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1;Volume I
;2
1.1;Title Page;3
1.2;Copyright Page;4
1.3;Preface;6
1.4;Table of Contents;9
1.5;1 Recent History of the Chemical Industry
1973 to the Millenium: The New Facts of World Chemicals Since 1973;11
1.5.1;I. OVERCAPACITIES AND THE SEARCH FOR REMEDIES;11
1.5.1.1;THE RESTRUCTURING OF SECTORS IN DISTRESS;12
1.5.1.2;THE NATIONALIZATION OF FRANCE'S CHEMICAL INDUSTRY;16
1.5.1.3;RESTRUCTURING IN ITALY AND SPAIN;18
1.5.1.4;ARAB COUNTRIES GAIN A FOOTHOLD;19
1.5.1.5;THE AMERICAN CHEMICAL INDUSTRY CAUGHT OFF BALANCE;19
1.5.1.6;COPING WITH SAFETY AND ENVIRONMENTAL PROBLEMS;22
1.5.1.7;SCIENTIFIC AND TECHNOLOGICAL BREAKTHROUGHS;23
1.5.1.7.1;Process Improvement;23
1.5.1.7.2;Product Development;24
1.5.1.8;THE CRAZE FOR BIOTECHNOLOGY;26
1.5.1.9;THE FINE CHEMICALS APPROACH;29
1.5.1.10;THE ATTRACTION OF SPECIALTY CHEMICALS;30
1.5.1.11;THE PAINT INDUSTRY;32
1.5.1.12;SURFACE-ACTIVE AGENTS;33
1.5.1.13;FLAVORS, FRAGRANCES, AND BEAUTY PRODUCTS;35
1.5.1.14;THE CHEMISTRY OF ADDITIVES;38
1.5.1.14.1;Additives for Plastics;39
1.5.1.14.2;Rubber Additives;40
1.5.1.14.3;Additives for Lubricants;41
1.5.1.14.4;Food Additives;43
1.5.1.15;PHOTOCHEMICALS;44
1.5.1.16;THE ALLIANCE OF CHEMICALS AND ELECTRONICS;46
1.5.1.17;CATALYSTS;47
1.5.1.18;RETROSPECT AND PROSPECT;48
1.5.2;II. THE PERIOD OF THE 1990s;50
1.5.2.1;THE CHEMICAL INDUSTRY UNDER PRESSURE FROM PUBLIC OPINION AND REGULATORY AUTHORITIES;50
1.5.2.2;THE STATUS OF SCIENCE AND TECHNOLOGY;52
1.5.2.3;THE NEW LANDSCAPE;53
1.5.2.4;THE TRIALS AND TRIBULATIONS OF THE PHARMACEUTICAL INDUSTRY;54
1.5.2.5;THE RESHUFFLING OF CHEMICAL ASSETS;55
1.5.2.6;THE IMPOSSIBLE MARRIAGE OF PHARMACEUTICALS WITH AGROCHEMICALS;56
1.5.2.7;THE FATE OF THE DYESTUFFS SECTOR;57
1.5.2.8;CONSOLIDATION IN THE FIELD OF SPECIALTY CHEMICALS;58
1.5.2.9;THE CASE OF FINE CHEMICALS;63
1.5.2.10;THE FURTHER CONCENTRATION OF THE INDUSTRIAL GAS BUSINESS;64
1.5.2.11;THE CHANGING TIES BETWEEN THE OIL AND CHEMICAL INDUSTRIES;65
1.5.2.12;THE ROLE OF ENTREPRENEURS AND PRIVATE EaUITY FUNDS;67
1.5.2.13;THE EVERLASTING PRESENCE OF CONTRARIANS;68
1.5.2.14;THE CASE OF JAPAN;71
1.5.2.15;THE CHEMICAL INDUSTRY AT THE BEGINNING OF THE THIRD MILLENNIUM;71
1.6;2 Economic Aspects of the Chemical Industry;73
1.6.1;DEFINITION OF THE CHEMICAL INDUSTRY;73
1.6.2;THE PLACE OF THE CHEMICAL INDUSTRY IN THE ECONOMY;75
1.6.3;CHARACTERISTICS OF THE CHEMICAL INDUSTRY;80
1.6.3.1;Investment Trends;80
1.6.3.2;Commercial Development and Competition Factors;80
1.6.3.3;Technological Orientation;82
1.6.3.4;Historical;83
1.6.3.5;Obsolescence and Dependence on Research;84
1.6.4;THE FUTURE;88
1.6.5;REFERENCES;91
1.7;3 Safety Considerations in the Chemical Process Industries;93
1.7.1;INTRODUCTION;93
1.7.2;INHERENTLY SAFER PLANTS
;94
1.7.2.1;Responsibility for Safety in Design and Operation;94
1.7.2.2;Review of Design Alternatives;94
1.7.2.3;Emergency Planning;95
1.7.2.4;Placement of Process andS to rage Areas;95
1.7.2.5;Storage of Hazardous Mate rials;95
1.7.2.6;Liquefied Gas Storage;96
1.7.2.7;Use of Open Struct ures;96
1.7.2.8;Need to Understand Reactive Chemicals Systems;97
1.7.2.9;Losses from Dust Explosions;98
1.7.2.10;Substitution of Less Hazardous Materials;99
1.7.2.11;Catastrophic Failure of Engineering Materials10- 12;100
1.7.2.12;Redundant Instrumentation and Control Systems13;100
1.7.2.13;Pressure Relief Systems;101
1.7.2.14;Safe and Rapid Isolation of Piping Systems and Equipment;102
1.7.2.15;Piping, Gaskets, and Valves;102
1.7.2.16;Avoidance of Inherently Unsafe Equipment;103
1.7.2.17;Pumps for Hazardous Service;104
1.7.3;TECHNICAL MANAGEMENT OF CHEMICAL PROCESS SAFETY;105
1.7.4;PROCESS SAFETY MANAGEMENT SYSTEMS;107
1.7.4.1;Some Tools for Evaluating Risks and Hazards;108
1.7.4.2;Some Tools for Evaluating Risks and Hazards;108
1.7.5;EVALUATION OF HAZARDS AND RISKS;109
1.7.5.1;HAZOP2,50-53;109
1.7.5.2;Operating Discipline;109
1.7.5.3;Risk Analysis and Assessment;110
1.7.5.4;Quantitative Risk Analysis (QRA);110
1.7.6;COMBUSTION HAZARDS;110
1.7.6.1;Introduction;110
1.7.6.2;Fire26;111
1.7.6.3;Flammability;113
1.7.6.4;Inert Gases;115
1.7.6.5;Mists and Foams;117
1.7.6.6;Ignition;118
1.7.7;STATIC ELECTRICITY;122
1.7.7.1;Introduction;122
1.7.7.2;Hazard Determinants;123
1.7.8;EXPLOSIONS;127
1.7.8.1;Deve lopment of Pressure;127
1.7.8.2;Deflagration;128
1.7.8.3;Detonations;128
1.7.8.4;Explosion Violence;129
1.7.9;BOILING LIQUID EXPANDING VAPOR EXPLOSIONS (BLEVES);131
1.7.10;DAMAGE ESTIMATES37;132
1.7.10.1;Explosion Consequences;132
1.7.10.2;Radiation Consequences;132
1.7.10.3;Unconfined Vapor Cloud Explosions (UVCE);132
1.7.10.4;Physical Explosions;134
1.7.11;MECHANICAL HEAT;136
1.7.12;VACUUM49;137
1.7.12.1;Protective Measures for Equipment;138
1.7.13;REGULATIONS
;138
1.7.13.1;Process Safety Management;138
1.7.13.2;Risk Management Plans (RMPs);144
1.7.13.3;Taxies Release Inventory;145
