Bioconversion of Waste Materials to Industrial Products

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Bioconversion of Waste Materials to Industrial

Products Second edition

Edited by

A . M . MARTIN Department of Biochemistry

Memorial University of Newfoundland St John's Canada

m SPRINGER SCIENCE+BUSINESS MEDIA, LLC

First edition 1991 Second edition 1998

© 1998 Springer Science+Business Media New York Originally published by Blackie Academic & Professional in 1998

Typeset in 10/12pt Times by Cambrian Typesetters, Frimley, Surrey

I S B N 978-1-4613-7668-2 I S B N 978-1-4615-5821-7 (eBook) DOI 10.1007/978-1-4615-5821-7

A l l rights reserved. N o part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publishers.

The publisher makes no representation, express or implied, with regard to the accuracy of the information contained in this book and cannot accept any legal responsibility or liability for any errors or omissions that may be made.

A catalogue record for this book is available from the British Library

Library of Congress Catalog Card Number: 97-76802

Printed on permanent acid-free text paper, manufactured in accordance with A N S I / N I S O Z39.48-1992 (Permanence of Paper).

Contents

List of contributors

Preface

Preface to the first edition

Part One: The Principles of Bioconversion of Waste Materials

1 The enzymic treatment of waste materials PETER GACESA and JOHN HUBBLE

1. Introduction 1.2 Factors influencing enzyme use

1.2.1 Sources of enzymes 1.2.2 Enzyme stability

1.3 Application of enzymes 1.3.1 Hydrolases 1.3.2 Nonhydrolytic enzymes

1.4 Enzymes with modified activities 1.4.1 Applications of molecular techniques 1.4.2 Nonaqueous/low water systems

1.5 Conclusions References

2 Processes with immobilized enzymes and cells SEVERIAN DUMITRIU and ESTEBAN CHORNET

xiii

xvii

xix

3

3 3 3 7

12 12 16 19 19 20 24 25

29

2.1 Current status of immobilized enzyme technology 29 2.1.1 Advantages and disadvantages of enzyme and cell immobilization 29 2.1.2 Immobilization of microorganisms or enzymes? 31

2.2 Immobilization procedures 31 2.2.1 Carriers 31 2.2.2 Methods of immobilization 32

2.3 Reactors for immobilized biomaterial systems 54 2.4 Waste conversion in the dairy industry 57

2.4.1 Bioconversion of whey 57 2.4.2 Milk processing 59

2.5 Bioconversion of cellulosic wastes 60 2.5.1 Conversion of cellulose to ethanol 60

2.6 Hemicellulose conversion 61 2.6.1 Conversion of xylose 62

2.7 Bioconversion of starch wastes 62 2.7.1 Simultaneous saccharification and fermentation of starch 63 2.7.2 Recovery of waste glucose solutions 69 2.7.3 Recovery of waste from beet sugar industry 71

VI CONTENTS

2.8 Immobilized enzymes in organic solvents 2.8.1 Bioconversion of lipids

2.9 Waste treatment 2.9.1 Methane bioconversion of wastes 2.9.2 Immobilized cells and waste water treatment

2.10 Immobilized microorganisms in waste gas purification References

3 Solid substrate fermentation: a biotechnological approach

73 76 78 78 83 89 91

to bioconversion of wastes 103 O. PAREDES-L6PEZ, S.H. GUZMAN-MALDONADO and A. ALPUCHE-SOLIS

3.1 Introduction 103 3.2 Critical factors for microbial growth on solid substrates 105

3.2.1 Water activity and moisture 105 3.2.2 Temperature 107 3.2.3 pH 109 3.2.4 Aeration and oxygen transfer 110 3.2.5 Mixing 112

3.3 Microbial growth patterns and control of fermentation 113 3.3.1 Microbial types and inoculum 113 3.3.2 Microbial growth patterns and growth rate 114 3.3.3 Control by physical and nutritional factors 117

3.4 Genetic engineering for biodegradation of lignocellulosic wastes 118 3.4.1 Lignin biodegradation 119 3.4.2 Cellulose bioconversion 123 3.4.3 Practical applications of a lignin biodegradation system 123

