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High-Yield Catalysed Organosolv Pulping of Non-Wood Fiber Sources

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High-Yield Catalysed Organosolv Pulping of Non-Wood Fiber Sources HIGH-YIELD CATALYSED ORGANOSOLV PULPING OF NON-WOOD FIBER SOURCES by DOMTNGGUS YAWALATA Ir., Pattimura University, 1987 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES (Faculty of Forestry) (Department of Wood Science) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA January 1996 © Dominggus Yawalata In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of The University of British Columbia Vancouver, Canada Date DE-6 (2/88) ABSTRACT Global demand of pulp, paper and paperboard increases by the year. In contrast, shortages in wood supply were reported in many countries. On the other hand, large quantities of available non-wood fibrous materials are under-utilized. Furthermore, reduction of the environmental impacts by the pulp industries is now enforced in many parts of the world. Diversification of the raw material to non-wood fiber sources and introduction of new pulping and bleaching technologies, which are environmentally friendly, are seen as alternatives to alleviate the problems mentioned above. Therefore, in this study neutral alkali earth metal (NAEM) salt catalysed organosolv pulping was used to pulp some non- wood fibrous materials (sugarcane rind, sisal and tebu-tebu), in addition to spruce (softwood) and mangrove (hardwood). The bleaching agent employed was alkaline acetone peroxide, a TCF (totally chlorine-free) bleaching process. Under the specified pulping conditions, the screened pulp yields were 56 %, 58 %, 54 %, 63 % and 47 % for spruce, mangrove, sugarcane rind, sisal and tebu-tebu, respectively. In using flow-through and batch cooking, the type of cook did not affect the pulp yield of mangrove and sugarcane rind but affected that of spruce, sisal and tebu-tebu. The pulp yield of spruce was higher (^ 5 %) in batch type of cooks than in percolation type of cooks, but that of sisal and tebu-tebu was slightly lower (^ 3 %) in the batch type of cooks. Contrary to expectations, the rate of deUgnification was found to be higher in batch type cooks for all species. Therefore, the cooking times required to achieve fiber liberation were found to be shorter in batch type of cooks than in percolation type of cooks. The total cooking time required to liberate the fibers in batch cooks was only 25 to 30 min for mangrove and all non-wood fibers, and 40 min for spruce. Surprisingly, it was found that complete fiber liberation, as per definition used in this study (less than 1 % screen rejects), could not be obtained in percolation type cooking of spruce although the cook had been extended to 90 min. In a 60 min cook, 96.4 % of all fibers were liberated. ii Employing extended cooking beyond the fiber liberation point in NAEM pulping remarkably reduced the Kappa numbers at the expense of pulp yield and viscosity. On interrupting the process at fiber liberation provides maximum fiber yield. In addition, pulping to fiber liberation (high yield) is justified by the fact that the NAEM pulps were found to be easily bleachable even at high Kappa number (> 50). This is demonstrated by the TCF bleaching trial in this study. Furthermore, the non-wood pulps were easier to bleach than the softwood (spruce). Bleachability of the pulps was species dependent. In this series, softwood (spruce) was found to be the most difficult to bleach. Brightness, viscosity and degree of deUgnification were found to be affected by the concentration of hydrogen peroxide, acetone, alkali (KOH) charge and pulp consistency. The presence of acetone, especially at 50 % concentration by weight, in the bleaching system was found to improve the brightness and degree of deUgnification, and possibly to some extent, reduced the degradation of the fibers. The strength properties of the pulps varied by species and were somewhat affected by the bleaching process. Spruce pulp was found to be the strongest pulp among the selected species, while sugarcane rind was the strongest and sisal the weakest pulp among the non-wood pulps. Bleaching was found to improve the tensile strength of wood pulps but reduced that of the non-wood fiber pulps. Bleaching also