Handbook of Pulp Edited by Herbert Sixta

Handbook of Pulp. Edited by Herbert Sixta Copyright 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30999-3

Further of Interest
H. Holik (Ed.)

Handbook of Paper and Board

2006, ISBN 3-527-30997-7

Handbook of Pulp

Edited by Herbert Sixta

Editor Dr. Herbert Sixta Lindenweg 7 4860 Lenzing Austria

&

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at <http://dnb.ddb.de>. 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Printed in the Federal Republic of Germany. Printed on acid-free paper. Cover Grafik-Design Schulz, Fugnheim Typesetting Khn & Weyh, Satz und Medien, Freiburg Printing Strauss GmbH, Mrlenbach Binding Litges & Dopf Buchbinderei GmbH, Heppenheim ISBN-13: ISBN-10: 978-3-527-30999-3 3-527-30999-3

This book is dedicated to my friend and teacher, Professor Dr. Dr. h.c. Josef (Joe) S. Gratzl.

VII

Contents
Preface XXIII XXVII XXIX

List of Contributors List of Abbreviations

Volume 1 Part I 1 1.1 1.2 1.3 1.4 1.5 2 2.1 2.1.1 2.1.1.1 2.1.1.2 2.1.1.3 2.1.1.4 2.1.1.5 2.1.2 2.1.2.1 2.1.2.2 2.1.2.3 Chemical Pulping 1 Introduction 3 Herbert Sixta Introduction 3 The History of Papermaking 4 Technology, End-uses, and the Market Situation Recovered Paper and Recycled Fibers 14 Outlook 15 Raw Material for Pulp 21 Gerald Koch Wood 21 Chemical Composition of Wood 22 Cellulose 23 Hemicelluloses 28 Lignin 30 Extractives 33 Inorganic Components 39 Wood Structure and Morphology 41 Ultrastructure and Distribution of Cell Wall Components 41 Lignification of the Cell Walls 44 Functional Elements of the Conducting System 46

Handbook of Pulp. Edited by Herbert Sixta (Ed.) Copyright 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30999-3

VIII

Contents

2.1.3 2.1.3.1 2.1.3.2 2.1.3.3 2.1.3.4 2.1.3.5 2.2 2.2.1 2.2.2 3 3.1 3.2 3.2.1 3.2.1.1 3.2.1.2 3.2.1.3 3.3 3.3.1 3.3.2 3.3.3 3.3.4 3.3.5 3.4 3.4.1 3.4.2 3.4.3 3.5 3.6 3.6.1 3.6.2 3.6.3 3.6.3.1 3.6.4 3.6.4.1 3.6.4.2 4 4.1 4.2 4.2.1 4.2.2

The Microscopic Structure of Wood 48 Cell Types 48 Softwood and Hardwood Structure 50 Reaction Wood 54 Juvenile Wood 56 Secondary Changes 56 Outlook 59 Nano-structure of Fibers 59 Topochemical Distribution of Lignin and Phenolic Extractives 61 Wood Yard Operations Jrg B. Ressel 69

Raw Material Storage 69 Debarking 71 Debarking Methods 72 Drum Debarker 72 Rotary Debarker 76 Ring Debarkers 77 Chipping and Screening 79 Disc Chipper 80 Drum Chipper 84 The Andritz HQ-Sizer and Rechipper 86 Chip Conditioner 87 Chipper Canter Line: Profiling Line in Softwood Sawmills Chip screening 89 Mechanical Screening 89 Wind Screening 93 Air Density Separator (ADS) 94 Process Control and Automation 95 Transport and Handling Systems 95 Log Handling 97 Stationary Conveyor Systems 97 Chip Storage 98 Chip Storage Systems 101 Wood Yard Losses and Waste Reduction 104 Specific Causes of Waste Generation 105 Pollution Prevention Options 105 Chemical Pulping Processes 109 Herbert Sixta, Antje Potthast, Andreas W. Krotschek Introduction 109 Kraft Pulping Processes 111 General Description 111 Kraft Cooking Liquors 113

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IX

4.2.3 4.2.3.1 4.2.3.2 4.2.3.3 4.2.3.4 4.2.3.5 4.2.3.6 4.2.3.7 4.2.3.8 4.2.4 4.2.4.1 4.2.4.2 4.2.4.3 4.2.4.4 4.2.4.5 4.2.5 4.2.5.1 4.2.5.2 4.2.5.3 4.2.6 4.2.6.1 4.2.6.2 4.2.6.3 4.2.7 4.2.7.1 4.2.7.2 4.2.8 4.2.8.1 4.2.8.2 4.2.8.3 4.3 4.3.1 4.3.2 4.3.3 4.3.4 4.3.4.1 4.3.4.2 4.3.4.3 4.3.5