1.7.14;HAZWOPER;145
1.7.14.1;More Information;145
1.7.15;THE PRINCIPAL REASON FOR MOST CHEMICAL PROCESS ACCIDENTS;145
1.7.15.1;Levels of Causes;146
1.7.16;CASE HISTORIES;146
1.7.16.1;Flixborough, England 19742;146
1.7.16.2;Bhopal, 1985 (C&EN Feb. 11, 1985;Technica 198954);147
1.7.16.3;Phillips Explosion, 198957;148
1.7.17;SUMMARY;152
1.7.18;REFERENCES;152
1.7.19;ADDITIONAL READING REFERENCES;154
1.7.19.1;Internet References and WEB pages;155
1.8;4 Managing an Emergency Preparedness Program;157
1.8.1;INTRODUCTION;157
1.8.1.1;Prevention, Prediction, and Preparation;157
1.8.1.2;Need for Emergency Preparedness Programs;158
1.8.2;PREVENTING AND PREDICTING EMERGENCIES: GETIING STARTED;159
1.8.3;HAZARD IDENTIFICATION AND MITIGATION;161
1.8.3.1;Process Safety Management Team;162
1.8.3.2;Identifying Hazards: PSRTeams;162
1.8.3.3;Review Methods;162
1.8.3.4;Recommendations and Reports;163
1.8.3.5;Mitigating Hazards: Release Detection and Mitigation;163
1.8.4;PREPARING FOR EMERGENCIES: IDENTIFYING AND EVALUATING RESOURCES;165
1.8.4.1;Personnel;165
1.8.4.2;Plans;166
1.8.4.3;Alarm Systems;168
1.8.4.4;Facilities for Protectionand Communication;169
1.8.5;DEVELOPING AN ERP;170
1.8.5.1;Plan Design;171
1.8.5.2;EMO Structure;171
1.8.6;TRAINING PERSONNEL;174
1.8.6.1;Fire Brigade Training;174
1.8.6.2;EMO Training;175
1.8.6.3;Employee Training;175
1.8.6.4;Facility Drills;176
1.8.7;INVOLVING THE COMMUNITY;176
1.8.7.1;Communications;176
1.8.7.2;Integrating Plans;178
1.8.7.3;Off-Site Warning;178
1.8.7.4;Local Emergency Plans;178
1.8.7.5;Local Emergency Planning Committees;179
1.8.7.6;Drills and Crit iques;179
1.8.8;LAWS, REGULATIONS, AND SUPPORT;180
1.8.8.1;Laws;180
1.8.8.2;Meeting the Requirements;181
1.8.8.3;Prevention and Preparation;181
1.8.8.4;Plans;181
1.8.8.5;Communications;181
1.8.8.6;Reports;182
1.8.8.7;Training, Drills, Audits , and Evaluations;184
1.8.8.8;Sources of Assistance;184
1.8.9;SELECT BIBLIOGRAPHY;184
1.8.9.1;Standards;185
1.8.10;SUGGESTED READING;185
1.8.10.1;Regulations;185
1.8.10.2;Prevention and Planning;185
1.8.11;LAWS, REGULATIONS, AND STANDARDS;186
1.8.11.1;Laws and Regulations;186
1.8.11.2;Transportation;187
1.9;5 Applied Statistical Methods and the Chemical Industry;188
1.9.1;INTRODUCTION;188
1.9.2;SIMPLE TOOLS OF DESCRIPTIVE STATISTICS;189
1.9.3;TOOLS OF ROUTINE INDUSTRIAL PROCESS MONITORING AND CAPABILITY ASSESSMENT;195
1.9.4;STATISTICAL METHODS AND INDUSTRIAL EXPERIMENTATION;201
1.9.4.1;Identifying Major Contributors to Process Variation;202
1.9.4.2;Discovering and Exploiting Patterns of Factor Influence on Responses;205
1.9.4.3;Mixture Experiments;211
1.9.4.4;Mechanistic Model Building;216
1.9.5;MODERN BUSINESS PROCESS IMPROVEMENT AND THE DISCIPLINE OF STATISTICS;217
1.9.6;CONCLUSION;218
1.9.7;REFERENCES;218
1.10;6 Green Engineering-Integration of Green Chemistry, Pollution Prevention, and Risk-Based Considerations;220
1.10.1;OVERVIEW;220
1.10.2;I. INTRODUCTION TO GREEN CHEMISTRY AND GREEN ENGINEERING;221
1.10.2.1;TWELVE PRINCIPLES OF GREEN CHEMISTRY
;224
1.10.2.2;PRINCIPLES OF GREEN ENGINEERING;226
1.10.3;II POLLUTION PREVENTION HEURISTICS FOR CHEMICAL PROCESSES;227
1.10.3.1;INTRODUCTION;227
1.10.3.2;HIERARCHICAL RULES FOR WASTE MINIMIZATION;228
1.10.3.2.1;Batch or Continuous?;229
1.10.3.2.2;Input-Output Structure;229
1.10.3.2.3;Recycle Structure of the Flowsheet;230
1.10.3.2.4;Reaction Systems;231
1.10.3.2.5;Separation Systems;231
1.10.3.2.6;Postprocessing and Product Section;232
1.10.3.2.7;Energy Systems;232
1.10.3.2.8;Auxiliary Equipments;233
1.10.3.3;HEURISTICS FOR GREEN REACTOR DESIGN;233
1.10.3.4;THE P2 RULES FOR SEPARATIONS DEVICES;234
1.10.3.4.1;Distillation Columns;234
1.10.3.4.2;Gas-Liquid Separation;235
1.10.3.4.3;Gas-Solid Separations;235
1.10.3.4.4;Liquid-Solid Separations;235
1.10.3.5;ACRONYMS;236
1.10.3.6;ACKNOWLEDGMENT;236
1.10.4;III UNDERSTANDING AND PREDICTION OF THE ENVIRONMENTAL FATE OF CHEMICALS;236
1.10.4.1;INTRODUCTION;236
1.10.4.2;TRANSLOCATION OF CHEMICALS IN THE ENVIRONMENT;236
1.10.4.2.1;Modeling the Environment;236
1.10.4.2.2;Translocation Processes in Air;237
1.10.4.2.3;Translocation Processes in Water;239
1.10.4.2.4;Translocation Processes in Soil;240
1.10.4.2.5;Translocation Processes Involving Biota;240
1.10.4.3;TRANSFORMATION OF CHEMICALS IN THE ENVIRONMENT;241
1.10.4.3.1;Biotic Transformation Processes;242
1.10.4.3.2;Abiotic Transformation Processes;243
1.10.4.4;THE CONNECTION BETWEEN CHEMICAL PROPERTIES AND ENVIRONMENTAL FATE;246
1.10.4.4.1;Traditional Chemical Properties;246
1.10.4.4.2;Specialized Chemical Properties;247
1.10.4.4.3;Sources of Chemical Property and Fate Data;248
1.10.4.5;HEURISTICS FOR PREDICTING ENVIRONMENTAL FATE;249
1.10.5;IV ENVIRONMENTAL PERFORMANCE ASSESSMENT FOR CHEMICAL PROCESS DESIGN;249
1.10.5.1;INTRODUCTION;249
1.10.5.2;OVERVIEW OF ENVIRONMENTAL ISSUES;249
1.10.5.3;ENVIRONMENTAL IMPACT ASSESSMENT: TIER I-TIER III;253
