogen bond by diluents (Grzenia et al., 2012).

Figure-3: Complex formation due to over loading; I (2, 1) acetic acid/amine complex and II (3, 1) acetic acid/amine complex, respectively (Tamada et al., 1990)

Extraction of Acetic Acid from PHL and TPHL

From Figure-4, it can be observed that distribution coefficient of acetic acid is much lower in PHL and TPHL than 1% MAA. At the stoichiometric ratio of 1, the KD value was 1.62, which was equivalent to 61.85% extraction from PHL (Table 5). Activated carbon treated PHL (TPHL) removed 80% of lignin, 90% of furfural, consequently slightly increased the distribution coefficient, KD to 1.74, which was equivalent to 63.53% of acetic acid extraction. The lower extraction of acetic acid from the PHL and TPHL may be due to the presence of furfural, lignin and other minor impurities like hydroxymethyl furfural (HMF), formic acid and levulinic acid in PHL and TPHL.

Figure-4: Variation of acetic acid extraction from PHL, TPHL and 1% MAA with stoichiometric mole ratio of amine and acetic acid at equal mass of two phase extraction

Figure-5: Effect of pH on the extraction of acetic acid from the PHL and TPH

Table-5: Effect of TOA concentration on extraction of acetic acid from PHL and TPHL (organic to aqueous ratio 1)

Distribution ratio [acid]org/ Sample Amine to acetic acid Recovery (%) [acid]aq 1.5 to 1 65.03±1.34 1.86

PHL 1.0 to 1 61.84±1.78 1.62

0.5 to 1 52.53±1.23 1.11 1.5 to 1 67.54±1.55 2.08

TPHL 1.0 to 1 63.53±4.55 1.74

0.5 to 1 55.69±1.76 1.26

The extraction of furfural, HMF, lignin, formic acid and levulinic acid were reported by Grzenia et al (Grzenia et al., 2010), where TOA and octanol used with polypropylene membrane to detoxified dilute sulfuric acid treated corn Stover hydrolysate. To overcome this fact the impurities must be removed prior to extraction as much as possible; sometimes combination of different diluents can be used to enhance distribution coefficient, increasing amine concentration up to a certain amount also helps to increase extraction (Harington & Hossain, 2008). The undissociated form of acetic acid increased with decreasing the pH of the solution. At pH values below the pKa (4.76) of acetic acid, the protonated/undissociated form of acetic acid is removed by forming an ion pair with amine (Grzenia et al., 2008). Extraction of acetic acid decreases rapidly as the pH of solution approaches the pKa because the anionic form is much better solvated with water than octanol. This hypothesis was further verified by decreasing pH value of PHL and TPHL by acetic acid, and total acetic acid concentration was considered in calculating acetic acid extraction. The recovery of acetic acid increased by 3.82% and 6.68% for PHL and TPHL, respectively, with decreasing pH value to 2.6 (Figure-5). From the above discussion, one may conclude that the extraction efficiency of acetic acid from PHL and TPHL was lower than the MAA because of comparatively higher pH in the PHL and TPHL (4.25 vs 2.62) and other impurities which may compete with acetic acid for the binding sites of organic phase. The acetic acid can be back-extracted by temperature swing, diluent swing, pH swing, distillation, volatile tertiary amine, such as trimethylamine and regenerated solvent (Ma et al., 2006). Regeneration of amine-carboxylic acid extracts can also be achieved by back-extraction of the acid into an aqueous solution of a strong base such as NaOH which sometime referred as pH swing regeneration.

Back Extraction of Acetic Acid from MAA

Table-6 shows the effect of volume of organic phase to aqueous phase on the back extraction of acetic acid from the loaded organic phase. At the organic to aqueous phase ratio of 1, the back extraction of acetic acid was 97%. An increase in the organic to aqueous ratio decreased the acetic acid recovery.

Table-6: Effect of organic to aqueous phase ratio on the back extraction of acetic acid of MAA from the loaded organic phase of MAA (Mole ratio of NaOH to acid was 1)

Alkali Org/aqueous Acetic acid recovery (%) Concentration(g/L) 40 46.44 150.8

20 68.8 118.1

10 76.0 65.6

5 95.4 40.8

2 97.44 16.6 NaOH 1 97.13 8.4

0.5 29.6 2.5

As shown in Table-6, at the organic to aqueous ratio 5, the acetic acid recovery was 95.4% which was equivalent to 40.8 g/L sodium acetate concentration. An acetic acid concentration of 150.8 g/L was obtained in an organic to aqueous ratio of 40, and the HAc recovery was 46.4%. A lower recovery of acetic acid at the higher organic to aqueous phase may be attributed to lower interaction of acid and alkali. Therefore, a thorough mixing would be important to achieve a good HAc recovery for the system, which was supported by our experimental results (total volume by factor 4, the back extraction increased by almost 2% for the better contact). Also, the lower HAc recovery at a higher Org/aqueous phase ratio may be compensated by a higher alkali to acid ratio (extraction efficiency increased by 2-3%).

Recycling of Regenerated TOA

Recycling of the regenerated/recovered solvent used in the process is an important issue in reactive extraction to make a viable process. To find the extraction efficiency of regenerated solvent after back extraction with sodium hydroxide, the same MAA and TPHL samples were extracted with regenerated TOA/Octanol and its HAc extraction efficiency was determined; subsequently, the HAc recovery in the NaOH regeneration step was also determined, and results are given in Table-7.

Table-7: Effect of solvent recycling on extraction and back extraction of acetic acid (Ahsan et al., 2013)

Acetic acid Extraction Efficiency Acetic acid back extraction Efficiency Recycle time % % MAA TPHL MAA TPHL 0 80.83 64.47 97.95 90.06 1 80.32 64.22 97.83 90.12 2 80.89 64.57 97.30 89.61 3 79.90 64.51 97.86 89.69 4 80.77 64.70 97.11 89.76 5 80.09 64.51 97.31 89.82 6 80.54 64.34 97.20 89.75 7 80.08 64.41 97.01 89.88 8 79.67 63.98 97.44 88.27 9 79.22 63.45 97.05 88.45

It’s shown that the HAc extraction efficiency in the extraction step and the HAc recovery in the back-extraction step remained essentially the same for the 9-cycling time studied. For the TPHL, the HAc extraction efficiency and the HAc recovery in the back-extraction step were 64.66% and 89.64%, respectively when using fresh TOA/Octanol, while they were 63.45% and 88.43%, respectively after the ninth recycling. The above results indicate that the recovered TOA-octanol can be successfully reused/ recycled in the process.

Conclusions

This paper highlights two potential separation technologies to recover acetic acid from the prehydrolysate (PHL) of the kraft-based dissolving pulp process. First, the adsorption concept, using activated carbon or lime mud, was followed to remove lignin present in the PHL. Then, two different approaches, the amine based resin treatment or the reactive extraction, were used to recover acetic acid. For the amine based resin treatment process, at equilibrium, the adsorption of acetic acid was 93 mg/g for MAA sample and 38.23 mg/g for TPHL at 25 °C. For the reactive extraction process using TOA/ octanol, the results showed that only 6% (equal mole ratio of acid and amine) of TOA can recover 80.48%, 61.85%, 63.53% of acetic acid from MAA, PHL and TPHL, respectively. To recover the acetic acid from the TOA/octanol and to reuse the extractant, a back-extraction was performed with aqueous sodium hydroxide solution. At equal mole and phase ratio, the back extraction yield of 97, 83 and 90% was obtained for MAA, PHL and TPHL, respectively. It was concluded that the proposed processes have potential in recovering acetic acid from the prehydrolysate.

Acknowledgement

The authors gratefully acknowledge the Grants of NSERC and Atlantic Innovation Fund (AIF) for financing this project.

References

1. Ahsan, L., Jahan, M. S., & Ni, Y. (2013). Recovery of acetic acid from the prehydrolysis liquor of kraft based dissolving pulp production process: sodium hydroxide back extraction from the trioctylamine/octanol system. Industrial & Engineering Chemistry Research, 52(26), 9270- 9275. 2. Ahsan, L., Jahan, M.S., Ni, Y. (2014), Recovering/concentrating of hemicellulosic sugars and acetic acid by nanofiltration and reverse osmosis from prehydrolysis liquor of kraft based hardwood dissolving pulp process. Bioresource Technology, 155, 111-115. 3. Ahsan, L., Jahan, M. S., Yang, G., & Ni, Y. (2016). Adsorption of acetic acid from pre-hydrolysis liquor from kraft-based dissolving pulp production using amine-based resin. J-FOR. Journal of Science & Technology for Forest Products and Processes, 5(3), 20-26. 4. Amidon, T. E., Wood, C. D., Shupe, A. M., Wang, Y., Graves, M., & Liu, S. (2008). Biorefinery: Conversion of woody biomass to chemicals, energy and materials. Journal of Biobased Materials and Bioenergy, 2(2), 100-120. 5. Bízek, V., Horáček, J., & Koušová, M. (1993). Amine extraction of citric acid: effect of diluent. Chemical Engineering Science, 48(8), 1447-1457. 6. Datta, D., Kumar, S., & Wasewar, K. L. (2011). Reactive extraction of benzoic acid and pyridine-3-carboxylic acid using organophosphoric and aminic extractant dissolved in binary diluent mixtures. Journal of Chemical & Engineering Data, 56(8), 3367-3375. 7. Fornell, R., & Berntsson, T. (2012). Process integration study of a kraft pulp mill converted to an ethanol production plant–Part A: Potential for heat integration of thermal separation units. Applied Thermal Engineering, 35, 81-90. 8. Grzenia, D. L., Dong, R. W., Jasuja, H., Kipper, M. J., Qian, X., & Wickramasinghe, S. R. (2012). Conditioning biomass hydrolysates by membrane extraction. Journal of Membrane Science, 415, 75-84. 9. Grzenia, D. L., Schell, D. J., & Wickramasinghe, S. R. (2008). Membrane extraction for removal of acetic acid from biomass hydrolysates. Journal of Membrane Science, 322(1), 189-195. 10. Grzenia, D. L., Schell, D. J., & Wickramsinghe, S. R. (2010). Detoxification of biomass hydrolysates by reactive membrane extraction. Journal of Membrane Science, 348(1), 6-12. 11. Harington, T., & Hossain, M. M. (2008). Extraction of lactic acid into sunflower oil and its recovery into an aqueous solution. Desalination, 218(1), 287-296. 12. Huang, H.-J., Ramaswamy, S., Al-Dajani, W. W., & Tschirner, U. (2010). Process modeling and analysis of pulp mill-based integrated biorefinery with hemicellulose pre-extraction for ethanol production: A comparative study. Bioresour Technol, 101(2), 624-631. 13. Li, H., Saeed, A., Jahan, M.S., Ni, Y., Van Heiningen, A. (2010), Hemicellulose removal from hardwood chips in the pre-hydrolysis step of the kraft-based dissolving pulp production process. Journal of Wood Chemistry and Technology, 30 (1), 48-60. 14. Liu, X., Fatehi, P., & Ni, Y. (2011). Adsorption of lignocelluloses dissolved in prehydrolysis liquor of kraft-based dissolving pulp process on oxidized activated carbons. Industrial & Engineering Chemistry Research, 50(20), 11706-11711. 15. Liu, X., Fatehi, P., & Ni, Y. (2012). Removal of inhibitors from pre-hydrolysis liquor of kraft- based dissolving pulp production process using adsorption and flocculation processes.Bioresour Technol, 116, 492-496. 16. Lv, H., Sun, Y., Zhang, M., Geng, Z., & Ren, M. (2012). Removal of acetic acid from fuel ethanol using ion-exchange resin. Energy & Fuels, 26(12), 7299-7307. 17. Ma, C., Li, J., Qiu, J., Wang, M., & Xu, P. (2006). Recovery of pyruvic acid from biotransformation solutions. Appl Microbiol Biotechnol, 70(3), 308-314.

18. Mao, H., Genco, J., Yoon, S.-H., Van Heiningen, A., & Pendse, H. (2008). Technical Economic Evaluation of a Hardwood Biorefinery Using the. Journal of Biobased Materials and Bioenergy, 2(2), 177-185. 19. Mateos-Espejel, E., Radiotis, T., & Jemaa, N. (2013). Implications of converting a kraft pulp mill to a dissolving pulp operation with a hemicellulose extraction stage. Tappi Journal, 12(2), 29-38. 20. Reisinger, H., & King, C. J. (1995). Extraction and sorption of acetic acid at pH above pKa to form calcium magnesium acetate. Industrial & Engineering Chemistry Research, 34(3), 845-852. 21. Sahin, S., Bayazit, S. S., Bilgin, M., & İnci, I. s. (2009). Investigation of formic acid separation from aqueous solution by reactive extraction: effects of extractant and diluent. Journal of Chemical & Engineering Data, 55(4), 1519-1522. 22. Shen, J., Fatehi, P., Soleimani, P., & Ni, Y. (2011). Recovery of lignocelluloses from pre-hydrolysis liquor in the lime kiln of kraft-based dissolving pulp production process by adsorption to lime mud. Bioresour Technol, 102(21), 10035-10039. 23. Tamada, J. A., Kertes, A. S., & King, C. J. (1990). Extraction of carboxylic acids with amine extractants. 1. Equilibria and law of mass action modeling. Industrial & Engineering Chemistry Research, 29(7), 1319-1326. 24. Yang, G., Jahan, M.S., Ahsan, L., Zheng, L., Ni, Y. (2013a) Recovery of acetic acid from pre- hydrolysis liquor of hardwood kraft-based dissolving pulp production process by reactive extraction with triisooctylamine, Bioresource Technology, 138, 253-258. 25. Yang, G., Jahan, M.S., Ahsan, L., Ni, Y. (2013b). Influence of the diluent on the extraction of acetic acid from the prehydrolysis liquor of kraft based dissolving pulp production process by tertiary amine. Separation and Purification Technology, 120, 341-345. 26. van Heiningen, A. (2006). Converting a kraft pulp mill into an integrated forest biorefinery. Pulp and Paper Canada, 107(6), 38-43. 27. Wei, M., Fan, L., Huang, J., & Chen, Y. (2006). Role of StarLike Hydroxylpropyl Lignin in Soy- Protein Plastics. Macromolecular Materials and Engineering, 291(5), 524-530.