3.5 Reactors for solid substrate fermentation 124 3.5.1 Tray fermenter 125 3.5.2 Rotating drum fermenter 126 3.5.3 Packed-column fermenter 126 3.5.4 Auger tube fermenter 127 3.5.5 Helical screw fermenter 127 3.5.6 Fluidized biomass fermenter 127 3.5.7 Miscellaneous types 128

3.6 Fermentation processes and compositional changes 130 3.6.1 SSF processes 130 3.6.2 Some currently practiced SSF processes 132

3.7 Advantages, disadvantages and future prospects of SSF 146 3.7.1 Advantages and disadvantages 146 3.7.2 Futureprospects 147

Acknowledgements 148 References 148

4 Composting processes 154 S.P. MATHUR

4.1 Introduction 154 4.2 Definition and principles of composting 156

4.2.1 Definition 156 4.2.2 Principles 156 4.2.3 Compost feedstocks 157 4.2.4 Requirements of optimal composting 160

4.3 Chemistry and biology of the compo sting process 176 4.4 The technology of composting 178

CONTENTS

4.4.1 Open systems 4.4.2 In-vessel (or reactor confined) systems

4.5 Criteria of compost maturity 4.5.1 C/N ratio 4.5.2 Absence of plant inhibitors 4.5.3 Absence of human pathogens 4.5.4 Other criteria

4.6 Uses of composts 4.7 Summary

References

Part Two: Bioconversion Applications

5 Bioprocessing of agro-residues to value added products V. S. BISARIA

5.1 Introduction 5.2 Characteristics of lignocellulosic materials and their pretreatment

5.2.1 Lignocellulosic materials 5.2.2 Physical and chemical constraints in enzymatic hydrolysis

of cellulose 5.2.3 Pretreatment of lignocellulosic residues

5.3 Properties, production and applications of cellulolytic enzymes 5.3.1 Properties of cellulases 5.3.2 Production of cellulases 5.3.3 Properties of hemicellulases 5.3.4 Production of xylanases 5.3.5 Application of cellulases and xylanases

5.4 Bulk chemicals from cellulose and hemicellulose 5.4.1 Glucose and xylose 5.4.2 Ethanol 5.4.3 Acetone-butanol 5.4.4 2,3-Butanediol

5.5 Future prospects Acknowledgement References

6 Use of photosynthetic bacteria for the production of SCP and chemicals from organic wastes KEN SASAKI, TOHRU TANAKA and SHIRO NAGAI

VB

179 184 184 186 186 186 187 187 188 189

197

197 201 201

204 204 210 210 213 218 219 220 222 222 228 235 236 237 238 238

247

6.1 Introduction 247 6.1.1 General characteristics of photosynthetic bacteria 247 6.1.2 Application of photosynthetic bacteria for SCP and chemical

production from organic wastes 248 6.2 SCP production from waste 250

6.2.1 Pineapple waste 250 6.2.2 Soybean waste 253 6.2.3 Cassava solid waste 254 6.2.4 Mandarin orange peel 256 6.2.5 Swine and cow dung waste 260 6.2.6 Cell yields and composition of PSB 263

6.3 Vitamin production 266 6.3.1 Vitamin B12 266 6.3.2 Ubiquinone 269

VIJI CONTENTS

6.4 5-Aminolevulinic acid production 270 6.4.1 ALA production from swine waste 272 6.4.2 ALA production from sewage sludge 275 6.4.3 ALA production by aerobic fermentation 276 6.4.4 Applications of ALA 278

6.5 Problems and future prospects 288 6.5.1 Problems 288 6.5.2 Future prospects 289

References 290

7 Utilization of starch industry wastes 293 SUDIP K. RAKSHIT

7.1 Introduction 293 7.2 Nature of cereal and tuber starches 293 7.3 Starch-based industrial products 294

7.3.1 Hydrolytic products and sweeteners 295 7.3.2 Food applications 296 7.3.3 Paper industry applications 298 7.3.4 Fermentative products from starch 299