Mass Transfer in Kraft Cooking 122 Purpose of Impregnation 122 Heterogeneity of Wood Structure 123 Steaming 130 Penetration 133 Diffusion 138 Diffusion Model 151 Effect of Impregnation on the Uniformity of Delignification 159 Numerical Solution of the Diffusion Model 163 Chemistry of Kraft Cooking 164 Antje Potthast Lignin Reactions 164 Reactions of Carbohydrates 174 Reactions of Extractives 181 An Overview of Reactions During Kraft Pulping 183 Inorganic Reactions 184 Kraft Pulping Kinetics 185 Herbert Sixta Introduction 185 Review of Kraft Cooking Models 188 Structure of a Selected Kinetic Model for Kraft Pulping 211 Process Chemistry of Kraft Cooking 229 Standard Batch Cooking Process 229 Modified Kraft Cooking 235 Polysulfide and Anthraquinone Pulping 306 Multistage Kraft Pulping 325 Prehydrolysis 325 Prehydrolysis: Kraft Pulping 345 Pulping Technology and Equipment 366 Andreas W. Krotschek Batch Cooking versus Continuous Cooking 366 Batch Cooking Technology and Equipment 367 Continuous Cooking Technology and Equipment 377 Sulfite Chemical Pulping 392 Herbert Sixta Introduction 392 Cooking Chemicals and Equilibria 395 Impregnation 403 Chemistry of (Acid) Sulfite Cooking 405 Antje Potthast Reactions of Lignin 407 Reactions of Carbohydrates: Acid Hydrolysis 416 Reactions of Extractives 425 Process Chemistry of Acid Sulfite Pulping 427 Herbert Sixta

Contents

4.3.5.1 4.3.5.2 4.3.6 4.3.6.1 4.3.6.2 4.3.6.3 4.3.6.4 4.3.6.5 5 5.1 5.2 5.2.1 5.2.2 5.2.3 5.2.4 5.2.5 5.3 5.3.1 5.3.2 5.3.3 5.3.4 5.3.5 5.4 5.4.1 5.4.2 5.4.3 5.4.4 5.4.5 5.4.6 5.4.7 5.5 5.5.1 5.5.2 5.5.3 5.5.4 5.5.5 5.6 5.6.1 5.6.2 5.6.2.1 5.6.2.2 5.6.3

Basic Technology 427 Influence of Reaction Conditions 449 Alternative Sulfite Pulping Concepts 465 Magnefite Process 466 Two-Stage Neutral Magnefite (Bisulfite-MgO) 467 Sivola Processes 468 Stora Processes (Hydrogen Sulfite or Monosulfite-Acid Sulfite) Alkaline Sulfite Pulping 475 Pulp Washing 511 Andreas W. Krotscheck Introduction 511 Pulp Washing Theory 512 Overview 512 Drainage 513 Compressive Dewatering 517 Diffusion 517 Sorption 519 Principles of Washing 523 Dilution/Extraction Washing 524 Displacement Washing 524 Compressive Dewatering 525 Multi-Stage Washing 526 Fractional Washing 528 Washing Parameters 528 Overview 528 Dilution Factor 529 Feed and Discharge Consistencies 532 pH 533 Entrainment of Air 534 Temperature 535 Equipment-Specific Parameters 535 Washing Efficiency 537 Overview 537 Wash Yield 537 Displacement Ratio 538 Norden Efficiency Factor 539 Standardized Norden Efficiency Factor 545 Washing Equipment 547 General Remarks 547 Rotary Drum Washers 547 Conventional Drum Washers 547 Drum Displacer 549 Belt Washers 551

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Contents

XI

5.6.4 5.6.4.1 5.6.4.2 5.6.5 5.6.6 6 6.1 6.2 6.2.1 6.2.2 6.2.3 6.2.4 6.3 6.3.1 6.3.1.1 6.3.1.2 6.3.2 6.3.2.1 6.3.2.2 6.3.2.3 6.3.2.4 6.3.2.5 6.3.3 6.3.3.1 6.3.3.2 6.3.3.3 6.4 6.4.1 6.4.2 6.4.3 6.4.4 6.4.5 6.5 6.5.1 6.5.2 6.5.2.1 6.5.2.2 6.5.2.3 6.5.3 6.5.3.1 6.5.3.2 6.6

Diffusion Washers 552 Atmospheric Diffuser 552 Pressure Diffuser 554 Roll Presses 556 In-Digester Washing 557 Pulp Screening, Cleaning, and Fractionation Andreas W. Krotscheck Introduction 561 Screening Theory 563 Introduction 563 Flow Regime 564 Fiber Passage and Reject Thickening 566 Selective Fiber Passage 570 Screening Parameters 572 Equipment Parameters 572 Screen Basket 572 Rotor 573 Operating Parameters 575 Reject Rate 575 Accept Flow Rate 575 Feed Consistency 577 Temperature 577 Rotor Tip Velocity 577 Furnish Parameters 578 Pulp Fibers 578 Contaminants 579 Entrained Air 579 Centrifugal Cleaning Theory 579 Introduction 579 Flow Regime 580 Sedimentation 581 Underflow Thickening 584 Selective Separation 585 Centrifugal Cleaning Parameters 586 Cyclone Parameters 586 Operating Parameters 587 Flow Rate and Pressure Drop 587 Feed Consistency 587 Temperature 587 Furnish Parameters 587 Pulp Fibers 587 Contaminants 588 Separation Efficiency 588 561

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Contents

6.6.1 6.6.2 6.6.2.1 6.6.2.2 6.7 6.7.1 6.7.1.1 6.7.1.2 6.7.1.3 6.7.1.4 6.7.1.5 6.7.2 6.8 6.8.1 6.8.2 6.8.2.1 6.8.2.2 6.8.3 6.9 6.9.1 6.9.2 6.9.2.1 6.9.2.2 6.9.3