SUBSTITUTION OF BCTMP FOR HARDWOOD KRAFT PULP IN WRITING AND PRINTING PAPER

Lies Indriati a1, Angga Kesuma b2, Juliani b3 aCenter for Pulp and Paper, Jl. Raya Dayeuhkolot 132, Bandung 40258, Indonesia bAcademy of Pulp & Paper Technology, Jl. Raya Dayeuhkolot 132, Bandung 40258, Indonesia [email protected] [email protected] [email protected]

ABSTRACT

Printing and writing paper are generally made from chemical pulps. Current papermaking technology developments have allowed the use of 100% hardwood bleached kraft pulp (HBKP) as fiber source. However, to further enhance the competitiveness of products, paper industries keep trying to reduce their production cost. The use of less expensive high yield pulps such as BCTMP (bleached chemo- thermomechanical pulp) is an interesting alternative. Some advantages of using BCTMP include high bulk, good opacity, and high stiffness. The laboratory experiments on substitution of BCTMP for HBKP from Acacia mangium have been carried out with various composition of furnish (0-15% BCTMP and 100-85% HBKP) and PFI refining revolutions of 0-3500. Before mixing, the HBKP was refined up to certain freeness, while it was no refining for BCTMP. Handsheets of 70 gsm were made from all composition variations and then tested for some physical and optical properties. In addition, in order to optimize the fiber development, separate-refining and combine-refining of BCTMP and HBKP have been investigated as well. Combine-refining was implemented for the pulps composition of 7% BCTMP and 93% HBKP. The results showed that the higher the BCTMP composition resulted in higher bulk, opacity and air permeability, but lower in smoothness, brightness, and physical strength. Combine- refining of 7% BCTMP and 93% HBKP improved opacity and physical strength of handsheet. At certain freeness, combined-refining requires less energy than that of separate-refining.

Keywords : BCTMP ; hardwood bleached kraft pulp ; Acacia mangium ; combine-refining, separate- refining

Introduction

The mixture of softwood bleached karft pulp (SBKP) and hardwood bleached kraft pulp (HBKP) are commonly utilized as fibre source of fine writing and printing paper. The content of SBKP is typically ranges from 5% to as high as 50% to enhance the physical strength of paper, while the rest (50% to 95%) is HBKP for improving paper formation, smoothness and printability [1]. The development of papermaking technology recently has allowed the use of 100% of HBKP for fine writing and printing paper production. Some paper mills in Indonesia have reported the use of 100% HBKP as their fibre source. However, in order to further enhance their product competitiveness, paper industries keep trying in reducing their production cost. Besides by the increasing filler content of paper [5], the usage of high yield pulp (HYP) for substitution of HBKP has been shown recently as one of effective way in reducing their production cost [1-5]. HYP has been moving towards optimizing the production process to tailor-made HYP with some specific pulp properties for a specific end-use in paper and board [4]. It was reported that the strength and brightness of HYP can be made in similar to HBKP with the unique features such as high bulk, large surface area, and high fines content [1]. HYP is pulp that optimizes the use of trees by utilizing a mechanical process with refiner plates in order to separate and extract the fibres from the wood [6]. HYP‘s mechanical pulping process has the advantage of converting approximately 90% of wood into pulp, versus approximately 45-50% converted using chemical pulping process [6]. The HYP production process includes wood chips pretreatment, refining, screening and cleaning, bleaching, drying, and pressing into a bale. The TCF (totally chorine-free) bleaching process is applied for HYP production [6]. The terms BCTMP (bleached chemo-

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 321 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 thermomechanical pulp) and HYP are the two terms that almost synonymous. BCTMP is the technical name used to describe one specific and common type of mechanical pulping process that can be used to produce HYP [6]. BCTMP is high yield bleached mechanical pulp which produced by treating wood chips with slight amount of chemicals, usually sodium sulphite, and steam before mechanical defiberation. The bleaching process uses non lignin destructive bleaching agent such as ozone or peroxide to retain yield [7]. The BCTMP technology is used for both softwood and hardwood [7, 8]. Generally, the pulping sequences include soaking wood chips in chemical followed by steaming and refining of wood chips [7]. Both softwood and hardwood BCTMP is a TCF pulp which use peroxide as a bleaching agent to levels between 60-80% of ISO brightness; even more there is a hardwood BCTMP with higher brightness, as high as 80-90% ISO. High brightness BCTMP is usually used for fine coated and uncoated writing and printing paper, while the lower one is used as a part of hardwood kraft replacement for tissue and towel production [7]. The use of BCTMP for paper furnish has a limitation in relation with paper permanence due to its high lignin content which resulted in yellowing of paper [2, 5, 8, 9]. That’s why the lignin content below 1% is required for paper with high brightness stability [2, 5, 8]. Numerous studies have tried the usage of BCTMP for substitution of HBKP in lightweight writing and printing paper grades. The rate of HYP substitution of 5 to 15 % in HBKP is reported for coated paper, while for uncoated paper the range is 10 to 25% [4]. The substitution of HYP up to 30% for HBKP in the presence of 50% SBKP reported was not impaired the strength and structure properties of sheets [1, 3]. Substitution of HBKP with HYP is reported reducing furnish cost while increasing paper bulk, opacity and stiffness [3, 4, 5]. At a given paper caliper, HYP can be used to reduce grammage, while at a given grammage, the higher bulk sheets contain HYP may increase paper stiffness. Due to its high fines content, HYP may improve sheet formation, but the surface smoothness of paper may be affected. HYP fibres tend to be high in wall-thickness and coarseness that cause the loss of paper smoothness [4]. Further refining treatment of HYP to optimize the mophology of HYP fibres have been studied. The combine refining on mixed furnish of BCTMP andEucalyptus bleached kraft pulp have been compared with its separate refining. This resulted that combine refining produce handsheets with improved smoothness and physical strength, while no differences in opacity and light scattering coefficient than that of separate refining [4]. This paper reports the laboratory experiments on the influence of BCTMP substitution for Acacia mangium bleached kraft pulp on handsheets properties in the absence of SBKP. In addition, the effect of separate refining and combine refining of mixed furnish is reported as well.

Experimental

Materials

In this investigation, the imported BCTMP from Canada and HBKP of Acacia mangium (HBKP) from integrated pulp and paper mill in Riau Province, Indonesia, were used.

Methods

Experiment 1: Refining of pulp

BCTMP and HBKP were soaked in distilled water for about 4 hours and then repulped in pulp disintegrator. The separate refining of each pulps was carried out in PFI mill to 0, 500, 2000, and 3500 revolutions and then tested for freeness respectively using Canadian Standard Freeness Tester.

Experiment 2: Furnish Mixing

Refined HBKP of each revolution was mixed with unrefined BCTMP with the composition as listed in Table 1. The handsheets of 70 gsm from each mixture were then made using Estenit Handsheet Former based on SCAN Method. After being conditioned at least for 24 hours in temperature of 23+1oC and 50+2% RH, the handsheets were tested for bulk, air permeability, roughness, brightness, opacity,

322 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8 tensile index, and internal bonding. The sheet bulk was calculated by dividing the sheet thickness with its grammage, as well as the tensile index which was calculated by dividing the tensile strength with its grammage.

Table 1. Furnish composition

Unrefined Refined HBKP (%) Code BCTMP (%) 0 rev. 500 rev. 2000 rev. 3500 rev. 1(A-D) 0 100 2(A-D) 7 93 3(A-D) 10 90 4(A-D) 12 88 5(A-D) 15 85

Experiment 3: Combine-Refining

In order to study how the combine-refining of BCTMP and HBKP affect the sheet properties, the mixture of 7% of BCTMP with 93% HBKP was refined simultaneously in PFI mill to 500, 2000, and 3500 revolutions. The handsheets of 70 gsm from refined mixed furnish were also made and then conditioned and tested for the same properties with that of handsheets from separate-refining. All measurements of pulp and sheets properties were conducted according to the relevant ISO standard methods, except the internal bonding of sheet was measured according to TAPPI Test Method.

Results and Discussion

Experiment 1: Refining of BCTMP

Freeness of BCTMP and Acacia mangium bleached kraft pulp (HBKP) refined separately and its combined refining are shown in Fig. 1. Eventhough the initial freeness of HBKP is lower than BCTMP, the freeness reduction of HBKP during refining was lower than that of BCTMP. In separate refining, at the 500 refining revolution, the freeness of BCTMP decreased significantly from 531 mL CSF to 264 mL CSF, while HBKP decreased from 449 mL CSF to 346 mL CSF. For this reason, the experiment of HBKP substitution by BCTMP was conducted by mixing the refined HBKP with unrefined BCTMP.

Fig 1. Freeness of Fig 2. Bulk of mixed Fig. 3. Air Fig. 4. Roughness BCTMP and HBKP furnish permeability of of mixed furnish (Se-Re) mixed furnish

Fig. 5. Brightness of Fig. 6. Opacity of Fig. 7. Tensile Fig. 8. Internal mixed furnish mixed furnish index of mixed bonding of mixed furnish furnish

Experiment 2: Furnish Composition

Effect of mixed furnish with various revolution of HBKP refining on handsheet properties are shown on Fig. 2-8. The results showed that refining revolution give a signifincant effect on sheet properties. The increase of refining revolution reduced the handsheet bulk, air permeability, roughness, brightness and opacity; while it increased the tensile index and internal bonding as well. As indicated by the reduction of its freeness along with the increasing of refining revolution (see Fig. 1 for HBKP), the refining of HBKP will increase fiber flexibility and fines content which affect the reduction of sheet bulk, air permeability and roughness. Refining of pulp may increase the fibrillation of fiber which increases the strength properties of paper produced. The improvement of sheet strength were also shown in Fig. 7 and 8 where the HBKP were refined before being mixed with BCTMP The increasing BCTMP in mixed furnish increased the handsheet bulk, air permeability, and roughness; while the handsheet brightness, tensile index and internal bonding were reduced. There was no significant effect to handsheet opacity. In the absence of long fiber, the use of 7% BCTMP for substitution of HBKP resulted the handsheet with optimum physical and optical properties, while the reduction of strength properties were still tolerable. This composition then was studied further in the experiment of combine refining of BCTMP and HBKP.

Fig. 9. Freeness Fig. 10. Bulk of Fig. 11. Air Fig. 12. Roughness of Co-ref mixed furnish (co- permeability of of mixed furnish BCTMP+HBKP ref) mixed furnish (co- (co-ref) ref)

Fig. 13. Brightness Fig. 14. Opacity of Fig. 15. Tensile Fig. 16. Internal of mixed furnish (co- mixed furnish (co- index of mixed bonding of mixed ref) ref) furnish (co-ref) furnish (co-ref)

Experiment 3: Combine Refining

As shown in Fig. 9, refining of mixed furnish at the composition of 7% BCTMP and 93% HBKP (combine-refining) resulted almost similar trend line of freeness reduction with the 100% HBKP. This result indicated that the freeness reduction was attributed totally to the HBKP refining. As stated before, the refining of BCTMP it self will dramatically reduced its freeness during the initial period of refining; in this study was during 500 refining revolutions. The use of BCTMP for substitution of HBKP is advantageous in some paper properties. However, there are some disadvantages particularly for paper strength properties. Refining is the main mechanical treatment of fiber to improved the strength of paper produced. In the initial trial, the unrefined BCTMP was mixed with HBKP which was refined at various refining revolution. To improve further the handsheet properties, the combine-refining of BCTMP and HBKP in certain composition were studied. The handsheet properties resulted from combine refining of 7% BCTMP and 93% HBKP in various refining revolution are shown in Fig, 9-15. The results showed that combine-refining improved the handsheets’ smoothness, opacity, tensile index, and internal bonding; and at the same time, it reduced the handsheets’ bulk, air permeability, and brightness.

Conclusion

Refining of BCTMP reduced its’ freeness dramatically; while the reduction of HBKP freeness was slower than that of BCTMP. In the absence of long fiber, 7% BCTMP may substitute HBKP while retaining the sheet properties. In general, the use of unrefined BCTMP as substution of refined HBKP increased bulk, air permeability, smoothness and opacity, but reduced brightness and strength preperties. Variation of refining revolution reduced bulk, air permeability, brightness & opacity; however it improved sheet smoothness and strength. The freeness trend line of 7% BCTMP and 93% HBKP mixture combined refining was almost similar to HBKP, and improved sheet smoothness, opacity & strength.

