Performance of Powdered and Granular Sugarcane Bagasse Activated Carbon in Removing Pollutants of Car Wash Wastewater

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PERFORMANCE OF POWDERED AND GRANULAR SUGARCANE BAGASSE ACTIVATED CARBON IN REMOVING POLLUTANTS OF CAR WASH WASTEWATER

NADZIRAH BINTI ZAYADI

UNIVERSITI TUN HUSSEIN ONN MALAYSIA PERFORMANCE OF POWDERED AND GRANULAR SUGARCANE BAGASSE ACTIVATED CARBON IN REMOVING POLLUTANTS OF CAR WASH WASTEWATER

NADZIRAH BINTI ZAYADI

A thesis submitted in fulfillment of the requirement for the award of the Degree of Master of Civil Engineering

Faculty of Civil and Environmental Engineering University Tun Hussein Onn Malaysia

MARCH 2017

iii

DEDICATION

Every challenging work needs self efforts as well as guidance

of elders especially those who were very close to our heart.

My humble efforts I dedicate to my loving

PARENTS

Whose affection, love, encouragement and prays make me

able to get such success and honor,

Along with hardworking and respected supervisors

ASSOC. PROF. DR. Nor Haslina Binti Hashim

ASSOC. PROF. Prof Dr. Rafidah Binti Hamdan

ASSOC. PROF. Dr. Aeslina Binti Abd Kadir

ACKNOWLEDGEMENT

In the name of Allah, The Most Gracious and Merciful, I would like to express my sincere appreciation to my supervisor, Assoc. Prof. Dr. Nor Haslina Binti Hashim, my co supervisor Assoc. Prof. Dr Rafidah Hamdan and Assoc. Prof. Dr. Aeslina Abd Kadir for the support given through out the duration for this research. The cooperation given by the Faculty of Civil and Environment Engineering at Universiti Tun Hussein Onn Malaysia is also highly appreciated. Appreciation also goes to everyone involved directly or indirectly towards the compilation of this thesis.

ABSTRACT

Water pollution is a challenge due to non source point of car wash wastewater, carries toxicity with little water quality treatment. Among various technologies of membrane application, oil separator and else, activated carbon is more promising. Research have been focused towards converting the agricultural wastes of sugarcane bagasse or Saccharum Officinarum into valuable product of activated carbon, due to adsorption properties. The objectives of this study are to characterize the car wash wastewater, optimized the activated carbon preparation and determine the optimum conditions for powdered and granular sugarcane bagasse activated carbon of Langmuir and Freundlich adsorption isotherms. In achieving the objectives, from wastewater characterization, an average value of chemical oxygen demand (COD), oil and grease (O&G), and surfactant as methylene blue absorbing substances (MBAS) were 461 ± 3 mg/L, 83 ± 5 mg/L, and 78 ± 47 mg/L respectively. Activated carbon prepared through chemical activation using phosphoric acid with different process parameters such as impregnation, carbonization temperature, and time. The optimum conditions achieved (20 % impregnation, 500 °C temperature for 2 hours) with 52 % and 41 % of COD and O&G removal, and constitutes microporous structure with iodine number of 749 mg/g and ash content of 12 %. About 81 % of carbon, 17 % oxide, and 95 % ethylene comprising of aromatics, hydroxyls and alcohol groups responsible to adsorb pollutants. The optimized conditions on pH, adsorbent dosage, size and contact time analysed between powdered and granular forms. The powdered size of 0.063 mm, attained maximum removal of COD, O&G and MBAS with 95 %, 94 % and 100 % at pH 8, dosage of 2 g/150 ml, for 3 hours contact. While, granular of 1.18 mm size have similar optimized conditions with 93 %, 85 %, and 90 % for COD, O&G and MBAS removal. The adsorption isotherm of Langmuir best fitted for powdered adsorbent, with maximum qmax of 0.031 mg/g and 0.006 mg/g for COD and O&G. This study highlighted the sugarcane bagasse activated carbon as an alternative adsorbent in removing pollutants of COD, O&G and MBAS of car wash wastewater. vi

ABSTRAK

Pencemaran air merupakan suatu cabaran untuk air dari sisa cucian kenderaan, kerana merupakan sumber pencemaran bukan titik, yang membawa sisa toksik tanpa rawatan. Selain daripada penggunaan membrane, separator minyak dan sebagainya, karbon aktif adalah contoh teknologi yang sesuai. Kajian telah dilakukan terhadap penukaran sisa agrikultur dari hampas tebu atau Saccharum Officinarum kepada karbon aktif, berdasarkan ciri-ciri penjerapan. Objektif kajian adalah, mengelaskan air sisa cucian kenderaan, pengoptimuman dalam penyediaan karbon aktif hampas tebu, dan pengoptimuman kondisi antara serbuk dan bentuk granular bersama Langmuir dan Freundlich isoterm. Untuk mencapai objektif tersebut, berdasarkan pengkelasan air, keperluan oksigen kimia (COD), minyak dan gris (O&G), dan surfaktan sebagai bahan penjerap methylene biru (MBAS) adalah 461 ± 3 mg/L, 83 ± 5 mg/L, and 78 ± 47 mg/L. Karbon aktif disediakan melalui proses aktivasi kimia menggunakan asid fosforik berdasarkan parameter penjerapan, suhu dan masa pembakaran. Nilai optimum penjerap adalah pada (20 % penyerapan, 500 °C dan 2 jam pembakaran) dengan 52 % dan 41 % nilai penyingkiran COD dan O&G, struktur mikropora dan nilai iodin sebanyak 749 mg/g dan kandungan debu 12 %. Sebanyak 81 % kandungan karbon, 17 % oksida, dan 95 % ethylene mempunyai kumpulan aromatik, hidroksil, dan alkohol. Kajian optimum terhadap sampel digunakan untuk mencari kadar dos penjerap, saiz, dan masa antara serbuk dan bentuk granular. Karbon aktif serbuk pada saiz 0.063 mm adalah maksimum 95 %, 94 % and 100 % pada COD, O&G dan MBAS pada pH 8, dos 2 g/150 ml pada 3 jam. Sementara itu, granular dengan saiz 1.18 mm mempunyai nilai optimum yang sama seperti bentuk serbuk dengan 93 %, 85 %, dan 90 % untuk COD, O&G dan MBAS. Penjerapan isoterm Langmuir adalah baik pada bentuk serbuk karbon aktif, dengan nilai maksimum qmax of 0.031 mg/g dan 0.006 mg/g untuk COD dan O&G. Kajian ini membincangkan karbon aktif hampas tebu sebagai salah satu alternatif untuk menyingkirkan COD, O&G and MBAS dari air sisa cucian kenderaaan.

CONTENTS

STATUS CONFIRMATION FOR MASTER’S THESIS TITLE i DECLARATION ii DEDICATION iii ACKNOWLEDGEMENT iv ABSTRACT v ABSTRAK vi CONTENTS vii LIST OF TABLES xiv LIST OF FIGURES xvi LIST OF EQUATIONS xx LIST OF SYMBOLS AND ABBREVIATIONS xxi LIST OF APPENDICES xxiii

CHAPTER 1 INTRODUCTION

1.1 Background of study 1 1.2 Problems statement 2 1.3 Objectives of study 4 1.4 Scope of study 4 1.5 Significance of the study 6

CHAPTER 2 LITERATURE REVIEW

2.1 Introduction 7 viii

2.2 Management of car wash industry in 8 Malaysia 2.3 Characteristic of car wash wastewater 9 2.4 Effect of car wash wastewater towards 11 environment 2.5 Water consuming in car washing 13 2.6 Legislation standards of car wash wastewater 14 2.7 Overview of car wash wastewater treatment 16 2.8 Production and Properties of Activated Carbon 19 2.8.1 Production of Activated Carbon 19 2.8.2 Physicochemical Properties of 23 Activated Carbon 2.8.2.1 Iodine number of activated 23 carbon 2.8.2.2 Ash content of activated 24 carbon 2.8.3 Factors affecting production of activated 25 carbon 2.8.3.1 Impregnating agent 25 2.8.3.2 Carbonization temperature 27 2.8.3.3 Carbonization time 28 2.8.4 Optimization parameter of activated 29 carbon 2.8.4.1 pH 29 2.8.4.2 Adsorbent sizes 30 2.8.4.3 Adsorbent dosage 31 2.8.4.4 Contact time 32 2.9 Adsorption of activated carbon from local 33 agricultural wastes 2.10 Criterias of sugarcane bagasse as an activated 37 carbon 2.11 Adsorption Equilibrium Study 43 2.11.1 Langmuir Isotherm 43 ix

