Biotechnology for Environmental Protection in the Pulp and Paper Industry PDF
Preview Biotechnology for Environmental Protection in the Pulp and Paper Industry
Biotechnology for Environmental Protection in the Pulp and Paper Industry Springer Berlin Heidelberg New York Barcelona Budapest Hong Kong London Milan Paris Singapore Tokyo Dr. PRATIMA BATPAI Dr. PRAMOD K. BATPAI Thapar Corporate Research & Development Centre Chemical Engineering Division PO Box 68 147001 Patiala India Professor Dr. RYUICHIRO KONDO Kyushu University Department of Forest Products Faculty of Agriculture Hakozaki, Higashi-ku 812-8581 Fukuoka Japan ISBN-13: 978-3-642-64271-5 Library of Congress Cataloging-in-Publication Data Bajpai, P. (Pratima) Biotechnology for environmental protection in the pulp and paper industry 1 Pratima Bajpai, Pramod K. Bajpai, Ryuichiro Kondo. p. cm. Includes bibliographical references. ISBN-13: 978-3-642-64271-5 e-ISBN-13: 978-3-642-60136-1 DOl: 10.107/978-3-642-60136-1 I. Wood-pulp - Biotechnology. 2. Wood-pulp industry - Environmental aspects. 3. Paper industry - Environmental aspects. 4. Paper chemistry. I. Bajpai,'Pramod K. II. Kondo, Ryuichiro, 1949- _ III. Title. TS1l76.6.B56B35 1999 676'.042 -dc21 99-30761 This work is subject to copyright. All rights reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Vedag_ Violations are liable for pros ecution under the German Copyright Law. © Springer-Vedag Berlin Heidelberg 1999 Softcover reprint of the hardcover 1st edition 1999 The use of general descriptive names, registered names, trademarks, etc. in the publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: Design & Production, Heidelberg Typesetting: Best-set Typesetter Ltd., Hong Kong SPIN 10693384 30/3136 - 5 4 3 2 1 0 - Printed on acid-free paper P. Bajpai . P.K. Bajpai . R. Kondo Biotechnology for Environmental Protection in the Pulp and Paper Industry With 27 Figures and 104 Tables Springer Acknowledgements We are grateful to Professor Kokki Sakai for his constant support and encour agement in the execution of this project. Our heartfelt gratitude goes to Mr. Koki Fujita for his assistance in a number of tasks in the preparation of this manuscript. We would also like to express our thanks to Dr. I. Reid for sug gesting a few good topics for this book. We offer our sincere thanks to the friends and organizations who provided us with information on the latest advances in their respective areas. Sincere appreciation is extended to Ms. Chie Takatsuka, Ms. Chie Ishihara, and Ms. Hirano Makiko for their help in word processing in the early stages of the preparation of the manuscript and to Mrs. Katsuko Mori for secretarial assistance. We would like to thank all the students/research scholars of the Wood Chemistry, Forest Products Department of Kyushu University for their help and cooperation. PKB and PB wish to express their particular gratitude to Professor M.P. Kapoor for granting them sabbatical leave to work at Kyushu University, and for supporting them on every step of the way. We were lucky to have numer ous peoples' help with various parts of this work. We are grateful to Mr. S.S. Gill for his invaluable help in word processing in the final stages of prepara tion. Also to Mr. A. Sappal and Mr. S.N. Sharma for their help in typing some chapters. The valuable help provided by Mr. S.S. Saini and Mr. B.c. Saini in preparing the drawings and figures and by Mr. S.P. Mishra, Mr. O.P. Mishra and Mr. Sanjay Kumar in proofreading and general organization are gratefully acknowledged. Our thanks also go to many others who gave us permission to use drawings and other illustrative material. Finally, we thank Springer-Verlag for their efforts in publishing the book. P. BAJPAI, P.K. BAJPAI, and R. KONDO Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2 Wood Pretreatment to Remove Toxic Extractives. . . . . . . . . . . . . . . . 13 3 Biopulping: a Less Polluting Alternative to CTMP . . . . . . . . . . . . . . . 29 4 Pulp Bleaching with Xylanases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 5 Pulp Bleaching with White Rot Fungi and Their Enzymes. . . . . . . . 