References

1. Hu, K., Ni, Y., Zhou, Y., Zou, X. (2006). “Substitution of hardwood kraft with aspen high-yield pulp in lightweight coated wood-free papers: Part I. Synergy of basestock properties,” Tappi J. 5(3), 21- 26. 2. Chen, Q., Ni, Y., He, Z. (2012). “Using cationic polymers to improve alkenyl succinic anhyfride (ASA) sizing efficiency in high-yield pulp containing furnish,”BioResources 7(3),3948-3959. 3. Hu, K., Ni, Y., Zou, X. (2004). “Substitution of aspen high-yield pulp for hardwood kraft pulp in fine papers and its effect on AKD sizing,” Tappi J. 3(8), 13-16. 4. Gao, Y., Huang, F., Rajabhandari, V., Li, K., Zhou, Y. (2009). “Effect of separate refining and co- refining of BCTMP/KP on paper properties,”Pulp and Paper Canada July/August, 28-33. © 2016 Published by Center for Pulp and Paper through 2nd REPTech 325 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

5. Pruzynski, P., Sirois, D. (2012). “Increase high-yield pulps in fine paper furnish,” RISIwww. ( sicemsaga.com/eng/img_news/increase%20high-yiled%20pulps%20fine%20paper%20furnish. pdf) 6. http://temcell.tembec.com/en/faqs 7. http://www.paperonweb.com/gradepl.htm 8. Cannell, E., Cockram, R. (2000). “The future of BCTMP,” Pulp & Paper (legacy.risiinfo.com/db_ area/archive/p_p_mag/2000/0005/feat2.htm 9. Pu, Y., Anderson, S., Lucia, L., Ragauskas, A.J. (2003). “Fundamentals of photobleaching lignin. Parta I: Photobehaviours of acetylated softwood BCTMP lignin,” Journal of Pulp and Paper Science 29(12), 401-406. 10. Anonymous (2000). “BCTMP: A pulp for all reasons?,” Pulp and Paper Canada (http:www.pulpand papercanada.com/news/bctmp-a-pulp-for-all-reasons-1000106738) 11. Li, K., Lei, X., Lu, L., Camm, C. (2010). “Surface characterization and surface modification of mechanical pulp fibres,”Pulp & Paper Canada, January/February, 28-33.

ISOLATION AND SCREENING OF THERMOPHILIC XYLANOLYTIC BACTERIAL STRAINS FROM INDONESIAN HOT SPRING

Krisna Septiningrum1, M. Khadafi, Saepulloh Center for Pulp and Paper, Jl. Raya Dayeuhkolot No. 132, Bandung 40258, Indonesia 1 [email protected]

ABSTRACT

Isolation of xylanolitic bacteria for hemicellulose extraction in paper-grades pulp conversion into dissolving pulp has been conducted. Xylanase was screened from bacteria which was isolated from geothermal spring sediments from Indonesia. There are 21 bacteria at 60° C and 10 bacteria at 50° C showed positive result when subjected to Congo Red plates. Six bacterial isolates showed the highest ratio of xylanolytic/cellulolytic were screened further by produced using Beech wood xylan as a sole carbon source. Bacterial no 2.1 and 10.1.b (pH 7, 60° C) and no 7 (pH 7, 50° C) showed high xylanase activity than others. Xylanase from three selected bacteria were produced further for 7 days, bacteria no 10.1.b showed highest activity when produced at day two, pH 7 with temperature 60° C. The acquired bacteria expected to be used in conversion process of paper pulp into dissolving pulp that appropriate with commercial standard.

Keywords: xylanase, xylanolitic bacteria, hot spring sediments, ratio of xylanolytic/cellulolytic

Introduction

Cellulose is one source of renewable material that can be used to produce some derivatives such as esters and ethers. One of the cellulose derivate is dissolving pulp that can be used to produce regenerated cellulose and cellulose derivatives with high purity and high reactivity. Two main processes in dissolving pulp productions are acid sulfite and pre-hydrolysis kraft. Total production of dissolving pulp using acid sulfite process is about 65% from total production; meanwhile other process contributes about 25% (Sixta, 2006). Dissolving pulp is highly pure pulp that exhibit higher cellulose content (over 90%) and low level of hemicelluloses, lignin, and extractives (<10%) with the cellulose reactivity (65% for hardwood and 75% for softwood), level uniformity of the molecular weight, high brightness, and a viscosity between 200-300 dm3 / kg (Köpcke et al., 2010, Li et al., 2012). Production of dissolving pulp present higher cost than paper-grades pulps because of the wood costs (production of dissolving pulp has a lower yield because in its process hemicellulose is dissolved and washed away), capital costs, chemicals costs, production rate and inventories and storage spaces (Hillman, 2006). Therefore, an alternative production technology such as converting or upgrading paper-grades pulps into dissolving pulp is a very interesting topic lately. The major problem in this converting process is paper-grades pulp contains lower cellulose content and higher hemicellulose content (Köpcke, 2010). Therefore, removing hemicellulose from the paper-grades pulp is crucial. High amount of hemicellulose (>10%) are undesirable impurities because they can effect the filterability, xanthation and strength of the end product (Christov and Prior, 1993). Methods for removing hemicelluloses can be done by using enzymatic process, chemical process (alkaline extraction step) or by combining these two processes. Alkaline extraction using alkaline solution is well known as an effective method to remove the hemicellulose; this process is cheap, has shorter reaction times, easier to perform and handles in large scales but in the other side this chemical also degrades cellulose and impacts its reactivity. Meanwhile, enzyme technology is less effective comparing with alkaline extraction step (Köpcke et al., 2010). And also, using enzyme in the manufacture of dissolving pulp requires longer reaction times and required more controlled system. However, this technology showing other advantages such as higher selectivity, more environmentally friendly Enzymatic depolymerization of hemicellulose to monomer sugars needs synergistic action of multiple enzymes. One of the enzymes is endo-xylanases (EC. 3.2.1.8), this enzyme play crucial role in xylan degradation. This enzyme catalyzes endohydrolysis of 1, 4-β-xylosidic linkages into short

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 327 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 oligosaccharides (Biely et al., 1985). The use of this enzyme in paper-grades pulp conversion has been limited by lack of enzyme active at neutral to alkaline pH and elevated temperature. Considering the industrial xylanase in the process of dissolving pulp manufacturing process, the aim of this study is isolation of xylanolitic bacteria from hot spring sediments. Hot spring habitat is selected because is the natural sink of thermophilic microorganism, which hopefully can provide thermo active enzymes (Bhagat et al., 2014).

Experimental

Materials

The media and chemicals used in the experiment were the basic ingredients for microbial cultures and analytical grades. All the materials were purchased from Merck, Sigma-Aldrich, Serva and Oxoid. Nutrient medium (Nakamura medium with modification) were used for screening of bacteria, bacterial activation and production of enzymes, containing (g / 100 mL): Beech wood xylan (Serva) 0.5% (w/v), peptone 0.5% (w/v), yeast extract 0.5% (w/v), K2HPO4 0.1% (w/v), MgSO4.7H2O 0.02% (w/v) and 100 mL of distilled water (Nakamura et al., 1993). pH of the medium was adjusted to initial pH 7 by 5% acetic acid (v/v) and to pH 8 with addition of Na2CO3 (0.05% (w/v).

Sample Collection and Isolation of Thermophilic Bacteria

Sample Collection

Hot spring sediment samples were collected from Kamojang hot spring, Pokja Wisata Kamojang Hijau, Kompleks PLN Kamojang Desa Laksana,Kecamatan Ibun, Garut. Samples were taken randomly, collected in sterile bottles, labeled, transported on ice and stored at 4 °C until analyses. The temperature of hot water was 79 - 81°C with pH ± 4 – 5, respectively.

Bacterial Enrichment, Isolation and Culture Maintenance

10 mL of sediment samples were inoculated using 50 mL of nutrient broth (NB) medium then incubated in the orbital shaker at 70°C, with shaking 110 rpm for 24 h. This enrichment procedure was conducted for 5 times until the bacterial suspensions able to growth well in the medium. The suspensions then were used as a source for bacterial isolation. Standard serial dilution method using Nutrient Agar (NA) medium was used to isolate the thermophilic bacteria. The suspension were spread on the agar medium, and then incubated at 50°C and 60°C in a bench top incubator for 24 to 48 h. To obtained pure culture, distinctive colonies from agar plates were pick up and transferred to fresh agar plate using four way streaks methods then incubated at 50°C and 60°C for 24 to 48 h, this purification step was repeated two times. The pure cultures were maintained in NA slant then keep it at 4°C.

Screening of Xylanase-Producing Bacteria

Qualitative Assay

The strains were initially screened for xylanase activity using modified Nakamura medium (Nakamura et al., 1993) pH 7 and 8 containing 0.5% (w/v) Beech wood xylan as a sole of carbon source. Beside that, cellulase activity was screened using CMC (Carboxyl Methyl Cellulose) as a carbon source. Xylanase and cellulose producing bacteria were selected using Theather and Wood method (1982). The bacteria that already growths for 48 h were flooded with 0.5% (w/v) Congo red for 15 min followed by repeated washing with 1M NaCl (w/v) for zone analysis (Cordeiro et al., 2002). Positive xylanase activity was detected by the presence of yellow halo zone against red background.

Quantitative Assay

Selected bacterial isolates were quantitatively assayed by growing them in modified Nakamura medium supplemented with 0.5% (w/v) Beech wood xylan. Bacterial inoculum (10 %, v/v) was inoculated then incubated under shaking conditions (130 rpm) at pH 7 and 8 with temperature 50°C or 60°C. After 72 h, all the fermented broth was harvested, centrifuged to separate the supernatant and cell pellet then the cell free supernatant (crude extract) was preserved using NaN3 0.02% and used for xylanase activity assay.

Bacterial Growth and Xylanase Production Pattern

To obtain bacterial growth and xylanase production pattern, selected bacteria was inoculated in the culture broth with Beech wood xylan as a sole carbon source. Bacterial suspension was incubated under shaking conditions (130 rpm) at 50°C and 60°C for 7 days. Number of bacterial cell and xylanase activity were assayed at regular intervals of 24 hours by measuring the bacterial cell using CFU methods and reducing sugars using Dinitro Salicylic Acid (DNSA) respectively.

Xylanase Assays

Xylanase activity was assayed according to Bailey et al. (1992) methods using DNSA method. The concentration of reducing sugars was measured as xylose equivalent at 520 nm. One unit (U) xylanase activity is defined as the amount of enzymes that produce 1 µmol xylose per minute under experimental condition. The enzyme activities were conducted in triplicate (n = 3).

Results and Discussions

Isolation and Screening of Xylanase-Producing Bacteria

Hot springs are interesting environments from which bacteria having thermotolerant enzymes can be isolated. There are 10 isolates (50°C) and 21 isolates (60°C) were obtained during the bacterial isolation step from hot spring sediments sample (Fig. 1). These isolates were selected according to differences in their colony morphology. All the bacteria were evaluated for xylanase production. A total of 10 (50°C) and 21 isolates (60°C) showed yellow halo zone against red background, showing its ability to produce extracellular xylanase when subjected on xylan medium as a sole carbon source along with other components at pH 7 and pH 8. Xylanolitic bacteria were selected based on xylanolytic index of xylan hydrolysis after 48 h. All bacteria that were able to produce xylanase then further screened by growing the bacteria in a medium containing CMC, to find out which bacteria were able to produce high xylanase with low cellulase.

(A) (B)

Fig. 1. Bacterial isolates from sediment hot spring (A) 50°C (B) 60°C

Bacteria that can produce cellulase was characterized by the formation of yellow zones with a red background around bacterial colonies. To find out the bacteria with the highest xylanase activity and lowest cellulase activity, ratio of xylanolytic against cellulolytic was calculated. Based on the calculation © 2016 Published by Center for Pulp and Paper through 2nd REPTech 329 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 results, six bacterial isolates i.e no 5, 6b and 7 from 50°C and no 2.1; 3.1.b and 10.1.b from 60°C were selected for further studies (Table 1).

Table 1. Qualitative screening result of six xylanase producing bacteria after incubated at pH 7 and 8 with temperature 50°C and 60°C for 48 h

Xylanolytic Index Cellulolytic index Ratio No pH pH pH 7 8 7 8 7 8 5 0.83 1.06 0.50 0.63 1.67 1.68 6b 0.74 0.85 0.00 0.60 - 1.42 7 0.75 0.81 0.00 0.73 - 1.11 2.1 0.93 1.06 0.79 0.48 1.18 2.22 3.1b 0.86 0.92 0.72 0.55 1.20 1.68 10.1b 0.88 0.97 0.63 0.75 1.39 1.30

- Xylanolytic and cellulolytic index is calculated based on ratio of diameter of clear zone divided by diameter of colony - Ratio = xylanolytic index / cellulolytic index

These six bacterial isolates which were able to produce xylanase with lowest cellulase then evaluated for xylanase production in shaking liquid xylan medium for 72 hours. Results showed that almost all the bacteria were able to produce xylanase when produced at pH 7 and 8 except isolate no 6 and 2.1 (Fig 2.). Three bacterial isolates that showed highest activity (isolates no 7, 2.1 and 10.1.b) was selected for further experiment. This results can not be used to determine which bacteria are best for xylanase production yet, therefore time course of bacterial growth and xylanase production pattern need to performed.

Bacterial Growth and Xylanase Production Pattern

This experiment was conducted by producing xylanase for 7 days using beech wood xylan as a sole carbon source. Addition of xylan into liquid medium is important because xylanase production need inducers such as xylan or other hemicellulose material (Kulkarni et al., 1999; Tseng et al., 2002). The growth of bacteria and xylanase assay were performed once per 24 h for 7 consecutive days (Fig 3.). The time course of growth for three bacteria followed similar pattern, it showed that the exponensial phase was obtained until day 1 then enter to stationary phase until the end of observation day.

