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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

XIV Contents

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 Suss

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 Suss

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 Suss

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