Kent and Riegel's Handbook of Industrial Chemistry and Biotechnology (eBook)

James A. Kent has extensive experiences as a chemical engineer and engineering educator. He most recently served as Chrysler Professor and Dean of Engineering and Science at the University of Detroit Mercy and, prior to that, he was Professor and Dean of Engineering at Michigan Technological University, and Professor of Chemical Engineering and Associate Dean for Research and Graduate Studies at West Virginia University. Dr. Kent’s industry experience included assignments as Research Engineer and Research Group Leader at Dow Chemical Company and Monsanto. He also served as editor of the sixth through ninth editions of the Handbook. Dr. Kent is a long time member of AIChE.

Volume I 
2 
Title Page 3
Copyright Page 4
Preface 6
Table of Contents 9
1 Recent History of the Chemical Industry* 1973 to the Millenium: The New Facts of World Chemicals Since 1973 11
I. OVERCAPACITIES AND THE SEARCH FOR REMEDIES 11
THE RESTRUCTURING OF SECTORS IN DISTRESS 12
THE NATIONALIZATION OF FRANCE'S CHEMICAL INDUSTRY 16
RESTRUCTURING IN ITALY AND SPAIN 18
ARAB COUNTRIES GAIN A FOOTHOLD 19
THE AMERICAN CHEMICAL INDUSTRY CAUGHT OFF BALANCE 19
COPING WITH SAFETY AND ENVIRONMENTAL PROBLEMS 22
SCIENTIFIC AND TECHNOLOGICAL BREAKTHROUGHS 23
Process Improvement 23
Product Development 24
THE CRAZE FOR BIOTECHNOLOGY 26
THE FINE CHEMICALS APPROACH 29
THE ATTRACTION OF SPECIALTY CHEMICALS 30
THE PAINT INDUSTRY 32
SURFACE-ACTIVE AGENTS 33
FLAVORS, FRAGRANCES, AND BEAUTY PRODUCTS 35
THE CHEMISTRY OF ADDITIVES 38
Additives for Plastics 39
Rubber Additives 40
Additives for Lubricants 41
Food Additives 43
PHOTOCHEMICALS 44
THE ALLIANCE OF CHEMICALS AND ELECTRONICS 46
CATALYSTS 47
RETROSPECT AND PROSPECT 48
II. THE PERIOD OF THE 1990s 50
THE CHEMICAL INDUSTRY UNDER PRESSURE FROM PUBLIC OPINION AND REGULATORY AUTHORITIES 50
THE STATUS OF SCIENCE AND TECHNOLOGY 52
THE NEW LANDSCAPE 53
THE TRIALS AND TRIBULATIONS OF THE PHARMACEUTICAL INDUSTRY 54
THE RESHUFFLING OF CHEMICAL ASSETS 55
THE IMPOSSIBLE MARRIAGE OF PHARMACEUTICALS WITH AGROCHEMICALS 56
THE FATE OF THE DYESTUFFS SECTOR 57
CONSOLIDATION IN THE FIELD OF SPECIALTY CHEMICALS 58
THE CASE OF FINE CHEMICALS 63
THE FURTHER CONCENTRATION OF THE INDUSTRIAL GAS BUSINESS 64
THE CHANGING TIES BETWEEN THE OIL AND CHEMICAL INDUSTRIES 65
THE ROLE OF ENTREPRENEURS AND PRIVATE EaUITY FUNDS 67
THE EVERLASTING PRESENCE OF CONTRARIANS 68
THE CASE OF JAPAN 71
THE CHEMICAL INDUSTRY AT THE BEGINNING OF THE THIRD MILLENNIUM 71
2 Economic Aspects of the Chemical Industry 73
DEFINITION OF THE CHEMICAL INDUSTRY 73
THE PLACE OF THE CHEMICAL INDUSTRY IN THE ECONOMY 75
CHARACTERISTICS OF THE CHEMICAL INDUSTRY 80
Investment Trends 80
Commercial Development and Competition Factors 80
Technological Orientation 82
Historical 83
Obsolescence and Dependence on Research 84
THE FUTURE 88
REFERENCES 91
3 Safety Considerations in the Chemical Process Industries 93
INTRODUCTION 93
INHERENTLY SAFER PLANTS* 94
Responsibility for Safety in Design and Operation 94
Review of Design Alternatives 94
Emergency Planning 95
Placement of Process andS to rage Areas 95
Storage of Hazardous Mate rials 95
Liquefied Gas Storage 96
Use of Open Struct ures 96
Need to Understand Reactive Chemicals Systems 97
Losses from Dust Explosions 98
Substitution of Less Hazardous Materials 99
Catastrophic Failure of Engineering Materials10- 12 100
Redundant Instrumentation and Control Systems13 100
Pressure Relief Systems 101
Safe and Rapid Isolation of Piping Systems and Equipment 102
Piping, Gaskets, and Valves 102
Avoidance of Inherently Unsafe Equipment 103
Pumps for Hazardous Service 104
TECHNICAL MANAGEMENT OF CHEMICAL PROCESS SAFETY 105
PROCESS SAFETY MANAGEMENT SYSTEMS 107
Some Tools for Evaluating Risks and Hazards 108
Some Tools for Evaluating Risks and Hazards 108
EVALUATION OF HAZARDS AND RISKS 109
HAZOP2,50-53 109
Operating Discipline 109
Risk Analysis and Assessment 110
Quantitative Risk Analysis (QRA) 110
COMBUSTION HAZARDS 110
Introduction 110
Fire26 111
Flammability 113
Inert Gases 115
Mists and Foams 117
Ignition 118
STATIC ELECTRICITY 122
Introduction 122
Hazard Determinants 123
EXPLOSIONS 127
Deve lopment of Pressure 127
Deflagration 128
Detonations 128
Explosion Violence 129
BOILING LIQUID EXPANDING VAPOR EXPLOSIONS (BLEVES) 131
DAMAGE ESTIMATES37 132
Explosion Consequences 132
Radiation Consequences 132
Unconfined Vapor Cloud Explosions (UVCE) 132
Physical Explosions 134
MECHANICAL HEAT 136
VACUUM49 137
Protective Measures for Equipment 138
REGULATIONS* 138
Process Safety Management 138
Risk Management Plans (RMPs) 144
Taxies Release Inventory 145
HAZWOPER 145
More Information 145
THE PRINCIPAL REASON FOR MOST CHEMICAL PROCESS ACCIDENTS 145
Levels of Causes 146
CASE HISTORIES 146
Flixborough, England 19742 146
Bhopal, 1985 (C& EN Feb. 11, 1985
Phillips Explosion, 198957 148
SUMMARY 152
REFERENCES 152
ADDITIONAL READING REFERENCES 154
Internet References and WEB pages 155
4 Managing an Emergency Preparedness Program 157
INTRODUCTION 157
Prevention, Prediction, and Preparation 157
Need for Emergency Preparedness Programs 158
PREVENTING AND PREDICTING EMERGENCIES: GETIING STARTED 159
HAZARD IDENTIFICATION AND MITIGATION 161
Process Safety Management Team 162
Identifying Hazards: PSRTeams 162
Review Methods 162
Recommendations and Reports 163
Mitigating Hazards: Release Detection and Mitigation 163
PREPARING FOR EMERGENCIES: IDENTIFYING AND EVALUATING RESOURCES 165
Personnel 165
Plans 166
Alarm Systems 168
Facilities for Protectionand Communication 169
DEVELOPING AN ERP 170
Plan Design 171
EMO Structure 171
TRAINING PERSONNEL 174
Fire Brigade Training 174
EMO Training 175
Employee Training 175
Facility Drills 176
INVOLVING THE COMMUNITY 176
Communications 176
Integrating Plans 178
Off-Site Warning 178
Local Emergency Plans 178