reduced the tear and burst strengths and folding endurance of spruce and all non-wood pulps. The strength losses were more severe for the non-wood pulps and less so for the wood (spruce) pulp. Folding endurance was affected most by bleaching among the other strength properties. The bleaching conditions applied in this study were not fully optimized. On comparing these results with some literature values of the strength properties for the species pulped by the NAEM process, it can be concluded that the NAEM process can produce non-wood pulps as good as, or even better than, those produced by the conventional pulping processes (kraft or soda). Except for spruce, for which the strength values are between sulfite and kraft pulps of the same species. iii TABLE OF CONTENT ABSTRACT ii TABLE OF CONTENT iv LIST OF TABLES vii LIST OF FIGURES viii ACKNOWLEDGEMENT ix 1.0. INTRODUCTION 1 2.0. LITERATURE REVIEW 6 2.1. Non-Wood Fiber Sources : Properties and Uses 6 2.1.1. Sugarcane rind (bagasse) 7 2.1.2. Sisal 10 2.1.3. Straw 11 2.1.4. Kenaf 12 2.2. Chemical Constituents of Lignocellulosics and Their Distribution in the Cell Wall 13 2.2.1. Lignin 15 2.2.2. Cellulose 16 2.2.3. Hemicelluloses 17 2.3. Organosol Pulping 18 2.3.1. Alcohol-based solvent pulping 19 2.3.1.1. Acidic alcohol-based solvent pulping 20 2.3.1.1.1. ALCELL process 26 2.3.1.2. Alkaline alcohol-based solvent pulping 28 2.3.1.2.1. ASAM process 29 2.3.1.2.2. ORGANOCELL™ process 32 2.3.2. Other solvent pulping processes 34 2.4. Organosotv Pulping of Non-Wood Fibers 34 2.5. Chemical Pulp Bleaching 37 2.5.1. Hydrogen p eroxide bleaclung 39 2.5.2. Bleaching by p eracids 44 2.5.3. Dimethyldioxirane (DMD) bleaching 46 2.6. Paper Strength Properties 50 iv 3.0. MATERIALS AND METHODS 54 3.1. Organosolv Pulping 54 3.1.1. Materials 54 3.1.1.1. Raw materials 54 3.1.1.2. Cooking liquor 55 3.1.2. Methods 55 3.1.2.1. Chemical analyses for raw materials 55 3.1.2.1.1. Klason lignin (Acid-insoluble lignin) 55 3.1.2.1.2. Acid-soluble lignin 56 3.1.2.1.3. Holocellulose 57 3.1.2.1.4. Alpha-cellulose 58 3.1.2.2. Organo solv pulp prep aration 58 3.1.2.2.1. Pulping procedure 58 3.1.2.2.1.1. Batch system 59 3.1.2.2.1.2. Percolation system 60 3.1.2.2.2. Pulp Washing 61 3.1.2.2.3. Pulp Screening 61 3.1.2.3. Chemical analyses for organosolv pulp 62 3.1.2.3.1. Kappa number 62 3.1.2.3.2. Viscosity 63 3.1.2.3.3. Alpha-cellulose 64 3.2. Organosolv Bleaching 65 3.2.1. Materials 65 3.2.2. Bleaching procedure 65 3.3. Paper Properties Testing 68 3.3.1. Materials 68 3.3.2. Methods .' 68 4.0. RESULTS 69 4.1. Organosolv Pulping 69 4.1.1. Chemical composition of raw materials 69 4.1.2. Pulp yield and chemical composition 70 4.1.3. Degree of delignification and carbohydrate recovery 72 4.1.4. Behavior of pH 75 4.2. Organosolv Bleaching 76 4.2.1. Single-A-stage bleaching sequence 76 4.2.2. Multiple-A-stage bleaching sequence 81 4.3. Paper Strength Properties 82 4.4. Fiber Length Measurement 88 5.0. DISCUSSION 91 5.1. High-Yield Chemical Pulp .91 5.1.1. Raw material 91 v 5.1.2. Reference pulping process and conditions 92 5.1.3. Organosol pulping 93 5.1.4. Effect of NAEM cooking variables 97 5.2. DeUgnification 99 5.3. Extended Cooking 107 5.4. Batch Versus Percolation Type of Cook 110 5.5. A Separate Pulping Trial Ill 5.6. Acetone Peroxide Bleaching Ill 5.6.1. Bleached pulp brightness 113 5.6.2. Degree of dehgiufication 115 5.6.3. Bleached pulp viscosity 116 5.6.4. The role of acetone 117 5.6.5. Comparative bleachability of different pulp species 117 5.7. Strength Properties of High Yield Organosol Pulp 121 5.7.1. Beatability and effect of beating 121 5.7.2. Effect of bleaching 123 5.7.3. Effect of fiber length 124 5.7.4. Comparative strength properties of different fiber sources . 126 6.0. CONCLUSIONS 129 REFERENCES 132 vi LIST OF TABLES 1. Fiber dimensions of some woods 6 2. Fiber dimensions of some non-wood plants. 7 3. Chemical composition of some lignocellulosic materials 14 4. Cooking conditions of ASAM pulping process 30 5. Cooking conditions of the modified ORGANOCELL process 33 6. Peracids 45 7. Chemical composition of the raw materials 69 8. Pulp yield and chemical analyses of the pulps from batch type cooks 70 9. Pulp yield and chemical analyses of the pulps from percolation type cooks 71 10.
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