65 6 Enzymatic Deinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 7 Treatment of Wastewaters with Anaerobic Technology. . . . . . . . . . . 109 8 Decolorization and Detoxification of Bleached Kraft Effluents. . . .. 141 9 Purification of Process Water In Closed-Cycle Mills. . . . . . . . . . . . . 171 10 Management of Wastewater Treatment Sludges.. ... .. . .. . .. .. . . 209 11 Biofiltration of Exhaust Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 239 Subject Index.. ... . . .. . . . ... ... . .. . .. . . . .. .. . .. ... .. . .. .. . 263 1 Introduction The pulp and paper industry comprises a large and growing portion of the world's economy. Pulp and paper production has increased globally and will continue to increase in the near future. Approximately 155 million tons of wood pulp are produced worldwide and about 260 million are projected for the year 2010.1 However, the industry is very capital-intensive, with small profit margins, which tends to limit experimentation, development, and incorpora tion of new technologies into the mills. To be able 'to cope with increasing demand, an increase in productivity and improved environmental perfor mance is needed, as the industry is also under constant pressure to reduce and modify environmental emissions to air and water. In the US, the pulp and paper industry ranks third, after primary metals and the chemical industry, in terms of freshwater withdrawal. It is believed that by the year 2000, the paper industry will have become the largest manufacturing user of water.2 However, the industry ranks fifth among the major industries in its contribution to the water-pollution problem, having thus had significant impact on the nation's streams; but the situation is improving rather than growing worse. Since 1976, many mills have built secondary biological waste treatment plants, by 1991,99% of the pulp and paper industry in US had sec ondary treatment or its equivalent. The fact that the majority of the mills have wastewater treatment has had a visible beneficial effect on water quality. Like any other large-scale industry, the pulp and paper industry exerts its own impact on the environment. Although the situation is improving year by year, pulp mills still release unpleasantly smelling sulfur compounds into the air and discharge wastewaters which enhance eutrophication and have toxic effects on the surrounding biota. Organochlorine compounds formed during the bleaching of chemical pulp have attracted most attention in recent years. Environmental Regulations While not all AOX (adsorbable organic halides) compounds are harmful to health or the environment, a number of them have been determined to be so. Rather than single out the harmful constituents of AOX for regulatory pur poses, regulatory agencies in Canada and Scandinavian countries have used AOX as the measure by which to set limits on different discharges. Such regu lations have forced the pulp and paper industry in Europe, Canada, and Japan, 2 1 Introduction and recently in the USA3 also, to reduce AOX discharges through a combina tion of process modifications and effluent treatment technologies. Europe While environmental regulations provided the impetus for the drive towards AOX reduction, today it is market force which is sustaining it. The Scandina vian industry today is moving beyond AOX reduction as a solution, and working towards total elimination of effluent discharge as the long-term solu tion to environmental problems. The Scandinavian pulp and paper industry is thoroughly convinced of the need to reduce and even eliminate AOX discharges. It does not require pressure from environmental regulations to spur it. In Sweden, the Licensing Board for Environmental Protection is an autonomous body responsible for setting the terms and conditions for grant ing of environmental permits. The board takes into account ecological, tech nological, and economical factors in setting the terms for permits. Regulatory limits for pulp and paper mills are set on an individual, case-by-case basis. As such, there is no set of effluent limits for the industry as a whole. However, the regulations are fairly similar for mills that produce a similar product; conse quently, from an