1.10.5.3.1;Early Process Design Evaluations: "Tier I" Assessment;253
1.10.5.3.2;Evaluations During Process Synthesis: "Tier II" Assessment;255
1.10.5.3.3;Detailed Evaluation of Process Flowsheets: "Tier III" Assessment;255
1.10.5.3.4;Hybrid Screening Evaluations: Combining "Tier I"-"Tier III"-Life Cycle Assessment;259
1.10.5.4;CONCLUSIONS;262
1.10.6;V LIFE-CYCLE ASSESSMENT;264
1.10.6.1;INTRODUCTION;264
1.10.6.2;GOAL AND SCOPE OF LCA;266
1.10.6.3;METHODS OF LIFE-CYCLE INVENTORY;267
1.10.6.4;IMPACT ASSESSMENT AND ANALYSIS;269
1.10.6.5;LCA IN PRACTICE;269
1.10.6.6;CONCLUSIONS;274
1.10.7;REFERENCES;274
1.10.8;ADDITIONAL SUGGESTED READING;279
1.10.8.1;Introduction to Green Chemistry and Green Engineering;279
1.10.8.2;2.2 Pollution Prevention Heuristics for Chemical Processes;279
1.10.8.3;2.3 Understanding and Prediction of the Environmental Fate of Chemicals;279
1.10.8.4;2.4 Environmental Performance Assessment for Chemical Process Design;280
1.10.8.5;2.4 Life-Cycle Assessment;280
1.11;7 Industrial Catalysis: A Practical Guide;281
1.11.1;THE IMPORTANCE OF CATALYSIS;281
1.11.2;HOW DOES A CATALYST WORK?;283
1.11.3;WHAT ARE THE CATALYTIC METALS AND METAL OXIDES?;283
1.11.4;THE STRUCTURE OF HETEROGENEOUS CATALYSTS;283
1.11.4.1;Rate-Limiting Steps for a Supported Catalyst;284
1.11.4.2;Selectivity;288
1.11.4.3;Catalyst Preparation;289
1.11.5;A HETEROGENEOUS CATALYTIC REACTION: AN EXAMPLE;290
1.11.6;ACTIVE CATALYTIC SITES;290
1.11.6.1;Reactor Types;291
1.11.6.2;Kinetics;291
1.11.6.3;Rate Models;294
1.11.6.4;Catalyst Deactivation;294
1.11.7;CATALYST CHARACTERIZATION;296
1.11.8;HOMOGENEOUS CATALYTIC REACTIONS;297
1.11.8.1;Commercial Applications;297
1.11.8.2;Petroleum Processing;297
1.11.9;CATALYSTS FOR CONTROLLING AUTOMOTIVE EMISSIONS;301
1.11.9.1;Oxidation Catalysts to Abate Unburned Hydrocarbon and CO Emissions;301
1.11.9.2;Three-Way Catalytic Conversion;302
1.11.9.3;Modern Catalytic Converter Systems;304
1.11.10;CATALYTIC HYDROGENATION OF VEGETABLE OILS FOR EDIBLE FOOD PRODUCTS;305
1.11.10.1;Triglycerides;305
1.11.11;FERTILIZERS AND HYDRO GENGENERATION;306
1.11.11.1;General Reactions;306
1.11.11.2;Hydrogen Generation for the Production of NH3;307
1.11.11.3;Ammonia Synthesis;309
1.11.11.4;Nitric Acid Synthesis;309
1.11.11.5;Pure Hydrogen Generation with Pressure Swing Adsorption (PSA) Purification;310
1.11.12;PRODUCTION OF BUTYRALDEHYDE: A HOMOGENEOUS CATALYTIC REACTION;311
1.11.12.1;Butyraldehyde;311
1.11.13;POLYETHYLENE AND POLYPROPYLENE FOR THE PRODUCTION OF PLASTICS;312
1.11.13.1;Polyethylene;312
1.11.13.2;Polypropylene;312
1.11.14;CATALYST CHALLENGES;313
1.11.15;REFERENCES;313
1.12;8 Environmental Chemical Determinations;315
1.12.1;INTRODUCTION;315
1.12.2;SIGNIFICANCE OF ENVIRONMENTAL CHEMICAL DETERMINATIONS;315
1.12.3;CHEMICAL ANALYSIS STRATEGIES;316
1.12.3.1;Samples and Sampling Strategies;316
1.12.3.2;Determination of Total Elements or Total Related Substances.;317
1.12.3.3;Determination of Specific Substances;318
1.12.3.4;Single-Analyte and Multi-Analyte Methods;320
1.12.3.5;Remote Laboratory Analyses and Field Analyses;320
1.12.3.6;Discrete Samples and Continuous Monitoring;321
1.12.3.7;Analytical Quality Assurance and Control;322
1.12.4;DEVELOPMENT AND DOCUMENTATION OF ANALYTICAL METHODS;322
1.12.4.1;Research Methods;322
1.12.4.2;Methods in Development;323
1.12.4.3;Methods Published by Standard-Setting Organizations;323
1.12.4.4;Methods Published or Referenced in Government Agency Regulations;323
1.12.5;CHARACTERISTICS OF ANALVTES, SAMPLES, AND SAMPLING TECHNIQUES;324
1.12.5.1;Volatile Analytes;324
1.12.5.2;Semivolatile Analytes;324
1.12.5.3;Nonvolatile Analytes;326
1.12.5.4;Condensed-Phase Samples;326
1.12.5.5;Vapor-Phase Samples;328
1.12.6;PROCESSING OF SAMPLES BEFORE DETERMINATION OF THE ANALVTES;330
1.12.7;CHROMATOGRAPHIC ANALYTICAL METHODS;331
1.12.7.1;Chromatographic Separation Techniques;331
1.12.7.2;Chromatography Detectors;333
1.12.8;NONCHROMATOGRAPHIC ANALYTICAL METHODS;334
1.12.8.1;Elemental Analysis;334
1.12.8.2;Organic and Inorganic Compounds and Ions;336
1.12.9;GLOSSARY;336
1.12.10;REFERENCES;337
1.12.11;SUGGESTED ADDITIONAL READING;337
1.13;9 Nanotechnology: Fundamental Principles and Applications;338
1.13.1;INTRODUCTION;338
1.13.2;A NEW REALM OF MATTER;339
1.13.3;SOLVATED METAL ATOM DISPERSION (SMAD) METHOD FOR THE PREPARATION OF NANOPARTICLES;340
1.13.3.1;Gold Nanoparticles;342
1.13.3.2;Silver Nanoparticles;344
1.13.3.3;Semiconductor Nanoparticles;345
1.13.3.4;Dielectrics (Insulator Nanoparticlesl;346
1.13.4;MODIFIED AEROGEL PROCEDURE (MAP);347
1.13.4.1;Metal Oxide Nanoparticles;348
1.13.5;MIXED METAL OXIDE NANOPARTICLES;349
1.13.6;APPLICATIONS;351
1.13.6.1;Catalysis-Dechlorination and Dehydrochlorination;351
1.13.6.2;Destructive Adsorption of Chemical Warfare ICW) Agents;351
1.13.7;MISCELLANEOUS APPLICATIONS;352
1.13.7.1;Environmental Chemistry;352
1.13.7.2;Photocatalysis;352