Screening and Cleaning Efficiency 588 Fractionation Efficiency 590 Removal Efficiency 590 Fractionation Index 591 Screening and Cleaning Applications 592 Selective Contaminant Removal 592 Knots 593 Shives 593 Bark 593 Sand and Stones 593 Metals and Plastics 594 Fractionation 594 Systems for Contaminant Removal and Fractionation 594 Basic System Design Principles 594 Systems for Contaminant Removal 596 Arrangement 596 Fiber Loss versus Efficiency 598 Systems for Fractionation 599 Screening and Cleaning Equipment 601 Pressure Screens 601 Atmospheric Screens 604 Secondary Knot Screens 604 Vibratory Screens 605 Hydrocyclones 605

Volume 2 7 Pulp Bleaching 609 Herbert Sixta, Hans-Ullrich Sss, Antje Potthast, Manfred Schwanninger, and Andreas W. Krotscheck General Principles 609 Classification of Bleaching Chemicals 610 Bleaching Operations and Equipment 613 Andreas W. Krotscheck Basic Rheology of Pulp-Liquor Systems 614 Generic Bleaching Stage Set-Up 616 Medium Consistency Pumps 617 Medium Consistency Mixers 619 High-Shear Mixers 620 Static Mixers 621 Atmospheric Steam Mixers 622 Medium Consistency Reactors 623 Atmospheric Upflow Reactors 623

7.1 7.2 7.2 7.2.1 7.2.2 7.2.3 7.2.4 7.2.4.1 7.2.4.2 7.2.4.3 7.2.5 7.2.5.1

Contents

XIII

7.2.5.2 7.2.5.3 7.2.6 7.2.7 7.2.8 7.3 7.3.1 7.3.2 7.3.2.1 7.3.2.2 7.3.2.3 7.3.2.4 7.3.2.5 7.3.2.6 7.3.2.7 7.3.3 7.3.3.1 7.3.3.2 7.3.3.3 7.3.4 7.3.4.1 7.3.4.2 7.3.5 7.3.5.1 7.3.5.2 7.3.5.3 7.3.5.4 7.3.5.5 7.3.5.6 7.3.5.7 7.3.5.8 7.3.6 7.3.6.1 7.3.6.2 7.3.6.3 7.3.6.4 7.3.6.5 7.3.7 7.3.7.1 7.3.7.2 7.3.7.3

Atmospheric Downflow Reactors 624 Pressurized Reactors 625 Blowtank 627 Agitators 627 Washing 628 Oxygen Delignification 628 Introduction 628 Chemistry of Oxygen Delignification 632 Manfred Schwanninger Bleachability 634 Lignin Structures and their Reactivity 634 Oxygen (Dioxygen) and its Derivatives 641 A Principal Reaction Schema for Oxygen Delignification 649 Carbohydrate Reactions in Dioxygen-Alkali Delignification Processes 657 Residual LigninCarbohydrate Complexes (RLCC) 666 Inorganics (Metals) and their Role in the Protection/ Degradation of Cellulose 668 Mass Transfer and Kinetics 671 Herbert Sixta Kinetics of Delignification 672 Kinetics of Cellulose Chain Scissions 685 Application of Surfactants 687 A Model to Predict Industrial Oxygen Delignification 688 Theoretical Base of the van Heiningen Model 690 Case Study 695 Process Variables 701 Temperature 701 Retention Time 702 Alkali Charge 703 pH Value 704 Final pH 705 Alkali Source 706 Oxygen Charge, Oxygen Pressure 707 Consistency 708 Pulp Components and Impurities 708 Effect of Metal Ion Concentration 708 Residual Lignin Structures 713 Carry-Over 716 Xylan Content 719 Selectivity of Oxygen Delignification 720 Process and Equipment 721 MC versus HC Technology 721 Process Technology 722 Process Equipment 731

XIV

Contents

7.3.8 7.4 7.4.1 7.4.2 7.4.2.1 7.4.2.2 7.4.3 7.4.4 7.4.4.1 7.4.5 7.4.5.1 7.4.5.2 7.4.5.3 7.4.6 7.4.7 7.5 7.5.1 7.5.2 7.5.3 7.5.4 7.5.4.1 7.5.4.2 7.5.4.3 7.5.5 7.5.5.1 7.5.5.2 7.5.5.3 7.5.5.4 7.5.5.5 7.5.5.6 7.5.5.7 7.5.5.8 7.5.5.9 7.5.5.10 7.5.6 7.5.6.1 7.5.6.2 7.5.6.3 7.5.7 7.5.7.1

Pulp Quality 733 Chlorine Dioxide Bleaching 734 Introduction 734 Physical and Chemical Properties and Definitions 735 Behavior of Chlorine Dioxide in Aqueous Solution 737 Inorganic Side Reactions during Chlorine Dioxide Bleaching of Wood Pulps 737 Generation of Chlorine Dioxide 741 Chemistry of Chlorine Dioxide Treatment 745 Manfred Schwanninger Chlorination Products 752 Performance of Chlorine Dioxide Bleaching 754 Standard Chlorine Dioxide Bleaching 754 Chlorine Dioxide Bleaching of Oxygen-Delignified Kraft Pulps 759 Modified Chlorine Dioxide Bleaching 761 Technology of Chlorine Dioxide Bleaching 770 Andreas W. Krotscheck Formation of Organochlorine Compounds 771 Ozone Delignification 777 Introduction 777 Physical Properties of Ozone 778 Ozone Generation 782 Chemistry of Ozone Treatment 785 Manfred Schwanninger Ozone Decomposition 786 Degradation of Lignin 790 Degradation of Carbohydrates 794 Process Conditions 798 Mass Transfer 798 Mixing and Mixing Time 802 Effect of Pulp Consistency 806 Effect of pH 811 Effect of Temperature 813 Effect of Transition Metal Ions 814 Effect of Carry-Over 816 Effect of Pretreatments and Additives 818 Effect of Sodium Borohydride after Treatment 822 Effect of Alkaline Extraction 824 Technology of Ozone Treatment 826 Andreas W. Krotscheck Medium-Consistency Ozone Treatment 826 High-Consistency Ozone Treatment 827 Ozone/Oxygen Gas Management 828 Application in Chemical Pulp Bleaching 829 Selectivity, Efficiency of Ozone Treatment of Different Pulp Types 829

