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 & All books published by Wiley-VCH are
carefully produced. Nevertheless, authors,
Dr. Herbert Sixta editors, and publisher do not warrant the
Lindenweg 7 information contained in these books,
4860 Lenzing including this book, to be free of errors.
Austria Readers are advised to keep in mind that
statements, data, illustrations, procedural
details or other items may inadvertently
be inaccurate.

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

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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,
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Printing Strauss GmbH, Mrlenbach
Binding Litges & Dopf Buchbinderei GmbH,
Heppenheim
ISBN-13: 978-3-527-30999-3
ISBN-10: 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

List of Contributors XXVII

List of Abbreviations XXIX

Volume 1

Part I Chemical Pulping 1

1 Introduction 3
Herbert Sixta
1.1 Introduction 3
1.2 The History of Papermaking 4
1.3 Technology, End-uses, and the Market Situation 8
1.4 Recovered Paper and Recycled Fibers 14
1.5 Outlook 15

2 Raw Material for Pulp 21

Gerald Koch
2.1 Wood 21
2.1.1 Chemical Composition of Wood 22
2.1.1.1 Cellulose 23
2.1.1.2 Hemicelluloses 28
2.1.1.3 Lignin 30
2.1.1.4 Extractives 33
2.1.1.5 Inorganic Components 39
2.1.2 Wood Structure and Morphology 41
2.1.2.1 Ultrastructure and Distribution of Cell Wall Components 41
2.1.2.2 Lignification of the Cell Walls 44
2.1.2.3 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 The Microscopic Structure of Wood 48

2.1.3.1 Cell Types 48
2.1.3.2 Softwood and Hardwood Structure 50
2.1.3.3 Reaction Wood 54
2.1.3.4 Juvenile Wood 56
2.1.3.5 Secondary Changes 56
2.2 Outlook 59
2.2.1 Nano-structure of Fibers 59
2.2.2 Topochemical Distribution of Lignin and Phenolic Extractives 61

3 Wood Yard Operations 69

Jrg B. Ressel
3.1 Raw Material Storage 69
3.2 Debarking 71
3.2.1 Debarking Methods 72
3.2.1.1 Drum Debarker 72
3.2.1.2 Rotary Debarker 76
3.2.1.3 Ring Debarkers 77
3.3 Chipping and Screening 79
3.3.1 Disc Chipper 80
3.3.2 Drum Chipper 84
3.3.3 The Andritz HQ-Sizer and Rechipper 86
3.3.4 Chip Conditioner 87
3.3.5 Chipper Canter Line: Profiling Line in Softwood Sawmills 88
3.4 Chip screening 89
3.4.1 Mechanical Screening 89
3.4.2 Wind Screening 93
3.4.3 Air Density Separator (ADS) 94
3.5 Process Control and Automation 95
3.6 Transport and Handling Systems 95
3.6.1 Log Handling 97
3.6.2 Stationary Conveyor Systems 97
3.6.3 Chip Storage 98
3.6.3.1 Chip Storage Systems 101
3.6.4 Wood Yard Losses and Waste Reduction 104
3.6.4.1 Specific Causes of Waste Generation 105
3.6.4.2 Pollution Prevention Options 105

4 Chemical Pulping Processes 109

Herbert Sixta, Antje Potthast, Andreas W. Krotschek
4.1 Introduction 109
4.2 Kraft Pulping Processes 111
4.2.1 General Description 111
4.2.2 Kraft Cooking Liquors 113
 Contents IX