Local Emergency Planning Committees 179
Drills and Crit iques 179
LAWS, REGULATIONS, AND SUPPORT 180
Laws 180
Meeting the Requirements 181
Prevention and Preparation 181
Plans 181
Communications 181
Reports 182
Training, Drills, Audits , and Evaluations 184
Sources of Assistance 184
SELECT BIBLIOGRAPHY 184
Standards 185
SUGGESTED READING 185
Regulations 185
Prevention and Planning 185
LAWS, REGULATIONS, AND STANDARDS 186
Laws and Regulations 186
Transportation 187
5 Applied Statistical Methods and the Chemical Industry 188
INTRODUCTION 188
SIMPLE TOOLS OF DESCRIPTIVE STATISTICS 189
TOOLS OF ROUTINE INDUSTRIAL PROCESS MONITORING AND CAPABILITY ASSESSMENT 195
STATISTICAL METHODS AND INDUSTRIAL EXPERIMENTATION 201
Identifying Major Contributors to Process Variation 202
Discovering and Exploiting Patterns of Factor Influence on Responses 205
Mixture Experiments 211
Mechanistic Model Building 216
MODERN BUSINESS PROCESS IMPROVEMENT AND THE DISCIPLINE OF STATISTICS 217
CONCLUSION 218
REFERENCES 218
6 Green Engineering-Integration of Green Chemistry, Pollution Prevention, and Risk-Based Considerations 220
OVERVIEW 220
I. INTRODUCTION TO GREEN CHEMISTRY AND GREEN ENGINEERING 221
TWELVE PRINCIPLES OF GREEN CHEMISTRY* 224
PRINCIPLES OF GREEN ENGINEERING 226
II POLLUTION PREVENTION HEURISTICS FOR CHEMICAL PROCESSES 227
INTRODUCTION 227
HIERARCHICAL RULES FOR WASTE MINIMIZATION 228
Batch or Continuous? 229
Input-Output Structure 229
Recycle Structure of the Flowsheet 230
Reaction Systems 231
Separation Systems 231
Postprocessing and Product Section 232
Energy Systems 232
Auxiliary Equipments 233
HEURISTICS FOR GREEN REACTOR DESIGN 233
THE P2 RULES FOR SEPARATIONS DEVICES 234
Distillation Columns 234
Gas-Liquid Separation 235
Gas-Solid Separations 235
Liquid-Solid Separations 235
ACRONYMS 236
ACKNOWLEDGMENT 236
III UNDERSTANDING AND PREDICTION OF THE ENVIRONMENTAL FATE OF CHEMICALS 236
INTRODUCTION 236
TRANSLOCATION OF CHEMICALS IN THE ENVIRONMENT 236
Modeling the Environment 236
Translocation Processes in Air 237
Translocation Processes in Water 239
Translocation Processes in Soil 240
Translocation Processes Involving Biota 240
TRANSFORMATION OF CHEMICALS IN THE ENVIRONMENT 241
Biotic Transformation Processes 242
Abiotic Transformation Processes 243
THE CONNECTION BETWEEN CHEMICAL PROPERTIES AND ENVIRONMENTAL FATE 246
Traditional Chemical Properties 246
Specialized Chemical Properties 247
Sources of Chemical Property and Fate Data 248
HEURISTICS FOR PREDICTING ENVIRONMENTAL FATE 249
IV ENVIRONMENTAL PERFORMANCE ASSESSMENT FOR CHEMICAL PROCESS DESIGN 249
INTRODUCTION 249
OVERVIEW OF ENVIRONMENTAL ISSUES 249
ENVIRONMENTAL IMPACT ASSESSMENT: TIER I-TIER III 253
Early Process Design Evaluations: "Tier I" Assessment 253
Evaluations During Process Synthesis: "Tier II" Assessment 255
Detailed Evaluation of Process Flowsheets: "Tier III" Assessment 255
Hybrid Screening Evaluations: Combining "Tier I"-"Tier III"-Life Cycle Assessment 259
CONCLUSIONS 262
V LIFE-CYCLE ASSESSMENT 264
INTRODUCTION 264
GOAL AND SCOPE OF LCA 266
METHODS OF LIFE-CYCLE INVENTORY 267
IMPACT ASSESSMENT AND ANALYSIS 269
LCA IN PRACTICE 269
CONCLUSIONS 274
REFERENCES 274
ADDITIONAL SUGGESTED READING 279
Introduction to Green Chemistry and Green Engineering 279
2.2 Pollution Prevention Heuristics for Chemical Processes 279
2.3 Understanding and Prediction of the Environmental Fate of Chemicals 279
2.4 Environmental Performance Assessment for Chemical Process Design 280
2.4 Life-Cycle Assessment 280
7 Industrial Catalysis: A Practical Guide 281
THE IMPORTANCE OF CATALYSIS 281
HOW DOES A CATALYST WORK? 283
WHAT ARE THE CATALYTIC METALS AND METAL OXIDES? 283
THE STRUCTURE OF HETEROGENEOUS CATALYSTS 283
Rate-Limiting Steps for a Supported Catalyst 284
Selectivity 288
Catalyst Preparation 289
A HETEROGENEOUS CATALYTIC REACTION: AN EXAMPLE 290
ACTIVE CATALYTIC SITES 290
Reactor Types 291
Kinetics 291
Rate Models 294
Catalyst Deactivation 294
CATALYST CHARACTERIZATION 296
HOMOGENEOUS CATALYTIC REACTIONS 297
Commercial Applications 297
Petroleum Processing 297
CATALYSTS FOR CONTROLLING AUTOMOTIVE EMISSIONS 301
Oxidation Catalysts to Abate Unburned Hydrocarbon and CO Emissions 301
Three-Way Catalytic Conversion 302
Modern Catalytic Converter Systems 304
CATALYTIC HYDROGENATION OF VEGETABLE OILS FOR EDIBLE FOOD PRODUCTS 305
Triglycerides 305
FERTILIZERS AND HYDRO GENGENERATION 306
General Reactions 306
Hydrogen Generation for the Production of NH3 307
Ammonia Synthesis 309
Nitric Acid Synthesis 309
Pure Hydrogen Generation with Pressure Swing Adsorption (PSA) Purification 310
PRODUCTION OF BUTYRALDEHYDE: A HOMOGENEOUS CATALYTIC REACTION 311
Butyraldehyde 311
POLYETHYLENE AND POLYPROPYLENE FOR THE PRODUCTION OF PLASTICS 312
Polyethylene 312
Polypropylene 312
CATALYST CHALLENGES 313
REFERENCES 313
8 Environmental Chemical Determinations 315
INTRODUCTION 315
SIGNIFICANCE OF ENVIRONMENTAL CHEMICAL DETERMINATIONS 315
CHEMICAL ANALYSIS STRATEGIES 316
Samples and Sampling Strategies 316
Determination of Total Elements or Total Related Substances. 317
Determination of Specific Substances 318
Single-Analyte and Multi-Analyte Methods 320
Remote Laboratory Analyses and Field Analyses 320
Discrete Samples and Continuous Monitoring 321
Analytical Quality Assurance and Control 322
DEVELOPMENT AND DOCUMENTATION OF ANALYTICAL METHODS 322
Research Methods 322
Methods in Development 323
Methods Published by Standard-Setting Organizations 323
Methods Published or Referenced in Government Agency Regulations 323
CHARACTERISTICS OF ANALVTES, SAMPLES, AND SAMPLING TECHNIQUES 324
Volatile Analytes 324
Semivolatile Analytes 324
Nonvolatile Analytes 326
Condensed-Phase Samples 326
Vapor-Phase Samples 328
PROCESSING OF SAMPLES BEFORE DETERMINATION OF THE ANALVTES 330
CHROMATOGRAPHIC ANALYTICAL METHODS 331
Chromatographic Separation Techniques 331