2.11.2 Freundlich Isotherm 44 2.12 Recycling of Spent Activated Carbon 45 2.13 Concluding remarks 46

CHAPTER 3 METHODOLOGY

3.1 Sampling location 49 3.2 Sampling method 52 3.3 Materials and apparatus 54 3.3.1 Materials 54 3.3.2 Chemicals 54 3.3.3 Equipments 56 3.4 Characterization of car wash wastewater 57 3.5 Analytical Method 57 3.5.1 Determination of pH 58 3.5.2 Determination of chemical oxygen 59 demand 3.5.3 Determination of oil and grease 59 3.5.4 Determination of surfactant as 60 methylene blue absorbing substances 3.5.5 Determination of heavy metals 63 3.5.6 Determination of anion molecules 63 3.5.7 Determination of total carbon 64 3.5.8 Determination of alkalinity 64 3.6 Preparation of synthetic car wash wastewater 65 3.7 Characterization of sugarcane bagasse 68 activated carbon 3.7.1 Element composition analysis 68 3.7.2 Surface chemistry analysis 68 3.7.3 Microscopy analysis 69 3.7.4 Particle distribution size analysis 70 3.8 Adsorption test of sugarcane bagasse 70 activated carbon x

3.8.1 Determination of iodine number 70 3.8.2 Determination of ash content 71 3.9 Preparation of sugarcane bagasse activated 72 carbon 3.10 Batch studies on effect of impregnating 74 percentage with phosphoric acid, temperature and time of carbonization 3.10.1 Effect of impregnating percentage 76 with phosphoric acid in removal of chemical oxygen demand and oil and grease 3.10.2 Effect of carbonization temperature 76 in removal of chemical oxygen demand and oil and grease 3.10.3 Effect of carbonization time in 76 removal of chemical oxygen demand and oil and grease 3.11 Optimization studies of sugarcane bagasse 77 activated carbon 3.11.1 Determination of optimum pH 77 3.11.2 Determination of optimum adsorbent 78 dosage 3.11.3 Determination of optimum adsorbent 79 size 3.11.4 Determination of optimum contact 79 time 3.12 Adsorption experiments 80 3.13 Concluding remarks 82

CHAPTER 4 RESULTS AND DISCUSSIONS

4.1 Introduction 83 4.2 Characterization of car wash wastewater 83 xi

4.3 Characterization of sugarcane bagasse 86 activated carbon as adsorbent 4.3.1 X-Ray Fluorescence Analysis 86 4.3.2 Field Electroscopy Scanning 88 Electron Microscopy Energy Dispersive X-ray Analysis 4.3.3 Fourier Transform-Infrared 93 Analysis 4.3.4 Particle size distribution of 95 sugarcane bagasse activated carbon 4.4 Adsorption test of sugarcane bagasse 97 activated carbon 4.4.1 Iodine number of sugarcane 97 bagasse activated carbon 4.4.2 Ash content of sugarcane bagasse 100 activated carbon 4.5 Batch studies on preparation of sugarcane 102 bagasse activated carbon 4.5.1 Effect of time, temperature of 102 carbonization and impregnating percentage with phosphoric acid on chemical oxygen demand removal 4.5.2 Effect of time, temperature of 104 carbonization and impregnating percentage of phosphoric acid on oil and grease removal 4.6 Optimization studies of powdered and 109 granular sugarcane bagasse activated carbon 4.6.1 Optimization of pH 109 4.6.2 Optimization of adsorbent dosage 113 4.6.3 Optimization of adsorbent sizes 116 xii

4.6.4 Optimization of contact time 120 4.7 Mechanism of adsorption isotherm 123 4.7.1 Adsorption isotherms of chemical 123 oxygen demand 4.7.1.1 Langmuir adsorption 123 isotherms of chemical oxygen demand 4.7.1.2 Freundlich adsorption 125 isotherms of chemical oxygen demand 4.7.2 Adsorption isotherms of oil and 127 grease 4.7.2.1 Langmuir adsorption 127 isotherms of oil and grease 4.7.2.2 Freundlich adsorption 129 isotherms of oil and grease 4.7.3 Adsorption isotherms of 130 surfactant as methylene blue absorbing substances 4.7.4 Adsorption isotherm constants of 131 chemical oxygen demand, oil and grease, and surfactant as methylene blue absorbing substances 4.8 Concluding remarks 134

CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS

5.1 Conclusions 135 5.2 Recommendations 136

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REFERENCES 139 APPENDICES 149

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LIST OF TABLES

2.1 Characteristic of car wash wastewater 9 2.2 Parameter limit of Industrial effluents for 14 Standard A and Standard B 2.3 Treatment of car wash wastewater 16 2.4 Different impregnating agent in chemical 26 activation of activated carbon preparation 2.5 Local agricultural wastes as an activated 33 carbon 2.6 Functional group of sugarcane bagasse and 41 sugarcane bagasse activated carbon 3.1 Summary of sampling and handling 53 requirements 3.2 List of chemicals 55 3.3 List of equipments 56 3.4 Composition of car wash wastewater 65 3.5 Summarization of chemical activation and 75 carbonization processes 3.6 (a) Working condition of isotherms study for 80 powdered and granular sugarcane bagasse activated carbon 3.6 (b) Isotherm models used in present study 81 4.1 Car wash wastewater characteristics (n=8) 85 4.2 Chemical composition of untreated and 87 sugarcane bagasse activated carbon

4.3 (a) Element compositions of untreated sugarcane 91 bagasse and treated sugarcane bagasse activated carbon 4.3 (b) Comparison of element composition for other 92 sugarcane bagasse activated carbon 4.4 Particle size distribution of sugarcane bagasse 96 activated carbon 4.5 Iodine number of sugarcane bagasse and 98 commercial activated carbon 4.6 Ash content of sugarcane bagasse and 100 commercial activated carbon 4.7 (a) Langmuir isotherm of powdered and granular 133 sugarcane bagasse activated carbon 4.7 (b) Freundlich isotherm of powdered and 133 granular sugarcane bagasse activated carbon 4.7 (c) Comparison of isotherm models with other 133 sugarcane bagasse activated carbon

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LIST OF FIGURES

2.1 SEM image (a) kapok fibre with 50μm and 500 22 magnification (Wahi et al., 2013) (b) sugarcane bagasse activated carbon with 20μm and 1000 magnification (Devnarain et al., 2002) (c) coal activated carbon and (d) coconut shell activated carbon (Jabit, 2007) 2.2 The acumulation of molecules adsorbate; the oil 36 and grease (O&G) molecules from solution of aqueous phase on the surface of adsorbent; activated carbon (Wahi, et al., 2013) 2.3 (a) Untreated bagasse (Lara et al., 2010); 39 Sugarcane bagasse activated carbon (b) With nitric acid (Worathanakul et al., 2010) (c) With potassium hydroxide (Irfan et al., 2011) (d) With phosphoric acid (Adinaveen et al., 2013) 3.1 Overview of study 48 3.2 (a) Drainage of car wash station 49 3.2 (b) Layout of car wash station 50 3.2 (c) Car washing activity 50 3.2 (d) Snow jet pressure car wash pumps 51 3.2 (e) Car wash wastewater effluents 51 3.3 Sugarcane bagasse activated carbon that have 58 been settled after stirred for one hour