4.2.3 Mass Transfer in Kraft Cooking 122

4.2.3.1 Purpose of Impregnation 122
4.2.3.2 Heterogeneity of Wood Structure 123
4.2.3.3 Steaming 130
4.2.3.4 Penetration 133
4.2.3.5 Diffusion 138
4.2.3.6 Diffusion Model 151
4.2.3.7 Effect of Impregnation on the Uniformity of Delignification 159
4.2.3.8 Numerical Solution of the Diffusion Model 163
4.2.4 Chemistry of Kraft Cooking 164
Antje Potthast
4.2.4.1 Lignin Reactions 164
4.2.4.2 Reactions of Carbohydrates 174
4.2.4.3 Reactions of Extractives 181
4.2.4.4 An Overview of Reactions During Kraft Pulping 183
4.2.4.5 Inorganic Reactions 184
4.2.5 Kraft Pulping Kinetics 185
Herbert Sixta
4.2.5.1 Introduction 185
4.2.5.2 Review of Kraft Cooking Models 188
4.2.5.3 Structure of a Selected Kinetic Model for Kraft Pulping 211
4.2.6 Process Chemistry of Kraft Cooking 229
4.2.6.1 Standard Batch Cooking Process 229
4.2.6.2 Modified Kraft Cooking 235
4.2.6.3 Polysulfide and Anthraquinone Pulping 306
4.2.7 Multistage Kraft Pulping 325
4.2.7.1 Prehydrolysis 325
4.2.7.2 Prehydrolysis: Kraft Pulping 345
4.2.8 Pulping Technology and Equipment 366
Andreas W. Krotschek
4.2.8.1 Batch Cooking versus Continuous Cooking 366
4.2.8.2 Batch Cooking Technology and Equipment 367
4.2.8.3 Continuous Cooking Technology and Equipment 377
4.3 Sulfite Chemical Pulping 392
Herbert Sixta
4.3.1 Introduction 392
4.3.2 Cooking Chemicals and Equilibria 395
4.3.3 Impregnation 403
4.3.4 Chemistry of (Acid) Sulfite Cooking 405
Antje Potthast
4.3.4.1 Reactions of Lignin 407
4.3.4.2 Reactions of Carbohydrates: Acid Hydrolysis 416
4.3.4.3 Reactions of Extractives 425
4.3.5 Process Chemistry of Acid Sulfite Pulping 427
Herbert Sixta
X Contents

4.3.5.1 Basic Technology 427

4.3.5.2 Influence of Reaction Conditions 449
4.3.6 Alternative Sulfite Pulping Concepts 465
4.3.6.1 Magnefite Process 466
4.3.6.2 Two-Stage Neutral Magnefite (Bisulfite-MgO) 467
4.3.6.3 Sivola Processes 468
4.3.6.4 Stora Processes (Hydrogen Sulfite or Monosulfite-Acid Sulfite) 472
4.3.6.5 Alkaline Sulfite Pulping 475

5 Pulp Washing 511

Andreas W. Krotscheck
5.1 Introduction 511
5.2 Pulp Washing Theory 512
5.2.1 Overview 512
5.2.2 Drainage 513
5.2.3 Compressive Dewatering 517
5.2.4 Diffusion 517
5.2.5 Sorption 519
5.3 Principles of Washing 523
5.3.1 Dilution/Extraction Washing 524
5.3.2 Displacement Washing 524
5.3.3 Compressive Dewatering 525
5.3.4 Multi-Stage Washing 526
5.3.5 Fractional Washing 528
5.4 Washing Parameters 528
5.4.1 Overview 528
5.4.2 Dilution Factor 529
5.4.3 Feed and Discharge Consistencies 532
5.4.4 pH 533
5.4.5 Entrainment of Air 534
5.4.6 Temperature 535
5.4.7 Equipment-Specific Parameters 535
5.5 Washing Efficiency 537
5.5.1 Overview 537
5.5.2 Wash Yield 537
5.5.3 Displacement Ratio 538
5.5.4 Norden Efficiency Factor 539
5.5.5 Standardized Norden Efficiency Factor 545
5.6 Washing Equipment 547
5.6.1 General Remarks 547
5.6.2 Rotary Drum Washers 547
5.6.2.1 Conventional Drum Washers 547
5.6.2.2 Drum Displacer 549
5.6.3 Belt Washers 551
 Contents XI