Chromatography Detectors 333
NONCHROMATOGRAPHIC ANALYTICAL METHODS 334
Elemental Analysis 334
Organic and Inorganic Compounds and Ions 336
GLOSSARY 336
REFERENCES 337
SUGGESTED ADDITIONAL READING 337
9 Nanotechnology: Fundamental Principles and Applications 338
INTRODUCTION 338
A NEW REALM OF MATTER 339
SOLVATED METAL ATOM DISPERSION (SMAD) METHOD FOR THE PREPARATION OF NANOPARTICLES 340
Gold Nanoparticles 342
Silver Nanoparticles 344
Semiconductor Nanoparticles 345
Dielectrics (Insulator Nanoparticlesl 346
MODIFIED AEROGEL PROCEDURE (MAP) 347
Metal Oxide Nanoparticles 348
MIXED METAL OXIDE NANOPARTICLES 349
APPLICATIONS 351
Catalysis-Dechlorination and Dehydrochlorination 351
Destructive Adsorption of Chemical Warfare ICW) Agents 351
MISCELLANEOUS APPLICATIONS 352
Environmental Chemistry 352
Photocatalysis 352
Plastics 352
Medicine 352
Electrochemistry 353
CONCLUSIONS 353
REFERENCES 353
10 Synthetic Organic Chemicals 355
CHEMICALS DERIVED FROM METHANE 356
Synthesis Gas 356
Chloromethanes 362
Acetylene 363
Hydrogen Cyanide 363
Carbon Disulfide 364
CHEMICALS DERIVED FROM ETHYLENE 364
Polyethylene 364
Ethylene Oxide 365
Chlorinated Ethanes and Ethylenes 369
Ethanol 374
Ethylbenzene 374
Acetaldehyde, Acetic Acid, Acetic Anhydride, Vinyl Acetate 376
Ethylene Oligomers (Alpha Olefinsl and Linear Primary Alcohols 381
Ethylene-Propylene Elastomers 381
Propionaldehyde 381
Other Ethylene Uses 381
CHEMICALS DERIVED FROM PROPYLENE 383
Polypropylene 383
Acrylonitrile 384
Propylene Oxide 384
Isopropyl Alcohol 385
Cumene 388
Oxo Chemicals 388
Propylene Oligomers: Dodecene and Nonene 389
Acrylic Acid and Esters 389
Epichlorohydrin 390
Glycerin 390
CHEMICALS DERIVED FROM BUTANES AND BUTYLENES 391
n-Butane Derivatives 392
Isobutanes 395
Butylenes 397
Isobutylene 398
Butadiene 400
HIGHER ALIPHATIC HYDROCARBONS 400
Cyclopentadiene 400
Isoprene 400
n-Paraffins and OIefins 401
Primary and Secondary Higher Alcohols 401
CHEMICALS DERIVED FROM BENZENE, TOLUENE, AND XYLENE 401
Chemicals from Benzene 401
Derivatives of Toluene 408
Chemicals from Xylene 409
Naphthalene Derivatives 412
REFERENCES 412
11 Chemistry in the Pharmaceutical Industry 414
INTRODUCTION 414
MEDICINAL CHEMISTRY 415
Research Strategies 417
Pharmacodynamics 418
Pharmacokinetics and Toxicity 418
Drug Delivery 419
Patents 419
Clinical Trials 420
Summary 421
CARDIOVASCULAR AGENTS 421
Hypertension 421
Congestive Heart Failure, Migraine, and Thrombolytic Agents 422
METABOLIC AGENTS 423
Hyperlipidemia 423
Diabetes 424
Obesity 425
GASTROINTESTINAL AND GENITOURINARY AGENTS 425
Antisecretory 425
Benign Prostatic Hyperplasia and Urinary Urge Incontinence 426
Erectile Dysfunction 426
PULMONARY AGENTS 427
Asthma and Allergic Rhinitis 427
INFLAMMATION AND OSTEOPOROSIS 427
Arthritis 427
Osteoporosis 428
CENTRAL NERVOUS SYSTEM AGENTS 428
Antidepressants 428
Anxiolytics 428
Bipolar Disorders, Schizophrenia, and Epilepsy 429
Alzheimer's Disease 429
INFECTIOUS DISEASES 430
Antibacterials 430
Antifungals 431
Antivirals 431
ANTINEOPLASTICS 432
MISCELLANEOUS AGENTS 433
Glaucoma and Nausea 433
Analgesics 434
SMALL MOLECULE HIGH THROUGHPUT SYNTHESIS 434
Discovery Libraries 435
Targeted Libraries 435
Optimization Libraries 436
CHEMICAL PROCESS R& D IN THE PHARMACEUTICAL INDUSTRY
Scheme-l 439
Scheme-2 439
Scheme-3 440
CONCLUSION 440
REFERENCES 440
12 Manufactured Textile Fibers 441
TEXTILE BACKGROUND 441
HISTORY 443
FIBER CONSUMPTION 444
RAYON 448
Chemical Manufacture 448
Wet Spinning 451
Cuprammonium, Nitrocellulose, and Cellulose Acetate Processes for Rayon 454
Textile Operations 454
Modified Viscose Rayon Fibers 456
Other New Developments 457
Environmentally Friendly High Wet Strength Rayon-Lyocell 457
CelLULOSE ACETATE 458
Historical 458
Manufacture of Cellulose Secondary Acetate 458
Manufacture of Cellulose Triacetate 460
Spinning Cellulose Acetate 461
PROTEIN FIBERS 464
NYLON 464
Historical 464
Manufacture 464
Melt spinning 466
Drawing 467
Other Nylons, Modifications, and New Developments 468
POLYESTERS 469
Historical 469
Manufacture 470
Drawing 471
Heat Setting 472
Textured Yarns 473
Staple Process 474
Continuous Filament Yarn Process Variants 474
Modifications and New Developments 475
ACRYLICS 476
Polymer Manufacture 476
Spinning 478
Bicomponent or Conjugate Spun Fibers 479
VINYL AND MODACRYLIC FIBERS 480
Vinyls 480
Modacrylics 481
ELASTOMERIC FIBERS 482
POLYOLEFIN FIBERS 483
Polypropylene 483
High Molecular Weight 487
ARAMIDS 490
Introduction 490
Manufacture 491
HIGH-TEMPERATURE-RESISTANT FIBERS 493
Meta-Aramid 493
PBI 494
POLYTETRAFLUOROETHYLENE 494
Historical 494
Manufacture 495
Fiber Manufacture 495
Properties 495
Expanded PTFE (ePTFE) 496
GLASS AND CARBON FIBERS 496
Glass 496
Carbon and Graphite Fibers 498
SULFAR 499
Historical 499
Manufacture 500
MICRODENIER FIBERS 500
NANOFIBERS 501
FIBER VARIANTS 502
Introduction 502
Physical Variants 502
Chemical Varia nt s 504
REFERENCES 506
SUGGESTED READING 507
13 Dye Application, Manufacture of Dye Intermediates and Dyes 509
INTRODUCTION 509
Dyeing 509
Synthetic Dyes 510
The Development of the U.S. Dyestuff Industry 511
TEXTILE FIBERS 513
Natural Fibers 513
Regenerated Fibers 514
Synthetic Fibers 515
DYE CLASSIFICATION 516
Acid Dyes 517
Azoic Dyes 519
Basic or Cationic Dyes 519
Direct Dyes 521
Disperse Dyes 526
Reactive Dyes 529
Sulfur Dyes 530
Vat Dyes 534
THE APPLICATION OF DYES 537
Fiber Preparation 537
Dye-Bath Preparation 537
Finishing 538
Dyeing Methods/Batch 539
PRINTING 539
PIGMENT DYEING AND PRINTING 541
NONTEXTILE USES OF DYES 541
Liquid Crystal Dyes 541
Ink-jet Dyes 541
Thermal and Pressure-Sensitive Printing 543
Organic Photoconductors and Toners 544
Infrared Absorbing Dyes 545
Laser Dyes 545
Biomedical Dyes 546
Hair Dyes 546
Photographic Dyes 548
DYE INTERMEDIATES 548
Nitration 549
Reduction 551
Amination 553
Sulfonation 554
Halogenation 557
Hydroxylation 559