1.13.7.3;Plastics;352
1.13.7.4;Medicine;352
1.13.7.5;Electrochemistry;353
1.13.8;CONCLUSIONS;353
1.13.9;REFERENCES;353
1.14;10 Synthetic Organic Chemicals;355
1.14.1;CHEMICALS DERIVED FROM METHANE;356
1.14.1.1;Synthesis Gas;356
1.14.1.2;Chloromethanes;362
1.14.1.3;Acetylene;363
1.14.1.4;Hydrogen Cyanide;363
1.14.1.5;Carbon Disulfide;364
1.14.2;CHEMICALS DERIVED FROM ETHYLENE;364
1.14.2.1;Polyethylene;364
1.14.2.2;Ethylene Oxide;365
1.14.2.3;Chlorinated Ethanes and Ethylenes;369
1.14.2.4;Ethanol;374
1.14.2.5;Ethylbenzene;374
1.14.2.6;Acetaldehyde, Acetic Acid, Acetic Anhydride, Vinyl Acetate;376
1.14.2.7;Ethylene Oligomers (Alpha Olefinsl and Linear Primary Alcohols;381
1.14.2.8;Ethylene-Propylene Elastomers;381
1.14.2.9;Propionaldehyde;381
1.14.2.10;Other Ethylene Uses;381
1.14.3;CHEMICALS DERIVED FROM PROPYLENE;383
1.14.3.1;Polypropylene;383
1.14.3.2;Acrylonitrile;384
1.14.3.3;Propylene Oxide;384
1.14.3.4;Isopropyl Alcohol;385
1.14.3.5;Cumene;388
1.14.3.6;Oxo Chemicals;388
1.14.3.7;Propylene Oligomers: Dodecene and Nonene;389
1.14.3.8;Acrylic Acid and Esters;389
1.14.3.9;Epichlorohydrin;390
1.14.3.10;Glycerin;390
1.14.4;CHEMICALS DERIVED FROM BUTANES AND BUTYLENES;391
1.14.4.1;n-Butane Derivatives;392
1.14.4.2;Isobutanes;395
1.14.4.3;Butylenes;397
1.14.4.4;Isobutylene;398
1.14.4.5;Butadiene;400
1.14.5;HIGHER ALIPHATIC HYDROCARBONS;400
1.14.5.1;Cyclopentadiene;400
1.14.5.2;Isoprene;400
1.14.5.3;n-Paraffins and OIefins;401
1.14.5.4;Primary and Secondary Higher Alcohols;401
1.14.6;CHEMICALS DERIVED FROM BENZENE, TOLUENE, AND XYLENE;401
1.14.6.1;Chemicals from Benzene;401
1.14.6.2;Derivatives of Toluene;408
1.14.6.3;Chemicals from Xylene;409
1.14.6.4;Naphthalene Derivatives;412
1.14.7;REFERENCES;412
1.15;11 Chemistry in the Pharmaceutical Industry;414
1.15.1;INTRODUCTION;414
1.15.2;MEDICINAL CHEMISTRY;415
1.15.2.1;Research Strategies;417
1.15.2.2;Pharmacodynamics;418
1.15.2.3;Pharmacokinetics and Toxicity;418
1.15.2.4;Drug Delivery;419
1.15.2.5;Patents;419
1.15.2.6;Clinical Trials;420
1.15.2.7;Summary;421
1.15.3;CARDIOVASCULAR AGENTS;421
1.15.3.1;Hypertension;421
1.15.3.2;Congestive Heart Failure, Migraine, and Thrombolytic Agents;422
1.15.4;METABOLIC AGENTS;423
1.15.4.1;Hyperlipidemia;423
1.15.4.2;Diabetes;424
1.15.4.3;Obesity;425
1.15.5;GASTROINTESTINAL AND GENITOURINARY AGENTS;425
1.15.5.1;Antisecretory;425
1.15.5.2;Benign Prostatic Hyperplasia and Urinary Urge Incontinence;426
1.15.5.3;Erectile Dysfunction;426
1.15.6;PULMONARY AGENTS;427
1.15.6.1;Asthma and Allergic Rhinitis;427
1.15.7;INFLAMMATION AND OSTEOPOROSIS;427
1.15.7.1;Arthritis;427
1.15.7.2;Osteoporosis;428
1.15.8;CENTRAL NERVOUS SYSTEM AGENTS;428
1.15.8.1;Antidepressants;428
1.15.8.2;Anxiolytics;428
1.15.8.3;Bipolar Disorders, Schizophrenia, and Epilepsy;429
1.15.8.4;Alzheimer's Disease;429
1.15.9;INFECTIOUS DISEASES;430
1.15.9.1;Antibacterials;430
1.15.9.2;Antifungals;431
1.15.9.3;Antivirals;431
1.15.10;ANTINEOPLASTICS;432
1.15.11;MISCELLANEOUS AGENTS;433
1.15.11.1;Glaucoma and Nausea;433
1.15.11.2;Analgesics;434
1.15.12;SMALL MOLECULE HIGH THROUGHPUT SYNTHESIS;434
1.15.12.1;Discovery Libraries;435
1.15.12.2;Targeted Libraries;435
1.15.12.3;Optimization Libraries;436
1.15.13;CHEMICAL PROCESS R&D IN THE PHARMACEUTICAL INDUSTRY;437
1.15.13.1;Scheme-l;439
1.15.13.2;Scheme-2;439
1.15.13.3;Scheme-3;440
1.15.14;CONCLUSION;440
1.15.15;REFERENCES;440
1.16;12 Manufactured Textile Fibers;441
1.16.1;TEXTILE BACKGROUND;441
1.16.2;HISTORY;443
1.16.3;FIBER CONSUMPTION;444
1.16.4;RAYON;448
1.16.4.1;Chemical Manufacture;448
1.16.4.2;Wet Spinning;451
1.16.4.3;Cuprammonium, Nitrocellulose, and Cellulose Acetate Processes for Rayon;454
1.16.4.4;Textile Operations;454
1.16.4.5;Modified Viscose Rayon Fibers;456
1.16.4.6;Other New Developments;457
1.16.4.7;Environmentally Friendly High Wet Strength Rayon-Lyocell;457
1.16.5;CelLULOSE ACETATE;458
1.16.5.1;Historical;458
1.16.5.2;Manufacture of Cellulose Secondary Acetate;458
1.16.5.3;Manufacture of Cellulose Triacetate;460
1.16.5.4;Spinning Cellulose Acetate;461
1.16.6;PROTEIN FIBERS;464
1.16.7;NYLON;464
1.16.7.1;Historical;464
1.16.7.2;Manufacture;464
1.16.7.3;Melt spinning;466
1.16.7.4;Drawing;467
1.16.7.5;Other Nylons, Modifications, and New Developments;468
1.16.8;POLYESTERS;469
1.16.8.1;Historical;469
1.16.8.2;Manufacture;470
1.16.8.3;Drawing;471
1.16.8.4;Heat Setting;472
1.16.8.5;Textured Yarns;473
1.16.8.6;Staple Process;474
1.16.8.7;Continuous Filament Yarn Process Variants;474
1.16.8.8;Modifications and New Developments;475
1.16.9;ACRYLICS;476
1.16.9.1;Polymer Manufacture;476
1.16.9.2;Spinning;478
1.16.9.3;Bicomponent or Conjugate Spun Fibers;479
1.16.10;VINYL AND MODACRYLIC FIBERS;480
1.16.10.1;Vinyls;480
1.16.10.2;Modacrylics;481
1.16.11;ELASTOMERIC FIBERS;482
1.16.12;POLYOLEFIN FIBERS;483
1.16.12.1;Polypropylene;483
1.16.12.2;High Molecular Weight;487
1.16.13;ARAMIDS;490