5.6.4 Diffusion Washers 552

5.6.4.1 Atmospheric Diffuser 552
5.6.4.2 Pressure Diffuser 554
5.6.5 Roll Presses 556
5.6.6 In-Digester Washing 557

6 Pulp Screening, Cleaning, and Fractionation 561

Andreas W. Krotscheck
6.1 Introduction 561
6.2 Screening Theory 563
6.2.1 Introduction 563
6.2.2 Flow Regime 564
6.2.3 Fiber Passage and Reject Thickening 566
6.2.4 Selective Fiber Passage 570
6.3 Screening Parameters 572
6.3.1 Equipment Parameters 572
6.3.1.1 Screen Basket 572
6.3.1.2 Rotor 573
6.3.2 Operating Parameters 575
6.3.2.1 Reject Rate 575
6.3.2.2 Accept Flow Rate 575
6.3.2.3 Feed Consistency 577
6.3.2.4 Temperature 577
6.3.2.5 Rotor Tip Velocity 577
6.3.3 Furnish Parameters 578
6.3.3.1 Pulp Fibers 578
6.3.3.2 Contaminants 579
6.3.3.3 Entrained Air 579
6.4 Centrifugal Cleaning Theory 579
6.4.1 Introduction 579
6.4.2 Flow Regime 580
6.4.3 Sedimentation 581
6.4.4 Underflow Thickening 584
6.4.5 Selective Separation 585
6.5 Centrifugal Cleaning Parameters 586
6.5.1 Cyclone Parameters 586
6.5.2 Operating Parameters 587
6.5.2.1 Flow Rate and Pressure Drop 587
6.5.2.2 Feed Consistency 587
6.5.2.3 Temperature 587
6.5.3 Furnish Parameters 587
6.5.3.1 Pulp Fibers 587
6.5.3.2 Contaminants 588
6.6 Separation Efficiency 588
XII Contents

6.6.1 Screening and Cleaning Efficiency 588

6.6.2 Fractionation Efficiency 590
6.6.2.1 Removal Efficiency 590
6.6.2.2 Fractionation Index 591
6.7 Screening and Cleaning Applications 592
6.7.1 Selective Contaminant Removal 592
6.7.1.1 Knots 593
6.7.1.2 Shives 593
6.7.1.3 Bark 593
6.7.1.4 Sand and Stones 593
6.7.1.5 Metals and Plastics 594
6.7.2 Fractionation 594
6.8 Systems for Contaminant Removal and Fractionation 594
6.8.1 Basic System Design Principles 594
6.8.2 Systems for Contaminant Removal 596
6.8.2.1 Arrangement 596
6.8.2.2 Fiber Loss versus Efficiency 598
6.8.3 Systems for Fractionation 599
6.9 Screening and Cleaning Equipment 601
6.9.1 Pressure Screens 601
6.9.2 Atmospheric Screens 604
6.9.2.1 Secondary Knot Screens 604
6.9.2.2 Vibratory Screens 605
6.9.3 Hydrocyclones 605

Volume 2

7 Pulp Bleaching 609

Herbert Sixta, Hans-Ullrich Sss, Antje Potthast, Manfred Schwanninger,
and Andreas W. Krotscheck
7.1 General Principles 609
7.2 Classification of Bleaching Chemicals 610
7.2 Bleaching Operations and Equipment 613
Andreas W. Krotscheck
7.2.1 Basic Rheology of Pulp-Liquor Systems 614
7.2.2 Generic Bleaching Stage Set-Up 616
7.2.3 Medium Consistency Pumps 617
7.2.4 Medium Consistency Mixers 619
7.2.4.1 High-Shear Mixers 620
7.2.4.2 Static Mixers 621
7.2.4.3 Atmospheric Steam Mixers 622
7.2.5 Medium Consistency Reactors 623
7.2.5.1 Atmospheric Upflow Reactors 623
 Contents XIII