0.012

0.01 0.008 0.006 0.004 0.002 0 Enzyme activity (U/mL) activity Enzyme 5 6b 7 2.1 3.1.b 10.1.b 50°C 60°C Isolates code, temperature pH 7 pH 8

Fig. 2. The result of xylanase activity of crude extract from bacterial isolates isolated at 50°C and 60°C

Activity Assay Condition: Phosphate Buffer 25 mM, pH 7 at 50°C

The production of extracellular xylanase by three bacterial isolates followed different pattern. The growth and production of extracellular xylanase for isolate no 7 showed that xylanase production started at the end of logaritmic phase (day 1), then stopped at day 2 and 3 (Fig 3A.). The xylanase production increased significantly on day 4 at late stationary phase, then decreasing with increased of incubation time. Moreover, based on xylanase production pattern, two peaks of xylanase activity were found on days 1 and 4, the existence of these two peaks may occur because of the de-novo synthesis of enzymes that are necessary for xylan hydrolysis (Heck et al., 2002). Different xylanase production pattern showed when isolate no 2.1 were grown in the liquid xylan medium, the formation of xylanase started from day 2 and reached a maxiumum at day 3 (Fig 3B.). Xylanase was produced during the stationary phase. Meanwhile, xylanase production was observed at day 1 when isolate no 10.1.b is grown on xylan medium (Fig 3C.). Xylanase activity increaced significantly at day 2 then decreased until the end of fermentation. Xylanase is produced in the middle of logaritmic phase, initial and at the end of stationary phase. An increase in xylanase activity during later stage of growth might be due to the release of small amount of xylanase from the aged cell entering into autolysis (Cordeiro et al., 2002). Based on three bacterial growth and xylanase production curve, xylanase production were not stable, probably caused by degradation of xylan polymer into smaller oligosaccharides by β-xylosidase which inhibit endoxylanase activity (Tuncer, 2000). Kulkarni et al. (1999) stated high concentration of xylooligosaccharides in the medium is able to repress the biosynthesis of endoxylanase. Thus, based on the three curve obtained can be concluded that isolate no 10.1.b was selected and will be used further for xylanase production. Xylanase production time is 48 h with initial medium pH 7 at 60°C during initial stationary phase.

9.00 0.005

7.50 0.004 6.00 0.003 4.50 0.002 3.00 1.50 0.001 Number Number of cells (Log)

0.00 0.000 (U/mL) activity Enzyme 0 1 2 3 4 5 6 7 Time (day)

Number of cells Xylanase activity

(A) (B)

9.00 0.05

7.50 0.04 6.00 0.03 4.50 0.02 3.00 1.50 0.01 Activity (U/mL) assay Activity Number Number of cells (Log) 0.00 0.00 0 1 2 3 4 5 6 7 Time (Day) Number of cells Enzyme activity

(C)

Fig. 3. Bacterial growth and xylanase production pattern of bacterial isolate no 7 (A), no 2.1 (B) and 10.1.b (C) • The crude extract for isolate no 7 is produced using xylan medium pH 7, incubated at 50°C for seven days • The crude extract for isolate no 2.1 and 10.1.are produced using xylan medium pH 7, incubated at 60°C for seven days • Activity assay condition: phosphate buffer 25 mM, pH 7 at 50°C

Conclusion

Xylanolytic producing bacteria was isolated and screened from geothermal spring sediments. 21 bacteria at 60° C and 10 bacteria at 50° C have been isolated and gave positive result when subjected to Congo Red plates. Six bacterial isolates which showed the highest ratio xylanolytic/ cellulolytic were observed further by produced it using liquid Beech wood xylan medium pH 7. Bacterial isolates no 2.1 and 10.1.b (60° C) and no 7 (50° C) showed high xylanase activity than others. Bacterial growth and xylanase production pattern was conducted for 7 days for each isolate, bacterial isolate no 10.1.b showed highest activity when produced at day two, pH 7 with temperature 60° C. The obtained bacteria need to identified further, while the produced enzymes needs to characterized to know its ability. Hopefully this bacterial isolates can be used in coverting paper-grades pulp into dissolving pulp.

Acknowledgements

We would like to acknowledge to all technicians in Center for Pulp and Paper, internship students that already helped us conducting this experiment. The financial support is funded by government fund 2016.

References

1. Bailey MJ, Biely P, Poutanen K. Interlaboratory testing of methods for assay of xylanase activity. Journal of Biotechnology 1992; 23: 257-270. 2. Bhagat D, Dudhagara P, Desai P. Production and characterization of thermoalkalistable xylanase from geothermal spring isolate. CIBTech Journal of Biotechnology 2014; 3 (4): 36-45. 3. Biely P, Mislovicova D and Toman R. Soluble chromogenic substrates for the assay of endo-1,4- beta-xylanases and endo-1,4- beta-glucanases. Analytical Biochemistry 1985; 114: 142-6. 4. Christov LP and Prior BA. Xylan removal from dissolving pulp using enzymes of Aureobasidium pullulans. Biotechnology Letters 1993; 15(12): 1269-74. 5. Cordeiro, C. A. M., Meire L. L. Martins, A.B. Luciano, R. F. da Silva. Production and properties of xylanase from thermophilic Bacillus sp. Brazilian Archives of Biology and Biotechnology 2002, 45(4): 413-418. 6. Heck, J. X., Plinho F. Hertz, Marco A. Z. Ayub. 2002. Cellulase and xylanase production by isolated Amazon Bacillus strains using soybean industrial residue based solid-state cultivation. Brazilian Journal of Microbiology, 33: 213-218. 7. Hillman D. Do Dissolving Pulps Really Dissolve? Paper Asia, 2006: 12-18. 8. Köpcke V, Ibarra D, Larsson PT and Ek M. Optimization of treatment sequences for the production of dissolving pulp from birch kraft pulp. Nordic Pulp and Paper Research Journal 2010, 25 (1): 31-8. 9. Köpcke V. Conversion of wood and non-wood paper-grade pulps to dissolving-grade pulps. Doctoral Thesis. Royal Institute of Technology. School of Chemical Science and Engineering, Department of Fibre and Polymer Technology. Division of Wood Chemistry and Pulp Technology; 2010. 10. Kulkarni N, Shendye A, Rao M. Molecular and biotechnological aspects of xylanase. FEMS Microbiological Reviews 1999, 23: 411-56. 11. Li D, Ibarra D, Köpcke V, Ek M. Production of dissolving grade pulps from wood and non-wood paper-grade pulps by enzymatic and chemical pretreatments. In: Liebner F, Rosenau T, editors. Functional Materials from Renewable Sources. American Chemical Society (ACS), ACS Symposium Series; 2012, p. 167-189. 12. Nakamura S, Wakabayashi K, Nakai R, Aono R, Horikoshi K. Purification and some properties of an alkaline xylanase from alkaliphilic Bacillus sp. strain 41M-1. Applied and Environmental Microbiology 1993; 59(7): 2311-16. 13. Sixta H. Chemical Pulping. Handbook of Pulp. Wiley-VCH Verlag GMbH &Co, KGaA, Weinheim; 2006, p. 3-19. 14. Teather RM, Wood PJ. Use of Congo Red-Polysaccharide interactions in enumeration and characterization of cellulolytic bacteria from the bovine rumen. Applied and Environmental

Microbiology 1982; 43(4): 777-80. 15. Tseng MJ, Yap MN, Ratanakhanokchai K, Kyu KL, Chen ST. Purification and characterization of two cellulase free xylanases from an alkaliphilic Bacillus firmus. Enzyme and Microbial Technology 2002; 30: 590-95. 16. Tuncer, M. Characterization of endoxylanase activity from Thermomonospora fusca BD25. Turkey Journal Biology 2000; 24: 737-752.

HIGH-YIELD PULP (HYP) APPLICATION IN FIBER-BASED PRODUCTS

Hongbin Liu Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology, 13th Avenue TEDA, Tianjin China, 300457 [email protected]

ABSTRACT

High-yield pulp (HYP) is a relatively new type of mechanical pulp of high qualities, including bleached chemi-thermo-mechanical pulp (BCTMP), alkaline peroxide mechanical pulp (APMP), and preconditioning refiner chemical-treatment alkaline peroxide mechanical pulp (P-RC APMP). The high yield of the pulp gives the better utilization of the raw materials, which makes it green, sustainability and environmentally friendly pulp. There has been an increasing interest in using high-yield pulp (HYP) to substitute for hardwood bleached kraft pulp (HWBKP) in high-end products such as fine papers, paper board and hygiene products, particularly in Asia. In this report, some of the most recent research findings are summarized. 1) HYP application in fine paper grades. The higher bulk requirement in terms of paper properties and manufacturing cost can be matched by hiring HYP addition. The effects of HYP on the optical properties, physical properties and print qualities of HYP-containing paper have been investigated. The synergistic effects of fillers and HYP have been examined. 2) HYP application in paperboard. HYP can provide the higher bulk and higher bending stiffness of the products. 3) HYP application in tissue and towel. HYP improves the bulk of the sheets and reduces the manufacturing cost.

Keywords: high-yield pulp (HYP); fine paper; paperboard; tissue and towel

BIODEGRADABLE POLYESTERS FROM BIOMASS-DERIVED MONOMERS

Rusli Daik1, Satriani Aga Pasma, Mohamad Yusof Maskat School of Chemical Sciences and Food Technology, Faculty of Science and Technology Universiti Kebangsaan Malaysia 43600 UKM Bangi, Selangor, Malaysia [email protected]

ABSTRACT

Oil palm empty fruit bunch fiber (OPEFB) is a lignocelllulosic waste from palm oil mills. It is a potential source of glucose and xylose which can be used as raw materials for high value products such as succinic acid. The interest in utilizing lignocellulosic waste for bioconversion to fuels and chemicals is increasing as it is cheap and renewable. The objective of the present study is to produce biodegradable polyesters from OPEFB-derived monomer using enzymatic polymerization. Cellulose was extracted from OPEFB by using organosolv method. Enzymatic hydrolysis of cellulose was carried out using Celluclast and Novozyme 188 at 40oC, with agitation rate of 145 rpm. Amount of enzyme and cellulose as well as reaction time were varied. The highest glucose concentration produced was 167.4 g/L (sugar recovery of 0.73 g/g from OPEFB). Succinic acid was produced when glucose was subjected to fermentation using Actinobacillus Succinogenes with highest concentration of 23.50 g/L. Biodegradable polyesters were produced when succinic acid together with 1,4-butanediol, glycerol and ethylene glycol, respectively were subjected to Lipase (Candida Antartica CALB) as the catalyst. Molecular weight obtained for poly(butylene succinate), poly(glycerol succinate) and poly(ethylene succinate) were 5.90x104, 6.20x104 and 4.53x104 g/mol, respectively. It was found that the polyesters produced degraded by almost 80% after 3 days when subjected to degrading enzyme.

Keywords : enzymatic polymerization; cellulose extraction; lignin degradation; green polymer

SOLID FUEL PRODUCTION FROM PAPER SLUDGE EMPLOYING HYDROTHERMAL TREATMENT AND ITS CO-COMBUSTION PERFORMANCE WITH COAL

Kunio Yoshikawa a1, Areeprasert Chinnathan b2 aTokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan bKasetsart University, 50 Ngam Wong Wan Rd., Chatuchak, Bangkok 10900, Thailand [email protected] [email protected]

ABSTRACT

This research aims to promote the hydrothermal treatment technology for the alternative solid fuel production from paper sludge and to investigate the co-combustion performance of the produced solid fuel with coal. First, paper sludge was pretreated by the subcritical hydrothermal treatment (HTT) in a lab-scale facility for implementation of the pilot-scale plant. In the lab-scale experiment, the temperature conditions were 180, 200, 220, and 240 °C at the pressure around 1.8–2.4 MPa, while it was 197 °C at 1.9 MPa in the pilot plant as the optimum condition. The holding time was 30 minutes in both cases. The hydrothermally produced solid fuel was evaluated in regards to its fuel properties, dewatering and drying performances, and mass distribution. Furthermore, the energy balance of the process was studied. Results showed that the higher heating value of the pretreated paper sludge was slightly improved by HTT. By mechanical dewatering, only 4.1% of moisture in the raw paper sludge can be removed while the 200 °C hydrothermally treated paper sludge showed 19.5% moisture reduction. According to the energy balance of the pilot plant, the recovered energy was significantly higher than the energy input, showing the feasibility of employing HTT to produce coal alternative solid fuel from paper sludge. Then the basic co-combustion test of the hydrothermally treated paper sludge with subbituminous coal was conducted. The solid fuel was produced from paper sludge by the hydrothermal pilot plant at the temperature of 197 °C and the pressure of 1.9 MPa for 30 minutes. NO emissions were tested by a batch- type fixed bed combustor. The result showed that the NO emissions could be reduced around 26–31% and, therefore, the mixture of coal and hydrothermally treated paper sludge (HTT-PS) yielded lower NO emission compared to the mixture of coal and raw paper sludge. NO conversion of the HTT-PS was lower than the original paper sludge. Finally, the slagging and fouling indices were calculated. The fouling and slagging tendencies of HTT-PS were improved. Finally, the practical co-combustion test was conducted. Fluidized bed co-combustion of raw paper sludge (Raw-PS) and hydrothermally treated paper sludge (HTT-PS) with either low (Lo-Coal) or high reactivity coal (Hi-Coal) was investigated. The paper sludge was treated in a pilot-scale hydrothermal reactor at 197 °C and 1.9 MPa for 30 minutes. South African bituminous and Thai subbituminous coals were selected as representative of Lo-Coal and Hi-Coal, respectively. A 110-mm bubbling fluidized bed combustor was used in this study. During the steady combustion tests, the nominal temperature was 850 °C, the fluidization velocity was 0.5 m/s, and the excess air was varied as 20%, 40%, and 60%. Co-combustion tests were conducted by feeding the sludge at the mixing ratio of 30% and 50% (mass basis) with coal. The focus of this study was on NOx emission and unburned carbon performance. Results showed that at 30% mixing ratio using HTT-PS instead of Raw-PS could reduce NOx emission by 3–6% and 9–17% in the case of Lo-Coal and Hi-Coal, respectively, and the loss of unburned carbon could be decreased by 15–18% and 36–53% for Lo- Coal and Hi-Coal, respectively. On the whole, the hydrothermally treated paper sludge showed better combustion performance and would be a better choice compared to the original raw paper sludge.