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3.4 (a) Pink colour of phenolphthalein slowly 61 disappeared 3.4 (b) Car wash wastewater and chlorofom part 61 3.4 (c) Chlorofom part turns bit bluish 61 3.4 (d) Chlorofom part was drained 61 3.5 (a) Surfactant extractions (colorless bit bluish 62 colours) 3.5 (b) Standard calibration curve for methylene blue 62 absorbing substances measurement 3.6 (a) Synthetic solution mixture 67 3.6 (b) Homogenization of synthetic solution 67 3.6 (c) Relative contributions of chemical oxygen 67 demand, surfactant as methylene blue absorbing substances, and oil and grease of synthetic car wash wastewater 3.7 (a) Bagasses after oven dried and cut in 1 cm size 72 3.7 (b) Sugarcane bagasse activated carbon 73 3.7 (c) Sugarcane bagasse activated carbon with flakes 74 form 3.7 (d) Schematic diagram for preparation of sugarcane 74 bagasse activated carbon 3.8 Shaking process of sugarcane bagasse activated 78 carbon 4.1 (a) Untreated sugarcane bagasse in 100 magnification 89 4.1 (b) Untreated sugarcane bagasse in 1000 89 magnification 4.1 (c) Sugarcane bagasse activated carbon in 100 89 magnification 4.1 (d) Sugarcane bagasse activated carbon in 1000 89 magnification

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4.1 (e) Untreated sugarcane bagasse (Lara et al., 2010) 89 4.1 (f) Sugarcane bagasse activated carbon with 89 phosphoric acid (Adinaveen et al., 2013) 4.2 (a) EDX spectrum analysis of untreated sugarcane 90 bagasse 4.2 (b) EDX spectrum analysis of treated sugarcane 91 bagasse activated carbon 4.3 FT-IR analysis of untreated sugarcane bagasse 94 and treated sugarcane bagasse activated carbon 4.4 Percentage particle sizes of sugarcane bagasse 97 activated carbon 4.5 (a) Effect of time, temperature of carbonization and 107 impregnating percentage of phosphoric acid on chemical oxygen demand removal 4.5 (b) Effect of time, temperature of carbonization and 108 impregnating percentage with phosphoric acid on oil and grease removal 4.6 (a) Removal percentage pollutants on powdered 112 and granular sugarcane bagasse activated carbon (%) via optimization of pH (adsorbent dosage of 2 g/150 ml for 1 hours stirring time; adsorbent size powdered: 0.063 mm; granular: 2.36 mm) 4.6 (b) Removal percentage pollutants on powdered 115 and granular sugarcane bagasse activated carbon (%) via optimization of adsorbent dosage (adsorbent size powdered: 0.063 mm; granular: 2.36 mm; pH 8; 1 hours stirring time) 4.6 (c) Removal percentage pollutants on powdered 118 sugarcane bagasse activated carbon (%) via optimization of particle sizes (adsorbent size dosage: 2g/150 ml for 1 hours stirring time; pH 8)

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4.6 (d) Removal percentage pollutants on granular 119 sugarcane bagasse activated carbon (%) via optimization of particle sizes (adsorbent size dosage: 2g/150 ml for 1 hours stirring time; pH 8) 4.6 (e) Removal percentage pollutants on powdered 122 and granular sugarcane bagasse activated carbon (%) via optimization of contact time (adsorbent size dosage: 2g/150 ml; adsorbent size powdered: 0.063 mm; granular: 1.18 mm; pH 8) 4.7 (a) Langmuir isotherm of chemical oxygen demand 124 by powdered sugarcane bagasse activated carbon 4.7 (b) Langmuir isotherm of chemical oxygen demand 124 by granular sugarcane bagasse activated carbon 4.7 (c) Freundlich isotherm of chemical oxygen 126 demand by powdered sugarcane bagasse activated carbon 4.7 (d) Freundlich isotherm of chemical oxygen 126 demand by granular sugarcane bagasse activated carbon 4.8 (a) Langmuir isotherm of oil and grease by 128 powdered sugarcane bagasse activated carbon 4.8 (b) Langmuir isotherm of oil and grease by granular 128 sugarcane bagasse activated carbon 4.8 (c) Freundich isotherm of oil and grease by 129 powdered sugarcane bagasse activated carbon 4.8 (d) Freundlich isotherm of oil and grease by 130 granular sugarcane bagasse activated carbon

LIST OF EQUATIONS

2.1 Langmuir equation 43 2.2 Freundlich equation 44 3.1 Chemical oxygen demand concentration 59 3.2 Oil and grease concentration 60 3.3 Surfactant as methylene blue absorbing 63 substances 3.4 (a) Phenolphthalein alkalinity 65 3.4 (b) Total alkalinity 65 3.5 Iodine number 71 3.6 Ash content 72

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LIST OF SYMBOLS AND ABBREVIATIONS

ICP-MS - Inductively Coupled Plasma-Mass Spectrometer XRF - X-Ray Fluorescence FE-SEM - Fine Electron Scanning Electron Microscopy-Energy Dispersive EDX X-Ray FT-IR - Fourier Transformed-Infrared Spectroscopy UTHM - Universiti Tun Hussein Onn Malaysia mg/ L - milligram per litre mg/ g - milligram per gram °C - Degree Celsius % - Percent g - gram ml - millilitre MBAS - surfactant as Methylene Blue Absorbing Substances pH - Potential of hydrogen SS - Suspended solids SBAC - Sugarcane bagasse activated carbon CAC - Commercial activated carbon COD - Chemical oxygen demand O&G - Oil and grease PSC - Powdered sugarcane bagasse activated carbon GSC - Granular sugarcane bagasse activated carbon PCC - Powdered commercial activated carbon GCC - Granular commercial activated carbon qmax - Maximum amount of concentration per unit weight of adsorbent

xxii

R2 - Correlation coefficeint b - Constant related to the affinity of binding sites with the adsorbent

Kf - Freundlich constant n - Heterogeneity factor

Ce - Equilibrium sorption capacity

xxiii

LIST OF APPENDICES

A Determination of surfactant in water 149 B Calculation of synthetic car wash wastewater 151 C Characteristic of car wash wastewater 152 D1 Iodine number 157 D2 Ash content 161 E Optimum condition for preparation of 165 sugarcane bagasse activated carbon F Optimization of pH, dosage, adsorbent size 166 and contact time G1 Chemical Oxygen Demand, COD (Langmuir 174 & Freundlich isotherm) G2 Oil and grease, O&G (Langmuir isotherm & 176 Freundlich isotherm) G3 Mehylene Blue Absorbing Substances, 178 MBAS (Langmuir isotherm & Freundlich isotherm)

CHAPTER 1

INTRODUCTION

1.1 Background of Study

Wastewater characteristics, which depend on wastewater source, are increasingly and becoming more toxic in recent times (Alade et al., 2011). A wastewater system can not mixed with the stormwater system, where it can contribute to the permeation of other pollutants towards the aquatic animals (Sanderson et al., 2006; Sablayrolles et al., 2010). Car wash is defined as a non-domestic installation for internal and external cleaning of cars by using water, cleaning solutions applying with finish products. Car washing wastewater consists of oils, elements from brake linings, rust, trace amounts of possibly chromium and soap used to wash the cars introduces phenols, dyes, acids, and ammonia (Zayadi et al., 2015). Car wash contains oily wastewater with toxic substances such as phenols, polyaromatic hydrocarbons, which are inhibitory to plant and animal growth, equally mutagenic and carcinogenic to human beings (Lan et al., 2009). Moreover, the wastewater from car washes may contain nutrients such as phosphorus, chemicals including nonyl phenols, linear alkylbenzene sulphonates (LAS) which are the most important synthetic anionic surfactants, and the principal constituents of surfactants subject pollutants from car wash wastewater which is slow to biodegrade generally (Oknich, 2002). Many particles and chemicals have been found in car wash wastewaters, hence the concentration and severity each element should be assessed and considered in treating the pollutants. The increases number of cars on roads have increased the number of car washes nowadays. The Environmental Pollution Agency (EPA) have reported, car washes is a non point source of pollution where the types and contaminants present during 2 washing cars will have a major effect upon the effluent characteristics (Brown, 2002). Hence, several treatments on car wash wastewater treatment have been used, such as ultrafiltration and nanofiltration membrane, oil separator and else (Zayadi et al., 2015). In Malaysia, the effluent discharges of car wash wastewater used Standard A and Standard B regulations based on Malaysia Sewage and Industrial Effluent Discharge. Malaysia cities currently, have increased in car volumes on the road. It have boost the car wash industry, leading to increase of car washes service, particularly in high population of residential area along the roads. However, car wash stations in Malaysia commonly have poor and improper sanitary drainage system of car wash wastewater discharges. They may have directly flowing their untreated effluents to the drains, then discharged it to streams, rivers and bays. Whereas, some effluents directly discharged to the ground, leads to the ground contamination.