7.2.5.2 Atmospheric Downflow Reactors 624

7.2.5.3 Pressurized Reactors 625
7.2.6 Blowtank 627
7.2.7 Agitators 627
7.2.8 Washing 628
7.3 Oxygen Delignification 628
7.3.1 Introduction 628
7.3.2 Chemistry of Oxygen Delignification 632
Manfred Schwanninger
7.3.2.1 Bleachability 634
7.3.2.2 Lignin Structures and their Reactivity 634
7.3.2.3 Oxygen (Dioxygen) and its Derivatives 641
7.3.2.4 A Principal Reaction Schema for Oxygen Delignification 649
7.3.2.5 Carbohydrate Reactions in Dioxygen-Alkali Delignification
Processes 657
7.3.2.6 Residual LigninCarbohydrate Complexes (RLCC) 666
7.3.2.7 Inorganics (Metals) and their Role in the Protection/
Degradation of Cellulose 668
7.3.3 Mass Transfer and Kinetics 671
Herbert Sixta
7.3.3.1 Kinetics of Delignification 672
7.3.3.2 Kinetics of Cellulose Chain Scissions 685
7.3.3.3 Application of Surfactants 687
7.3.4 A Model to Predict Industrial Oxygen Delignification 688
7.3.4.1 Theoretical Base of the van Heiningen Model 690
7.3.4.2 Case Study 695
7.3.5 Process Variables 701
7.3.5.1 Temperature 701
7.3.5.2 Retention Time 702
7.3.5.3 Alkali Charge 703
7.3.5.4 pH Value 704
7.3.5.5 Final pH 705
7.3.5.6 Alkali Source 706
7.3.5.7 Oxygen Charge, Oxygen Pressure 707
7.3.5.8 Consistency 708
7.3.6 Pulp Components and Impurities 708
7.3.6.1 Effect of Metal Ion Concentration 708
7.3.6.2 Residual Lignin Structures 713
7.3.6.3 Carry-Over 716
7.3.6.4 Xylan Content 719
7.3.6.5 Selectivity of Oxygen Delignification 720
7.3.7 Process and Equipment 721
7.3.7.1 MC versus HC Technology 721
7.3.7.2 Process Technology 722
7.3.7.3 Process Equipment 731
XIV Contents

7.3.8 Pulp Quality 733

7.4 Chlorine Dioxide Bleaching 734
7.4.1 Introduction 734
7.4.2 Physical and Chemical Properties and Definitions 735
7.4.2.1 Behavior of Chlorine Dioxide in Aqueous Solution 737
7.4.2.2 Inorganic Side Reactions during Chlorine Dioxide Bleaching of Wood
Pulps 737
7.4.3 Generation of Chlorine Dioxide 741
7.4.4 Chemistry of Chlorine Dioxide Treatment 745
Manfred Schwanninger
7.4.4.1 Chlorination Products 752
7.4.5 Performance of Chlorine Dioxide Bleaching 754
7.4.5.1 Standard Chlorine Dioxide Bleaching 754
7.4.5.2 Chlorine Dioxide Bleaching of Oxygen-Delignified Kraft Pulps 759
7.4.5.3 Modified Chlorine Dioxide Bleaching 761
7.4.6 Technology of Chlorine Dioxide Bleaching 770
Andreas W. Krotscheck
7.4.7 Formation of Organochlorine Compounds 771
7.5 Ozone Delignification 777
7.5.1 Introduction 777
7.5.2 Physical Properties of Ozone 778
7.5.3 Ozone Generation 782
7.5.4 Chemistry of Ozone Treatment 785
Manfred Schwanninger
7.5.4.1 Ozone Decomposition 786
7.5.4.2 Degradation of Lignin 790
7.5.4.3 Degradation of Carbohydrates 794
7.5.5 Process Conditions 798
7.5.5.1 Mass Transfer 798
7.5.5.2 Mixing and Mixing Time 802
7.5.5.3 Effect of Pulp Consistency 806
7.5.5.4 Effect of pH 811
7.5.5.5 Effect of Temperature 813
7.5.5.6 Effect of Transition Metal Ions 814
7.5.5.7 Effect of Carry-Over 816
7.5.5.8 Effect of Pretreatments and Additives 818
7.5.5.9 Effect of Sodium Borohydride after Treatment 822
7.5.5.10 Effect of Alkaline Extraction 824
7.5.6 Technology of Ozone Treatment 826
Andreas W. Krotscheck
7.5.6.1 Medium-Consistency Ozone Treatment 826
7.5.6.2 High-Consistency Ozone Treatment 827
7.5.6.3 Ozone/Oxygen Gas Management 828
7.5.7 Application in Chemical Pulp Bleaching 829
7.5.7.1 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
XVI Contents