1.16.13.1;Introduction;490
1.16.13.2;Manufacture;491
1.16.14;HIGH-TEMPERATURE-RESISTANT FIBERS;493
1.16.14.1;Meta-Aramid;493
1.16.14.2;PBI;494
1.16.15;POLYTETRAFLUOROETHYLENE;494
1.16.15.1;Historical;494
1.16.15.2;Manufacture;495
1.16.15.3;Fiber Manufacture;495
1.16.15.4;Properties;495
1.16.15.5;Expanded PTFE (ePTFE);496
1.16.16;GLASS AND CARBON FIBERS;496
1.16.16.1;Glass;496
1.16.16.2;Carbon and Graphite Fibers;498
1.16.17;SULFAR;499
1.16.17.1;Historical;499
1.16.17.2;Manufacture;500
1.16.18;MICRODENIER FIBERS;500
1.16.19;NANOFIBERS;501
1.16.20;FIBER VARIANTS;502
1.16.20.1;Introduction;502
1.16.20.2;Physical Variants;502
1.16.20.3;Chemical Varia nt s;504
1.16.21;REFERENCES;506
1.16.22;SUGGESTED READING;507
1.17;13 Dye Application, Manufacture of Dye Intermediates and Dyes;509
1.17.1;INTRODUCTION;509
1.17.1.1;Dyeing;509
1.17.1.2;Synthetic Dyes;510
1.17.1.3;The Development of the U.S. Dyestuff Industry;511
1.17.2;TEXTILE FIBERS;513
1.17.2.1;Natural Fibers;513
1.17.2.2;Regenerated Fibers;514
1.17.2.3;Synthetic Fibers;515
1.17.3;DYE CLASSIFICATION;516
1.17.3.1;Acid Dyes;517
1.17.3.2;Azoic Dyes;519
1.17.3.3;Basic or Cationic Dyes;519
1.17.3.4;Direct Dyes;521
1.17.3.5;Disperse Dyes;526
1.17.3.6;Reactive Dyes;529
1.17.3.7;Sulfur Dyes;530
1.17.3.8;Vat Dyes;534
1.17.4;THE APPLICATION OF DYES;537
1.17.4.1;Fiber Preparation;537
1.17.4.2;Dye-Bath Preparation;537
1.17.4.3;Finishing;538
1.17.4.4;Dyeing Methods/Batch;539
1.17.5;PRINTING;539
1.17.6;PIGMENT DYEING AND PRINTING;541
1.17.7;NONTEXTILE USES OF DYES;541
1.17.7.1;Liquid Crystal Dyes;541
1.17.7.2;Ink-jet Dyes;541
1.17.7.3;Thermal and Pressure-Sensitive Printing;543
1.17.7.4;Organic Photoconductors and Toners;544
1.17.7.5;Infrared Absorbing Dyes;545
1.17.7.6;Laser Dyes;545
1.17.7.7;Biomedical Dyes;546
1.17.7.8;Hair Dyes;546
1.17.7.9;Photographic Dyes;548
1.17.8;DYE INTERMEDIATES;548
1.17.8.1;Nitration;549
1.17.8.2;Reduction;551
1.17.8.3;Amination;553
1.17.8.4;Sulfonation;554
1.17.8.5;Halogenation;557
1.17.8.6;Hydroxylation;559
1.17.8.7;Oxidation;561
1.17.8.8;Other Important Reactions;561
1.17.9;DYE MANUFACTURE;562
1.17.9.1;Nitro Dyes;564
1.17.10;Ala DYES;564
1.17.10.1;Monoazo Dyes;568
1.17.10.2;Disazo Dyes;569
1.17.10.3;Polyazo Dyes;573
1.17.11;TRIPHENYLMETHANE DYES;575
1.17.12;XANTHENE DYES;576
1.17.13;ANTHRAQUINONE AND RELATED DYES;577
1.17.13.1;Anthraquinone Disperse Dyes;577
1.17.13.2;Anthraquinone Acid Dyes;581
1.17.13.3;Anthraquinone Basic Dyes;583
1.17.13.4;Anthraquinone Reactive Dyes;583
1.17.14;VAT DYES;585
1.17.14.1;Anthraquinone;585
1.17.15;INDIGOID AND THIOINDIGOID;588
1.17.16;SULFUR DYES;589
1.17.17;PHTHALOCYANINE DYES;592
1.17.18;FLUORESCENT BRIGHTENERS(COLORLESS "DYES");593
1.17.19;PRODUCTION AND SALES;596
1.17.20;REFERENCES;599
1.18;14 The Chemistry of Structural Adhesives: Epoxy, Urethane, and Acrylic Adhesives;601
1.18.1;INTRODUCTION;601
1.18.1.1;Adhesion;601
1.18.1.2;Curing;602
1.18.1.3;Adhesion Mechanisms;604
1.18.1.4;Surfaces;605
1.18.2;EPOXY STRUCTURAL ADHESIVES;606
1.18.2.1;Introduction;606
1.18.2.2;Commercial Epoxy Resins;607
1.18.2.3;Epoxy Cure Chemistry;611
1.18.2.4;Evolution;616
1.18.2.5;Summary;616
1.18.3;URETHANE STRUCTURAL ADHESIVES;616
1.18.3.1;Introduction;616
1.18.3.2;Isocyanate Preparation;617
1.18.3.3;Isocyanate Reactions;617
1.18.3.4;Important Isocyanates;619
1.18.3.5;Blocked Isocyanates;621
1.18.3.6;Evolution;621
1.18.3.7;Summary;622
1.18.4;ACRYLIC STRUCTURAL ADHESIVES;623
1.18.4.1;Introduction;623
1.18.4.2;Acrylic Monomers;623
1.18.4.3;Curing;624
1.18.4.4;Formulation;626
1.18.4.5;Summary;628
1.18.5;HYBRID ADHESIVES;628
1.18.6;EVOLUTION;629
1.18.7;CONCLUSION;629
1.18.8;REFERENCES;630
1.19;15 Synthetic Resins and Plastics;633
1.19.1;INTRODUCTION;633
1.19.1.1;Definition;633
1.19.1.2;History;633
1.19.1.3;Advantages of Plastics over Conventional Materials;634
1.19.1.4;Markets for Plastics;634
1.19.1.5;Major Classes of Plastic Materials;635
1.19.2;PART I. POLYMER CHEMISTRY;635
1.19.2.1;MOLECULAR WEIGHT;635
1.19.2.2;CHAIN STRUCTURE;636
1.19.2.3;CHEMICAL STRUCTURE;636
1.19.2.4;MORPHOLOGY;637
1.19.2.5;TRANSITION TEMPERATURES;638
1.19.2.5.1;Glass Transition Temperature (Tg);638
1.19.2.5.2;Crystallization and Melting Points (TM);639
1.19.2.6;POLYMERIZATION;640
1.19.2.6.1;Step-Reaction Polymerization;640
1.19.2.6.2;Chain-Reaction Polymerization;641
1.19.2.6.3;Coordination Polymerization;643
1.19.2.7;POLYMERIZATION METHODS;645
1.19.2.7.1;Bulk Polymerization;645
1.19.2.7.2;Solution Polymerization;645
1.19.2.7.3;Suspension Polymerization;645
1.19.2.7.4;Emulsion Polymerization;646
1.19.2.8;COPOLYMERIZATION;646
1.19.2.8.1;Random Copolymerization;647
1.19.2.8.2;Block and Graft Copolymers;647
1.19.2.9;MECHANICAL PROPERTIES;648
1.19.2.9.1;Viscoelasticity;648
1.19.2.9.2;Failure Behavior;650
1.19.3;PART II. COMMERCIAL PLASTIC MATERIALS;651
1.19.3.1;CLASSES OF FAMILIES OF COMMERCIAL PLASTICS;651
1.19.3.1.1;Commodity Thermoplastics;651