Keywords : Paper sludge; Hydrothermal treatment; Solid fuel production; Co-combustion, Coal alternative fuel

ENERGY EFFICIENCY IMPROVEMENT AND COST SAVING OPPORTUNITIES FOR COMPRESSED AIR SUPPLY

Silvy Djayanti Center of Industrial Pollution Prevention Technology, Semarang, Indonesia [email protected]

ABSTRACT

Paper Manufacturing Industry is one of the major users of electrical and thermal energy. Therefore, usage energy in industries particularly paper industries required to conduct their energy savings. One of equipment that need a lot of energy. Usability of the compressor is supply compressed air to the pneumatic power to paper manufacture machine. In this factory, they have two compressors. One of compressor in north side, and the other one in south side. Both has same type are screw type MM-75. After observation has been done to compressors unit, identified that north compressor have leak so that losses at system of 75.53%. South compressor has leaks in system of 67.37%. Method of this study is carried out by direct measurements in compressor units by measuring the parameters of power, load-unload time, and Free Air delivery (FAD). According daily operational, the compressor setting with pressure in 4-5 bars and the other one compressor setting from 3-4 bar for pneumatic system on the machine. Energy conservation in this compressors can be done with optimizing compress process. Potential energy savings can be reach by allocating fresh air that suction from the compressor the air supplied from the outside has a temperature of 29oC-31oC with humidity 65%-70% so that it can optimize compressors engine performance. The utilization fresh air can be done by installing drain pipes to the compressor area outdoors.

Keywords : Compress air, Compressor, Energy, Leak, Paper manufacturing

Introduction

Compressed air is used widely throughout industry and is often considered the “fourth utility” at many facilities. Almost every industrial plant, from a small machine to an immense pulp and paper mill, has some type of compressed air system. Therefore, compressed air system in paper manufacturing is very vital. So the facility cannot operate without it. In This paper manufacturing facilities, air compressors use more electricity than any other type of equipment. Inefficiencies in compressed air systems can therefore be significant. Energy savings from system improvements can range from 20 to 50 percent or more of electricity consumption (McKane et al. 1999). So maintenance and internal audit very importance to find out inefficiency of energy use in compressed air system. In this study, discussing about compressed air system using in paper manufacturing to utilizing of this system for generate compressed air to provide pneumatic power to generate paper machine. This factory has two compressors, they are in air compressors systems plant that has the same type is screw compressor MM-75, Power 75 kW, Capacity 12.1 m3/minute, and tank capacity 2.0 m3. As daily purposes, compressors are operated interchangeably, however if production capacity were very full, both compressors are operated simultaneously. Where one of the compressor units is operating, the other compressor is stand-by. In the process operation, the compressor on setting in 4-5 bars while the machine needs ranging from 3-4 bar for pneumatic system on the machine. This study will analyze the energy consumption and savings in compressors because supposed conducted study to find out some problem that is leak and inefficiency in the compressed air system and then can be able to decided next step to energy efficiency improvement immediately.

Compressor Tipes

Reciprocating compressors

Reciprocating compressors work through the action of a piston in a cylinder. Pressure can be developed on one or both sides of the piston. They are usually the most expensive to buy, install and

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 341 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 maintain, and require large foundations due to their size and the vibrations they cause. Despite these disadvantages, reciprocating compressors have their uses. They are good for high-pressure applications (13 bar pressure and above) and for high air quality applications. They are also the most efficient for quite small applications (in the 1–4 kW range).

Screw compressors

Screw, or rotary, compressors use two meshing helical screws, rotating in opposite directions at high speed, to compress air. These compressors are usually the lowest cost to purchase and install. They lose efficiency rapidly at part load unless variable output compressors are used.

Vane compressors

Vane compressors have a rotor with steel sliding vanes within an eccentric housing. The vanes form pockets of air that are compressed as the rotor turns until an exhaust port is exposed. Vane compressors have similar energy efficiency to screw compressors, but often have better air quality.

Centrifugal compressors

Centrifugal compressors use high-speed rotating impellors to accelerate air. To reach operating pressures, several impellor stages are required. They have relatively low installation costs, but are expensive to buy because they are precision machines, however, they are generally economical in large sizes, in the 200 kW and above range. They are efficient down to around 60% of their design output, below which they have little turndown in their energy consumption.

Table 1. Advantage and Disadvantage Types of Compressors

Compressor Advantages Disadvantages Reciprocating Efficiency: Suitable for high pressures, Can be High noise levels, High 7.8 – 8.5 kW/m/min relatively small size and weight, maintenance, Suitable for Smaller initial cost, Simple maintenance weight smaller procedures, Efficient multi stage compression available

Screw Efficiency : 6,4-7,8 Simple operation, lower temperatures, High energy use, low air kW/m3/min Low maintenance, quiet, compact, quality vibration free, commercialy available, variable speed units with relatively good turndown.

Vane Simple operation, lower temperature, Limited range of capacity, quiet, low maintenance low air quality

Centrifugal Efficiency : Energy efficient, large capacity, quiet, High initial cost, inefficient 5,8-7 kW/m3/min high air quality. at low capacity, specialised maintenance, only water- cooled models available.

Reduce Leakage

Leaks can waste up to 50% of the compressed air produced by your compressor. Reducing leakage is a key measure that can be used to improve energy efficiency. Table 2 provides an indication of the cost of leaks.

Measuring leakage

If there is a flow meter installed immediately after your air compressor or receiver, measuring leakage is as simple as reading this flow meter when all compressed air equipment is turned off and all outlet valves are closed. Similarly, if you obtained data for the load profile as outlined in the previous step, then you simply need to ensure that you record data for the system load while all equipment uses of compressed air are turned off. If flow metering is not available to you, there are two methods that may be used to determine system leakage.

Table 2. Indication of the cost of Leaks

Equivalent Hole Quantity of Air Lost in Annual Energy Waste Annual Cost of Diameter (mm) Leaks (L/s) (kWh) Leaks ($) 0.4 0.2 133 13 0.8 0.8 532 53 1.6 3.2 2126 213 3.2 12.8 8512 851 6.4 51.2 34040 3404 12.7 204.8 1336192 13619

Finding leaks

Leaks can occur in any number of places, such as: • hoses and couplings • pipes and pipe joints • pressure regulators • valves left open • equipment left running or not isolated • threaded fittings not properly sealed with thread sealant or dirty

Apart from listening for leaks, which can be deceptively unreliable in a noisy environment, there are two key ways to find compressed air leaks. The simplest is to brush soapy water over areas suspected of leaking and look for bubbling. Although cheap and simple, this can be a very time-consuming process. The second is ultrasonic leak detection. Ultrasonic detectors can pinpoint leaks very accurately and quickly by detecting the signature ultrasound signals of high-pressure leaks. They can operate in noisy plant environments, so equipment does not have to be turned off. While some training is required in their use, operators can become competent after less than an hour.

Fixing leaks

Fixing leaks often involves tightening or replacing connections, fixing holes in pipes or repairing damaged equipment such as pressure regulators. Often, simply cleaning and applying thread sealant to fittings will help. Replacing equipment will be necessary in some situations.

Leak management program

Once leaks are regularly being repaired, the implementation of practices to avoid leaks getting out of control will ensure that the compressed air system remains efficient.These practices can include: • Regular inspection and maintenance of compressed air equipment • Regular inspection of air pipes, bends and valves • Ensuring that all air lines are properly supported so as not to cause leaks through excess stress

• Removing or properly isolating any unused parts of the pipe distribution network or unused pressure regulators • Implementing a leak reporting program among staff. Making staff aware of the cost to the business from leaks and encouraging them to actively report leaks is an important step, as they are always present on the shop floor and are best placed to notice any changes.

Method

Figure 1. Flow Chart Diagram of Study

In this study using the method of data collection: 1. Literature Study, conduct learning from literature such as books, journals, materials for energy audit results, training modules, browsing internet and other information. 2. Observation Start conduct interviews, metering and analyzing. Metering in this field including compressor electricity and leak detector.The typical metering equipment used to measure and trend the energy consumption of a VSD compressor are: • Handheld (or portable) power meters to measure true RMS voltage, current, power, and power factor at all common loading conditions. • Current transducers for measuring load current while metering (preferably with a linearity accuracy of ±1.0% of the reading). Recording amp loggers are acceptable as long as spot measurements of compressor power are performed with a handheld kW meter at various loadings. • Watt-hour transducers to measure true power (kW) of one, two, or three phases of a system. • Meter recorders (data loggers) with adequate storage capacity to match logging interval and measurement frequency. • The selected measurement equipment should always be installed on the line side of a VSD compressor, not on the load side. Measurements from the output of a VSD compressor can lead to significant data errors. In the pre- and post-retrofit measurement periods, all regularly operating compressors serving a common system should be logged simultaneously regardless of quantity of compressors. Often post-retrofit only measurements are taken and the pre-retrofit power profile is estimated using the post-retrofit CFM (from kW to CFM conversions) and generic control curves for the baseline control method. • Conduct measuring leakage with Ultrasonic Leak Detectors. An ultrasonic leak detector with a frequency response of 35–45 kHz be used to conduct compressed air leak surveys.

Result and Conclusion

The compressor system in this paper factory enabled for supply compressed air into the paper machine to give power pneumatic on the equipment. The existing conditions of the compressor consist of 2 (two) units with a centralized compressor each capacity are 75 kW. Based on the factory, both of compressors operate interchangeably but if production were full both are operated simultaneously. When one of the compressors is operating, the other compressors is standby. In operation, the compressor pressure setting in range 4-5 bars while the compressor needs range from 3-4 bar for pneumatic system. The observation results on the compressor unit, this following picture the compressors system of this paper factory.

Figure 2. Compressed Air System in Paper factory

Figure 3. Electricity Load Profile on Figure 4. Electricity Load Profile on Compressor Compressor Unit (North Side) Unit (South Side)

Figure 3 illustrates a typical electricity demand profile, showing the electricirty demand is 75 kW. The fact the average demand is only a small fraction of the peak demand is a sign that the compressor is not efficient anymore, not running at its highest efficiency point and its must be wasting energy. Figure 4 ilustrated the compressor still in good condition however its necessary conduct maintenance and check for leakage. In this compressors also conduct obtained a graph of the power consumption with and without dryer over the same period of time as the load profile above. By combining these two graphs, it is could see how the efficiency of the system changes over time. The efficiency of the system is kW per L/s. The lower the kW/L/s, the more efficient the system. The compressed air system may be more effective if the profile is flattened or, in other words, if the large switching loads can be operated at different times so that the demand is more stable. If, purging

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 345 Proceedings of 2nd REPTech ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016 function can be run while a major line or piece of plant is not running, the load profile will be more constant. In some cases, it may be more efficient to place certain loads on a separate system. If there is one load that only operates after hours while all others operate during the day, it could be placed on a separate (point of use) compressor so that the main compressor system can be shut down and not have to run inefficiently at part-load. Although there are now two compressors, the overall efficiency of two systems will be greatly improved.

Figure 5. Compressor System Layout

Based on figure 5 above, electricity load and measurement can defined compressor performance. For more detail information, below is description compressor performance in this paper factory.

Table 3. Compressor Performance Datas

Compressor No. Parameter MM-75 MM-75 Unit (North Side) (South Side) 1 Type Screw/ MM-75 Screw/ MM-75 2 Air Supply Pneumatic

3 Power (PDesign) 75 75 kW 4 Capasity 12.1 12.1 m3/minute

5 Power (PActual) 52 75.38 kW

6 Initial Pressure (P1) 4.0 4.0 Bar

7 Final Pressure (P2) 5.0 5.0 Bar

8 Atmosferic Pressure (P0) 1.01 1.01 Bar 9 Holding Tank Volume (V) 2.0 m3

10 Time P2 0.67 0.50 minute 11 Free Air Delivery (FAD) 2.96 3.95 m3/minute 178 237 m3/hour 12 Load Time (T) 80 60 seconds 13 Unload Time (t) 40 30 seconds 14 Leak of System 75.53% 67.37% % 9.14 8.15 m3/minute 15 Specific Energy Consumption 17.56 19.09 kW/(m3/minute) 16 Allowed Leakage 10% 1.21 1.21 m3/minute 17 Prevented Leakage 7.93 6.94

Table 3 showing that both compressors performan works on maximum load i.e 52 kW (north side) and 75.38 kW 346 © 2016 Published by Center for Pulp and Paper through 2nd REPTech Proceedings of 2nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

(south side) . Based on load condition, compressor in North side and south side loading condition relatively stable, however electricity occur extremely volatile in north compressor. When the compressor suffered load-unload condition the compressor have relative value 0.1 kW. The difference in those values is quite high if compared with load value. This indicated that compressor in North side have severe leakage.

Formulation of FAD based approach

Based from exsisting data, FAD value can be determined as seen below : 1. Filling Time of compressed air, t, refers to amount of tank volume, V multiplied with difference pressure devided with amount of required free air multiplied with ambient pressure.