8 Pulp Purification 933

Herbert Sixta
8.1 Introduction 933
8.2 Reactions between Pulp Constituents and Aqueous Sodium Hydroxide
Solution 935
8.3 Cold Caustic Extraction 942
8.3.1 NaOH Concentration 942
8.3.2 Time and Temperature 944
8.3.3 Presence of Hemicelluloses in the Lye 945
8.3.4 Placement of CCE in the Bleaching Sequence 948
8.3.5 Specific Yield Loss, Influence on Kappa Number 949
8.3.6 Molecular Weight Distribution 951
8.4 Hot Caustic Extraction 952
8.4.1 Influence of Reaction Conditions on Pulp Quality and Pulp Yield 953
8.4.1.1 NaOH Charge and Temperature in E, (EO), and (E/O) Treatments 953
8.4.1.2 Xylan versus R18 Contents 957
8.4.1.3 Purification versus Viscosity 959
8.4.1.4 Purification versus Kappa Number and Extractives 960
8.4.1.5 Composition of Hot Caustic Extract 961
8.4.2 MgO as an Alternative Alkali Source 962

9 Recovery 967
Andreas W. Krotscheck and Herbert Sixta
9.1 Characterization of Black Liquors 967
9.1.1 Chemical Composition 967
9.1.2 Physical Properties 970
9.1.2.1 Viscosity 970
9.1.2.2 Boiling Point Rise (BPR) 970
9.1.2.3 Surface Tension 971
9.1.2.4 Density 971
9.1.2.5 Thermal Conductivity 972
9.1.2.5 Heat Capacity [8,11] 972
9.2 Chemical Recovery Processes 973
9.2.1 Overview 973
9.2.2 Black Liquor Evaporation 974
9.2.2.1 Introduction 974
9.2.2.2 Evaporators 975
9.2.2.3 Multiple-Effect Evaporation 977
9.2.2.4 Vapor Recompression 979
9.2.3 Kraft Chemical Recovery 980
9.2.3.1 Kraft Recovery Boiler 980
9.2.3.2 Causticizing and Lime Reburning 986
9.2.3.3 The Future of Kraft Chemical Recovery 992
9.2.4 Sulfite Chemical Recovery 994
 Contents XVII

10 Environmental Aspects of Pulp Production 997

Hans-Ulrich Sss
10.1 Introduction 997
10.2 A Glimpse of the Historical Development 998
10.3 Emissions to the Atmosphere 1002
10.4 Emissions to the Aquatic Environment 1004

10.5 Solid Waste 1006

10.6 Outlook 1007

11 Pulp Properties and Applications 1009

Herbert Sixta
11.1 Introduction 1009
11.2 Paper-Grade Pulp 1010
11.3 Dissolving Grade Pulp 1022
11.3.1 Introduction 1022
11.3.2 Dissolving Pulp Characterization 1024
11.3.2.1 Pulp Origin, Pulp Consumers 1024
11.3.2.2 Chemical Properties 1026
11.3.2.3 Supramolecular Structure 1041
11.3.2.4 Cell Wall Structure 1047
11.3.2.5 Fiber Morphology 1051
11.3.2.6 Pore Structure, Accessibility 1052
11.3.2.7 Degradation of Dissolving Pulps 1056
11.3.2.8 Overview of Pulp Specification 1060

II Mechanical Pulping 1069

Jrgen Blechschmidt, Sabine Heinemann, and Hans-Ulrich Sss

1 Introduction 1071
Jrgen Blechschmidt and Sabine Heinemann

2 A Short History of Mechanical Pulping 1073

Jrgen Blechschmidt and Sabine Heinemann

3 Raw Materials for Mechanical Pulp 1075

Jrgen Blechschmidt and Sabine Heinemann
3.1 Wood Quality 1075
3.2 Processing of Wood 1076
XVIII Contents