1.19.3.1.2;Engineering and Specialty Thermoplastics;657
1.19.3.1.3;Thermoplastic Elastomers;663
1.19.3.1.4;Thermoset Plastics;665
1.19.3.2;GENERAL CONSIDERATIONS;672
1.19.3.2.1;Structure-Property Relationships;672
1.19.3.2.2;Additives;673
1.19.3.2.3;Critical Properties: Challenges to the Plastics Industry;674
1.19.3.2.4;Fire Performance;676
1.19.3.2.5;Health and Environment;676
1.19.3.2.6;Recycling;676
1.19.4;PART III. PLASTIC PROCESSING;677
1.19.4.1;RHEOLOGY;677
1.19.4.1.1;Fundamental Concepts;677
1.19.4.1.2;Instrumental Measurement of Flow Properties;678
1.19.4.1.3;Practical Effects of Flow Properties;678
1.19.4.2;EXTRUSION;679
1.19.4.2.1;Basic Functions;680
1.19.4.2.2;Major Processes and Products;681
1.19.4.3;INJECTION MOLDING;682
1.19.4.3.1;Introduction;682
1.19.4.3.2;Injection Molding Cycle (Fig. 15.291;682
1.19.4.3.3;Variations and Details;683
1.19.4.4;REACTION INJECTION MOLDING;684
1.19.4.4.1;Overview;684
1.19.4.4.2;Ingredients;684
1.19.4.4.3;Equipment and Process;685
1.19.4.4.4;Other Polymers;685
1.19.4.5;STRUCTURAL FOAM;685
1.19.4.5.1;Definition;685
1.19.4.5.2;General Description;686
1.19.4.5.3;Degree of Expansion;686
1.19.4.5.4;Benefits;686
1.19.4.5.5;Problems in Structural Foaming;686
1.19.4.6;LOW-DENSITY FOAMS;686
1.19.4.6.1;Polyurethane;686
1.19.4.6.2;Polystyrene;687
1.19.4.6.3;Polyvinyl Chloride;687
1.19.4.6.4;Polyethylene;688
1.19.4.6.5;Blow Molding;688
1.19.4.7;THERMOFORMING;689
1.19.4.8;ROTATIONAL MOLDING("ROTOMOLDlNG");689
1.19.4.9;POWDER COATING;690
1.19.4.9.1;Fluid Bed Coating;690
1.19.4.9.2;Electrostatic Fluid Bed;690
1.19.4.9.3;Electrostatic Spray;690
1.19.4.10;CALENDERING;691
1.19.4.11;VINYL PLASTISOL PROCESSING;691
1.19.4.12;LIQUID CASTING PROCESSES;692
1.19.4.13;COMPRESSION MOLDING AND TRANSFER MOLDING;693
1.19.4.14;REINFORCED PLASTICS PROCESSING;694
1.19.4.14.1;Matched Die Molding Processes;694
1.19.4.14.2;Open Molding;695
1.19.4.14.3;Special Processes;696
1.19.5;REFERENCES FOR PART I;696
1.19.6;REFERENCES FOR PART II;697
1.19.7;REFERENCES FOR PART III;698
1.20;16 Rubber;699
1.20.1;INTRODUCTION;699
1.20.2;RUBBER CONCEPTS;700
1.20.3;POLYMER STRUCTURE;701
1.20.3.1;Macrostructure;701
1.20.3.2;Microstructure;702
1.20.3.3;Network Structure;703
1.20.4;RUBBER PROPERTIES;703
1.20.4.1;Elasticity-The Retractive Force;703
1.20.4.2;Glass Transition Temperature;704
1.20.4.3;Crystallinity;704
1.20.5;RUBBER USE;705
1.20.5.1;Compounding;705
1.20.5.2;Processing;706
1.20.6;NATURAL RUBBER;706
1.20.6.1;Uses;707
1.20.7;POLYISOPRENE;708
1.20.7.1;Monomer Production;708
1.20.7.2;Polymer Production Process;708
1.20.7.3;Use;709
1.20.8;STYRENE-BUTADIENE RUBBER;709
1.20.8.1;Monomer Production;709
1.20.8.2;Polymer Production Process;710
1.20.8.3;Emulsion Process;710
1.20.8.4;Solution Process;712
1.20.8.5;Functional Solution SBR;713
1.20.9;POLYBUTADIENE (BR);714
1.20.9.1;Monomer Production;714
1.20.9.2;Polymer Production Process;714
1.20.9.3;Uses;715
1.20.10;ETHYLENE-PROPYLENE RUBBER;716
1.20.10.1;Monomer Production;716
1.20.10.2;Polymer Production;716
1.20.11;BUTYL RUBBER;717
1.20.11.1;Monomer Production;717
1.20.11.2;Production Process;717
1.20.11.3;Properties and Use;718
1.20.12;NITRILE RUBBER;718
1.20.12.1;Monomer Production;718
1.20.12.2;Polymer Production;718
1.20.12.3;Properties and Use;718
1.20.13;HYDROGENATED NITRILE RUBBER;718
1.20.13.1;Uses;719
1.20.14;CHLOROPRENE RUBBER;719
1.20.14.1;Monomer Production;719
1.20.14.2;Production Process;719
1.20.14.3;Properties and Uses;719
1.20.15;SILICONE ELASTOMERS;720
1.20.15.1;Monomer Production;720
1.20.15.2;Polymer Production;720
1.20.15.3;Uses;720
1.20.16;POLYURETHANE RUBBER;721
1.20.16.1;Raw Materials;721
1.20.16.2;Uses;721
1.20.17;MODIFIED POLYETHYLENE RUBBERS;721
1.20.17.1;Chlorinated Polyethylene;722
1.20.17.2;Chlorosulfonated Polyethylene;722
1.20.18;THERMOPLASTIC ELASTOMERS (TPE);722
1.20.18.1;Block Copolymers;722
1.20.18.2;Uses;723
1.20.18.3;lonomers;723
1.20.18.4;Uses;724
1.20.18.5;Metallocene Elastomers;724
1.20.18.6;Rubber-Plastic Alloys;724
1.20.18.7;Uses;724
1.20.19;PLASTICIZED POLYVINYL CHLORIDE;725
1.20.19.1;Monomer Production;725
1.20.19.2;Production Process;725
1.20.19.3;Properties and Use;725
1.20.20;FLUOROCARBON ELASTOMERS;725
1.20.20.1;Uses;726
1.20.21;REFERENCES;726
1.21;17 The Agrochemical Industry;729
1.21.1;INTRODUCTION;729
1.21.1.1;Scope of the Chapter;729
1.21.1.2;History;730
1.21.2;ROLE OF THE AGROCHEMICAL INDUSTRY;730
1.21.3;CHARACTERISTICS OF THE AGROCHEMICAL INDUSTRY;749
1.21.3.1;Government Regulation;749
1.21.3.2;Manufacture of Agrochemicals;751
1.21.3.3;Classes of Agrochemicals;751
1.21.4;DELIVERY SYSTEMS OF AGROCHEMICALS;770
1.21.4.1;Obsolescence of Agrochemicals;770
1.21.5;PRODUCTS OF THE AGROCHEMICAL INDUSTRY;770
1.21.6;STRUCTURAL BASIS OF AGROCHEMICALS;784
1.21.6.1;Organophosphorous Agrochemicals;784
1.21.6.2;Organochlorine;785
1.21.6.3;Chloracetanilides;788
1.21.6.4;Aryloxyphenoxypropionic Acids (Cereal Herbicides);790