Contents

XV

7.5.7.2 Effect of Ozonation on the Formation of Carbonyl and Carboxyl Groups 840 7.5.7.3 Effect of Ozonation on Strength Properties 841 7.5.7.4 Typical Conditions, Placement of Z in a Bleaching Stage 843 7.6 Hydrogen Peroxide Bleaching 849 Hans-Ullrich Sss 7.6.1 Introduction 849 7.6.2 H2O2 Manufacture 850 7.6.3 Physical Properties 850 7.6.4 Chemistry of hydrogen peroxide bleaching 853 Manfred Schwanninger 7.6.4.1 Decomposition of H2O2 854 7.6.4.2 Residual Lignin 856 7.6.4.3 Carbohydrates 859 7.6.5 Process Parameters 860 Hans-Ullrich Sss 7.6.5.1 Metals Management 860 7.6.5.2 Alkaline Decomposition of H2O2 862 7.6.5.3 Thermal Stability of H2O2 and Bleaching Yield 863 7.6.5.4 Pressurized Peroxide Bleaching 866 7.6.6 Technology of H2O2 Bleaching 866 Andreas W. Krotscheck 7.6.6.1 Atmospheric Peroxide Bleaching 866 7.6.6.2 Pressurized Peroxide Bleaching 867 7.6.7 Application in Chemical Pulp Bleaching 868 Hans-Ullrich Sss 7.6.7.1 Stabilization of Brightness with H2O2 873 7.6.7.2 Catalyzed Peroxide Bleaching 877 7.6.7.3 Application in TCF Sulfite Pulp Bleaching 877 7.6.7.4 Activators for H2O2 Bleaching 880 7.7 Peracetic Acid in Pulp Bleaching 880 7.8 Hot Acid Hydrolysis 883 7.9 Alternative Bleaching Methods 885 7.10 Bleach Plant Liquor Circulation 887 Andreas W. Krotscheck 7.10.1 Introduction 887 7.10.2 Intra-Stage Circulation and Circulation between Stages 888 7.10.3 Open and Closed Operation of Bleaching Stages 890 7.10.4 Construction Material Compatibility 893 7.10.5 Implications of Liquor Circulation 893

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Contents

8 8.1 8.2 8.3 8.3.1 8.3.2 8.3.3 8.3.4 8.3.5 8.3.6 8.4 8.4.1 8.4.1.1 8.4.1.2 8.4.1.3 8.4.1.4 8.4.1.5 8.4.2 9 9.1 9.1.1 9.1.2 9.1.2.1 9.1.2.2 9.1.2.3 9.1.2.4 9.1.2.5 9.1.2.5 9.2 9.2.1 9.2.2 9.2.2.1 9.2.2.2 9.2.2.3 9.2.2.4 9.2.3 9.2.3.1 9.2.3.2 9.2.3.3 9.2.4

Pulp Purification Herbert Sixta

933

Introduction 933 Reactions between Pulp Constituents and Aqueous Sodium Hydroxide Solution 935 Cold Caustic Extraction 942 NaOH Concentration 942 Time and Temperature 944 Presence of Hemicelluloses in the Lye 945 Placement of CCE in the Bleaching Sequence 948 Specific Yield Loss, Influence on Kappa Number 949 Molecular Weight Distribution 951 Hot Caustic Extraction 952 Influence of Reaction Conditions on Pulp Quality and Pulp Yield 953 NaOH Charge and Temperature in E, (EO), and (E/O) Treatments 953 Xylan versus R18 Contents 957 Purification versus Viscosity 959 Purification versus Kappa Number and Extractives 960 Composition of Hot Caustic Extract 961 MgO as an Alternative Alkali Source 962 Recovery 967 Andreas W. Krotscheck and Herbert Sixta Characterization of Black Liquors 967 Chemical Composition 967 Physical Properties 970 Viscosity 970 Boiling Point Rise (BPR) 970 Surface Tension 971 Density 971 Thermal Conductivity 972 Heat Capacity [8,11] 972 Chemical Recovery Processes 973 Overview 973 Black Liquor Evaporation 974 Introduction 974 Evaporators 975 Multiple-Effect Evaporation 977 Vapor Recompression 979 Kraft Chemical Recovery 980 Kraft Recovery Boiler 980 Causticizing and Lime Reburning 986 The Future of Kraft Chemical Recovery 992 Sulfite Chemical Recovery 994

Contents

XVII

10 10.1 10.2 10.3 10.4 10.5 10.6 11 11.1 11.2 11.3 11.3.1 11.3.2 11.3.2.1 11.3.2.2 11.3.2.3 11.3.2.4 11.3.2.5 11.3.2.6 11.3.2.7 11.3.2.8