7.4 Extraction procedures and starch industry waste streams 301 7.4.1 General extraction procedure 301 7.4.2 By-product and effluent streams 303

7.5 Utilization and treatment of starch industry wastes 304 7.5.1 Production of single cell proteins 304 7.5.2 Protein extraction from potato processing 308 7.5.3 Energy recovery from liquid streams 309 7.5.4 Miscellaneous 311

7.6 Conclusion 312 References 312

8 Bioconversion of food processing wastes 316 G.TH. KROYER

8.1 Introduction 316 8.2 Characteristics of food processing wastes 317 8.3 Biotechnological processes in food processing waste treatment 318 8.4 Production of biomass from food processing wastes 319 8.5 Meat and fish processing wastes 322 8.6 Fruit and vegetable processing wastes 324 8.7 Dairy industry wastes 329 8.8 Wastes from the fermentation industry 332 8.9 Conclusion and future outlook 333

References 335

9 Bioconversion of cheese whey to organic acids 342 R.D. TYAGI and D. KLUEPFEL

9.1 Introduction 342 9.2 Production of whey 342 9.3 Pollution control 343 9.4 Current disposal methods of whey 344 9.5 Global utilization of whey 346 9.6 Management strategies 346 9.7 Lactic acid 347

9.7.1 Microorganisms involved in lactic acid fermentation 348

CONTENTS

9.7.2 Batch process 9.7.3 Continuous process 9.7.4 Product inhibition in lactic acid fermentation 9.7.5 Immobilized cell process

9.8 Acetic acid and propionic acid 9.9 Conclusions

Acknowledgement References

10 Lignocellulosic wastes: biological conversion P. S. CHAHAL and D. S. CHAHAL

10.1 Introduction 10.2 Composition and structure of lignocelluloses

10.2.1 Cellulose 10.2.2 Hemicelluloses 10.2.3 Lignin 10.2.4 Protein 10.2.5 Extraneous materials

10.3 Pretreatment of lignocelluloses 10.4 Biological conversions

10.4.1 Liquid-state fermentation 10.4.2 Solid-state fermentation

10.5 Utilization of the lignin component of lignocelluloses 10.5.1 Ligninase/ligninolytic enzymes 10.5.2 Production ofligninases

10.6 Problems in bioconversion and future trends References

11 Bioconversion of waste water from the pulp and paper industry K. EL HAIl, V. SACHDEVA and R.D. TYAGI

IX

349 353 357 362 367 371 372 372

376

376 377 379 384 385 388 388 388 388 389 398 409 409 412 415 416

423

11.1 Introduction 423 11.2 Source of effluent from the pulp and paper industry 424

11.2.1 Pulping process 425 11.2.2 Bleaching process 426

11.3 Characteristics of waste water from pulp and paper mills 427 11.3.1 Biodegradable part 427 11.3.2 Wood compounds 428 11.3.3 Parts with difficulty in or absence of biodegradability 429 11.3.4 Toxic substances 430

11.4 Treatment technologies 430 11.4.1 Internal treatment 430 11.4.2 External treatment 432

11.5 Biotechnological applications in the pulp and paper industry 434 11.5.1 Pulp manufacture 434 11.5.2 Bleaching of pulp 435

11.6 Evaluation of the potential for effluent use from the pulp and paper industry in bioconversion 436

11.7 Suitability of spent sulfite liquor for the bioconversion of by-products 437 11.8 Effluent treatment by conversion to by-products 438

11.8.1 Bioconversion of cellulose and lignocellulose materials present in pulp and paper waste waters 439

11.&.2 Production of ethyl alcohol from cellulosic by-products 441 11.9 Major difficulties in bioconversion 443

x

11.10 Conclusions Acknowledgements References

CONTENTS

444 445 445

12 Fisheries waste biomass: bioconversion alternatives A.M. MARTIN

449

12.1 Introduction 449 12.1.1 Antecedents of the recovery of fisheries wastes and by-products 450

12.2 Hydrolytic processes for the recovery of fish protein 452 12.2.1 Enzymatic methods 456 12.2.2 Methods employing microorganisms 457

12.3 Biological methods for the recovery of chitin and chitosan 459 12.4 Biological water treatment of fisheries wastes 463 12.5 Composting of fisheries offal 464 12.6 Other products from fisheries waste biomass 465

12.6.1 Fermentation substrates 465 12.6.2 Enzymes from fish biomass 466 12.6.3 Media for the cultivation of edible mushrooms 467

12.7 Conclusions 469 12.7.1 Present developments 469 12.7.2 Future trends 471

References 471

13 Production of Bacillus thuringiensis biopesticides using waste materials 480 MARIA DE LOURDES TIRADO MONTIEL, RAJESHWAR D.