Oxidation 561
Other Important Reactions 561
DYE MANUFACTURE 562
Nitro Dyes 564
Ala DYES 564
Monoazo Dyes 568
Disazo Dyes 569
Polyazo Dyes 573
TRIPHENYLMETHANE DYES 575
XANTHENE DYES 576
ANTHRAQUINONE AND RELATED DYES 577
Anthraquinone Disperse Dyes 577
Anthraquinone Acid Dyes 581
Anthraquinone Basic Dyes 583
Anthraquinone Reactive Dyes 583
VAT DYES 585
Anthraquinone 585
INDIGOID AND THIOINDIGOID 588
SULFUR DYES 589
PHTHALOCYANINE DYES 592
FLUORESCENT BRIGHTENERS(COLORLESS "DYES") 593
PRODUCTION AND SALES 596
REFERENCES 599
14 The Chemistry of Structural Adhesives: Epoxy, Urethane, and Acrylic Adhesives 601
INTRODUCTION 601
Adhesion 601
Curing 602
Adhesion Mechanisms 604
Surfaces 605
EPOXY STRUCTURAL ADHESIVES 606
Introduction 606
Commercial Epoxy Resins 607
Epoxy Cure Chemistry 611
Evolution 616
Summary 616
URETHANE STRUCTURAL ADHESIVES 616
Introduction 616
Isocyanate Preparation 617
Isocyanate Reactions 617
Important Isocyanates 619
Blocked Isocyanates 621
Evolution 621
Summary 622
ACRYLIC STRUCTURAL ADHESIVES 623
Introduction 623
Acrylic Monomers 623
Curing 624
Formulation 626
Summary 628
HYBRID ADHESIVES 628
EVOLUTION 629
CONCLUSION 629
REFERENCES 630
15 Synthetic Resins and Plastics 633
INTRODUCTION 633
Definition 633
History 633
Advantages of Plastics over Conventional Materials 634
Markets for Plastics 634
Major Classes of Plastic Materials 635
PART I. POLYMER CHEMISTRY 635
MOLECULAR WEIGHT 635
CHAIN STRUCTURE 636
CHEMICAL STRUCTURE 636
MORPHOLOGY 637
TRANSITION TEMPERATURES 638
Glass Transition Temperature (Tg) 638
Crystallization and Melting Points (TM) 639
POLYMERIZATION 640
Step-Reaction Polymerization 640
Chain-Reaction Polymerization 641
Coordination Polymerization 643
POLYMERIZATION METHODS 645
Bulk Polymerization 645
Solution Polymerization 645
Suspension Polymerization 645
Emulsion Polymerization 646
COPOLYMERIZATION 646
Random Copolymerization 647
Block and Graft Copolymers 647
MECHANICAL PROPERTIES 648
Viscoelasticity 648
Failure Behavior 650
PART II. COMMERCIAL PLASTIC MATERIALS 651
CLASSES OF FAMILIES OF COMMERCIAL PLASTICS 651
Commodity Thermoplastics 651
Engineering and Specialty Thermoplastics 657
Thermoplastic Elastomers 663
Thermoset Plastics 665
GENERAL CONSIDERATIONS 672
Structure-Property Relationships 672
Additives 673
Critical Properties: Challenges to the Plastics Industry 674
Fire Performance 676
Health and Environment 676
Recycling 676
PART III. PLASTIC PROCESSING 677
RHEOLOGY 677
Fundamental Concepts 677
Instrumental Measurement of Flow Properties 678
Practical Effects of Flow Properties 678
EXTRUSION 679
Basic Functions 680
Major Processes and Products 681
INJECTION MOLDING 682
Introduction 682
Injection Molding Cycle (Fig. 15.291 682
Variations and Details 683
REACTION INJECTION MOLDING 684
Overview 684
Ingredients 684
Equipment and Process 685
Other Polymers 685
STRUCTURAL FOAM 685
Definition 685
General Description 686
Degree of Expansion 686
Benefits 686
Problems in Structural Foaming 686
LOW-DENSITY FOAMS 686
Polyurethane 686
Polystyrene 687
Polyvinyl Chloride 687
Polyethylene 688
Blow Molding 688
THERMOFORMING 689
ROTATIONAL MOLDING("ROTOMOLDlNG") 689
POWDER COATING 690
Fluid Bed Coating 690
Electrostatic Fluid Bed 690
Electrostatic Spray 690
CALENDERING 691
VINYL PLASTISOL PROCESSING 691
LIQUID CASTING PROCESSES 692
COMPRESSION MOLDING AND TRANSFER MOLDING 693
REINFORCED PLASTICS PROCESSING 694
Matched Die Molding Processes 694
Open Molding 695
Special Processes 696
REFERENCES FOR PART I 696
REFERENCES FOR PART II 697
REFERENCES FOR PART III 698
16 Rubber 699
INTRODUCTION 699
RUBBER CONCEPTS 700
POLYMER STRUCTURE 701
Macrostructure 701
Microstructure 702
Network Structure 703
RUBBER PROPERTIES 703
Elasticity-The Retractive Force 703
Glass Transition Temperature 704
Crystallinity 704
RUBBER USE 705
Compounding 705
Processing 706
NATURAL RUBBER 706
Uses 707
POLYISOPRENE 708
Monomer Production 708
Polymer Production Process 708
Use 709
STYRENE-BUTADIENE RUBBER 709
Monomer Production 709
Polymer Production Process 710
Emulsion Process 710
Solution Process 712
Functional Solution SBR 713
POLYBUTADIENE (BR) 714
Monomer Production 714
Polymer Production Process 714
Uses 715
ETHYLENE-PROPYLENE RUBBER 716
Monomer Production 716
Polymer Production 716
BUTYL RUBBER 717
Monomer Production 717
Production Process 717
Properties and Use 718
NITRILE RUBBER 718
Monomer Production 718
Polymer Production 718
Properties and Use 718
HYDROGENATED NITRILE RUBBER 718
Uses 719
CHLOROPRENE RUBBER 719
Monomer Production 719
Production Process 719
Properties and Uses 719
SILICONE ELASTOMERS 720
Monomer Production 720
Polymer Production 720
Uses 720
POLYURETHANE RUBBER 721
Raw Materials 721
Uses 721
MODIFIED POLYETHYLENE RUBBERS 721
Chlorinated Polyethylene 722
Chlorosulfonated Polyethylene 722
THERMOPLASTIC ELASTOMERS (TPE) 722
Block Copolymers 722
Uses 723
lonomers 723
Uses 724
Metallocene Elastomers 724
Rubber-Plastic Alloys 724
Uses 724
PLASTICIZED POLYVINYL CHLORIDE 725
Monomer Production 725
Production Process 725
Properties and Use 725
FLUOROCARBON ELASTOMERS 725
Uses 726
REFERENCES 726
17 The Agrochemical Industry 729
INTRODUCTION 729
Scope of the Chapter 729
History 730
ROLE OF THE AGROCHEMICAL INDUSTRY 730
CHARACTERISTICS OF THE AGROCHEMICAL INDUSTRY 749
Government Regulation 749
Manufacture of Agrochemicals 751
Classes of Agrochemicals 751
DELIVERY SYSTEMS OF AGROCHEMICALS 770
Obsolescence of Agrochemicals 770
PRODUCTS OF THE AGROCHEMICAL INDUSTRY 770
STRUCTURAL BASIS OF AGROCHEMICALS 784
Organophosphorous Agrochemicals 784
Organochlorine 785
Chloracetanilides 788
Aryloxyphenoxypropionic Acids (Cereal Herbicides) 790
ROLE OF CHIRALITY 793
Basis of Chemistry Used in Synthesis of Agrochemicals 796
Case Study-Chemistry and Manufacture of Metolachlor 796
Usage of Agrochemicals 797
BIOTECHNOLOGY FOR FARM PRODUCTIVITY 798