3.2.1 Wood Log Storage 1076

3.2.2 Wood Log Debarking 1076
3.2.3 Wood Log Chipping 1078

4 Mechanical Pulping Processes 1079

Jrgen Blechschmidt and Sabine Heinemann
4.1 Grinding Processes 1079
4.1.1 Principle and Terminology 1079
4.1.2 Mechanical and Thermal Processes in Grinding 1080
4.1.2.1 Softening of the Fibers 1080
4.1.2.2 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
5.1 Basic Principles and Parameters 1113
5.2 Machines and Aggregates for Screening and Cleaning 1114
5.3 Reject Treatment and Heat Recovery 1121

6 Bleaching of Mechanical Pulp 1123

Hans-Ulrich Sss
6.1 Bleaching with Dithionite 1124
6.2 Bleaching with Hydrogen Peroxide 1126
6.3 Technology of Mechanical Pulp Bleaching 1134

7 Latency and Properties of Mechanical Pulp 1137

Jrgen Blechschmidt and Sabine Heinemann
7.1 Latency of Mechanical Pulp 1137
7.2 Properties of Mechanical Pulp 1138
 Contents XIX

III Recovered Paper and Recycled Fibers 1147

Hans-Joachim Putz

1 Introduction 1149

2 Relevance of Recycled Fibers as Paper Raw Material 1153

3 Recovered Paper Grades 1157

3.1 Europe 1157

3.2 North America and Japan 1161
3.2.1 United States 1162
3.2.2 Japan 1163

4 Basic Statistics 1165

4.1 Utilization Rate 1167
4.2 Recovery Rate 1170
4.3 Recycling Rate 1173
4.4 Deinked Pulp Capacities 1174
4.5 Future Development of the Use of Recovered Paper 1175

5 Collection of Recovered Paper 1177

5.1 Pre-Consumer Recovered Paper 1178
5.2 Post-Consumer Recovered Paper 1178
5.2.1 Pick-Up Systems 1178
5.2.2 Drop-Off Systems 1179
5.3 Efficiency of Different Collection Systems 1180
5.4 Municipal Solid Waste 1181

6 Sources of Recovered Paper 1183

7 Sorting, Handling, and Storage of Recovered Paper 1187

7.1 Sorting 1187

7.2 Handling 1189
7.3 Storage 1190

8 Legislation for the Use of Recycled Fibers 1191

8.1 Europe 1192
8.2 United States of America 1195
8.3 Japan 1198

Appendix: European List of Standard Grades of Recovered Paper and

Board (February, 1999) 1203
XX Contents

IV Analytical Characterization of Pulps 1211

Erich Gruber

1 Fundamentals of Quality Control Procedures 1213

1.1 The Role of QC 1214
1.2 Basics of QC-statistics 1214
1.3 Sampling 1216
1.4 Conditions for Testing and/or Conditioning 1216
1.5 Disintegration 1217

2 Determination of Low Molecular-Weight Components 1219

2.1 Moisture 1219
2.2 Inorganic Components 1219
2.2.1 Ashes 1220
2.2.1.1 Total Ash 1220
2.2.1.2 Sulfated Ash 1220
2.2.1.3 Acid-Insoluble Ash 1220
2.2.2 Determination of Single Elements 1221
2.2.2.1 Survey of Chemical Procedures 1221
2.2.2.2 Atomic Absorption Spectroscopy (AAS) 1222
2.2.2.3 X-ray Fluorescence Spectroscopy (XFS) 1223
2.2.2.4 Electron Spectroscopy for Chemical Application (ESCA) 1223
2.3 Extractives 1224
2.3.1 Water Extractives 1224
2.3.1.1 Test Water 1224
2.3.1.2 Cold Water Extraction 1225
2.3.1.3 Hot Water Extraction 1225
2.3.1.4 Analysis of Water Extracts 1225
2.4 Chlorine Compounds 1225