TYAGI and JOSE R. VALERO

13.1 Introduction 480 13.2 Characteristics of Bacillus thuringiensis 481

13.2.1 Taxonomy 481 13.2.2 Metabolism 482

13.3 Genetic characteristics 483 13.3.1 Localization and organization of crystal producing genes 483

13.4 Toxicity (crystal-spore complex) 484 13.4.1 Characteristics 484 13.4.2 Synthesis 484 13.4.3 Specificity 485 13.4.4 Mode of action 486

13.5 Effect of medium composition and operation conditions on the production of crystal-spore complex 487 13.5.1 Temperature and pH 487 13.5.2 Process options for Bt production 488 13.5.3 Aeration - 490 13.5.4 Mineral elements 491 13.5.5 Nitrogen and amino acids 492 13.5.6 Carbon source 493

13.6 Alternative raw materials for Bt biopesticide production 495 13.6.1 Production of Bt subsp. thuringiensis on alternate protein-rich

raw materials 495 13.6.2 Production of Bt subspecies entomocidus, kurstaki, aizawai,

finitimus and galleriae from various raw materials 496 13.6.3 Production of Bt subsp. israelenis (Bti) using different raw materials 500

13.7 Toxicity determinations - 504 13.7.1 Bioassays 505 13.7.2 Tests in vitro 506

CONTENTS

13.8 Applications of Bt biopesticides 13.8.1 Utilization of Bt for control of lepidopteran pests 13.8.2 Utilization of Bt for control of dipteran pests 13.8.3 Utilization of Bt for control of coleopteran pests

13.9 Conclusions -Acknowledgements References

14 Biorecovery of metals from mining wastes DA VID S. HOLMES

14.1 Historical perspective 14.2 Significance of biomining 14.3 Copper dump bioleaching

14.3.1 Economics of dump bioleaching 14.3.2 Microbiology 14.3.3 Problems 14.3.4 Technical solutions

14.4 Heap bioleaching 14.5 Concentrate bioleaching 14.6 In situ bioleaching 14.7 Uranium bioleaching 14.8 Bio-oxidation of gold ore

14.8.1 Principles 14.8.2 Opportunities

14.9 Development of new strains of microorganisms 14.9.1 Introduction 14.9.2 Fauna and flora of a bioleaching operation 14.9.3 Isolation of new strains from the environment 14.9.4 Selection and adaptation of naturally occurring strains 14.9.5 Classical genetic mutation 14.9.6 Genetic engineering

14.10 Conclusions 14.11 Summary Acknowledgements References

Index

Xl

507 507 508 508 509 509 510

517

517 518 519 521 522 526 526 527 527 528 528 529 529 532 533 533 533 537 537 539 539 540 542 542 542

547

Contributors

A. Alpuche-Solis

V.S. Bisaria

D.S. Chahal

P.S. Chahal

E. Chornet

S. Dumitriu

K. El Haji

P. Gacesa

Depto. de Biotecnologia y Bioquimica, Unidad Irapuato, Centro de Investigaci6n y de Estudios Avanzados del lPN, Apdo. Postal 629, 36500 Irapuato, Gto., Mexico

Department of Biochemical Engineering and Biotechnology, Indian Institute of Technology - Delhi, Hauz Khas, New Delhi - 110 016, India

DC Enterprises, Inc., 3979 Acadia, Laval, Quebec, Canada, H7T IG3

Biotechnology Research Institute, National Research Council of Canada, 6100 Royalmount Avenue, Montreal, Quebec, Canada, H4P 2R2