Regulatory Scene Regarding Products of Biotechnology 807
FUTURE DIRECTIONS 809
Allelopathy 809
Biorational Approach to Chemical Synthesis 809
REFERENCES 810
18 Petroleum and Its Products 811
THE NATURE OF PETROLEUM 811
Hydrocarbon Forms 811
Largest Energy Supplier 812
From Well to Refinery 812
PRODUCT 816
Refined Products 817
Product Specifications 817
Product Yields 819
Petrochemicals 819
REFINING SCHEMES 820
Feedstock Identification 821
Crude Oil Pretreatment 822
Crude Oil Fractions 822
GASOLINE 823
Volatility 825
Sulfur Content 825
Octane Number 826
DISTILLATES 827
Residuals 828
PRODUCING MORE LIGHT PRODUCTS 828
Cracking 829
Vacuum Distillation 829
Reconstituting Gases 830
A MODERN REFINERY 830
Petrochemicals 830
PROCESS DETAILS 832
Crude Desalting 832
Crude Distillation 833
Hydrotreating 834
Catalytic Reforming 836
Catalytic Cracking 839
Coking 841
Hydrocracking 842
Alkylation 844
Ether Processes 846
FUTURE TRENDS 848
Costs and Drivers 849
Technology Options 849
REFERENCES 852
Index 853
Volume II 
875 
Title Page 
876 
Copyright Page 
877 
Preface 879
Table of Contents 
882 
19 Coal Technology for Power, Liquid Fuels, and Chemicals 
884 
INTRODUCTION 884
ORIGIN AND CLASSIFICATION OF COAL 
885 
Coal Structure 888
Coal Composition and Analyses 891
COAL MINING AND PREPARATION 894
Surface Mining 894
Underground Mining 894
Coal Preparation 895
Coarse-Coal Cleaning 897
Medium-Coal Cleaning 897
Fine-Coal Cleaning 897
Chemical Coal Cleaning 899
COAL UTILIZATION 899
Environmental Concerns Related to Coal Use 
899 
COMBUSTION 900
Combustion Equipment 900
Boiler Types 904
Pollution Controls 905
Advances in Combustion Technology 907
COKE PRODUCTION 908
Nonrecovery Cokemaking 908
Byproduct Coke Production 909
Direct Coal Utilization in the Steel Industry 
910 
Mild Gasification 911
GASIFICATION 911
Chemistry of Coal Gasification 912
Types of Coal Gasifiers 914
Gasification for Power Generation 917
Descriptions of Selected Gasification Processes 
919 
COAL LIQUEFACTION 926
Pyrolysis-Based Processes 926
Factors Affecting Coal Pyrolysis 926
Utilization and Characterization of Pyrolysis Products 
928 
Direct Coal Liquefaction 929
Chemistry of Direct Coal Liquefaction 930
Direct Coal Liquefaction Processes 930
Direct Coal Liquefaction and the Future 935
Indirect Coal Liquefaction 935
PETROCHEMICAL FEEDSTOCKS 941
Chemicals from Coal* 942
Examples of Chemicals Production from Coal 
944 
REFERENCES 945
20 Natural Gas 
948 
CHARACTERISTICS 948
OCCURRENCE OF NATURAL GAS 950
EVOLUTION OF THE U.S. NATURAL GAS INDUSTRY 
952 
U.S. MARKETED PRODUCTION4-6 952
NATURAL GAS LIQUIDS 955
U.S. NATURAL GAS RESERVES 956
STRUCTURE OF THE U.S. NATURAL GAS INDUSTRY 
956 
WORLD NATURAL GAS 958
GAS-TO-L1QUIDS TECHNOLOGY 958
PREPARING NATURAL GAS FOR TRANSMISSION AND SALE 
960 
PROCESSING FOR L1aUIDS RECOVERY 963
A NEW POTENTIAL SOURCE FOR NATURAL GAS 
965 
METHANE CONVERSION PROCESSES 966
Indirect Conversion via Syngas 966
Indirect Conversion via Nonsyngas Intermediates 
967 
Direct Methane Conversion to Hydrocarbons and Chemical Derivatives 
967 
Oxidative Coupling to Higher Hydrocarbons 
967 
Partial Oxidation to Chemical Derivatives 
969 
Pyrolysis or Cracking 969
Other Direct Conversion Processes 970
Methane Ammoxidation 970
Methane Reductive Nitrilization 970
A DIFFERENT VIEW OF THE ORIGINS OF NATURAL GAS 
971 
Natural Gas from Biological Origins 971
Natural Gas from Nonbiological Origins 972
Natural Gas Release from Lower Crust and Mantle Domains 
972 
SUMMARY FOR METHANE AND NATURAL GAS FUTURE SOURCING 
973 
REFERENCES 974
21 The Nuclear Industry 
976 
INTRODUCTION 976
STATUS AND OUTLOOK 978
NUCLEAR SAFETY 983
THE EARTH'S ENERGY SUPPLY AND USE 
986 
NUCLEAR PROCESSES 989
Radioactive Decay 989
Fission 990
Fusion 992
Nuclide Production 994
Fission Products 994
Neutron Transmutation Products 996
Neutron Activation Products 997
Uses 997
Charged Particle Transmutation Products 998
REACTOR MATERIALS PROCESSING 998
Isotope Enrichment 999
Zirconium Production 1000
THE URANIUM FUEL CYCLE 1002
Mining 1003
Milling 1003
Fuel Preparation 1003
Spent Fuel Reprocessing 1010
RADIOACTIVE WASTE MANAGEMENT 1016
Liquid Waste Treatment 1018
Airborne Waste Treatment 1018
Solid Waste Treatment 1019
Storage of Spent Fuel 1020
Low-Level Waste Disposal 1021
TRANSPORTATION OF NUCLEAR MATERIALS 
1021 
THE NUCLEAR REACTOR 1022
Light Water Reactors 1024
CANDU Heavy Water Reactor 1028
Liquid Metal Fast Breeder Reactor 1029
Other Nuclear Reactors 1029
RADIATION PROCESSING 1030
RADIOISOTOPE APPLICATIONS 1031
Radiation Sources 1031
Radioisotope Thermoelectric Generators 1031
Tracers 1032
Nuclear Medicine 1032
REFERENCES 1034
22 Synthetic Nitrogen Products 
1037 
NITROGEN 1037
Characteristics 1037
Nitrogen Production Processes 1038
NITROGEN FIXATION 1038
Nitrogen Oxides 1038
Ammonia 1039
NITROGEN CONSUMPTION 1040
ENVIRONMENTAL ISSUES 1042
AMMONIA PRODUCTION 1043
HYDROGEN PRODUCTION 1044
Manufacturing Processes 1046
Feed Pretreatment 1048
Prereformer 1048
Reformers 1049
Reformer Catalysts 1049
Reformer Materials of Construction 1049
Waste Heat Recovery 1050
Hydrogen Production Costs and Capital Costs 
1050 
Other Reforming Processes 1050
Reliability and Revamps 1051
Small-Scale Reforming 1052
Technology Suppliers 1053
Partial Oxidation Processes 1054
Technology Suppliers 1055
Initial Purification of Synthesis Gas 1058
Alkazid Process 1062
aMDEA Process 1062
Benfield Process 1062
Catacarb Process 1062
Fluor Solvent Process 1062
Giammarco-Vetrocoke Process 1062
Hi Pure Process 1063
Purisol Process 1063
Rectisol Process 1063
Selexol Process 1063
Shell Sulfinol Process 1063
Pressure Washing with Monoethanolamine (MEA) 
1063 
Retrofits of CO2 Removal System 1063
Final Purification of Synthesis Gas 1064
Compression 1065
AMMONIA SYNTHESIS 1065
Reaction Rate 1065
Catalysts 1067
Energy Efficiency 1069
Ammonia Plant Design 1069
Ammonia Separation 1069