exhaustive survey of discharge limits in place at the various mills, one can determine allowable discharge levels for mills producing differ ent products. In general terms, Table 1.1 lists the limits for discharges from pulp mills in Sweden.4 Regulations required that by the end of 1995, all mills decrease their emissions of organic chlorine to 1 kg/ton for softwood kraft pulp, and 0.5 kg/ton for sulfite or hardwood kraft pulp, which has been further reduced to 0.5 and 0.3 kg/ton, respectively. Table 1.1. Regulatory emission limits for Swedish pulp mills Parameter Discharge limit (kg/ton pulp) 1991 1995 1999 BODs 10-20 COD 10-20 TSS 40-70 TOCI Softwood 2.0 1.0 0.5 Hardwood 1.0 0.5 0.3 AOX Softwood 2.5 Hardwood 1.3 Nitrogen 0.3 Phosphorus 0.1 Based on data from Ref. 4. Environmental Regulations 3 In Finland, regulatory trends in general have closely followed those in Sweden. The AOX discharge has steadily decreased from 3.7 kg/ton in 1989 to less than 1 kg/ton by 1995. Effluent discharge limits in Norway are imposed and permits granted by the State Pollution Control Authority on a mill-by-mill basis, based on the condi tions of the receiving body of water, with limits being stricter for discharge to lakes and. fjords than to the sea. Effluent regulations in Germany are set up by the Ministry of Environment, based on recommendations by various experts. The enforcement of the regu lations is through the levying of what is known as discharge fees. Mills that exceed the discharge limits set by the regulations are liable to pay the discharge fees. The effluent limits for pulp and paper mills in Germany are given in Table 1.2.5 French regulations do not have AOX standards or discharge limits; however, mills are expected to measure their AOX discharge levels periodically. The reg ulations do set discharge limits for TSS, BODs, and··COD for pulp and non integrated paper mills. Portugal has specific emission limits for discharges to water from pulp and integrated paper mills as shown in Table 1.3.5 Regulations for general chemi cal industries are applicable to nonintegrated paper mills. In Austria, the AOX discharge limit was fixed at O.75-1.5kg/ton in 1994, which has been further reduced to O.5-1.0kg/ton after 1995.6 Table 1.2. Regulatory emission limits for pulp and paper mills in Germany Mill type Discharge limit (kg/ton) BODs COD AOX Paper Mills Wood-free unsized 3 0.04 Wood-free sized 2 6 0.04 Wood-free highly refined 3 9 0.04 Wood-free coated 2 0.02 Wood-containing 3(5)" 0.01 Recycle fiber-based 5 0.012 Chemical pulp mills 5b 70b 1.0 "COD of 5 kg/ton when >50% of pulp is TMP, or when a substantial part of the pulp is bleached with peroxide. b24-h composite samples. Based on data from Ref. 5. 4 1 Introduction Table 1.3. Discharge limits for pulp and integrated paper mills in Portugal Mill type Discharge limit (kg/ton) TSS BODs COD AOX Unbleached kraft pulp - 1991 2.5 5 1996 1.5 3 35 Bleached kraft pulp 1991 10 9 1996 3 6 50 1.5 Bleached sulfite pulp 1991 12.5 45 1996 6 25 120 1.5 Integrated kraft liner 1991 4 6 1996 2 4 30 Based on data from Ref. 5. Table 1.4. AOX discharge limits in Canada Province Year AOX limit (kg/ton) Ontario 1991 2.5 British Columbia 1992-1993 2.5 (Softwood) 3.8 (Hardwood) Quebec 1992 2.5 (Softwood) 1.5 (Hardwood) 1995 1.5 (Softwood) 0.5 (Hardwood) Based on data from Ref. 7. North America Canada, though behind Scandinavia in achieving AOX reduction goals, is aggressively setting targets and demanding that its pulp and paper industry meet them. Tables 1.4 and 1.5 summarize the salient points of regulations by the various provinces.7 The regulations developed by British Columbia (Table 1.5) are the most stringent in the country. Very similar regulations are being developed by Ontario. the United States did not have specific discharge limits on AOX, but did have a limit on dioxin discharge. The Clean Water Act of 1987 listed dioxin as a toxic compound. In an exhaustive study of 104 US bleached pulp mills in 1988-1989, the EPA measured concentrations of 2,3,7,8-TCDD and 2,3,7,8- TCDF in the effluents. A further in-depth study of 25 mills resulted in the con-
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