Department of Chemical University of Sherbrooke, Quebec, Canada, J1K 2Rl

Department of Chemical University of Sherbrooke, Quebec, Canada, J1K 2Rl

Engineering, Sherbrooke,

Engineering, Sherbrooke,

Institut National de la Recherche Scientifique, Universite du Quebec, INRS-Eau, 2700 rue Einstein, CP 7500, Sainte-Foy, Quebec, Canada, G 1 V 4C7

Faculty of Science and Manchester Metropolitan Manchester Ml 5GD, UK

Engineering, University,

S.H. Guzman-Maldonado Depto. de Biotecnologia y Bioquimica, Unidad Irapuato, Centro de Investigaci6n y de Estudios Avanzados del lPN, Apdo. Postal 629,36500 Irapuato, Gto., Mexico

XIV

D.S. Holmes

J. Hubble

D. Kluepfel

G. Th. Kroyer

A.M. Martin

S.P. Mathur

S. Nagai

O. Paredes-Lopez

S.K. Rakshit

V. Sachdeva

K. Sasaki

T. Tanaka

CONTRIBUTORS

Department of Biological Sciences, University of Santiago, Avda. Bernardo O'Higgins, Santiago, Chile

School of Chemical Engineering, University of Bath, Claverton Down, Bath, BA2 7AY, UK

Institut Armand-Frappier, 531 boul. Des Prairies, CP 100, Succ. L-Q-R, Ville de Laval, Quebec, Canada, H7N 4Z3

Institute of Food Chemistry and Technology, Technical University Vienna, Getreidemarkt 9, A-1060 Vienna, Austria

Department of Biochemistry, Memorial University of Newfoundland, St John's, Newfoundland, Canada, AlB 3X9

Compost & Peat Specialist, Inc., 169 Castlefrank Road, Kanata, Ontario, Canada, K2L 1T3

Yaegaki Research Institute, Mukudani, Hayashidacho, Himeji 679-42, Japan

Depto. de Biotecnologfa y Bioqufmica, Unidad Irapuato, Centro de Investigacion y de Estudios Avanzados del lPN, Apdo. Postal 629,36500 Irapuato, Gto., Mexico

Bioprocess Technology Program, Asian Institute of Technology, PO Box 4, Khlong Luang, Pathum Thani 12120, Thailand

Institut National de la Recherche Scientifique, Universite du Quebec, INRS-Eau, 2700 rue Einstein, CP 7500, Sainte-Foy, Quebec, Canada, G1V 4C7

Material Science and Engineering, Graduate School of Hiroshima, Denki Institute of Technology, Nakano, Akiku, Hiroshima 739-03, Japan

Cosmo Research Institute, Gongendo, Satte, Saitama 340---01, Japan

CONTRIBUTORS xv

M. de L. Tirado Montiel Comisi6n Nacional del Agua, 15 Poniente 1317, Puebla, Pue., Mexico, CP 72000

R.D. Tyagi Institut National de la Recherche Scientifique, Universite du Quebec, INRS-Eau, 2700 rue Einstein, CP 7500, Sainte-Foy, Quebec, Canada, G 1 V 4C7

J.R. Valero Laurentian Forestry Center, 1055 rue du PEPS, PO Box 3800, Sainte-Foy, Quebec, Canada, G 1 V 4C7

Preface

The general objectives of the first edition of this book, published in 1991, still remain valid. The existence of pollution-associated problems created by wastes, the scarcity of places to dispose of the wastes and the need to save valuable resources which are part of the refuse of modern society are universally acknowledged. Recycling, which could contribute to solving some of the most serious problems affecting human economic performance at present and in the future, is gaining appreciation as a viable commercial activity. Since the publication of the first edition of this book, increased recognition has been given to bioconversion of wastes as one of the most appropriate methods to return to the environment resources previously extracted from it.

This book is designed as a study of the biotechnological methods for the recovery of wastes. As its name indicates, it emphasizes the recycling objective of the bioconversion, i.e. the production of industrial products from wastes. The chapters deal with the scientific and technological bases of the bioconversion processes involved, the problems and advantages associated with each, the products arising from the operations, and trends and future possibilities.