Ammonia Synthesis 1072
Large Capacity Ammonia Plants 1072
Ammonia Production Costs 1072
USES OF AMMONIA 1072
Chemical Production and Other Uses 1072
DISTRIBUTION AND STORAGE 1073
Ammonia Toxicity 1073
Ammonia Quality 1074
Distribution and Storage 1074
Ammonia Price 1075
NITRIC ACID 1075
Physical Properties 1075
Processes 1077
Uses of Nitric Acid 1086
AMMONIUM NITRATE 1086
Processes 1087
Production 1088
UREA 1089
Processes 1090
Production 1092
Storage and Distribution 1092
Uses 1093
MELAMINE 1093
Processes 1093
Production 1094
Uses 1094
ALIPHATIC AMINES 1094
Methylamines 1096
Other Alkyl Amines 1098
Uses 1099
ETHANOLAMINES AND SECONDARY PRODUCTS 
1099 
Ethanolamine Process 1099
Secondary Products of Ethanolamine 1101
Ethylenediamine Production 1101
Ethylenediamine Uses 1102
HEXAMETHYLENETETRAMINE (HEXAMINE) 
1102 
Hexamine Processes 1102
HVDRAZINE 1103
Processes 1103
HYDROGEN CYANIDE 1105
Safety 1107
Manufacture 1108
Production 1112
Uses 1113
ANILINE 1114
Processes 1114
OTHER COMPOUNDS 1115
REFERENCES 1118
23 Phosphorus and Phosphates 
1127 
INTRODUCTION 1127
PHOSPHATE ROCK 1127
Minerals 1128
Resources and Ores 1129
Mining 1129
Beneficiation 1130
Production and Value 1134
CHEMICAL PROCESSING OF PHOSPHATE ROCK 
1135 
Thermal Process for Phosphorus and Phosphoric Acid 
1135 
Industrial Phosphates 1135
Wet Process Phosphoric Acid 1137
Dihydrate Process 1138
Major Dihydrate Processes 1139
Hemihydrate Processes for Phosphoric Acid 
1143 
Unit Operations 1145
Superphosphoric Acid 1146
WET PROCESS ACID BY-PRODUCTS 
1147 
Phosphogypsum 1147
Fluorine Recovery 1148
Uranium Recovery from Wet Process Phosphoric Acid 
1148 
Animal Feed Supplements 1148
Purified Phosphoric Acid 1148
Environmental Aspects 1150
REFERENCES 1150
24 Fertilizers and Food Production 
1152 
INTRODUCTION 1152
OVERVIEW OF THE FERTILIZER INDUSTRY 
1155 
RAW MATERIALS FOR FERTILIZER PRODUCTION 
1158 
NITROGEN FERTILIZERS 1159
Natural Organics 1160
Nitrogen Fertilizers from Synthetic Ammonia 
1160 
Miscellaneous Low-Volume Nitrogen Fertilizers 
1164 
PHOSPHATE FERTILIZERS 1165
Natural Organic Phosphate Fertilizers 1165
Fertilizers from Mineral Phosphates 1166
Miscellaneous Low-Volume Phosphate Fertilizers 
1173 
POTASSIUM SALTS 1175
Potassium Minerals 1177
Potassium Sulfate 1177
Potassium Nitrate 1178
Potassium Phosphates 1178
COMPOUND FERTILIZERS 1179
Nongranular Mixtures 1180
Compound Granulars 1180
Bulk Blends 1184
Fluid Mixtures 1186
Controlled-Release Fertilizers 1190
Physical Quality of Fertilizers 1194
REFERENCES 1195
25 Sulfur and Sulfuric Acid 
1198 
SULFUR 1198
Transportation and Storage 1199
Solidification and Melting 1200
Development of the Sulfur Industry 1202
Sulfur Production Processes 1203
Recovered Sulfur 1204
Production and Consumption of Sulfur 1206
SULFURIC ACID 1209
Uses of Sulfuric Acid 1210
Development of the Sulfuric Acid Industry 
1210 
Manufacture of Sulfuric Acid by the Contact Process 
1213 
Sulfur Dioxide Production 1213
Single vs. Double Contact Process 1217
Oxidation of SO2 
1217 
Absorption of SO3 
1218 
Acid Cooling 1218
Other Modifications to the Sulfuric Process36 
1218 
Other Sources of Sulfuric Acid 1220
Production and Consumption of Sulfuric Acid 
1220 
REFERENCES 1222
26 Salt, Chlor-Alkali, and Related Heavy Chemicals 
1224 
SODIUM CHLORIDE** 1224
SODA ASH 1226
SODIUM BICARBONATE 1230
SODIUM SULFATE 1230
SODIUM SULFIDES 1233
SODIUM THIOSULFATE 1233
SODIUM SULFITE 1234
SODIUM BISULFITE 1234
SODIUM HYPOSULFITE (HYDROSULFITE) 
1234 
SODIUM PHOSPHATES 1235
SODIUM SILICATE 1235
CHLOR-ALKALI (CHLORINE AND CAUSTIC SODA) 
1237 
HYDROCHLORIC ACID 1249
BROMINE AND BRINE CHEMICALS* 1249
BLEACHES 1252
SODIUM CHLORATE 1254
REFERENCES 1254
27 Industrial Gases 
1256 
OVERVIEW 1256
NITROGEN 1262
OXYGEN 1262
ARGON 1263
HYDROGEN 1263
HELIUM 1268
CARBON DIOXIDE 1268
LIQUEFIED NATURAL GAS 1270
ACETYLENE 1271
NITROUS OXIDE 1273
REFERENCES 1274
28 Wood and Wood Products 
1275 
INTRODUCTION 1275
WOOD STRUCTURE 1276
CHEMICAL COMPOSITION AND FIBER STRUCTURE 
1279 
PULP AND PAPER 1281
Wood Preparation 1285
Mechanical Pulping 1286
Chemical Pulping 1286
Biomechanical Pulping 1293
Screening and Cleaning of Wood Pulp 1294
Bleaching of Wood Pulp 1294
Biotechnology-Biopulping and Biobleaching 
1295 
Recycling 1296
Stock Preparation 1296
Papermaking Process 1297
Finishing and Converting 1301
Environmental Protection 1301
BOARD AND STRUCTURAL MATERIALS 1302
Lumber 1302
Plywood 1303
Fiberboard 1303
Particleboard and Oriented Strandboard (OSB) 
1303 
Modified Wood and Wood Composites 1305
PRESERVATIVE TREATMENT OF WOOD 1309
Preservative Chemicals 1309
Preservation Process 1310
Preservative Retention 1311
Nonconventional Wood Preservation 1312
FIRE-RETARDANT TREATMENT OF WOOD 1313
Fire-Retardant Formulations 1313
CONVERSION OF WOOD TO ENERGY, FUELS, AND CHEMICALS 
1314 
Direct Combustion 1315
Saccharification-Fermentation 1316
Thermal Decomposition 1320
Thermochemical Liquefaction 1325
NAVAL STORES 1326
Gum Naval Stores 1327
Wood Naval Stores 1328
Sulfate Naval Stores 1328
Uses of Naval Stores Products 1329
ADDITIONAL CHEMICALS FROM WOOD 1330
Tannins and Other Extractives 1330
Furfural 1330
Vanillin 1331
Dimethyl Sulfide and DMSO 1331
Medicinals 1331
Biotechnology Chemicals 1331
REFERENCES 1332
SELECTED REFERENCES 1333
29 Pigments, Paints, Polymer Coatings, Lacquers, and Printing Inks 
1335 
INTRODUCTION 1335
VOC REGULATIONS 1337
Southwest 1338
Midwest 1338
East 1339
HAZARDOUS WASTE REGULATIONS 1339
TECHNICAL TRENDS IN COATINGS 1339
POWDER COATINGS 1341
Electron Beam (EBI and Ultraviolet (UV) Curable Coatings 
1341 
Current Automotive Coating Trends 1342
Coatings for Plastics 1343
New Cross-Linking Technologies 1344
PRINTING INKS 1344
PIGMENTS 1346
Inorganic Pigments 1346
Organic Pigments 1348
Pearlescent Pigments 1349
Aluminum Pigments 1350
LACQUERS 1350
REFERENCES 1351
30 Industrial Biotechnology: Discovery to Delivery 