1.21.7;ROLE OF CHIRALITY;793
1.21.7.1;Basis of Chemistry Used in Synthesis of Agrochemicals;796
1.21.7.2;Case Study-Chemistry and Manufacture of Metolachlor;796
1.21.7.3;Usage of Agrochemicals;797
1.21.8;BIOTECHNOLOGY FOR FARM PRODUCTIVITY;798
1.21.8.1;Regulatory Scene Regarding Products of Biotechnology;807
1.21.9;FUTURE DIRECTIONS;809
1.21.9.1;Allelopathy;809
1.21.9.2;Biorational Approach to Chemical Synthesis;809
1.21.10;REFERENCES;810
1.22;18 Petroleum and Its Products;811
1.22.1;THE NATURE OF PETROLEUM;811
1.22.1.1;Hydrocarbon Forms;811
1.22.1.2;Largest Energy Supplier;812
1.22.1.3;From Well to Refinery;812
1.22.2;PRODUCT;816
1.22.2.1;Refined Products;817
1.22.2.2;Product Specifications;817
1.22.2.3;Product Yields;819
1.22.2.4;Petrochemicals;819
1.22.3;REFINING SCHEMES;820
1.22.3.1;Feedstock Identification;821
1.22.3.2;Crude Oil Pretreatment;822
1.22.3.3;Crude Oil Fractions;822
1.22.4;GASOLINE;823
1.22.4.1;Volatility;825
1.22.4.2;Sulfur Content;825
1.22.4.3;Octane Number;826
1.22.5;DISTILLATES;827
1.22.5.1;Residuals;828
1.22.6;PRODUCING MORE LIGHT PRODUCTS;828
1.22.6.1;Cracking;829
1.22.6.2;Vacuum Distillation;829
1.22.6.3;Reconstituting Gases;830
1.22.7;A MODERN REFINERY;830
1.22.7.1;Petrochemicals;830
1.22.8;PROCESS DETAILS;832
1.22.8.1;Crude Desalting;832
1.22.8.2;Crude Distillation;833
1.22.8.3;Hydrotreating;834
1.22.8.4;Catalytic Reforming;836
1.22.8.5;Catalytic Cracking;839
1.22.8.6;Coking;841
1.22.8.7;Hydrocracking;842
1.22.8.8;Alkylation;844
1.22.8.9;Ether Processes;846
1.22.9;FUTURE TRENDS;848
1.22.9.1;Costs and Drivers;849
1.22.9.2;Technology Options;849
1.22.10;REFERENCES;852
1.23;Index;853
2;Volume II
;875
2.1;Title Page
;876
2.2;Copyright Page
;877
2.3;Preface;879
2.4;Table of Contents
;882
2.5;19 Coal Technology for Power, Liquid Fuels, and Chemicals
;884
2.5.1;INTRODUCTION;884
2.5.2;ORIGIN AND CLASSIFICATION OF COAL
;885
2.5.2.1;Coal Structure;888
2.5.2.2;Coal Composition and Analyses;891
2.5.3;COAL MINING AND PREPARATION;894
2.5.3.1;Surface Mining;894
2.5.3.2;Underground Mining;894
2.5.3.3;Coal Preparation;895
2.5.3.4;Coarse-Coal Cleaning;897
2.5.3.5;Medium-Coal Cleaning;897
2.5.3.6;Fine-Coal Cleaning;897
2.5.3.7;Chemical Coal Cleaning;899
2.5.4;COAL UTILIZATION;899
2.5.4.1;Environmental Concerns Related to Coal Use
;899
2.5.5;COMBUSTION;900
2.5.5.1;Combustion Equipment;900
2.5.5.2;Boiler Types;904
2.5.5.3;Pollution Controls;905
2.5.5.4;Advances in Combustion Technology;907
2.5.6;COKE PRODUCTION;908
2.5.6.1;Nonrecovery Cokemaking;908
2.5.6.2;Byproduct Coke Production;909
2.5.6.3;Direct Coal Utilization in the Steel Industry
;910
2.5.6.4;Mild Gasification;911
2.5.7;GASIFICATION;911
2.5.7.1;Chemistry of Coal Gasification;912
2.5.7.2;Types of Coal Gasifiers;914
2.5.7.3;Gasification for Power Generation;917
2.5.7.4;Descriptions of Selected Gasification Processes
;919
2.5.8;COAL LIQUEFACTION;926
2.5.8.1;Pyrolysis-Based Processes;926
2.5.8.2;Factors Affecting Coal Pyrolysis;926
2.5.8.3;Utilization and Characterization of Pyrolysis Products
;928
2.5.8.4;Direct Coal Liquefaction;929
2.5.8.5;Chemistry of Direct Coal Liquefaction;930
2.5.8.6;Direct Coal Liquefaction Processes;930
2.5.8.7;Direct Coal Liquefaction and the Future;935
2.5.8.8;Indirect Coal Liquefaction;935
2.5.9;PETROCHEMICAL FEEDSTOCKS;941
2.5.9.1;Chemicals from Coal
;942
2.5.9.2;Examples of Chemicals Production from Coal
;944
2.5.10;REFERENCES;945
2.6;20 Natural Gas
;948
2.6.1;CHARACTERISTICS;948
2.6.2;OCCURRENCE OF NATURAL GAS;950
2.6.3;EVOLUTION OF THE U.S. NATURAL GAS INDUSTRY
;952
2.6.4;U.S. MARKETED PRODUCTION4-6;952
2.6.5;NATURAL GAS LIQUIDS;955
2.6.6;U.S. NATURAL GAS RESERVES;956
2.6.7;STRUCTURE OF THE U.S. NATURAL GAS INDUSTRY
;956
2.6.8;WORLD NATURAL GAS;958
2.6.9;GAS-TO-L1QUIDS TECHNOLOGY;958
2.6.10;PREPARING NATURAL GAS FOR TRANSMISSION AND SALE
;960
2.6.11;PROCESSING FOR L1aUIDS RECOVERY;963
2.6.12;A NEW POTENTIAL SOURCE FOR NATURAL GAS
;965
2.6.13;METHANE CONVERSION PROCESSES;966
2.6.13.1;Indirect Conversion via Syngas;966
2.6.13.2;Indirect Conversion via Nonsyngas Intermediates
;967
2.6.13.3;Direct Methane Conversion to Hydrocarbons and Chemical Derivatives
;967
2.6.13.4;Oxidative Coupling to Higher Hydrocarbons
;967
2.6.13.5;Partial Oxidation to Chemical Derivatives
;969
2.6.13.6;Pyrolysis or Cracking;969
2.6.13.7;Other Direct Conversion Processes;970
2.6.13.8;Methane Ammoxidation;970
2.6.13.9;Methane Reductive Nitrilization;970
2.6.14;A DIFFERENT VIEW OF THE ORIGINS OF NATURAL GAS
;971
2.6.14.1;Natural Gas from Biological Origins;971
2.6.14.2;Natural Gas from Nonbiological Origins;972
2.6.14.3;Natural Gas Release from Lower Crust and Mantle Domains
;972
2.6.15;SUMMARY FOR METHANE AND NATURAL GAS FUTURE SOURCING
;973
2.6.16;REFERENCES;974
2.7;21 The Nuclear Industry
;976
2.7.1;INTRODUCTION;976
2.7.2;STATUS AND OUTLOOK;978
2.7.3;NUCLEAR SAFETY;983
2.7.4;THE EARTH'S ENERGY SUPPLY AND USE