Where P2 is filling final Pressure (bar), andP1 is Filling initial pressure (bar), and P0 is ambien pressure (bar), and V is tank volume (Liter), and T is time (minute), and C is required free air (Liter/ minute).

2. Air Debit, Q refers to difference pressure devided by amount of ambient pressure multiplied by volume of tank per time.

Defined Correction Factor (F) : (273 + 1t )/(273 + t2)

3. Determine of FAD refers to Air debit, Q multiplied by Correction Factor.

Where F is correction factor, and FAD is Free air Delivery (liter/minute)

Conclusion

Based on compressor operating condition, after observation done, identified that compressor of North side leakage occured 75.53% and compressor of South side has leakage oocured is 67.37%. The leakage was caused by ambien air in surrounding compressors is extremely high has about 40oC and outside humidity (ambient RH) also high has from 70%-80% so that air that compressed is still has high temperature and still contains water vapor [H2O] so the compression process become expands quickly and it is not optimal. Potential energy savings can be made by allocating air that suctioned from outside of compressors because the air compressor is the area outside the area of the compressor has a temperature of 29oC-31oC with humidity 65%-70% so that it can optimize engine compressors performan. The utilization of outside air can be done by installing drain pipes to outdoors of the compressor area. By utilizing the air outside of compressor area, so that the energy savings obtained as follows. From datas of Table 4 improving the efficiency can be reached with efforts below : 1. Maintenance. a. Ongoing filter inspection and maintenance. Blocked filters increase the pressure drop across the filter, which wastes system energy. By inspecting and periodically cleaning filters, filter pressure drops may be minimized. Generally, when pressure drops exceed 2 psi to 3 psi, particulate and lubricant removal elements should be replaced. Regular filter cleaning and replacement has been projected to reduce compressed air system energy consumption by around 2% (Radgen and Blaustein 2001).

b. Keeping compressor motors properly lubricated and cleaned. Poor motor cooling can increase motor temperature and winding resistance, shortening motor life and increasing energy consumption. Compressor lubricant should be changed every 2 to 18 months and periodically checked to make sure that it is at the proper level. In addition, proper compressor motor lubrication will reduce corrosion and degradation of the system. c. Inspection of drain traps to ensure that they are not stuck in either the open or closed position and are clean. d. Maintaining the coolers on the compressor to ensure that the dryer gets the lowest possible inlet temperature. e. Replacing air lubricant separators according to specifications or sooner. f. Checking water-cooling systems regularly for water quality (pH and total dissolved solids), flow, and temperature. Water-cooling system filters and heat exchangers should be cleaned and replaced per the manufacturer’s specifications. g. Minimizing compressed air leak throughout the systems. h. Applications requiring compressed air should be checked for excessive pressure, duration, or volume.

2. Monitoring.

In addition to proper maintenance, a continuous monitoring system can save significant energy and operating costs in compressed air systems. Effective monitoring systems typically include the following: a. Pressure gauges on each receiver or main branch line and differential gauges across dryers, filters, etc. b. Temperature gauges across the compressor and its cooling system to detect fouling and blockages. c. Flow meters to measure the quantity of air used. d. Dew point temperature gauges to monitor the effectiveness of air dryers. e. Kilowatt-hour meters and hours run meters on the compressor drive Checking of compressed air distribution systems after equipment has been reconfigured to be sure that no air is flowing to unused equipment or to obsolete parts of the compressed air distribution system. f. Checking for flow restrictions of any type in a system, such as an obstruction or roughness, which can unnecessarily raise system operating pressures. The highest pressure drops are usually found at the points of use, including undersized or leaking hoses, tubes, disconnects, filters, regulators, valves, nozzles and lubricators (demand side), as well as air/lubricant separators, after-coolers, moisture separators, dryers and filters.

3. Leak reduction.

Air leaks can be a significant source of wasted energy. In addition to increased energy consumption, leaks can make air-powered equipment less efficient, shorten equipment life, and lead to additional maintenance costs and increased unscheduled downtime. Leaks also cause an increase in compressor energy and maintenance costs. The common areas for leaks are couplings, hoses, tubes, fittings, pressure regulators, open condensate traps and shut-off valves, pipe joints, disconnects, and thread sealants. To detect leaks is to use an ultrasonic acoustic detector, which can recognize the high frequency hissing sounds associated with air leaks. Leak detection and repair programs should be ongoing efforts.

4. Controls.

The primary objectives of compressor control strategies are to shut off unneeded compressors and to delay bringing on additional compressors until needed. a. Start/stop (on/off) controls, in which the compressor motor is turned on or off in response to the discharge pressure of the machine. Start/stop controls can be used for applications with very low duty cycles and are applicable to reciprocating or rotary screw compressors. b. Load/unload controls, or constant speed controls, which allow the motor to run continuously but

unloads the compressor when the discharge pressure is adequate. In most cases, unloaded rotary screw compressors still consume 15% to 35% of full-load power while delivering no useful work. Hence, load/unload controls can be inefficient. c. Modulating or throttling controls, which allow the output of a compressor to be varied to meet flow requirements by closing down the inlet valve and restricting inlet air to the compressor.

Acknowledgements

The author would like to thank The Center of Industrial Pollution Prevention Technology Semarang for supporting equipment for the measurement in one of Paper manufacture in Central Java- Indonesia. The author also would like to thank to the team for the support in order to successfully complete this project . For the paper factory which has contribution in the discussion, the author would also like to thank, especially to the the factory team, who were very excited and antusiastic to make they factory bettter with this program.

References

1. DOE. Compressed Air Tip Sheet #3, “Minimize Compressed Air Leaks.” Compressed Air Challenge, 2013 2. “Improving Compressed Air System Performance.” Compressed Air Challenge, US, November 2003 3. Klass JK, Eric Massanet, Tengfang Xu, Ern Worrell. Energy Efficient And Cost Saving Opportunities for The Pulp and Paper Industry. October 2009 4. McKane, A., J. P. Ghislain, and K. Meadows. Compressed Air Tip Sheet #3, “Minimize Compressed Air Leaks.” Compressed Air Challenge, 2013 5. Radgen, P. and E. Blaustein (Eds.). Compressed Air Systems in the European Union, Energy, Emissions, Savings Potential and Policy Actions. LOG_X Verlag, GmbH, Stuttgart, Germany.; 2001 6. Victoria Government, “Energy Efficiency Best Practice Guide Compressed Air System.” Sustainability Victoria, 2009

INDEX OF AUTHORS

International Symposium on 2nd Resource Efficiency in Pulp and Paper Technology

Adi Susanto 205 Kunio Yoshikawa 339 Aep Surachman 215 Kunitaka Toyofuku 1 Ahmad Zakaria 179 Laboni Ahsan 309 Andoyo Sugiharto 291 Leh Cheu Peng 119, 249 Andri Taufick Rizaluddin 273 Lies Indriati 321 Angga Kesuma 321 Ligia Santosa 273 Areeprasert Chinnathan 339 Lilik Tri Mulyantaraa 193 Atanu Kumar Das 193 M. Khadafi 327 Avik Khan 309 Mardianto 187 Baobin Wang 309 Marjani 113 Chong Yin Hui 119, 249 Martha Aznury 135 Christine Chirat 127, 199 Mazlan Ibrahim 119 David Bahrin 283 Mega Nur Sasongko 93 Deded S. Nawawi 45 Miho Hatanaka 109 Dian Anggraini Indrawan 35 Mohamad Yusof Maskat 337 Dian Apriyanti 109 Muhammad Arif Susetyo 283 Dodi Frianto 67 Muhammad Nurwahidin 205 Dominique Lachenal 127, 199 Ng Shi Teng 249 Eka Novriyanti 59, 67 Noorbaity 233 Eko B. Hardiyanto 27 Nurkholis Hamidi 93 Farah Fahma 169 Opik Taupik Akbar 59 Gustan Pari 35, 169 Parnidi 113 Han Roliadi 35 Petrus Gunarso 89 Hendro Risdianto 155 Poh Beng Teik 119 Henggar Hardiani 155, 215 Ponadi 205 Henny Rochaeni 179 Prayitno Goenarto 89 Herri Susanto 283 Qanytah 169 Himsar Ambarita 223 Robert Junaidi 135 Hiroshi Ohi 1, 193 Roni Maryana 193 Hongbin Liu 335 Rossi Margareth Tampubolon 35 I. N. G. Wardana 93 Rusli Daik 337 Is Helianti 147 Ruspandi 109 Jadigia Ginting 143, 187 Saepulloh 327 Jaksen M. Amin 135 Saptadi Darmawan 35 Jing Shen 309 Sari Farah Dina 223 John Cameron 301 Sari Hasanah 73 Jordan Perrin 199 Satriani Aga Pasma 337 Juliani 321 Silvy Djayanti 341 Kanti Rizqiania 67 Siti Masriani Rambe 223 Keiichi Nakamata 193 Sri Purwati 215 Khaswar Syamsu 169 Sri Yatmani 143 Kholisul Fatikhin 83 Susi Sugesty 155, 291 Koentari Adi Soehardjo 11 Syamsudin 257 Krisna Septiningrum 327 Takuya Akiyama 45 Kristaufan Joko Pramono 215, 301 Tanaka Ryohei 279

Teddy Kardiansyah 155 Wieke Pratiwi 291 Theresia Mutia 155 Wittri Djasmasari 179 Tomoya Yokoyama 45 Wiwi Prastiwinarti 233 Toshiharu Enomae 51, 99 Xingye An 309 Trismawati 93 Yanto Lawi 223 Untung Basuki 205 Yeni Aprianis 59 Untung Setyo Budi 113 Yinchao Xu 51 Victor Alberto Valentino 135 Yonghao Ni 309 Vu Thang Do 193 Yuji Matsumoto 45 Wan Rosli Wan Daud 119 Yustinus Purwamargapratala 143, 179, Wasrin Syafii 45 187 Wawan Kartiwa Haroen 239 Yusup Setiawan 215

LIST OF PARTICIPANT

International Symposium on 2nd Resource Efficiency in Pulp and Paper Technology

No. Nama Peserta Perusahaan / Lembaga 1 A. Suryaman Dinas Perindustrian dan Perdagangan Jawa Barat 2 Abdul Ghoni Center for Pulp and Paper 3 Achmad Nur Choliq ATPK 4 Aep Surachman Center for Pulp and Paper 5 Adi Susanto Unisbank Semarang 6 Adil Suprayitno Center for Pulp and Paper 7 Aep Surachman Center for Pulp and Paper 8 Agus Kurnia Nugraha PT. Fajar Surya Swadaya 9 Agus Kustiawan Center for Pulp and Paper 10 Agus Sutaro Center for Pulp and Paper 11 Agy Fauzi Center for Pulp and Paper 12 Ahmad Zakaria Polytechnic of AKA Bogor 13 Aldila Ramdhani Sukma Amala Center for Pulp and Paper 14 Andi Lukman Bandung Science and Technology Institute 15 Andika Firmansyah ATPK 16 Andoyo Sugiharto Center for Pulp and Paper 17 Andri Taufick Rizaluddin Center for Pulp and Paper 18 Andriyana Center for Pulp and Paper 19 Anne Indriati Kusumawardani CV. Fortuna Kusuma Raharja 20 Anting Wulandari Bogor Agricultural University 21 Ari Liberto BASF 22 Arief Budimulyo BASF 23 Arief Rakhman Center for Pulp and Paper 24 Arif Aulia PT. Pura Barutama 25 Aryan Wargadalam Assosiation of Pulp and Paper Indonesia 26 Aryana Padawidagda PT. Valmet 27 Asep Dadang Rachmat Center for Pulp and Paper 28 Asri Peni Wulandari University of Padjadjaran 29 Aswin Hardinasri Chandra CV. Unipack Kartonindo 30 Atang Syarifudin Center for Pulp and Paper 31 Ati Nurhayati Center for Pulp and Paper 32 August Sinaga Asia Pulp and Paper 33 Ayi Mufti Agency for Assessment and Application of Technology 34 Budi Susanto Center for Material and Technical Products 35 Chandra Apriana Purwita Center for Pulp and Paper 36 Chong Yin hui University of Sains Malaysia 37 Chris Hartanto PT. Valmet 38 Cindy PT. RAPP

39 Cucu Center for Pulp and Paper 40 Dadang Suhendar Agency for Assessment and Application of Technology 41 Darmawan Center for Pulp and Paper 42 David Bahrin Bandung Institute of Technology 43 Deded Sarip Nawawi Bogor Agricultural University 44 Dedek Kurniawan Institute of Technology and Science Bandung (ITSB) 45 Deden Rosid Waltam Agency for Assessment and Application of Technology 46 Dedy Sofyan Hidayat Center for Pulp and Paper 47 Desak Gede Sri Andayani Indonesian Institute of Sciences (LIPI) 48 Devi Mei Hana Nurfiyah Center for Pulp and Paper 49 Dian Anggraini Indrawan Center for Forest Product Research and Development 50 Dian Apriyanti Sinarmas Foresty 51 Dian Fajar Vitianingrum Agency for Assessment and Application of Technology 52 Dian Novianto Center for Pulp and Paper 53 Dimas PT. Ditek Jaya 54 Djamil Agency for Assessment and Application of Technology 55 Dodik Catur P. Polimedia 56 Dody H. Dinas Perindustrian dan Perdagangan Jawa Barat 57 Dwiyarso Joko Wibowo Center for Pulp and Paper 58 Dominique Lachenal Grenoble INP-pagora, France 59 Eddy Siswanto Metal Industries Development Center 60 Edwin K. Silabat Bandung Institute of Technology 61 Edi Wahjono Agency for the Assessment and Application of Technology 62 Edi Sutopo Directorate of Estate and Forest Product Industry 63 Eka Novriyanti Research and Development Institute of Fiber of Forest Plant 64 Eko Bhakti Hardiyanto Gajah Mada University 65 Eko Budi Utomo PT. Silva Rimba Lestari 66 Emma Safarina Ertaviani Center for Pulp and Paper 67 Eneng Maryani Center for Ceramics 68 Endang TVRI 69 Entis Center for Pulp and Paper 70 Enung Fitri M. Center for Pulp and Paper 71 Evi Oktavia Center for Pulp and Paper 72 Fachrurozi Center for Pulp and Paper 73 Fahmi Hamdani University of Padjadjaran 74 Farah Fahma Bogor Agricultural University 75 Farah Nabila Agency for the Assessment and Application of Technology 76 Faridh Hardiana Center for Pulp and Paper 77 Feby Anggita ATPK 78 Fenny Nilawati Kusuma PT. Silva Rimba Lestari 79 Freddy Senjaya University of Padjadjaran 80 Frederikus Tunjung Seta Center for Pulp and Paper 81 Galuh Yuliani Universitas Pendidikan Indonesia (UPI) 82 Ganis Lukmandaru University of Gajah Mada