1.2 Problems Statement

The increase in car numbers on roads altogether, have furthered increased the car wash stations in Malaysia where, each car washing have generated 150 L to 600 L of wastewater. The oil and grease, O&G, chemical oxygen demand, COD and surfactants as MBAS (Methylene Blue Absorbing Substances) have been reported as most contaminants in car wash wastewater (Brown, 2002; Yasin et al., 2012; Baddor et al., 2014; Shete & Shinkar, 2014). Though Malaysia have their own environmental quality regulations of Standard A and Standard B for Discharge of Industrial Effluent or Mixed Effluent 2009, but this particular regulation is seldom enforced leads to little attention is given to the car wash industry (Lau et al., 2013). Treatment of car wash wastewater includes membrane application (Lau et al., 2013; Shete & Shinkar, 2014), oil separator (Al- Odwani et al., 2007; Fall et al., 2007) and else. An example of on site conventional treatments includes the oil separator usually focused on organic removal such as COD and O&G but, less investigation were made on inorganic such as MBAS removal. Surfactant as MBAS carries alkaline chemical compounds together with alcohol in solvents and other complex agents. However, when using the oil separator, it was failed to keep values to permissible limit of Standard B, 10 mg/L. The formation of O&G emulsions due to MBAS where the, MBAS molecule surround O&G droplets with a layer of MBAS molecule give them 3 a water-soluble coating, have reducing the efficiency amount of O&G and MBAS removal (Yasin et al., 2012). Recent years, adsorption had been carried out as an alternative of conventional treatment. Adsorption of car wash wastewater such as flocculation, coagulation (Butler et al., 2013); alum and ferrous sulphate as coagulants have been applied by using low cost adsorbents (Radin Mohamed et al., 2014). However, the selective adsorbents should be chosen from promising adsorbents with least costs, economic friendly and readily available materials. Adsorption via activated carbon from local agricultural wastes such as chitosan (Wahi et al., 2013); rice husk (Nekoo & Shohreh, 2013), and else have removed 70 % to 99 % of O&G in car wash wastewater with limited researchs on COD and MBAS removal. Previous studies on sugarcane bagasse or Saccharum officinarum towards industrial wastewater have succeedly removed 46 % to 84 % of COD (Nekoo & Shohreh, 2013; Azmi et al., 2014; Gaikwad & Mane, 2015), 80 % of O&G (Sarkheil & Tavakoli, 2015) and 77 % to 95 % of MBAS (Co et al., 2012; Bilal et al., 2013). It has 50 % cellulose, 27 % polyoses, and 23 % lignin with hydroxyl, carbonyl, aromatic group and other composition of polymers responsible for an excellent adsorbent capacity (Gusmao et al., 2012). In adsorption processes, to ensure the porosity of the fibrous bagasse stems produced the best quality of an activated carbon, the activated carbon preparation should be optimized in term of the temperature, time and impregnation percentage (Adinaveen et al., 2013). Moreover, it is important to study the different environmental parameters such as pH, adsorbent dosage, sizes, contact time, and the morphological analysis to ensure sugarcane bagasse activated carbon can be performed at optimum condition. The adsorbent sizes of powder and granule yields different performances towards pollutant removals. For example, a study on membrane process on granular activated carbon have removed 95 % of MBAS, whereas the powdered activated carbon, the problems reported including a long backwash time and cake formation over membrane surfaces (Taylor & Zahoor, 2014). Hence, there is a need for Malaysia to develop on site treatments using locally available material of sugarcane bagasse. Thus, it is significant to study on characterization and optimization of sugarcane bagasse activated carbon in both powder and granule forms. 4

1.3 Objectives of Study

This study aims to investigate the capability of sugarcane bagasse activated carbon in removing pollutants from car wash wastewater. Three correlative objectives were outlined to achieve the aims.

1) To characterize the physical and chemical composition of car wash wastewater discharges.

2) To optimize the impregnation of carbonized sugarcane bagasse activated carbon via optimum value of phosphoric acid impregnating percentage, temperature and carbonization time.

3) To optimize the value of pH, adsorbent dosage, size, and contact time of powdered sugarcane bagasse activated carbon, and granular sugarcane bagasse activated carbon and with the adsorption isotherms.

1.4 Scope of Study

The study consist of field activities and laboratory work. Field activities were carried out at Johor Bahru, where samples were collected from car wash station. Field activities were carried out at early stage for characterization of wastewater, during preparation of activated carbon and last stage of batch study for powdered and granular activated carbon. Laboratory work including preliminary study, preparation of activated carbon, adsorption test, optimization study, adsorbent characteristic before and after treatment of optimization study, removal efficiency of COD, surfactant as MBAS and O&G via optimum study. The experiments were conducted in accordance with standard operations of Standard Method for the Examination of Water and Wastewater (2012) for collections and measurements promulgated for eight weeks.

i. Preliminary study involving the characterization of car wash wastewater and working ranges of car wash wastewater. 5

ii. Preparation of sugarcane bagasse activated carbon as an adsorbent for optimization consisting the percentage of impregnated bagasse via phosphoric acid for 10 %, 20 %, 30 %, 40 % and 50 % for temperature carbonization of 500 °C, 600 °C, 700 °C at 1 hour, 2 hours and 3 hours for 2 g of adsorbent at 125 rpm on room conditions. The optimization then, was determined based on the removal efficiency on car wash wastewater for COD and O&G parameters.

iii. Powdered sugarcane bagasse and granular sugarcane bagasse were prepared from sugarcane bagasse activated carbon produced with the optimum preparation conditions; 20 % of phosphoric acid impregnation, at 500 °C for 2 hours carbonization. The sugarcane bagasse activated carbon were classified based on ASTM D2862 test method. The selected sizes were powdered with (0.3 mm, 0.212 mm, 0.15 mm, 0.075 mm, 0.063 mm) and granular (2.36 mm, 2 mm, 1.4 mm, 1.18 mm, 0.6 mm).

iv. For optimization study, the values of pH were varied to pH 3, 7, 8, and 9; adsorbent dosage of 0.6 g, 1 g, 2 g, 4 g and 6 g whereas, the contact time of 0.5 hours, 1 hour, 3 hours, 12 hours, and 24 hours for all selected sizes of powdered and granular sugarcane bagasse activated carbon. The optimized value then, analysed for the adsorption of Langmuir and Freundlich isotherm for COD, O&G, and MBAS pollutants.

v. The morphological characteristics of the adsorbent were carried out by using FE-SEM EDX, functional group with FTIR and element composition with XRF.

1.5 Significance of Study

Car wash treatments including of membranes, oxidation, and else. However, the car wash owners seldom applied the treatment for their stations due to the affordability, where the low cost treatment is a need (Radin Mohamed et al., 2014). Generally, the conventional treatment of oil separator may remove above 70 % of COD and O&G, but seldom analysed to MBAS removal, even the pollutant have been 6 awared by Environmental Pollution Agency in 1980 (Bilal et al., 2013). Therefore, it is important to study and propose treatment suitable to remove those pollutants using other alternative treatment. For industrial wastewater treatment, the other potential treatment usually applied are commercial activated carbon. Literature survey indicates, rather than commercial activated carbon, varieties of local agricultural wastes were manufacturing as an activated carbon (Gottipati, 2012). Sugarcane bagasse available abundantly, with 54 million dry tones bagasse are produced annually around the world (Fasoto et al., 2014). The bagasse generates a lot of waste that could serve as a reliable feedstock to obtain carbons with good adsorptive properties. Reuse the sugarcane bagasse wastes, throw by the sugarcane juice stalls and sugar industry for its sucrose content, will reduce the amount of wastes throw every day. The conversion of sugarcane bagasse to activated carbon would have dual advantages of producing a low cost adsorbent material for environmental protection, while at the same time reduce the need for land filling, disposal and open burning. This process is also an economic friendly treatment, as it is non polluting to our environment. In Malaysia, sugarcane bagasse were available obtained with cheap, reasonable prices, high carbon and low inorganics content, favourable for the production of activated carbon. Moreover, it has high potential to remove 90 % of pollutants in wastewater, than other local agricultural wastes (Bilal et al., 2013). Hence, adsorption of sugarcane bagasse activated carbon will be a technically feasible and economically attractive approach replacing conventional treatments. Therefore, this study offers, an economic low cost agricultral wastes as an activated carbon from sugarcane bagasse wastes for car wash wastewater treatment.

CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

With the increasing development of the economy and improvement of human life, wastewater discharged by the municipal, industrial and commercial sectors have been adversely affected and threatening our environment. In Malaysia, with total population of 28 million peoples, the vehicles sales report revealed that the total vehicle sales volume in 2012, between January was 301 units, June was 224 units and, forecasted to reach a new record of 615,000 units at the end of 2012 compared to 605,156 units and 600,123 units in 2010 and 2011, respectively (Radin Mohamed et al., 2014). Due to the demand in vehicle own nowadays, large number of cars were seen on roads, leading the mushrooming of car wash industry sectors (Bhatti et al., 2011). It offer consumers an easy, time saving, and practical way to wash and remove the dirt, grime and oil from their cars. Car washes providing the external and internal cleaning of cars, consisting of a roll over (in which the washing installation moves over the car), an automatic car wash (in which the car is pulled through the washing installation) and a self-car wash (Boussu et al., 2007). The processes removing of oil and dirt, and then treatment to provide protection. Degreasing solvents and cleaning agents remove traffic grime and particulate matter on cars, then the subsequent application of wax, polishes and protects coatings (Genuino et al., 2012). Car washing consume large capacities of fresh water on a daily basis. Our modern daily life and restricted schedules nowadays forcing people often take their cars for cleaning and rinsing purposes resulting high amount of wastewater generated, rather than washing cars at home. A car wash study in Kuwait have stated that if the car wash station operates 12 hours/ day, and an assumption of one car being washed 8 per hour, then there are 25,200 cars washed on a daily basis. An average of 100 galloons of fresh water used to wash a car makes the total fresh water consumption above 2.5 million galloons/day. However, the large capacity of water contains hazardous pollutants in the wastewater, including the sand and dust, phosphates, oil and grease, organic matter, heavy metals and surfactants which may go into the stormwater system and eventually ending up into rivers causing severe damage to aquatic systems (Al-Odwani et al., 2007; Lau et al., 2013).

2.2 Management of car wash industry in Malaysia

Most countries including of Malaysia were still behind in developing conscious for the wastewater produced by car wash industries (Bhatti et al., 2011). Cars that are washed in the street with the improper management of wastewater discharges can pollute the rivers. The surfactants, oil and grease and other pollutants that run off the car into the drains, will eventually flow to the storm water system without any treatment. Even, the measured pollutant concentrations in car wash discharge were more similar to the levels found in wastewater, than in runoff stormwater (Azhari, 2010; Sablayrolles et al., 2010). The accumulated sediments during washing cars consisting concentrations of contaminants, where the sludge is considered a controlled or hazardous waste, including of metals, elevated levels of oil and grease, and unacceptable levels of acidity or alkalinity (Azhari, 2010). The awareness of the environmental issues and restricting the environmental regulations on effluent discharged from industries is increased. Malaysia have their own environmental quality regulations, but this particular regulation is seldom enforced to the car wash industry. It is generally perceived by the public that the wastewater from car washing is not severely contaminated compared with other industrial wastewaters (Lau et al., 2013). Hence, little attention is given to the car wash industry (Abagale et al., 2013).

2.3 Characteristic of car wash wastewater

Car washing consumed greater amount of water during cleaning process involving the use of chemicals and hence, producing wastewater with a high concentration of surfactants, oils, greases and other organic matters where, the mixed effluents makes the car wash wastewater toxic to aquatic life (Zaneti et al., 2011). The characteristics of car wash wastewater were characterized as summarized in Table 2.1.

Table 2.1: Characteristic of car wash wastewater

Parameter Units Values Researchers Minimum Maximum Mean

pH - - - 8 Tony & Bedri (2014) - - 8 Yasin et al., (2012) - - 8-9 Radin Mohamed et al., (2014) - - 9 Shete & Shinkar (2014) Chemical Oxygen mg/L 78 738 408 Lau et al., (2013) Demand (COD) - - 288 Shete & Shinkar (2014) - - 572 Kuokkanen et al., (2013) - - 1330 Yasin et al., (2012) - - 241 Zaneti et al., (2011) - - 488 Juarez et al., (2015) Biochemical mg/L - - 178 Kuokkanen et al., oxygen demand (2013)

(BOD5) - - 133 Zaneti et al., (2011) 11 12 - Lau et al., (2013) - - 540 Yasin et al., (2012) Surfactant as mg/L - - 96 Kuokkanen et al., methylene blue (2013) absorbing - - 35 Baddor et al., (2014) substances (MBAS)

Table 2.1 (continued)

24 32 28 Shahbazi et al., (2013) - - 68 Juarez et al., (2015) Oil and grease mg/L 10 1750 880 Zaneti et al., (2011) (O&G) 1 84 - Bhatti et al., (2011) 670 1530 - Yasin et al., (2012) Suspended solids mg/L 147 202 - Radin Mohamed et (SS) al., (2014) 110 644 - Bhatti et al., (2011) - - 286 Good et al., (2011) 230 Hsu et al., (2011)

A number of studies reported the pH of car wash wastewater normally were 8 (Yasin et al., 2012; Tony & Bedri, 2014), 8 to 9 (Radin Mohamed et al., 2014), and 9 (Shete & Shinkar, 2014). The pH 8 was observed from the hand car wash stations (Yasin et al., 2012; Tony & Bedri, 2014). Compared with the slightly high value of alkaline surfactants ingredients applied during automatic car washes, resulting pH 9 (Radin Mohamed et al., 2014; Shete & Shinkar, 2014). Chemical oxygen demand (COD) presented by Lau et al., (2013) in car wash stations in the city of Johor Bahru shows the COD were within ranges of 78 mg/L till 738 mg/L. The foreign countries such as India recorded 288 mg/L of COD (Shete & Shinkar, 2014); Italy with 572 mg/L (Kuokkanen et al., 2013); and Brazil with 241 mg/L (Zaneti et al., 2011). The higher COD observed in Pakistan with 1330 mg/L where the sampling were taken at service oil station, contributing by diesel, gasoline, waste engine oil, and oil emulsions from washing cars (Yasin et al., 2012). BOD shows the biodegradable organic contaminants present in the wastewater. BOD based on review by Kuokkanen et al., (2013) have nearly BOD values of 178 mg/L in Italy and 133 mg/L in Brazil (Zaneti et al., 2014). A study of BOD by Lau et al., (2013) in Johor Bahru have lower value than the other reviews, 11 mg/L to 12 mg/L. In car wash wastewater, BOD was caused by the animal dung and bird droppings that are washed away with water. Emulsified oil from engine washing and detergents used to wash vehicles contributes to higher levels of BOD. Though there was an oil water separator used as on site treatments to treat car wash wastewater, the 11 rarely used have caused all wash water goes into the sewer system directly, resulting the high concentration of 540 mg/L (Yasin et al., 2012). Panizza et al., (2005) have summarized the use of surfactants as the cleaning agent for car washing purposes. Surfactant comprising of water-soluble (hydrophilic) and a water-insoluble (hydrophobic) component. As a result of this structure, the molecules of surfactants align themselves and surrounds the oil and grease (O&G) droplets with a layer of surfactant molecule to enable the water soluble coating to remove the dirts (Zaneti et al., 2011). Generally, synthetic detergents used for cars washing are anionic surfactants as (MBAS). Kuokkanen et al., (2013) has 96 mg/L MBAS, higher than Baddor et al., (2014) and Shahbazi et al., (2013), with 32 mg/L and 24 mg/L respectively. The MBAS with high chemical contents of Linear alkylbenzene sulfonates (LAS) might surround the O&G droplets with a layer of MBAS molecules to give them a water soluble coating. Hence, failed to have less values in effluent (Yasin et al., 2012). On the other hand, Zaneti et al., (2014) and Yasin et al., (2012) reported with 1750 mg/L and 1530 mg/L of O&G respectively. According to the Zaneti et al., (2014), oil separator devices have no efficiency in removing O&G, due to the formation of stable emulsions in the wastewater caused by MBAS. Sand, silts and soils present as suspended solids (SS) in car wash wastewater. These colloidal materials make the wastewater turbid as well. The SS were within 110 mg/L to 286 mg/L based on reviews. The following SS were 230 mg/L SS (Hsu et al., 2011); 147 mg/L to 202 mg/L SS (Radin Mohamed et al., 2014); and 286 mg/L of SS from Good et al., (2011). A maximum concentration of 644 mg/L of SS denoted by Bhatti et al., (2011). SS are predominantly inorganic matter, that can be mainly explained by the particles and dust attached to the wheels and body parts of cars. Based on the reviews in Table 2.1, the organic contaminants were higher than the inorganic in car wash wastewater. Therefore, the organic contaminants including of the COD, O&G and MBAS were selected as the important parameters in this study.