3 Macromolecular Composition 1227

3.1 Lignin Content 1227
3.2 Extent of Delignification 1228
3.2.1 Roe Number 1228
3.2.2 Chlorine Number 1228
3.2.3 Kappa Number (Permanganate Number) 1228
3.3 Alkali Resistance and Solubility 1229
3.3.1 Alkali-Soluble Components 1229
3.3.2 a-, b-, and c-cellulose 1229
3.3.3 R18 and S18 values 1230
3.4 Composition of Polysaccharides 1231
3.4.1 Determination of Monosaccharides after Hydrolysis 1231
3.4.1.1 Gas Chromatography 1231
3.4.1.2 Thin-Layer Chromatography 1232
 Contents XXI

3.4.1.3 Liquid Chromatography 1232

3.4.2 Determination of Pentosans after Hydrolysis 1233
3.4.3 Determination of Uronic Acids after Hydrolysis 1233
3.5 Functional Groups 1234
3.5.1 Carbonyl Functions 1234
3.5.1.1 Copper Number 1235
3.5.1.2 Sodium Borohydride Method 1236
3.5.1.3 Hydrazine Method 1236
3.5.1.4 Oxime Method 1236
3.5.1.5 Girard-P Method 1237
3.5.1.6 Cyanohydrin Method 1237
3.5.1.7 Fluorescent Dying 1237
3.5.2 Carboxyl Functions 1238
3.6 Degree of Polymerization (Molecular Mass) 1239
3.6.1 Solvents for Cellulose 1240
3.6.1.1 CUOXAM 1241
3.6.1.2 CUEN 1241
3.6.1.3 Iron Sodium Tartrate (EWNN) 1241
3.6.2 Diverse Average Values of Molecular Mass and Index of
Nonuniformity 1241
3.6.3 Methods to Determine Molar Mass (Molecular Weight) 1243
3.6.3.1 Osmosis 1243
3.6.3.2 Scattering Methods 1245
3.6.4 Viscosity Measurements 1248
3.6.4.1 Solution Viscosity as a Measure of Macromolecular Chain Length 1248
3.6.4.2 Viscosity Measurements on Cellulose Pulps 1251
3.6.5 Molecular Weight Distribution 1251
3.6.5.1 Fractional Precipitation or Solution 1251
3.6.5.2 Size-Exclusion (Gel-Permeation) Chromatography 1252

4 Characterization of Supermolecular Structures 1257

4.1 Crystallinity 1257

4.1.1 Degree of Crystallinity 1257
4.1.1.1 X-Ray Diffraction 1259
4.1.1.2 Solid-phase NMR-Spectroscopy 1261
4.1.1.3 Reaction Kinetics 1262
4.1.1.4 Density Measurements 1262
4.1.2 Dimension of Crystallites 1263
4.1.3 Orientation of Crystallites 1265
4.2 Accessibility, Voids, and Pores 1265
4.2.1 Porosity 1266
4.2.2 Accessible Surface 1267
4.3 Water and Solvent Retention 1268
XXII Contents

4.3.1 Total Water Uptake 1268

4.3.2 Free and Bound Water 1268

5 Fiber Properties 1269

5.1 Identification of Fibers 1269

5.1.1 Morphological Characterization 1269
5.1.2 Visible and UV Microscopy 1271
5.1.3 Electron Microscopy 1271
5.2 Fiber Dimensions 1272
5.2.1 Fiber Length and Width 1273
5.2.1.1 Microscopic Methods and Image Analysis 1273
5.2.1.2 Fiber Fractionation by Screening 1274
5.2.2 Coarseness 1275
5.3 Mechanical Properties 1275
5.3.1 Single Fiber Properties 1275
5.3.1.1 Wet Fiber Properties 1275
5.3.1.2 Mechanical Properties of Dry Fibers 1277
5.3.2 Sheet Properties 1278
5.3.2.1 Preparation of Laboratory Sheets for Physical Testing 1278
5.3.2.2 Determination of Mechanical Pulp Sheet Properties 1279
5.4 Optical Properties of Laboratory Sheets 1279