83 Gatot Ibnu Santosa Institute of Technology and Science Bandung (ITSB) 84 Gatot H.K. Center for Pulp and Paper 85 Gustan Pari Forest Products Research and Development Center 86 Gusti Dwi Intan Lestari Mulawarman University 87 Haerudin PT. IKPP Serang 88 Haitang Liu Tianjin University of Science and Technology 89 Hana Rachmanasari Center for Pulp and Paper 90 Haris Munandar Agency for Research and Development of Industry 91 Harsono Ministry of Agriculture 92 Hendi Sumiardi Center for Pulp and Paper 93 Hendro Risdianto Center for Pulp and Paper 94 Hendy Kuswaendi Center for Pulp and Paper 95 Henggar Hardiani Center for Pulp and Paper 96 Henky Setyawan PT. RAPP 97 Hepy Moiras PT. IKPP Serang Mill 98 Herman Supriadi Puslitbang TIKI 99 Heronimus Judi Tjahjono Center for Pulp and Paper 100 Herri Susanto Bandung Institute of Technology 101 Hiroshi Ohi University of Tsukuba, Japan 102 Hongbin Liu Tianjin University of Science and Technology 103 Ika Atsari Dewi University of Brawijaya 104 Ika Nofi Hastuti University of Winayamukti 105 Ike Rostika Center for Pulp and Paper 106 Is Helianti Agency for Assessment and Application of Technology 107 Iyep Ependi PT. IKPP Tangerang 108 Iva Vilaili ATPK 109 Iwan Herdiwan Center for Pulp and Paper 110 Iwan Kurnia Center for Pulp and Paper 111 Jadigia Ginting BATAN 112 James Tirtowijoyo Young PT. Pabrik Kertas Indonesia 113 Jati Pambudi Indraprasta University 114 Jati R. Polimedia 115 Jemirin Center for Pulp and Paper 116 Jessica Yonaka Asia Pulp and Paper 117 Jimmy Lee Expert, Korea 118 Jimmy Lim ATPK 119 Joko Pratomo Center for Pulp and Paper 120 Joni Arda Center for Pulp and Paper 121 Jordan Perrin Grenoble INP-Pagora 122 Juliana Sibarani Center for Pulp and Paper 123 Kamaludin PT. Evonik 124 Kanda Center for Pulp and Paper 125 Kelik Heriyono PT. Graha Kerindo Utama

Kepala Dinas Perindag Kota 126 PEMDA Bandung 127 Khairul Hasibuan PT. RAPP 128 Kholisul Fatikhin PT. IKPP Tangerang Mill 129 Koentari Adi Soehardjo Center for Material and Technical Product 130 Krisna Septiningrum Center for Pulp and Paper 131 Kristaufan Joko Pramono Center for Pulp and Paper 132 Kunio Yoshikawa Tokyo Institute of Techcnology 133 Kunitaka Toyofuku Japan TAPPI 134 Kurniawan Prambudi Utomo AMIK BSI 135 Kusnan Rahmin PT. RAPP 136 Leh Ceu Peng University of Science Malaysia 137 Liana Bratasida Indonesia Pulp and Paper Association 138 Lies Indriati Center for Pulp and Paper 139 Ligia Santosa Center for Pulp and Paper 140 Lilik Tri Mulyantara University of Tsukuba 141 Lina Mulyawati Agency for Assessment and Application of Technology 142 Lucia Indrarti Indonesia Institute of Sciences (LIPI) 143 M. Gadang H. Hartawan PT. OKI Pulp & Paper Mills 144 Maulana ATPK 145 Mardi PT. Tetra Pak 146 Martha Aznury Politeknik Negeri Sriwijaya 147 Martina ATPK 148 Misbah Fikrianto Polimedia 149 M. Khadafi Center for Pulp and Paper 150 M. Kodiat Prianggodo Center for Pulp and Paper 151 Muhammad Nurwahidin Politeknik Negeri Media Kreatif Jakarta 152 Mukharomah Nur Aini Center for Pulp and Paper 153 Mulyana PT. Ditek Jaya 154 Mungki Septian Romas Center for Pulp and Paper 155 Myoung-Ku Lee Kangwoon National University, Korea 156 Nadia Ristanti Center for Pulp and Paper 157 Nam Soo Kim Chairman of KITMA, Ministry of Industry, Korea 158 Nasrullah RCL Syiah Kuala University 159 Nena Andrina Restu Center for Pulp and Paper 160 Ni Nyoman Tri Puspaningsih Airlangga University 161 Niki Gumilar Center for Pulp and Paper 162 Niknik Nurhayati Agency for Assessment and Application of Technology 163 Nina Elyani Center for Pulp and Paper 164 Nita Oktavia Wiguna Agency for Assessment and Application of Technology 165 N. Harijono Bandung Institute of Technology 166 Noorbaity Politeknik Negeri Jakarta

167 Novika Meirilyn PT. Valmet Indonesia 168 Nurhadiningrum Y. Center for Pulp and Paper 169 Nurlaili Fidayanti A. UIN Bandung 170 Nurmalisa Lisdayana Bogor Agricultural University 171 Nursyamsu Bahar ATPK 172 Octariana Putri Center for Pulp and Paper 173 Octianne DJ Politeknik STTT Bandung Research and Development Institute for Forest Plant Fiber 174 Opik Taupik Akbar Technology 175 Parnidi Sweetener and Fiber Crops Research Institute 176 Paryono Center for Pulp and Paper 177 Petrus Gunarso PT. RAPP 178 Pipin Marlina Center for Pulp and Paper 179 Prima Besty Asthary Center for Pulp and Paper 180 Putra Hadi PT. Lontar Papyrus Pulp & Paper Industry 181 Putri Dwi Sakti Khatomdani Center for Pulp and Paper 182 Prayitno PT. RAPP 183 Puguh Widodo Agency for Assessment and Application of Technology 184 Qanytah Bogor Agricultural University 185 Qodri Khasanah Manufacture Company 186 R. Basiya Unisbank Semarang 187 Rr. Citra Rapati Dit. IHHP 188 Raden Ian Drajat Center for Pulp and Paper 189 Rendy PT. Pura Nusapersada 190 Reynaldo Biantoro Center for Pulp and Paper 191 Reza Andreanto PT. Tetra Pak 192 Ridwan Yahya Universitas Bengkulu 193 Rina Masriani Center for Pulp and Paper 194 Rina S. Soetopo Center for Pulp and Paper 195 Rita Alim PT. RAPP 196 Rizki Arisandi Gajah Mada University 197 Rizky Aulia Prasastidewi Agency for Assessment and Application of Technology 198 Rodziah PT. IKPP 199 Romi Pranowo Center for Pulp and Paper 200 Rudi C. Polimedia 201 Rushdan bin Ibrahim Forest Research Institute Malaysia 202 Rusli Daik University Kebangsaan Malaysia 203 Sabki PT. RAPP 204 Saepullah ATPK 205 Saepulloh Center for Pulp and Paper Center of Research and Development Non Timber Forest 206 Saptadi Darmawan Product Technology 207 Sarah Bonita Asia Pulp and Paper

208 Sarmada Politeknik Media Kreatif 209 Sari Farah Dina Center for Research and Standardization Industry Medan 210 Sari Hasanah Arsip Nasional Republik Indonesia 211 Setiananingsih Center for Pulp and Paper 212 Siti Fatonah Center for Pulp and Paper 213 Soni M. Ikhsan Center for Pulp and Paper 214 Sonny Kurnia Wirawan Center for Pulp and Paper 215 Sony Sulaksono Center for Textile 216 Srihartini Center for Pulp and Paper 217 Stephen Tirtowidjojo PT. Pabrik Kertas Indonesia 218 Subyakto Biomaterial LIPI 219 Sudarmin A.L. Center for Pulp and Paper 220 Suhartini APKI 221 Suhendra Wiriadinata Asia Pulp and Paper 222 Sulaeman Yusuf Indonesian Institute of Sciences 223 Sumardi Indra BASF 224 Supomo Center for Ceramics 225 Suprapto, DEA Sepuluh November Institute of Technology 226 Supriadi Agency for Assessment and Application of Technology 227 Sutedja Center for Pulp and Paper 228 Syamsudin Center for Pulp and Paper 229 Syeni Chandra CV. Unipack Kartonindo 230 Takdir Aziz Center for Pulp and Paper 231 Tanaka Ryohei Forestry and Forest Products Research Institute, Japan 232 Tandi Muharam PT. Valmet Indonesia 233 Tatok Hermanto ATPK 234 Theresia Mutia Center for Textile 235 Tien Johanna Asia Pulp and Paper 236 Timo Honkola PT. Valmet Indonesia 237 Tina Martina Politeknik STTT Bandung 238 Titin Fatimah S. Center for Pulp and Paper 239 Tjandra Setiadi Institut Teknologi Bandung, Indonesia 240 Toharudin ATPK 241 Toni Rachmanto Center for Pulp and Paper 242 Tony Bastian Center for Pulp and Paper 243 Tony Wenas April Group 244 Toshiharu Enomae University of Tsukuba, Japan 245 Tri Hanurawati Center for Pulp and Paper 246 Trismawati Brawijaya University 247 Trismillah Agency for Assessment and Application of Technology 248 Ula Center for Pulp and Paper 249 Vanda Diani PT. Bakrie Building Industries

250 Vinca Safrani Asia Pulp and Paper 251 Wachyudin Aziz Center for Pulp and Paper 252 Wahyu H. Laksono PT. Evonik Indonesia 253 Wasrin Syafii Bogor Agricultural University 254 Wawan Kartiwa H. Center for Pulp and Paper 255 Widya Astianti Center for Pulp and Paper 256 Wieke Pratiwi Center for Material and Technical Product 257 Wibian Fajar Irianto ATPK 258 Wildan PT. RAPP 259 Wisnu Wiguna PT. Tetra Pak 260 Wiwik Prastiwinarti Politeknik Negeri Jakarta 261 Yana TVRI 262 Yanah Suryanah Arsip Nasional Republik Indonesia 263 Yang Yang Setiawan BPPI 264 Yani Kurniawati Center for Pulp and Paper 265 Yayan S. Center for Pulp and Paper 266 Yinchao Xu University of Tsukuba 267 Yohanes Suhari Unisbank Semarang 268 Yonghao Ni University of New Brunswick 269 Yoveni Yanimar Fitri Center for Pulp and Paper 270 Yuji Matsumoto The University of Tokyo 271 Yulistyne Pikiran Rakyat 272 Yustinus Purwamargapratala BATAN 273 Yusup Bunyamin Center for Pulp and Paper 274 Yusup Setiawan Center for Pulp and Paper 275 Zeily Nurachman Bandung Institute of Technology

DISCUSSION

International Symposium on 2nd Resource Efficiency in Pulp and Paper Technology

PLENNARY SESSION

Presenter : Prof Yong Haou Ni Notulis : Sonny Kurnia W Time : 11.15 WIB

RECOVERY ACETIC ACID FROM PREHYDROLISATE OF CANADIAN HARDWOOD

1. Prof. Heri S, ITB Answer: a. Did you identified the best biomass for the experiment? b. Do you have already economic evaluation? c. Did you use chemical to prehydrolisis, because it more like hydrothermal ? Answer: a. The biomass are mix from aspen, that have rich acetic acid group. If we want to use other biomass we have to identified how much the acetic acid group in that biomass. b. It is not to compare with natural gas production, so it will need more eco-enggeneering analysis. c. Yes, it’s commercially named prehydrolysed , no chemical use, only steam. It will different if we used softwood

2. Prof. Lachenal Question : For activated carbon, how to reactivated again? Answer : By using srong NaOH solution

3. Nursyamsu Bahar Question : Do you utilize the lignin that removed? Answer : yes, it will joined with black liquor.

Presenter : Prof Kunio Yoshikawa Notulis : Sonny Kurnia W Time : 11.43 WIB

SOLID FUEL PRODUCTION FROM PAPER SLUDGE EMPLOYING HYDROTHERMAL TREATMENT AND IT’S COMBUSTION PERFORMANCE WITH COAL

1. Prof. You Hau NI Question : Do you take care consideration about energy , specially energy balance? Answer : - Yes, original paper sludge 100%, and final product 53.1 %. - Dewatering using naturally deconter - To improve draining rate by using green house to drain the waste

2. Dr. Lachenal Question : How did you defined 200° C is optimum heat treatment ? Answer : bassically if we increase temperature will increase hydrothermal

3. Prof. Agus S. Question : Do you think water liquid produced is acetic acid ? Answer : Yes, it is posibly.

PARAREL SESSION A1

Presenter : Jordan Perin Notulis : Sonny Kurnia W Time : 13.47 WIB

YELLOWING OF DISSOLVING PULP: ROLE OF CO AND COOH

1. Judi Tjahjono, CPP Question : what is different of physical strength between ECF and TCF bleaching ? Answer : we do not testing the physical properties, but from aother research physical properties rather same, only for tearing ECF higher than TCF.