2.4 Effect of car wash wastewater towards environment

People nowadays are still behind to develop conscious for the wastewater produced by car wash industries. In Malaysia, the car wash stations does not have improper management on managing the car wash wastewater, where the wastewater 12 were discharged to the drains or grounds without further any treatment. The surfactants as (MBAS), oil and grease (O&G) and other pollutants that run off the car into the drains, go into the storm water system. Bhatti et al., (2011) have emphasized that any pollutants in storm water end up in river was considered non point source pollution. Moreover, stormwater that enters the river does not undergo treatment before it is discharged into waterways. Therefore, wastewater carried were polluted to the rivers and our stormwater system. The most common sources of car wash wastewater are organic matters which contributing the high concentration of chemical oxygen demand (COD). The sand, silts, muds and dusts were released particles from the road surfaces and the tires of the cars. COD in wastewater shows the presence of contaminants that are stable and not easily biodegradable. Diesel, gasoline, waste engine oil, surfactants, all contributes COD in car wash wastewater. The presence of those pollutants to stormwater leads to aesthetic losses caused by foam, which can cause toxic effects on ecosystems and changes in biodiversity (Nekoo et al., 2013). When the surfactant as MBAS was being applied to wash cars, the other alkaline chemical components such as alcohols in solvents and other complex agents were released. An increase in MBAS to a surface water body leads to excessive plant growth and decays. This creates low dissolved oxygen levels, changes in animal populations, and an overall degradation of water quality and aquatic habitat (Zaneti et al., 2014). A study by Yasin et al., (2012) have stated that the oil and grease (O&G) were present in the wastewater because of the vehicles have leaked engines and oil spills on the washing floors, flowing to stormwater system. Though the oil separator used as on site treatments, it was failed to keep values of O&G to 10 mg/L in effluent because of the formation of O&G emulsions due to MBAS. Compounds in petroleum hydrocarbons in O&G are highly toxic. In the surface water environment, from Wahi et al., (2013), it can cause harm to wildlife through direct physical contact, contamination by ingestion, and the destruction of food sources and habitats. Moreover, the formation of O&G layer limits the oxygen penetration into water and thus, caused toxic effects on microorganisms responsible for biological treatment of wastewater. Overall, the car wash wastewater when released to stormwater system, without being treated were harmful to environment and ecosystem system. Hence, to 13 control the amount of pollutants, an effective and low cost treatment should be awared and developed in managing the car wash wastewater.

2.5 Water consuming in car washing

Car wash stations located in Kuwait based on Al-Odwani et al., (2007) are among those activities that consume great capacity of water produced. An average of 50 to 100 gallons of fresh water is consumed to perform a complete professional wash on a single car. It is estimated that 2.5 million gallons of freshwater is consumed daily in car wash stations. Besides, about 25 % of freshwater have been used to perform final rinses during cleaning cars. This large capacity of water carried away pollutants from car wash wastewater, which may eventually end up in the sea, causing severe damage to the marine life environment (Al-Odwani et al., 2007). Bhatti et al., (2011) presents a study about water consuming during washing cars. An average of 100 L water is consumed per car and at least 10m3 of water is discharged from a car wash station per day, there is still a large amount of water consumed in city. Besides, a study in Malaysia from Lau et al., (2013), an average of 150 L to 600 L of car wash wastewater were produced from every car washing, where there is no restricted amount regulated for every car washing. However, for example in Queensland, Australia and some countries in Europe, it is restricted to use less than 70 L of fresh water for a car wash (Lau et al., 2013). Due to the amount of the water usage and the water quality, from a viewpoint of environmental protection, an effective treatments should be applied to ensure an effective utilization of water resources. Furthermore, a small space and high efficient treatments with low cost maintenances are required for car wash station. Considering the greater amount of wastewater discharged, the installation of a wastewater treatment system is not just a process to cope with the environmental problem to meet the environmental discharge requirements. Therefore, a ways to recover the rinsed water for reuse purpose should be awared to create a sustainable solution in this industry (Lau et al., 2013). 14

2.6 Legislation standards of car wash wastewater

Greywater standard on car wash wastewater have been established in other countries United States (Queensland, Massachusetts and Washington), Australia (New South Wales), and Europe (Swedish). In United States, countries such as Queensland, Massachusetts and Washington have included the standards for the car wash wastewater including in greywater system. The chemical oxygen demand, COD and oil and grease, O&G was less applicable in United States and Australia countries, where the pollutant focused are surfactant as methylene blue absorbing substances, MBAS releasing phosphorus (P) element, suspended solid (SS) and else. Moreover, the permissible limit of phosphorus element, must be less than 27 mg in Queensland country, less than 37 mg in Massachusetts, and less than 26 mg in Washington. Apart from that, the Swedish Environmental Protection Agency (EPA) in Europe, has standardized the COD with 588 mg/L and phosphorus with 7.5 mg/L. Malaysia has not established greywater standard for the quality of effluent discharges to receiving waters. However, the effluent discharges of car wash wastewater used Standard A and Standard B based on Malaysia Sewage and Industrial Effluent Discharge. Literature survey present the researchs of car wash wastewater in Malaysia generally focused on COD, O&G and SS, however less focused on MBAS concentration (Lau et al., 2013). Table 2.2 shows the parameter limits of effluents for Standard A and Standard B. The COD permissible limit is 200 mg/L, O&G with 10 mg/L, and no standard limit applicable for MBAS.

Table 2.2: Parameter limit of Industrial effluents for Standard A and Standard B

Standard Parameter Unit A B Temperature °C 40 40 pH - 6-9 5.5-9 Biochemical Oxygen Demand mg/L 2 40

(BOD5 at 20 °C) Chemical Oxygen Demand mg/L 80 200 (COD) 15

Table 2.2 (continued)

Suspended solids (SS) mg/L 50 100 Mercury (Hg) mg/L 0.005 0.05 Cadmium (Cd) mg/L 0.01 0.02

Chromium, Hexavalent (Cr6) mg/L 0.05 0.05

Chromium, Trivalent (Cr3) mg/L 0.2 0.1 Arsenic (As) mg/L 0.05 0.10 Cyanide (Cn) mg/L 0.05 0.10 Lead (Pb) mg/L 0.1 0.5 Manganese (Mn) mg/L 0.2 1 Nickel mg/L 0.2 1 Tin mg/L 0.2 1 Zinc (Zn) mg/L 2 2 Boron (B) mg/L 1 4 Iron (Fe) mg/L 1 5 Silver (Ag) mg/L 0.1 1 Aluminium (Al) mg/L 10 15 Selenium (Se) mg/L 0.02 0.5 Barium (Ba) mg/L 1 2 Fluoride (F) mg/L 2 5 Formaldehyde mg/L 1 2 Phenol mg/L 0.001 1 Free Chlorine (Cl) mg/L 1 2 Sulphide (S) mg/L 0.5 0.5 Oil and grease (O&G) mg/L 1 10 Ammoniacal Nitrogen (AN) mg/L 10 20 Colour ADMI 100 200

Source: Department of Environmental Quality Act (Industrial Effluents) Regulations 2012

Based on the standard from the other countries, the standard applied in Malaysia should should awared by the surfactant released MBAS discharges, from car wash wastewater adopted with effluents for Standard A and Standard B. 16

2.7 Overview of car wash wastewater treatment

A few number of technologies have been adopted as a treatment for car wash wastewater. The details of the treatment is in Table 2.3 indicates that each treatments has its own different removal efficiency in term concentration of organic and inorganic pollutants via physical-chemical treatments as reviewed (Zayadi et al., 2015).