Although relatively few years have passed from the publication of the first edition, accelerated advances in the areas to which this book is devoted have resulted in a significant overhaul of the book's content. In addition to updating the information presented, a new edition provides the opportunity to review the work done previously, and to try to add to it. As a consequence, most of the chapters in the first edition have been thoroughly revised, some of them becoming completely new chapters. Also, some subjects not included in the first edition have been added.

The contents of the book have been organized into two parts. The chapters in Part One are oriented more towards the principles of the bioconversion operations, while the chapters in Part Two consider the characteristics of the main groups of waste materials, and specific technologies for their bioprocessing and the production of valuable products.

As was indicated in the first edition, although a single book cannot cover all of the areas of such a large and expanding field, this book will provide useful and up-to-date information to the academic, industrial and scientific communities. The inclusion of technological examples should illustrate, to those working on the solution of waste disposal problems as administrators,

xviii PREFACE

consultants or in government, the advantages and potential of bio­conversion methods.

Antonio M. Martin St John's, Newfoundland Canada

May 1997

Preface to the first edition

When focusing on the latest stages of human development, many factors have been long identified as representative of both mankind's successes and failures. Industrialization, rising standards of living and the exploita­tion of new materials and energy sources, while characteristics of progress, are also a source of new problems such as overpopulation, increased urbanization, the energy crisis and pollution, to mention only a few. More recently, the problem of wastes from processing operations and their disposal has gained full-fledged public recognition.

In the past, problems associated with wastes were not given special treatment by society, and generally they were recognized as specific problems of the institutions which generated them: cities, industries, and agriculture. Indeed, before the advent of the modern chemical and processing industry of the present century, most of the wastes were recycled, and before the population explosion of the last decades, it appeared that there was enough space on eath to simply dump wastes and allow nature to dispose of those which were biodegradable.

This situation is no longer sustainable. There is increasing recognition of the pollution-associated problems created by wastes, the scarcity of places to dispose of them, and the need to save the valuable resources which are part of the refuse of our present 'throwaway' society. The recycling of resources is becoming a valid and viable economic activity and is increasingly mentioned as a solution to some of the most pressing problems which will affect mankind's future economic performance.

Bioconversion of wastes has been the natural way to return to the environment the resources previously extracted from it. It is expected that the development of biotechnology will facilitate the acceleration of this natural recycling process, which is being made necessary by our present and future levels of popUlation densities and their increasing demands.

This book is designed as a study of the biotechnological methods for the recovery of wastes, emphasizing the recycling objective of the bio­conversion, i.e. the production of industrial products from wastes. In conducting this study, it is this book's objective that its various chapters deal with the scientific and technological bases of the bioconversion processes involved, the problems and advantages associated with each, the products arising from the operations, and future trends and possibilities. If relevant to their content, individual chapters also deal with processing methods required to concentrate and purify the complex mixture of waste

xx PREFACE TO FIRST EDITION

materials, applied before the biological step ('upstream' operations), and present an overview of the economic basis for the bioconversion process discussed.

This book is not intended to be a specialized study of the biodegradation processes involved, which will be presented in a second volume currently being prepared. Although the bioconversion processes have been traditionally applied to products of biological origin, such as agricultural, fisheries, forestry and food processing wastes, the present volume also deals with areas where novel bioconversion processes are also applicable, such as some mineral- and hydrocarbon-based industrial operations.

The contents of the book have been organized in two sections. Chapters in Section 1 are oriented more toward the principles or fundamentals of the bioconversion operations, while Chapters in Section 2 consider the characteristics of the main groups of waste materials and the specific technologies for bioprocessing and recycling them.

This book cannot cover all of the areas of a presently increasing, expanding field of research. However, it is expected that this book will provide useful and updated information to the academic, industrial and scientific communities, including ecologists and environmentalists. By including technological examples which will allow and encourage the use of bioconversion methods for the solution of waste disposal problems, this book could act as a guide to administrators, consultants, and governments.

Antonio M. Martin