1352 
INTRODUCTION 1352
DISCOVERY OF ORGANISMS AND MOLECULES 
1353 
Microbial Diversity 1353
Screening and Selection 1355
Cell Engineering 1356
Molecular Engineering 1358
DEVELOPMENT OF A PRODUCTION PROCESS 
1359 
Strain 1359
Fermentation Process 1360
Sterilization 1360
Microbial Kinetics 1361
Ideal Types of Fermentors 1362
Oxygen Transfer Considerations 1365
Scale-Up/Down and Control 1365
Instrumentation and Control 1367
RECOVERY OF FERMENTATION PRODUCTS 
1368 
Separation of Proteins and Peptides 1371
Fermentor Harvest and Primary Recovery 
1372 
Formulation 1376
Whole Cell Recovery 1381
Separation of Small Molecules and Metabolites 
1381 
Regulatory Considerations 1383
DELIVERY OF PRODUCTS 1383
Organic Acids and Polymers 1383
Amino Acids 1399
Vitamins and Neutraceuticals 1405
Antibiotics 1407
Biopharmaceuticals 1410
Enzymes 1412
FUTURE: BIOREFINERIES 1412
Acknowledgment 1413
REFERENCES 1413
31 Industrial Enzymes and Biocatalysis 
1416 
INTRODUCTION 1416
INDUSTRIAL ENZYMES-PRODUCTION AND APPLICATIONS 
1417 
Amylases 1419
Glucose Isomerase 1421
Proteases 1422
Cellulases 1424
Lipases 1426
INDUSTRIAL BIOCATALVSIS 1426
Biocatalyst Discovery and Engineering 1428
Biocatalytic Processes 1432
Immobilized Enzymes 1433
Whole Cell Biocatalysis 1437
BIOREACTOR CONFIGURATIONS 1439
Nonaqueous Biocatalysis 1442
Products of Biocatalysis 1443
Future Trends in Biocatalysis 1456
SUMMARY AND CONCLUSION 1459
REFERENCES 1459
32 Industrial Production of Therapeutic Proteins: Cell Lines, Cell Culture, and Purification 
1462 
Cells Used For Industrial Production 1468
Expression Systems 1468
HOST CELL LINES 1468
Identifying High-Expressing Cells 1469
Cell Banking 1470
Cell Stability 1471
MEDIA 1471
Commercial Serum-Free Media 1471
Approaches for Serum-Free Medium Development 
1472 
Serum-Free Adaptation 1474
BIOREACTOR SYSTEMS 1475
Stirred-Tank Systems 1475
Disposable Bioreactors 1476
Modes of Bioreactor Operation 1477
CELL CULTURE PROCESS AND CONTROL 
1477 
Process Parameters 1478
Mitigating Effects of Physical and Chemical Stress 
1478 
Fed-Batch Process Control and Optimization 
1480 
Perfusion Process Control and Optimization 
1480 
Scale-Up of Mammalian Cell Bioreactors 
1480 
PURIFICATION PROCESS 1481
Generic Processes 1482
Clarification of Broth 1482
Capture of Product 1483
Removal of Impurities 1484
Strategies for Scaling Up Purification Processes 
1485 
ACKNOWLEDGMENTS 1486
REFERENCES 1486
33 Biomass Conversion 
1490 
AN INTRODUCTION TO BIOMASS AND THE BIOREFINERY 
1490 
WHAT IS BIOMASS? 1490
The Structure and Composition of Biomass 
1491 
CONVERTING BIOMASS INTO ENERGY AND OTHER PRODUCTS 
1492 
Biological Versus Thermochemical Processing 
1492 
THE BIOREFINERV 1495
BIOMASS, FOSSIL ENERGY SAVINGS, AND GREENHOUSE GAS MITIGATION 
1496 
Life-Cycle Assessments of Biopower 1496
Life-Cycle Assessments of Biofuels 1497
COST PROJECTIONS FOR FUELS AND POWER FROM BIOMASS 
1497 
The Competitiveness of Biopower 1497
The Competitiveness of Biofuels 1499
BIOMASS AS A SUSTAINABLE AND SUBSTANTIAL ENERGY SOURCE 
1499 
Biomass as a Substantial Source of Energy-Balancing the Demands on our Land 
1499 
MICROBIAL BIOETHANOL PRODUCTION 1503
ETHANOL FERMENTATION SCHEMES 1503
METABOLIC PATHWAY ENGINEERING 1504
PERFORMANCE ASSESSMENT 1505
FUTURE DIRECTIONS 1505
BIOMASS ANALYSIS AND COMPOSITIONAL VARIABILITY 
1506 
INTRODUCTION 1506
The Importance of Reliable Compositional Methods for Biomass Analysis 
1506 
The Need for Accurate, Real-Time Biomass Analysis Methods 
1507 
Heterogeneity and Biomass Analysis 1507
Genetic Factors That May Contribute to Cell Wall Compositional Variability 
1508 
Environmental Factors That May Contribute to Variance 
1510 
Analytical Variance 1511
PORTFOLIO METHODS 1511
Wet Chemical Methods 1511
EXTRACTIVES DETERMINATION 1514
Carbohydrate Determination 1514
Lignin Determination 1514
Protein Determination 1515
Other Feedstock Constituents 1515
Degradation Products 1515
Reconstructing the Composition of the Original Biomass Sample 
1515 
APPLICATION OF METHODS 1517
Biomass Process Monitoring and Improvement 
1517 
Survey of Corn Stover Compositional Diversity 
1517 
Genetic Screening and Cell-Wall Genomics 
1521 
FUTURE APPLICATIONS 1521
SUMMARY AND CONCLUSIONS 1522
BIOCATALYSTS FOR BIOMASS DECONSTRUCTION 
1522 
SUMMARY OF PLANT CELL WALL STRUCTURE 
1522 
ENZYMATIC HYDROLYSIS OF PLANT CELL WALL COMPONENTS 
1523 
CELLULASES 1525
Endoglucanases 1526
Exoglucanases 1526
Endoglucanases and ß-Glucosidases 
1526 
TOTAL CELLULASE ACTIVITY MEASUREMENTS 
1526 
The IUPAC Filter Paper Assay 1526
General Non-IUPAC Cellulases Assays 1528
Mathematical Modeling 1529
Endocellulase Activity Measurement 1529
Viscometric Assays 1529
Exocellulase Activity Measurements 1530
ß-Glucosidase Activity Measurements 
1530 
HEMICELLULASES 1531
General Hemicellulase Assays 1531
Hemicellulose Debranching Enzymes 1532
Hemicellulose Depolymerization Enzymes 
1533 
PECTINASES 1535
CHEMICAL CATALYSIS FOR BIOMASS DECONSTRUCTION 
1536 
INTRODUCTION 1536
SCOPE OF THE REVIEW 1538
SEPARATION OF BIOPOLYMERS FROM BIOMASS RAW MATERIALS 
1539 
Dilute Acid Pretreatments 1539
Solvent Separation Processes 1539
Steam Explosion and Related Processes 1540
The Kraft Process 1540
DECONSTRUCTION OF BIOREFINERY RAW MATERIALS AND BIOPOLYMERS TO MONOMERIC PRODUCTS 
1542 
Polymeric Carbohydrate Hydrolysis Processes 
1542 
Carbohydrate Pyrolysis 1542
Carbohydrate Oxidation 1543
Carbohydrate Dehydration 1543
Lignin Deconstruction 1546
CONCLUSIONS 1547
THERMOCHEMICAL BIOMASS CONVERSION 
1547 
INTRODUCTION 1547
PYROLYSIS 1550
Fast Pyrolysis 1551
Slow Pyrolysis 1552
GASIFICATION 1553
Gasifier Reactor Designs 1554
Biomass-Gasification Product Gas 1555
Syngas Cleanup and Conditioning 1556
Integrated Gasification Combined Cycle 1558
Fuel Cell Applications 1559
Syngas to Liquid Fuels 1559
COMBUSTION 1560
Co-Firing 1563