6 Papermaking Properties of Pulps 1281

6.1 Beating 1281

6.2 Drainage Resistance 1281
6.3 Drainage (Dewatering) Time 1283
6.4 Aging 1284
6.4.1 Accelerated Aging 1284

Index 1291
 XXIII

Preface

Pulp is a fibrous material resulting from complex manufacturing processes that

involve the chemical and/or mechanical treatment of various types of plant mate-
rial. Today, wood provides the basis for approximately 90% of global pulp produc-
tion, 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 Pro-
cesses 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 Charac-
terization 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
XXIV 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, cover-
ing 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 bleach-
ing chemistry and technology. High-purity pulps are important raw materials for
the production of high added-value cellulose products, and the necessary purifica-
tion 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 analyti-
cal 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 com-
mitment.
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), Hans-
Georg Richter of the BFH, Germany (Part I, Chapter 2), Rudolf Patt of the Univer-
sity 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 Wes-
tin 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 cook-
ing and oxygen delignification kinetics. I also owe sincere thanks to the manage-
ment of Lenzing AG for the assistance granted to me by their library services.
 XXV

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 presen-
tation of this book, and the personnel at Wiley-VCH for their cooperation and skil-
ful editorial work.

Lenzing, H. Sixta
December 2005

Handbook of Pulp. Edited by Herbert Sixta

Copyright 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30999-3
 XXVII

List of Contributors

Jrgen Blechschmidt Antje Potthast

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

Handbook of Pulp. Edited by Herbert Sixta

Copyright 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-30999-3
XXVIII List of Contributors

Herbert Sixta Hans-Ulrich Sss

Lenzing AG Degussa AG
Business Unit Pulp Global Competence Center
Werkstrae 1 Active Oxygen Products
4860 Lenzing O2-AO-AT, 913-120
Austria Rodenbacher Chaussee 4
63594 Hanau
Germany
 List of Abbreviations XXIX

List of Abbreviations

4OMeGlcA 4-O-methyl-bd-glucuronic acid-(12)-xylose)

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

DIP deinked pulp

DP degree of polymerization
DSC differential scanning calorimetry
DTPA diethylene triamino penta-acetate
EAPC enhanced alkali profile cooking
ECCSA effective capillary cross-sectional area
ECF elemental chlorine-free
EDR equivalent displacement ratio
EDXA energy dispersive X-ray analysis
EPA Environmental Protection Agency
ERPA European Recovered Paper Association
ERPC European Recovered Paper Council
ESCA electron spectroscopy for chemical analysis
ESR electron spin resonance
EUGROPA European Paper Merchants Association
FBSKP fully bleached softwood kraft pulp
FEAD 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 molecular weight distribution

NCG noncondensable gases
NHV net heating value
NHWA National Household Recovery Analysis
NMR nuclear magnetic resonance
NPEs non-process elements
NSSC neutral sulfite semi-chemical
ODE ordinary differential equation
OXE oxidation equivalent
PAD pulsed amperometric detection
PCDD polychlorinated dibenzo-p-dioxins
PCDF polychlorinated dibenzofurans
PDI polydispersity index
PGW pressure groundwood
PHK prehydrolysis kraft pulp
PRMP pressurized refiner mechanical pulp
PSA pressure swing adsorption
RAC Recycling Advisory Council
RDH rapid displacement heating
RLLC residual lignincarbohydrate complex
RMP refiner mechanical pulp
RTS retention time, temperature, speed
SAXS small-angle X-ray scattering
SC supercalendered
SEM scanning electron microscopy
SET single electron transfer
SGW stone groundwood
SRV solvent retention value
SSL spent sulfite liquor
TCF totally chlorine free
TEM transmission electron microscopy
TEQ toxic equivalency quantity
TGW thermo groundwood
TMP thermomechanical pulp
TOC total organic carbon
ToF-SIMS time-of-flight secondary ion mass spectroscopy
TRS total reduced sulfur
TSS total suspended solids
TTA total titrable alkali
UCC upper cooking circulation
UMSP scanning UV microspectrophotometry
VOC volatile organic compounds
VSA vacuum swing adsorption

WAXS wide-angle X-ray scattering

XXXII List of Abbreviations

WRV water retention value

XFS X-ray fluorescence spectroscopy
XPS X-ray photoelectron spectroscopy