Environmental Aspects of Pulp Production Hans-Ulrich Sss

997

Introduction 997 A Glimpse of the Historical Development 998 Emissions to the Atmosphere 1002 Emissions to the Aquatic Environment 1004 Solid Waste 1006 Outlook 1007 Pulp Properties and Applications Herbert Sixta 1009

Introduction 1009 Paper-Grade Pulp 1010 Dissolving Grade Pulp 1022 Introduction 1022 Dissolving Pulp Characterization 1024 Pulp Origin, Pulp Consumers 1024 Chemical Properties 1026 Supramolecular Structure 1041 Cell Wall Structure 1047 Fiber Morphology 1051 Pore Structure, Accessibility 1052 Degradation of Dissolving Pulps 1056 Overview of Pulp Specification 1060

II

Mechanical Pulping 1069 Jrgen Blechschmidt, Sabine Heinemann, and Hans-Ulrich Sss Introduction 1071 Jrgen Blechschmidt and Sabine Heinemann A Short History of Mechanical Pulping 1073 Jrgen Blechschmidt and Sabine Heinemann Raw Materials for Mechanical Pulp 1075 Jrgen Blechschmidt and Sabine Heinemann Wood Quality 1075 Processing of Wood 1076

3 3.1 3.2

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Contents

3.2.1 3.2.2 3.2.3 4 4.1 4.1.1 4.1.2 4.1.2.1 4.1.2.2

Wood Log Storage 1076 Wood Log Debarking 1076 Wood Log Chipping 1078 Mechanical Pulping Processes 1079 Jrgen Blechschmidt and Sabine Heinemann

Grinding Processes 1079 Principle and Terminology 1079 Mechanical and Thermal Processes in Grinding 1080 Softening of the Fibers 1080 Defibration (Deliberation) of Single Fibers from the Fiber Compound 1083 4.1.3 Influence of Parameters on the Properties of Groundwood 1084 4.1.4 Grinders and Auxiliary Equipment for Mechanical Pulping by Grinding 1087 4.1.4.1 Pocket Grinders 1089 4.1.4.2 Chain Grinders 1090 4.1.4.3 Pulp Stones 1092 4.1.5 Pressure Grinding 1095 4.2 Refiner Processes 1098 4.2.1 Principle and Terminology 1098 4.2.2 Mechanical, Thermal, and Chemical Processes in the Refiner Process 1100 4.2.3 Machines and Aggregates for Mechanical Pulping by Refining 1104 5 Processing of Mechanical Pulp and Reject Handling: Screening and Cleaning 1113 Jrgen Blechschmidt and Sabine Heinemann Basic Principles and Parameters 1113 Machines and Aggregates for Screening and Cleaning Reject Treatment and Heat Recovery 1121 Bleaching of Mechanical Pulp 1123 Hans-Ulrich Sss Bleaching with Dithionite 1124 Bleaching with Hydrogen Peroxide 1126 Technology of Mechanical Pulp Bleaching 1134 Latency and Properties of Mechanical Pulp 1137 Jrgen Blechschmidt and Sabine Heinemann Latency of Mechanical Pulp 1137 Properties of Mechanical Pulp 1138 1114

5.1 5.2 5.3 6 6.1 6.2 6.3 7 7.1 7.2

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XIX

III

Recovered Paper and Recycled Fibers Hans-Joachim Putz Introduction 1149

1147

1 2 3 3.1 3.2 3.2.1 3.2.2 4 4.1 4.2 4.3 4.4 4.5 5 5.1 5.2 5.2.1 5.2.2 5.3 5.4 6 7 7.1 7.2 7.3 8 8.1 8.2 8.3

Relevance of Recycled Fibers as Paper Raw Material Recovered Paper Grades 1157 Europe 1157 North America and Japan United States 1162 Japan 1163

1153

1161

Basic Statistics 1165 Utilization Rate 1167 Recovery Rate 1170 Recycling Rate 1173 Deinked Pulp Capacities 1174 Future Development of the Use of Recovered Paper Collection of Recovered Paper 1177 Pre-Consumer Recovered Paper 1178 Post-Consumer Recovered Paper 1178 Pick-Up Systems 1178 Drop-Off Systems 1179 Efficiency of Different Collection Systems Municipal Solid Waste 1181 Sources of Recovered Paper 1183

1175

1180

Sorting, Handling, and Storage of Recovered Paper 1187 Sorting 1187 Handling 1189 Storage 1190 Legislation for the Use of Recycled Fibers 1191 Europe 1192 United States of America 1195 Japan 1198 Appendix: European List of Standard Grades of Recovered Paper and Board (February, 1999) 1203

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Contents

IV

Analytical Characterization of Pulps 1211 Erich Gruber Fundamentals of Quality Control Procedures 1213 The Role of QC 1214 Basics of QC-statistics 1214 Sampling 1216 Conditions for Testing and/or Conditioning 1216 Disintegration 1217 Determination of Low Molecular-Weight Components 1219 Moisture 1219 Inorganic Components 1219 Ashes 1220 Total Ash 1220 Sulfated Ash 1220 Acid-Insoluble Ash 1220 Determination of Single Elements 1221 Survey of Chemical Procedures 1221 Atomic Absorption Spectroscopy (AAS) 1222 X-ray Fluorescence Spectroscopy (XFS) 1223 Electron Spectroscopy for Chemical Application (ESCA) 1223 Extractives 1224 Water Extractives 1224 Test Water 1224 Cold Water Extraction 1225 Hot Water Extraction 1225 Analysis of Water Extracts 1225 Chlorine Compounds 1225 Macromolecular Composition 1227 Lignin Content 1227 Extent of Delignification 1228 Roe Number 1228 Chlorine Number 1228 Kappa Number (Permanganate Number) 1228 Alkali Resistance and Solubility 1229 Alkali-Soluble Components 1229 a-, b-, and c-cellulose 1229 R18 and S18 values 1230 Composition of Polysaccharides 1231 Determination of Monosaccharides after Hydrolysis 1231 Gas Chromatography 1231 Thin-Layer Chromatography 1232