ACKNOWLEDGMENT 1564
REFERENCES 1564
34 Animal and Vegetable Fats, Oils, and Waxes 
1590 
BIOTECHNOLOGY IN AGRICULTURE AND PROCESSING 
1590 
Human Survival Is Biotechnology 1590
Genetic Messages 1592
Water Activity 1593
Herbicide- and Insect-Resistant Oilseed Crops 
1594 
Concerns About Transgenic Crops 1596
Drivers and Tools for the Future 1598
Biotechnology Practices in Soybean Production and Processing 
1599 
INTRODUCTION TO LIPIDS 1601
Recent Fats and Oils Industry Changes 1601
AOCS, an Information Source 1602
Nutrition and Health Implications 1603
NOMENCLATURE AND MOLECULAR STRUCTURES 
1603 
General 1603
Fatty Acids 1604
Triacylglycerols 1610
Oxidation 1610
Biohydrogenation and Conjugated Linoleic Acids 
1611 
Fatty Acid and Triacylglycerol Melting Characteristics 
1612 
Polymorphism and Crystal Types 1612
OTHER LIPIDS 1615
Waxes 1615
Terpenes 1615
Sterols 1618
Fat-Soluble Vitamins 1618
Phosphatides 1621
FATS AND OILS SOURCES AND CONSUMPTION 
1622 
Production 1622
Changes in Sources 1623
Consumption 1625
EXTRACTION OF FATS AND OILS 1626
Basic Processes 1626
SCREW PRESS OPERATIONS 1626
Decanters and Centrifuges 1627
Olive Oil 1629
Coconut Oil 1629
Palm Oil 1629
ANIMAL FATS AND FISH OilS 1630
Extraction of lards and Tallows 1630
Inedible Animal Products 1631
Restaurant Greases 1631
Animal Fat Specifications, Production, and Utilization 
1632 
Fish Oils 1632
Feeding Animal and Marine Fats 1632
ROW CROP OILSEEDS PROCESSING 1634
Extraction Plants 1634
Seed Preparation for Extraction 1636
Solvent Extractors 1641
Solvents 1641
Desolventizing-Toasting 1644
Miscella Refining 1645
REFINING OF VEGETABLE FATS AND OILS 
1645 
Oil Receiving and Handling 1645
Phosphatides Degumming, Lecithin Uses 
1647 
Alkali Neutralization 1649
Silica Gel Adsorption 1651
Bleaching 1651
OILS AND FATS MODIFICATION 1652
Solid Fat Index/Solid Fat Content 1652
Thermal Fractionation 1654
Hydrogenation 1656
Interesterification 1659
Deodorization/Physical Refining 1663
NOTES ON MAJOR ROW CROP OILSEEDS 
1666 
Soybean 1666
Cottonseed 1667
Rapeseed/Canola 1668
Sunflowerseed 1668
Peanut 1669
TRANS FATS NUTRITIONAL LABELING 1669
EDIBLE USES OF FATSAND OILS 1671
Antioxidants 1671
Nonionic Surfactants and Emulsifiers 1673
Table Oils 1673
Frying Oils 1674
Specialty Oils 1676
Margarines And Spreads 1677
Shortenings 1681
Other Edible Applications 1681
INDUSTRIAL USES OF FATS AND OILS 1682
Timeline 1682
Chemurgy Revisited 1683
Industrial Oils Utilization 1683
Fatty Acid Methyl Esters, Biodiesel 1684
Other Industrial Applications 1687
ANALYTICAL METHODS 1688
REFERENCES 1691
35 Sugar and Other Sweeteners 
1698 
INTRODUCTION 1698
SUGAR 1699
History8 
1699 
RAW SUGAR PRODUCTION 1699
Crystal Quality 1709
Bagasse 1709
Direct Consumption Sugar 1711
Edible Products from the Mill 1711
New Technology 1711
CANE SUGAR REFINING 1712
Affination and Melting 1712
Purification 1713
Crystallization 1715
Remelt Sugar 1716
Packaging and Storing Refined Granulated Sugar 
1716 
Specialty Sugars 1716
BEET SUGAR 1717
AGRICULTURE 1718
Harvesting and Beet Handling 1718
Extraction of the Juice 1719
Juice Purification 1719
Evaporation and Standard Liquor 1720
Extending the Processing Cycle-Thick Juice Storage 
1721 
Crystallization, Centrifuging, and Drying 1721
MOLASSES DESUGARIZATION 1721
Sugar Recovery from Beet Molasses 1721
Desugarization of Cane Molasses 1722
PROCESS CONTROL AND INSTRUMENTATION 
1722 
CANE AND BEET SUGAR PRODUCTION 1723
SUGAR CONSUMPTION AND USAGE 1723
DERIVATIVES OF SUCROSES - UCROCHEMISTRY 
1723 
SWEETENERS DERIVED FROM STARCH 1724
Starch Conversion 1725
Acid Hydrolysis of Starch 1725
Acid-Enzyme Hydrolysis 1726
Enzyme-Enzyme Hydrolysis 1726
Crystalline Dextrose 1727
Crystalline Fructose 1727
High Fructose Corn Syrup (HFCS) 1727
MOLASSES 1727
OTHER SWEETENERS 1728
REGULATION AND TRADE IN SUGAR 1729
ENVIRONMENTAL CONCERNS 1730
Issues of Genetic Engineering 1730
REFERENCES 1731
36 Soap, Fatty Acids, and Synthetic Detergents 
1735 
SOAP AND FATTY ACIDS 1735
Introduction 1735
Chemistry 1735
Manufacturing Technology 1736
Raw Materials 1737
Functional Properties of Soap 1738
Manufacturing Processes 1738
Fatty Acids 1745
Fractionation and Physical Separation 1745
Fat Refining 1746
Fat Splitting Processes 1746
Fatty Acid Distillation 1751
Special Separation Methods 1754
SYNTHETIC DETERGENTS 1755
Characteristic Features of Surfactants 1756
Raw Materials for Surfactant Production 1757
Intermediates for Surfactant Production 1759
World Surfactant Consumption 1763
Anionic Surfactants 1763
Nonionic Surfactants 1769
Amphoteric Surfactants 1771
Cationic Surfactants 1771
Detergent Additives 1772
Production of Synthetic Detergents 1775
Agglomeration 1778
Liquid Detergent Processing 1779
Detergent Trends 1780
LIST OF ABBREVIATIONS USED IN THE TEXT 
1781 
REFERENCES 1781
37 Chemical Explosives and Rocket Propellants 
1783 
PART I. CHEMICAL EXPLOSIVES 1783
INTRODUCTION 1783
COMMERCIAL EXPLOSIVES MARKET 1783
CHEMISTRY OF COMBUSTION AND EXPLOSION 
1785 
HISTORICAL DEVELOPMENT 1788
CLASSIFICATION OF EXPLOSIVES 1790
STRUCTURAL CHARACTERISTICS OF EXPLOSIVES 
1793 
EXPLOSIVES MANUFACTURING AND USE 
1793 
TNT 12,4,6-Trinitrotoluene) 1794
RDX and HMX 1794
HNS 12,2',4,4',6,6'-Hexanitrostilbene) 1794
TATB (1,3,5-Triamino-2,4,6-trinitrobenzenel 
1796 
DDNP (2-Diazo-4,6-dinitrophenol) 
1796 
PETN (Pentaerythritol Tetranitrate) 
1797 
NG (Nitroglycerin or Glyercol Trinitrate) 
1797 
Dynamite 1798
Packaged Explosives 1798
Ammonium Nitrate and ANFO 1800
Bulk Emulsions 1801
INITIATION SYSTEMS 1806
Non-Electric Initiation 1808
PART II. ROCKET PROPELLANTS 1809
PRINCIPLES OF ROCKET PROPULSION 1810
TYPES OF PROPELLANTS 1811
SOLID PROPELLANTS 1812
Composite Propellants 1814
Liquid Propellants 1819
Liquid Fuels 1825
ADVANCED MONOPROPELLANT STUDIES 
1827 
BIPROPELLANT APPLICATIONS 1828
BIPROPELLANT FUELS 1828
IGNITION DELAY 1829
REFERENCES 1832
Index 1835