Table 2.3: Treatment of car wash wastewater

Type of Percentage No Results Parameter Reference treatments removal (%) Ultrafiltration membrane 75 PS-100 75 Panpanit, S. C-100 TOC 75 (2001) C-30 75 Nanofiltration membrane 98 Ultrafiltration membrane 56.1 - 82.4 PVDF 100 Lau, W. J. et PES 30 COD 54.9 - 83.9 al., (2012) 1 Membranes Nanofiltration membrane 70.9 - 91.5 NF 270 TDS 82.2 Shete & TSS 81.1 Ultrafiltration membrane Shinkar COD 67.5 (2014) O&G 75 Non-woven membrane COD 70.2 Hsu et al., filtration with bio- SS 95.7 (2011) carriers Membrane MBR+BAC with dose of COD 95 - 97.5 bioreactor process 2g/L O&G 98.3 - 99 (MBR) with COD 91 - 96.3 2 Tri (2002) biological MBR without BAC activated carbon O&G 95.2 - 97.5 (BAC) process Hydrophilic and Hydrophilic membrane MBAS 85 - 100 Boussu et al., 3 hydrophobic NF270 COD 78 - 98 (2007) membrane Hydrophobic membrane MBAS 53 - 100

Table 2.3 (continued)

NFPES 10 COD 33 78 COD 30 - 61 4 Ultraviolet Perkowski et BOD5 64 - 84 oxidation al., (2006) TOC 25 - 68 Cu (II) 55 Pb (II) 85.5 Hay bales and Zn (II) 65.9 Good et al., 5 grass TSS 85.9 (2011)

3− PO 4 25.3 TSS 69.4 - 90.4 Fe-Fe electrode 65.4 - 79.2 6 Electrochemical Al-Fe electrode COD 39.2 - 48.1 Das (2010) Al-Al electrode 56.2 - 69.2 O&G 80 Fall et al., 7 Oil separator Gravity oil separator TSS 88 (2007) COD 74 Chemical O&G 96 oxidation by COD 93 aeration, alum (80 TDS 74 Bhatti et al., 8 mg/L), waste pH 14 (2011) hydrogen Turbidity 94 peroxide DO 78 (2.5 ml/L) Flocculation TSS 91 column flotation, Turbidity 91 Zaneti et al., 9 sand filtration and TC 95 (2014) final chlorination

Notes: *PS-100= ultrafiltration membrane-polysulfone with molecular weight cut off (MWCO) 100 kDalton, C-100= ultrafiltration membrane-cellulose with MWCO 100 kDalton, C-30= ultrafiltration membrane- cellulose with MWCO 30 kDalton, PVDF 100= Polyvinylidene with 100 kDalton, PES 30= Polyethersulfone with 30 kDalton, NF 270= polyamide with 300 Dalton, NF 270= polyamide with with 170 Dalton (hydrophilic membrane), NFPES 30= polyethersulfone with 1200 Dalton (hydrophobic membrane) *COD= Chemical oxygen demand, TOC= Total organic carbon, TDS=Total dissolved solid, TSS=Total suspended solids,O&G= Oil and grease, BOD5= Biochemical oxygen demand at day 18

3- 5, Cu (II)= Copper, Pb(II)= Lead, Zn(II)= Zinc, PO4 = Phosphate, DO= Dissolved oxygen, TC= Total carbon

Membrane technologies commonly used in wastewater treatment in removing COD, O&G, MBAS, and other biodegradable contaminants (Panpanit, 2001; Boussu et al., 2007; Hsu et al., 2011; Lau et al., 2013; Shete & Shinkar, 2014). The O&G attained removal between 70 % to 80 %, compared with MBAS, COD and else, which above 80 % removal as reviewed in Table 2.3. The O&G was not absorbed directly to the membranes due to the negative charge repulsion between anionic emulsion and membrane surface, hence resulting the inefficiency removal than other pollutants. However, a study by Tri (2002) present the removal above 90 % of O&G with membrane technologies added with biological activated carbon in their study. The aid of the activated carbon in membrane technologies helps in the adsorption of O&G molecules and improved the bioreactor adsorption processes (Tri, 2002). Hydrophilic membrane presents 85 % to 100 % of surfactant, higher removal than hydrophobic membrane 53 % removal onwards (Boussu et al., 2007). The treatment on car wash wastewater in removing O&G also presented with performances of gravity oil separator (Fall et al., 2007) and oil separator (Al-Odwani et al., 2007). Even the removal of O&G removed by gravity and oil separator were above 90 %, however the authors concluded the system does not allow producing an effluent that complies with the discharge limits established in the sewage system (Al- Odwani et al., 2007; Fall et al., 2007). Bhatti et al., (2011) presented study of chemical oxidation in removing pollutant of O&G, COD, TSS and else in car wash wastewater. The chemical oxidation including process of aeration for oil water separation, alum treatment for pollutant removal with aid of hydrogen peroxide. The aeration responsible to separate the oil and water by trapping the O&G by the air bubbles carrying oxygen, resulting 96 % removal percentage of O&G and 93 % of COD. This study concluded, the chemical oxidation processes has potential in reducing the maintenance cost and requires less space without any pH control, yielding an alternative treatment in car wash wastewater treatment. Zaneti et al., (2014) studied on flocculation, filtration and chlorination processes in car wash wastewater. Flocculation allows the removal of organic matters and colours of wastewater. However, the treatment should be furthered studied with 19 the other processes, depends on the proper selection of flocculant and proper designed of system to improve the operations, and proceeed for the next step of treatment. During the chlorination, the chlorine disinfection deactivated the microorganism lives resulting death of different mechanisms. As the results, the coupled system of the treatment effective with removal of TSS, turbidity, TOC were 99 %, 91 %, and 95 %. Overall, the treatment processes as presented in Table 2.3, have highlighted and focused on the organic contaminants removal. However, less alternative towards treatments were made towards MBAS, as it presented as the main cleaning agent of cleaning processes during washing cars. In spite of using conventional methods and simple treatment strategies for car wash wastewater treatment system, a wide range of any low cost potential wastewater treatment should have been investigated and studied. A study in adsorption processes by using activated carbon may offer the advantages in car wash wastewater treatment, as it can removed those organic contaminants. If it is possible in developing other low cost and simple treatment differ from the treatment that have been reviewed, then these treatments may offer many advantages and commercially attracting consumers and developers of car wash stations, and hence contribute to the way of minimizing pollutants of car wash wastewater (Zayadi et al., 2015).

2.8 Production and Properties of Activated Carbon

Activated carbon used extensively for adsorbing contaminants in wastewater treatment. In section 2.8, discussion described on nature of activated carbon surfaces, production processes, various basic properties of activated carbon, low cost adsorbent of agricultural wastes, adsorption test method to characterize the ability of activated carbons to adsorb molecules of different sizes with adsorption equilibria of Langmuir isotherm.

2.8.1 Production of Activated Carbon

Activated carbon has been used for controlling air pollution, water pollution, odors, and environmental protection causing its demands to increase. The term of activated carbon is come from the word “carbon” and “active”. Carbon defined as raw material 20 undergoes carbonization process. Whereas, active is a material in carbon condition which undergoes an activation process to open a pore of surface area to increase adsorption rate of activated carbon (Zayadi et al., 2014). Activation has two phase processes. It requiring burn off decomposition products and enlargement of pores in the carbonized material (Bhatnagar & Minocha, 2006). The source material will be dehydrated and carbonized slowly by heating with temperature ranging of 400 °C and 900 °C in the absence of air, followed by controlled oxidation to activate the carbon. The reactions which occur during activation are of the type shows in Eq. (2.1). The reactions cause solid carbon, C to be converted to gaseous state. Thereby, it creating number of pores in the the carbon, and activation enlarges the pore openings (Cooney, 2000).