1 1.1 1.2 1.3 1.4 1.5 2 2.1 2.2 2.2.1 2.2.1.1 2.2.1.2 2.2.1.3 2.2.2 2.2.2.1 2.2.2.2 2.2.2.3 2.2.2.4 2.3 2.3.1 2.3.1.1 2.3.1.2 2.3.1.3 2.3.1.4 2.4 3 3.1 3.2 3.2.1 3.2.2 3.2.3 3.3 3.3.1 3.3.2 3.3.3 3.4 3.4.1 3.4.1.1 3.4.1.2

Contents

XXI

3.4.1.3 3.4.2 3.4.3 3.5 3.5.1 3.5.1.1 3.5.1.2 3.5.1.3 3.5.1.4 3.5.1.5 3.5.1.6 3.5.1.7 3.5.2 3.6 3.6.1 3.6.1.1 3.6.1.2 3.6.1.3 3.6.2 3.6.3 3.6.3.1 3.6.3.2 3.6.4 3.6.4.1 3.6.4.2 3.6.5 3.6.5.1 3.6.5.2 4 4.1 4.1.1 4.1.1.1 4.1.1.2 4.1.1.3 4.1.1.4 4.1.2 4.1.3 4.2 4.2.1 4.2.2 4.3

Liquid Chromatography 1232 Determination of Pentosans after Hydrolysis 1233 Determination of Uronic Acids after Hydrolysis 1233 Functional Groups 1234 Carbonyl Functions 1234 Copper Number 1235 Sodium Borohydride Method 1236 Hydrazine Method 1236 Oxime Method 1236 Girard-P Method 1237 Cyanohydrin Method 1237 Fluorescent Dying 1237 Carboxyl Functions 1238 Degree of Polymerization (Molecular Mass) 1239 Solvents for Cellulose 1240 CUOXAM 1241 CUEN 1241 Iron Sodium Tartrate (EWNN) 1241 Diverse Average Values of Molecular Mass and Index of Nonuniformity 1241 Methods to Determine Molar Mass (Molecular Weight) 1243 Osmosis 1243 Scattering Methods 1245 Viscosity Measurements 1248 Solution Viscosity as a Measure of Macromolecular Chain Length Viscosity Measurements on Cellulose Pulps 1251 Molecular Weight Distribution 1251 Fractional Precipitation or Solution 1251 Size-Exclusion (Gel-Permeation) Chromatography 1252 Characterization of Supermolecular Structures 1257 Crystallinity 1257 Degree of Crystallinity 1257 X-Ray Diffraction 1259 Solid-phase NMR-Spectroscopy 1261 Reaction Kinetics 1262 Density Measurements 1262 Dimension of Crystallites 1263 Orientation of Crystallites 1265 Accessibility, Voids, and Pores 1265 Porosity 1266 Accessible Surface 1267 Water and Solvent Retention 1268

1248

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Contents

4.3.1 4.3.2 5 5.1 5.1.1 5.1.2 5.1.3 5.2 5.2.1 5.2.1.1 5.2.1.2 5.2.2 5.3 5.3.1 5.3.1.1 5.3.1.2 5.3.2 5.3.2.1 5.3.2.2 5.4 6 6.1 6.2 6.3 6.4 6.4.1 Index

Total Water Uptake 1268 Free and Bound Water 1268 Fiber Properties 1269

Identification of Fibers 1269 Morphological Characterization 1269 Visible and UV Microscopy 1271 Electron Microscopy 1271 Fiber Dimensions 1272 Fiber Length and Width 1273 Microscopic Methods and Image Analysis 1273 Fiber Fractionation by Screening 1274 Coarseness 1275 Mechanical Properties 1275 Single Fiber Properties 1275 Wet Fiber Properties 1275 Mechanical Properties of Dry Fibers 1277 Sheet Properties 1278 Preparation of Laboratory Sheets for Physical Testing 1278 Determination of Mechanical Pulp Sheet Properties 1279 Optical Properties of Laboratory Sheets 1279 Papermaking Properties of Pulps 1281 Beating 1281 Drainage Resistance 1281 Drainage (Dewatering) Time 1283 Aging 1284 Accelerated Aging 1284 1291