2. Prof Young Hou Ni Question : in proccess at mill there is CS2 proccess how about that? Answer : we did not do that proccess, we study effect quinon on yellowing TCF pulp , do not lower brightness.

Presenter : Dr. Andri Taufick Rizaludin Notulis : Sonny Kurnia W Time : 14.09 WIB

ELEMENTARY CHLORINE FREE BLEACHING USING PEROXYMONOSULFURIC ACID ON HARDWOOD PULP

1. Prof. You Hao Ni Question : Have you concern to take more long bleaching stage? Answer : more long sequence the stage bleaching, we can more fixed quality of pulp

and increasing of brightness pulp and we can decreased ClO2 consumption. In the future study

we can combine stage of bleaching for example by adding O2 and H2O2.

2. Jordan Perin Question : Dou consider posibility to add D stage ? Answer : in PSA stage we will have acid condition, and lignin have already react with PSA so it will decrease effectifity of D stage.

3. Dr. Lachenal

Question : what is the reason to keep ClO2 ? Answer : TCF is good for enviromental, but in Indonesia we have do stage by stage, and it still consumption by many pulp mill, but in the future we in Indonesia will apply TCF bleaching.

Presenter : Lilik Tri Mulyantira Notulis : Sonny Kurnia W Time : 14.34 WIB

MODIFIED OPERATION OF LABORATORY REFINER FOR OBTAINING DRIED THERMOCHEMICAL PULP

1. Dr.Hong Bin Liu Question : what is the most important quality, how about coarseness? Answer : the most important quality is length of fibre and amount good fibre, so to preparing MDF impregnation 2% peroxide is enough. Usually we expecting to reduce fibre coarseness.

2...... , Malaysia Question : EFB contain high silica, how about that? Answer : Silica will contribute to browning

D1, 15 November 2016

Presenter : Prof. Dr. Ir. Ni Nyoman Tri Puspaningsih (13.45 – 14.10)

Adri – IPB

Question : How does the application?

Answer : Lacase added continuously at varying retention time of laccase

Presenter : Rizki Arisandi (14.50-15.05)

Darono

Question : If it is detected that the pulp contains extractive impact on the quality, how the anticipation?

Answer : Looking for raw materials bark on less than sapwood because the bark consists of at most extractive. If already existed in paper machines can be minimized by saponification.

B3, 16 November 2016

Presenter : Dr. Petrus Gunarso (14.00-14.25)

Theresia Mutia-BBT

Question : It is not easy to your company to control the fire, how to do it?

Answer : Fire is also our mill problem, fire happening not in community land but more in areas that are not managed (really unmanaged), in our procedure, if in the wild area is not the responsibility of the industry, but we also try to educate communities near industrial areas in order to jointly conserve forests

Question : There is a global issue, that the land be left open burning to get a new land, how about that?

Answer : That issue is very sensitive and politically, I will not answer, which we certainly do not do it

Presenter : Eka Novriyanti (14.40-15.25)

1. Susi Sugesty

Question : Just to make sure, whether third level bamboo cooking process can be applied to bamboo cooking?

Answer : Yes, until the bamboo ready for bleaches

2. Dominique Lachenal

Question : Why choose a pre-hydrolyzed bamboo use 2.5% acetic acid? Do've tried just using water at high temperatures?

Answer : Because acetic acid can break the lignin, we do not try to pre hidrolyzed only with water.

Suggestion: Try to compare if using just water but the high temperature (above 100 ° C), because if only with water alone can be more economically valuable, so do not need chemicals.

Presenter : Dian Apriyanti (14.55-15.10)

Sabki

Question : The parameters of what can be known if we are analyzing using NIR spectroscopy?

Answer : The NIR’s predict : Basic wood density, cellulose, extractive, lignin and pulp yield.

DISCUSSION OF B1 SESSION

Presenter : Prof. Rusli Daik Institution : Universiti Kebangsaan Malaysia Court reporter : Yoveni Yanimar Fitri Title : Biodegradable Polyesters from Biomass-Derived Monomers

Question 1 Liana Bratasida : Have you already analyze about the best economic of your research ?

Answer 1 Yes, we did it. It is probably bit to brave to manage the usually material was high value. It is visible if we compact cost highly improve macro enzyme.

Presenter : Yusup Setiawan Institution : Center for Pulp and Paper Court reporter : Yoveni Yanimar Fitri Title : Utilization of Paper Mill Rejects Waste as a Raw Material of Composite Boards

Question 1 Theresia Mutia (Center for Textile) : a. This is no parameters for textile standard. Could you explain about this ? b. Can you compare to SNI ?

Answer 1 a. We have sent letter to Puslitbang Pemukiman about the data of modulus of elasticity and internal bond, but until now, we didn’t get the data. b. In SNI 2008, thickness maximum 25 %. In GIS, maximum 12% for thickeness.

Presenter : Prima Besty Asthary Institution : Center for Pulp and Paper Court reporter : Yoveni Yanimar Fitri Title : The Potential Use of Sludge Cake from Paper Mill Wastewater Treatment as Absorbent

Question 1 Liana Bratasida : How we can use the absorbent resulted of the research ?

Answer 1 The product used to absorb oil in the water.

Presenter : Kristaufan Joko Pramono Institution : Center for Pulp and Paper Court reporter : Yoveni Yanimar Fitri Title : The impact of the Internet on Consumption and Production of Paper Products

Question 1 Edwin (ITB) : a. The data collected until 2012. Do you have any data until 2016 ? b. Do you have forecase, the trend print for the newsprint is still trending down ?

Answer 1 a. The data coming from FAO. Today is 2016 so I think the data obtain until 2014. b. About forecase, the packaging paper is really confidence the imerging the internet technology.

DISCUSSION OF B2 SESSION

Presenter : Theresia Mutia Institution : Center for Textile Court reporter : Yoveni Yanimar Fitri Title : Fiber and bamboo Pulp for Composite

Question 1 Subki (RAPP) : a. Did you analyze about component that give affect to the composite ? b. How about the age of bamboo ? c. In your opinion, composite lignin will distract of the properties or not ?

Answer 1 a. Based on slide 12 “Important Lignin…”, the ash doesn’t affect the composite. b. Almost 3 years old. c. From the literature, the average of lignin is necessary for tube. If we get the lignin ± 5% (see figure 13), can compare to fiber board that have lignin 14% ( 3 x than pulp)

Presenter : Chong Yin Hui Institution : Universiti Sains Malaysia Court reporter : Yoveni Yanimar Fitri Title : The Effects of Alkaline Pre-Impregnation Proir Soda-Anthraguinone Pulping on Oil Palm Empty Fruit Bunch Fiber

Question 1 Subki (RAPP) : How many repeatation of cooking in your research ?

Answer 1 Two repeatations

Presenter : Dr. Leh Cheu Peng Institution : Universiti Sains Malaysia Court reporter : Yoveni Yanimar Fitri Title : Improved Oxygen Delignification : A comparison Study Between Tropical Mixed Hardwood Kraft Pulp and Oil Palm Fiber Soda-Anthraquinone Pulp

Question 1 Theresia Mutia (Center for textile) : What is your opinion about the economic point a view ?

Answer 1 We can reduce the chemical

Question 2 Lilik (Tsukuba University) : Hardwood selectivity increase anthraquinone protect from degradation of using maximum condition. Have you try oxygen delignification ? How does it compare ?

Answer 2 We try any oxygen delignification with additive. We still need verification about it.

Presenter : Lies Indriati Title : Substitution of BCTMP for hardwood kraft pulp in writing and printing paper Institution : Center for Pulp and paper Time : Session II November 15th, 2016 15.20-1540

Evi Octavia, CPP

For overall properties, which one is better for writing and printing paper? high yield pulp (BCTMP) or HBKP? Actually HBKP is the common raw material for printing paper. HBKP is made by chemical pulping which is followed by bleaching process. The process can cause water pollution especially when bleaching process is not Elemental Chlor Free (ECF) or Total Chlor Free (TCF) bleaching. In environmental view, BCTMP is better than HBKP because use less chemical.

BCTMP is less expansive compared to HBKP so in my opinion, using BCTMP for substitution of HBKP can reduce production cost.

Presenter : Sari Hasanah Title : The Damage of Paper-Based Archives in Four Archival Institutions Institution : National Archives of Indonesia Time : Session II November 15th, 2016 15.40-15.55

Toshiharu Enomoe, Tsukuba University o How do you evaluate or judge that the damage in the archives is classified as chemical damage? We classify the damage in the archives using Archives Damage Atlas which is a tool for assessing damage of archival documents and Universal Procedure Archives Assessment o How do you identify that the damage in the archives is caused by chemical? In the Archives Damage Atlas, the damage of archival document can be classified as binding and text block damage, chemical damage, mechanical damage, pest infestation, water damage o Do you measure the pH in damage classification of the archives? We do not measure the pH of the archives. We just observe the condition of the archives physically and then compared to the damage classification base on the Archives Damage Atlas. We measured the pH of some archives but not all the samples of the archives collected ware measured. In pH measurement, we did not use instrument but we used the indicator universal of pH

Evi Octavia, CPP o In conclusion, you mention that the most damage of paper based archive is slight damage but you also mention that the most damage of paper based archival is classified as chemical damage which is moderate or serious damage. Can you explain that? If the damage of archives is classified base on its severity, most damage of archives is slight damage but when we classify the damage base on the cause, most damage of the archives is chemical damage. Moderate or serious damage is mostly caused by chemical factors o Do you have standard to assess the severity of the damage? I want to know from which year the archive is taken as the sample or how old is the sample of the archives? We use Archives Damage Atlas which and Universal Procedure Archives Assessment for assessing damage of archival documents. For basic assessment we use simple measurement. If the archive cannot be read, the damage is classified as serious damage and If we use careful handling but the archive is still broken then the damage is classified as serious damage The sample archives are taken from four archival institutions. The age of the archives is not same and it depends on the institution where the archives ware taken. The oldest archive taken as sample is from VOC period around 1600.

Presenter : Gustan Pari Title : A Review: Recent Research In Paper Packaging For Food Institution : - Time : Session II November 15th, 2016 16.25-16.40

Moderator o What do you think about the future trend of packaging paper? The future trend of packaging paper is still increase because the imported packaging paper in recent years is still increasing especially paper for special purposes o What kind of paper? It is paperboard especially for transportation from one island to another island. For example, to transport banana from Lampung Sumatra Island to Jakarta Java Island so the banana still in good condition and no damage because of transportation

DISCUSSION OF S1 SESSION

Presenter : Jeffry Fielkow Institution : PT. Tetrapak Court reporter : Yoveni Yanimar Fitri & Kristaufan Joko Pramono Title : -

Question 1 Aswin : How to compare with plastic ?

Answer 1 Compare with plastic, polyaluminum and selling plastic can substitute the value

Question 2 Muchammad Kodiat Prianggodo (Center for Pulp and Paper) : What are the profiles of the recycle entrepreneurs and what the obstacles in this industry?

Answer 2 The profile are varies from small to big businesses. The most difficult thing we have experienced is the sustainability of raw material, especially for the smaller business. That is way we keep trying to bring awereness to our end customers to seperate the used cartoon so that we can recycle it.

Question 3 Jimmy (ATPK) : How is the difference of fibre quality around the world ?

Answer 3 The quality of fibre is consistent world wide.

Presenter : Aryana Padawidagda Institution : PT. Valmet Court reporter : Yoveni Yanimar Fitri & Kristaufan Joko Pramono Title : -

Question 1 Martina : Is the change of refiner for design only ?

Answer 1 It is different on the both refiners.

Question 2 Lilik (Tsukuba University) : - How to adjust clearance ? - How much the maximum the of chip material on material inside ?

- The answer is the picture on the slide, it is technical stuffs.

Question 3 Steven : - How much the comparison for fiber being refined ?

Answer 3 - It’s about 50% versus 80%.

DISCUSSION OF C2 SESSION

Presenter : Syamsudin Institution : Center for Pulp and Paper Court reporter : Hendro Risdianto Title :

Question 1 Ganis Lukmandaru - Gadjah Mada University > the product of gassification is terpentine, is it come from sofwood or hadwood?

Answer 1 > Turpentine will be released from pulping of both hardwood and softwood

NOTULENSI

Presenter : Gadang H Hartawan Institution : PT OKI pulp and paper Court reporter : Hendro Risdianto Title :

Question 1 Ganis Lukmandaru - Gadjah Mada University > Is the gassification suitable for wood or other materials?

Answer 1 > Basically, gassification process is suitable which consist of higher volatile matter

Question 2 APRIL > Why PT OKI choose the gasdification ?

Answer 2 location of PT OKI is far from energy sources, so this technology s very suitable especially for bark and fines

Question 3 Tjandra Setiadi - ITB > what is the advantages of gasifier to other method?

Answer 3 This method has high thermasl efficiency about 65℅

Presenter : Kholisul Fatikhin Institution : PT Indah Kiat Pulp and Paper -Tangerang Mill Court reporter : Hendro Risdianto Title :

Question 1 Ida indrayani How long your mill get the certification of ISO 50001?

Answer 1 about 1 year