퐶 (푠표푙푖푑) + 퐻2푂(푓푙푢푖푑) → 퐻2(푔푎푠) + 퐶푂(푔푎푠)

퐶 (푠표푙푖푑) + 퐶푂2(푔푎푠) → 2퐶푂(푔푎푠) 1 퐶 (푠표푙푖푑) + ⁄2 퐻2푂 (푓푙푢푖푑) → 퐶푂(푔푎푠) (2.1)

Moreover, the adsorption plays significant roles in environment pollution control. The process of adsorption involved the separation of substances from one phase by accumulation and concentration at the surface of another. The processes can take place in solid liquid phase, solid solid phase and solid gas phases. During adsorption processes, the adsorbing phase generally known as the adsorbate. Whereas, the material adsorbed at the surface of the adsorbing phase is the adsorbate. The processes of adsorption was resulted from the universal van der waals reaction and the electrostatic forces interacted between the adsorbate and the atom of the adsorbent surfaces (Kandasamy et al., 2012). Ali et al., (2012) have described about adsorption. Adsorption used as one of the wastewater treatment due to its ease, and inexpensive operation. Adsorption best removed the organic pollutants, which it can be up to 99 % removal. During adsorption, in wastewater treatment, the process occurred between solid adsorbent and wastewater. Adsorbate known as the pollutants being adsorbed whereas, adsorbent is the adsorbing phases (Ali et al., 2012). Zaneti et al., (2011) summarized about the liquid phase adsorption in wastewater. In liquid phase adsorption, the process considering the phenomenon 21 among adsorbing molecules of the liquid molecules with the adsorbent, where the interactions occured between the sorbent and the liquid depend on structural and the solid of sorbent surface. The growth of microorganism, involving the production of biofilm were observed on the surface of activated carbon after being used. Biofilm defined as the accumulation of microorganism onto a surface mainly controlled by the bulk and surface transport phenomena. The substrate must be transported from the bulk liquid to the biofilms outer surface where it has to diffuse into the biofilm for its metabolism. The factors that influence the rate of substrate utilization within a biofilm are substrate mass transport to the biofilm, diffusion of the substrate into the biofilm, utilization kinetics within the biofilm, the growth yield of the substrate and the physical factors affecting the biofilm detachment (Chowdhury et al., 2012). In adsorption, the important factor governing the pollutant adsorption by natural adsorbent is the surface morphological structure. The distribution of pores in activated carbons vary significant depending upon the raw material with Scanning Electron Microscopy (SEM). Figure 2.1 shows, microtube structure of kapok fibre (a), hollow cylindrical tube of bagasse (b), honey combed structure with distinctive wall (c) and closed pore structure of coconut shell (d).

(a) (b)

Figure 2.1: SEM image (a) kapok fibre with 50 µm and 500 magnification (Wahi et al., 2013) (b) sugarcane bagasse activated carbon with 20 µm and 1000 magnification (Devnarain et al., 2002) (c) coal activated carbon and (d) coconut shell activated carbon (Jabit, 2007)

Qureshi et al., (2008) have summarized that activated carbon have vast network of pores with different sizes to bind and detach small and large molecules of pollutants during adsorption processes. Generally, the adsorbents consisting of different porous structures including of micropores (smaller than 2nm), mesopores (between 2 to 50 nm), and macropores (larger than 50 nm). Beside that, the adsorption in micropores of activated carbon commonly is a pore filling processes, where the molecules of atoms or any pollutants was filling the active sites of the pores on the surface of activated carbon. Moreover, the size of adsorbate are comparable with the micropores size. Micropores are very important for aqueous applications such as wastewater treatment, as they are closest in size to many of the target pollutants. Whereas, the mesopores and macropores providing a diffusion pathways to the internal pores and serve as adsorption sites for larger compounds pollutants. However, the more packed closely micropores were much better to access by molecules compared with mesopores and macropores. Hence, large amount of adsorbent pores consisting of micropores were essential in producing the greater adsorption processes towards pollutants (Qureshi et al., 2008). 23

2.8.2 Physicochemical Properties of Activated Carbon

Activated carbon is an excellent adsorbent due to its practical ability in removing pollutants in wastewater commonly. It has strong affinity in binding organic substances in wastewater. However, the activated carbon need to have good properties in term of physical and chemical properties in order to have great active sites during adsrption processes. As reviewed by Qureshi et al., (2008), the physical and chemical or physicochemical properties was described as surface chemistry of activated carbon consisting of iodine number, ash content, yield test, particle density test and else. However, the iodine number and ash content were considered in this study.

2.8.2.1 Iodine number of activated carbon

The adsorption test for iodine is a simple and quick test indicating the surface area of activated carbons (Mutegoa et al., 2014). The iodine number determination measuring the adsorption of iodine from an aqueous solution on the adsorbents. Beside that, iodine number quantify the amount of micropores where it indicates the surface area of activated carbon (Itodo et al., 2010 and Mutegoa et al., 2014). For example, the iodine number was 585 mg/g (Nimje et al., 2013) and 986 mg/g for coconut shell (Das, 2014). Whereas, Martinez et al., (2012) have iodine number within 700 to 1100 mg/g due to the intensified activation condition during preparation, where it produce a wider pore structure of coconut shell activated carbon with high iodine number. Moreover, the iodine number were depends also to their chemical activation processes, requiring the burn off raw material in producing activated carbon (Martinez et al., 2012). Different activated carbon resulting different amount of iodine number where iodine number for sugarcane bagasse were 500 to 1593 mg/g (Journal et al., 2005; Chen et al., 2012; Soussa et al., 2012; Fasoto et al., 2014; Mutegoa et al., 2014; Gaikwad & Mane, 2015), coconut shell within 585 to 1000 mg/g (Martinez et al., 2012; Nimje et al., 2013; Das, 2014) and cassava peel of 543 mg/g (Nimje et al., 2013). Sugarcane bagasse have iodine number of 647.94 to 889.37 mg/g when impregnating with 20 % phosphoric acid (Chen et al., 2012). 24

Gaikwad & Mane (2015) have stated that iodine number of 500 mg/g adsorbed into adsorbent resulting an effective of activated carbon towards adsorption processes. High activated carbon generally, were due to the high degree of activation temperature during preparation of activated carbon. It is because, when the temperature of activation were higher which in ranges of 400 °C to 900 °C, the pores on the surface of activated carbon have enlarged and resulting the forming of new micropores on the surface of adsorbents. Hence, the high iodine number were performing well in removing small sized of pollutants in wastewater, rather than lower iodine number. Moreover, the higher iodine number adsorbed affecting great results in the adsorption process. When many micropores were found on the surface of activated carbon, during the adsorption process between adsorbent and wastewater, the surface of activated carbon itself will not being easily saturated, as it has a large number of available pores to be occupied (Fasoto et al., 2014).

2.8.2.2 Ash content of activated carbon

In producing activated carbon, ash content is an indicator of the quality of an activated carbon. Generally, ash forms due to the high buring of activated carbon and longer contact time during production. When the number of ash content is higher, the decrease in adsorption process happened. The ash will blocked the pores, resulting saturated diffusion towards active binding site of activated carbon, and then lowered the removal efficiency of pollutants during wastewater treatment. Hence, a good activated carbon should have lower in ash content value, and high carbon content to ensure its good results in adsorption processes (Chowdury et al., 2012). The best activated carbon should have lower ash content. The ash content were as followed where, sugarcane bagasse with 18 % and 20 % (Hugo, 2010), 16 % and 27 % (Fasoto et al., 2014), and 15 % (Gaikwad & Mane, 2015). As described by Fasoto et al., (2014), the higher ash content consists mostly higher metal oxides. The metal oxides commonly contaminating the activated carbon itself, hence resulting inefficiency when using in wastewater treatment. The best activated carbon should have low ash contents (Hugo, 2010). This hence, results the ash content of coconut shell with 2 % and 5 % (Nimje et al., 2013; Das, 2014), rice husk and oil cake with 4 % and 6 % respectively (Das, 2014).

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