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Preface
Pulp is a fibrous material resulting from complex manufacturing processes that involve the chemical and/or mechanical treatment of various types of plant material. Today, wood provides the basis for approximately 90% of global pulp production, while the remaining 10% originates from annual plants. Pulp is one of the most abundant raw materials worldwide which is used predominantly as a major component in the manufacture of paper and paperboard, and with increasing importance also in the form of a wide variety of cellulose products in the textile, food, and pharmaceutical industries. The pulp industry is globally competitive and attractive from the standpoint of sustainability and environmental compatibility. In many ways, this industry is an ideal example of a desirable, self-sustaining industry which contributes favorably to many areas of our daily lives. Moreover, there is no doubt that it will continue to play an important role in the future. Although the existing pulp technology has its origins in the 19th century, it has still a very high potential of further innovations covering many areas of science. Knowledge of the pulping processes has been greatly extended since Pulping Processes the unsurpassed book of Sven A. Rydholm was first published in 1965. Not only has the technology advanced and new technology emerged, but our knowledge on structureproperty relationships has also deepened considerably. It is self-evident that the competitiveness of pulp and its products produced thereof can only be maintained through continuous innovations at the highest possible level. A recent publication which comprised a series of 19 books on Papermaking Science and Technology, and was edited by Johan Gullichsen and Hannu Paulapuro, provided a comprehensive account of progress and current knowledge in pulping and papermaking. The aim of the present book, however, is initially to provide a short, general survey on pulping processes, followed by a comprehensive review in certain specialized areas of pulping chemistry and technology. Consequently, the book is divided into four part: Part I, Chemical Pulp; Part II, Mechanical Pulp; Part III, Recovered Paper and Recycled Fibers; and Part IV, the Analytical Characterization of Pulps. In Part I, Chapter 2 and 3 describe the fundamentals of wood structure and woodyard operations, whilst in Chapter 4 emphasis is placed on the chemistry
Handbook of Pulp. Edited by Herbert Sixta Copyright 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30999-3

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Preface

and technology of both kraft and sulfite pulping, the mass transfer of cooking liquor into wood structure and chemical kinetics in alkaline pulping operations. The current technologies of dissolving pulp manufacture are also reviewed, covering both multi-stage alkaline and acid sulfite pulping. Considerable effort was devoted in the subsequent chapters to present the fundamentals of pulp washing, screening, cleaning, and fractionation. These important mechanical pulping operations are followed by a comprehensive review of the state-of-the-art bleaching chemistry and technology. High-purity pulps are important raw materials for the production of high added-value cellulose products, and the necessary purification processes are introduced in a separate chapter. A short overview on chemical recovery processes and pulp properties concludes Part I. Parts II and III provide a survey of the latest technologies on mechanical pulp and recovered paper and recycled fibers. Finally, Part IV deals with the analytical characterization of pulps. Since the wood and pulp components are closely associated within the cell wall, the analytical characterization covers not only molecular but also supramolecular structures. A project such as this could never have succeeded without input from contributors of the very highest standard. I would like to express my sincere appreciation to the contributors, for the high quality of their work and for their enthusiasm and commitment. Individual sections of the manuscripts have been reviewed in detail by several friends and colleagues, and in this respect the suggestions and critical comments of Josef Bauch of the University of Hamburg, Germany (Part I, Chapter 2), HansGeorg Richter of the BFH, Germany (Part I, Chapter 2), Rudolf Patt of the University of Hamburg, Germany (Part I, Chapters 3, 4 and 7), Othar Kordsachia of the BFH, Germany (Part I, Chapters 4, 7, 8 and 11), Richard Berry of Paprican, Point Claire, Canada (chlorine dioxide bleaching peracetic acid in pulp bleaching, hot acid hydrolysis and Chapter 10 in Part I, hydrogen peroxide bleaching in Part I and II), Chen-Loung Chen and Michail Yu. Balakshin of NC State University, USA (chemistry of kraft and sulfite pulping), John F. Kadla of the University of British Columbia, Vancouver, Canada (chemistry of oxygen-, ozone and hydrogen peroxide bleaching), Adriaan R.P. van Heiningen of the University of Maine, USA (oxygen delignification, ozone bleaching), James A. Olson of the University of British Columbia, Vancouver, Canada (Part I, chapter 6), Andrea Borgards, R&D Lenzing AG, Austria (Part I, Chapter 8), Hans Gr-stlinger of Lenzing Technik, Austria (bleaching technology), Wojciech Juljanski of Lenzing Technik, Austria (pulping technology) and Mikael Lucander, Ilkka Nurminen and Christoffer Westin of the Oy Keskuslaboratorio, Espoo, Finland (Part II, Mechanical Pulping) are gratefully acknowledged. Moreover, I am very indebted to Alois Ecker of Lenzing Technik for his valuable support for the mathematical computations of kraft cooking and oxygen delignification kinetics. I also owe sincere thanks to the management of Lenzing AG for the assistance granted to me by their library services.

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In addition to my gratitude to all of these people, I also thank my family for their great patience, understanding, and inspiring support. Last, but not least, I would like to thank the publishers for the attractive presentation of this book, and the personnel at Wiley-VCH for their cooperation and skilful editorial work. Lenzing, December 2005 H. Sixta

Handbook of Pulp. Edited by Herbert Sixta Copyright 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30999-3

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List of Contributors
Jrgen Blechschmidt Wachbergstrasse 31 01326 Dresden Germany Erich Gruber TU-Darmstadt Makromolekulare Chemie Nachwachsender Rohstoffe 64283 Darmstadt Germany Sabine Heinemann KCL Science and Consulting Pulp and Paper P.O. Box 70 Espoo Finland Gerald Koch Federal Research Centre for Forestry and Forest Products Institute for Wood Biology and Wood Protection Leuschnerstrasse 91 21031 Hamburg Germany Andreas W. Krotscheck Lenzing Technik GmbH Pulp Technology Division 4680 Lenzing Austria Antje Potthast University of Natural Resources and Applied Life Sciences Vienna Department of Chemistry and Christian-Doppler-Laboratory Muthgasse 18 1190 Vienna Austria Hans-Joachim Putz Paper Technology and Mechanical Process Engineering Darmstadt University of Technology Alexanderstrasse 8 64283 Darmstadt Germany Jrg B. Ressel Department of Wood Science University of Hamburg Leuschnerstrasse 91 21031 Hamburg Germany Manfred Schwanninger BOKU University of Natural Resources and Applied Life Sciences Vienna Department of Chemistry Division of Biochemistry Muthgasse 18 1190 Vienna Austria

Handbook of Pulp. Edited by Herbert Sixta Copyright 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30999-3

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List of Contributors

Herbert Sixta Lenzing AG Business Unit Pulp Werkstrae 1 4860 Lenzing Austria

Hans-Ulrich Sss Degussa AG Global Competence Center Active Oxygen Products O2-AO-AT, 913-120 Rodenbacher Chaussee 4 63594 Hanau Germany

List of Abbreviations

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List of Abbreviations
4OMeGlcA AAS AEC AF&PA AFM AHG AMT AOX ASAM B.I.R. BAT BLG BLGCC BLPS CCE CCOA CDE CE CEPI CGW CI CMP COD CRMP CTC CTMP CTO CZE DAE DD DDA DDJ 4-O-methyl-bd-glucuronic acid-(12)-xylose) atomic absorption spectroscopy anion-exchange chromatography American Forest & Paper Association atomic force microscopy anhydroglucose accepted modern technology adsorbable organic halogen alkaline sulfite with anthraquinone and methanol Bureau International de la Rcupration best available technology black liquor gasification black liquor gasification with combined cycle black liquor dissolved polysaccharides cold caustic extraction carbazole-9-carboxylic acid [2-(2-aminooxy-ethoxy)-ethoxy]-amide cupri-ethylene-diamine-solution causticizing efficiency Confederation of European Paper Industries chemigroundwood crystallinity index chemimechanical pulp chemical oxygen demand chemi-refiner mechanical pulp charge transfer complex chemi-thermomechanical pulp, crude tall oil capillary zone electrophoresis differential algebraic equation drum displacer dynamic drainage analyzer dynamic drainage jar

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List of Abbreviations

DIP DP DSC DTPA EAPC ECCSA ECF EDR EDXA EPA ERPA ERPC ESCA ESR EUGROPA FBSKP FEAD

deinked pulp degree of polymerization differential scanning calorimetry diethylene triamino penta-acetate enhanced alkali profile cooking effective capillary cross-sectional area elemental chlorine-free equivalent displacement ratio energy dispersive X-ray analysis Environmental Protection Agency European Recovered Paper Association European Recovered Paper Council electron spectroscopy for chemical analysis electron spin resonance European Paper Merchants Association fully bleached softwood kraft pulp European Federation of Waste Management and Environmental Services FEFCO European Federation of Corrugated Board Manufacturers FE-SEM field emission-SEM FSP fiber saturation point FTIR Fourier transmission infra-red GPC gel-permeation chromatography GSA General Services Administration HCE hot caustic extraction HEDP hydroxy ethylene 1,1-diphosphonic acid HHV higher heating value HP-AEC high-performance anion-exchange chromatography HVLC high-volume low-concentration INTERGRAF International Confederation of Printing and Allied Industries IPPC Integrated Pollution and Prevention Control ISEC inverse size-exclusion chromatography I-TEQ International Toxicity Equivalent LCC lignincarbohydrate complex LMS laccase-mediator-system LODP level-off DP LVHC low-volume high-concentration LWC lightweight coated MCC modified cooking circulation MFA microfibril angle MHW Ministry of Health and Welfare MITI Ministry of International Trade and Industry MOW mixed office waste MSW municipal solid waste

List of Abbreviations

XXXI

MWD NCG NHV NHWA NMR NPEs NSSC ODE OXE PAD PCDD PCDF PDI PGW PHK PRMP PSA RAC RDH RLLC RMP RTS SAXS SC SEM SET SGW SRV SSL TCF TEM TEQ TGW TMP TOC ToF-SIMS TRS TSS TTA UCC UMSP VOC VSA WAXS

molecular weight distribution noncondensable gases net heating value National Household Recovery Analysis nuclear magnetic resonance non-process elements neutral sulfite semi-chemical ordinary differential equation oxidation equivalent pulsed amperometric detection polychlorinated dibenzo-p-dioxins polychlorinated dibenzofurans polydispersity index pressure groundwood prehydrolysis kraft pulp pressurized refiner mechanical pulp pressure swing adsorption Recycling Advisory Council rapid displacement heating residual lignincarbohydrate complex refiner mechanical pulp retention time, temperature, speed small-angle X-ray scattering supercalendered scanning electron microscopy single electron transfer stone groundwood solvent retention value spent sulfite liquor totally chlorine free transmission electron microscopy toxic equivalency quantity thermo groundwood thermomechanical pulp total organic carbon time-of-flight secondary ion mass spectroscopy total reduced sulfur total suspended solids total titrable alkali upper cooking circulation scanning UV microspectrophotometry volatile organic compounds vacuum swing adsorption wide-angle X-ray scattering

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List of Abbreviations

WRV XFS XPS

water retention value X-ray fluorescence spectroscopy X-ray photoelectron spectroscopy