;986
2.7.5;NUCLEAR PROCESSES;989
2.7.5.1;Radioactive Decay;989
2.7.5.2;Fission;990
2.7.5.3;Fusion;992
2.7.5.4;Nuclide Production;994
2.7.5.5;Fission Products;994
2.7.5.6;Neutron Transmutation Products;996
2.7.5.7;Neutron Activation Products;997
2.7.5.8;Uses;997
2.7.5.9;Charged Particle Transmutation Products;998
2.7.6;REACTOR MATERIALS PROCESSING;998
2.7.6.1;Isotope Enrichment;999
2.7.6.2;Zirconium Production;1000
2.7.7;THE URANIUM FUEL CYCLE;1002
2.7.7.1;Mining;1003
2.7.7.2;Milling;1003
2.7.7.3;Fuel Preparation;1003
2.7.7.4;Spent Fuel Reprocessing;1010
2.7.8;RADIOACTIVE WASTE MANAGEMENT;1016
2.7.8.1;Liquid Waste Treatment;1018
2.7.8.2;Airborne Waste Treatment;1018
2.7.8.3;Solid Waste Treatment;1019
2.7.8.4;Storage of Spent Fuel;1020
2.7.8.5;Low-Level Waste Disposal;1021
2.7.9;TRANSPORTATION OF NUCLEAR MATERIALS
;1021
2.7.10;THE NUCLEAR REACTOR;1022
2.7.10.1;Light Water Reactors;1024
2.7.10.2;CANDU Heavy Water Reactor;1028
2.7.10.3;Liquid Metal Fast Breeder Reactor;1029
2.7.10.4;Other Nuclear Reactors;1029
2.7.11;RADIATION PROCESSING;1030
2.7.12;RADIOISOTOPE APPLICATIONS;1031
2.7.12.1;Radiation Sources;1031
2.7.12.2;Radioisotope Thermoelectric Generators;1031
2.7.12.3;Tracers;1032
2.7.12.4;Nuclear Medicine;1032
2.7.13;REFERENCES;1034
2.8;22 Synthetic Nitrogen Products
;1037
2.8.1;NITROGEN;1037
2.8.1.1;Characteristics;1037
2.8.1.2;Nitrogen Production Processes;1038
2.8.2;NITROGEN FIXATION;1038
2.8.2.1;Nitrogen Oxides;1038
2.8.2.2;Ammonia;1039
2.8.3;NITROGEN CONSUMPTION;1040
2.8.4;ENVIRONMENTAL ISSUES;1042
2.8.5;AMMONIA PRODUCTION;1043
2.8.6;HYDROGEN PRODUCTION;1044
2.8.6.1;Manufacturing Processes;1046
2.8.6.2;Feed Pretreatment;1048
2.8.6.3;Prereformer;1048
2.8.6.4;Reformers;1049
2.8.6.5;Reformer Catalysts;1049
2.8.6.6;Reformer Materials of Construction;1049
2.8.6.7;Waste Heat Recovery;1050
2.8.6.8;Hydrogen Production Costs and Capital Costs
;1050
2.8.6.9;Other Reforming Processes;1050
2.8.6.10;Reliability and Revamps;1051
2.8.6.11;Small-Scale Reforming;1052
2.8.6.12;Technology Suppliers;1053
2.8.6.13;Partial Oxidation Processes;1054
2.8.6.14;Technology Suppliers;1055
2.8.6.15;Initial Purification of Synthesis Gas;1058
2.8.6.16;Alkazid Process;1062
2.8.6.17;aMDEA Process;1062
2.8.6.18;Benfield Process;1062
2.8.6.19;Catacarb Process;1062
2.8.6.20;Fluor Solvent Process;1062
2.8.6.21;Giammarco-Vetrocoke Process;1062
2.8.6.22;Hi Pure Process;1063
2.8.6.23;Purisol Process;1063
2.8.6.24;Rectisol Process;1063
2.8.6.25;Selexol Process;1063
2.8.6.26;Shell Sulfinol Process;1063
2.8.6.27;Pressure Washing with Monoethanolamine (MEA)
;1063
2.8.6.28;Retrofits of CO2 Removal System;1063
2.8.6.29;Final Purification of Synthesis Gas;1064
2.8.6.30;Compression;1065
2.8.7;AMMONIA SYNTHESIS;1065
2.8.7.1;Reaction Rate;1065
2.8.7.2;Catalysts;1067
2.8.7.3;Energy Efficiency;1069
2.8.7.4;Ammonia Plant Design;1069
2.8.7.5;Ammonia Separation;1069
2.8.7.6;Ammonia Synthesis;1072
2.8.7.7;Large Capacity Ammonia Plants;1072
2.8.7.8;Ammonia Production Costs;1072
2.8.8;USES OF AMMONIA;1072
2.8.8.1;Chemical Production and Other Uses;1072
2.8.9;DISTRIBUTION AND STORAGE;1073
2.8.9.1;Ammonia Toxicity;1073
2.8.9.2;Ammonia Quality;1074
2.8.9.3;Distribution and Storage;1074
2.8.9.4;Ammonia Price;1075
2.8.10;NITRIC ACID;1075
2.8.10.1;Physical Properties;1075
2.8.10.2;Processes;1077
2.8.10.3;Uses of Nitric Acid;1086
2.8.11;AMMONIUM NITRATE;1086
2.8.11.1;Processes;1087
2.8.11.2;Production;1088
2.8.12;UREA;1089
2.8.12.1;Processes;1090
2.8.12.2;Production;1092
2.8.12.3;Storage and Distribution;1092
2.8.12.4;Uses;1093
2.8.13;MELAMINE;1093
2.8.13.1;Processes;1093
2.8.13.2;Production;1094
2.8.13.3;Uses;1094
2.8.14;ALIPHATIC AMINES;1094
2.8.14.1;Methylamines;1096
2.8.14.2;Other Alkyl Amines;1098
2.8.14.3;Uses;1099
2.8.15;ETHANOLAMINES AND SECONDARY PRODUCTS
;1099
2.8.15.1;Ethanolamine Process;1099
2.8.15.2;Secondary Products of Ethanolamine;1101
2.8.15.3;Ethylenediamine Production;1101
2.8.15.4;Ethylenediamine Uses;1102
2.8.16;HEXAMETHYLENETETRAMINE (HEXAMINE)
;1102
2.8.16.1;Hexamine Processes;1102
2.8.17;HVDRAZINE;1103
2.8.17.1;Processes;1103
2.8.18;HYDROGEN CYANIDE;1105
2.8.18.1;Safety;1107
2.8.18.2;Manufacture;1108
2.8.18.3;Production;1112
2.8.18.4;Uses;1113
2.8.19;ANILINE;1114
2.8.19.1;Processes;1114
2.8.20;OTHER COMPOUNDS;1115
2.8.21;REFERENCES;1118
2.9;23 Phosphorus and Phosphates
;1127
2.9.1;INTRODUCTION;1127
2.9.2;PHOSPHATE ROCK;1127
2.9.2.1;Minerals;1128
2.9.2.2;Resources and Ores;1129
2.9.2.3;Mining;1129
2.9.2.4;Beneficiation;1130
2.9.2.5;Production and Value;1134
2.9.3;CHEMICAL PROCESSING OF PHOSPHATE ROCK
;1135
2.9.3.1;Thermal Process for Phosphorus and Phosphoric Acid
;1135
2.9.3.2;Industrial Phosphates;1135
2.9.3.3;Wet Process Phosphoric Acid;1137
2.9.3.4;Dihydrate Process;1138
2.9.3.5;Major Dihydrate Processes;1139
2.9.3.6;Hemihydrate Processes for Phosphoric Acid
;1143
2.9.3.7;Unit Operations;1145
2.9.3.8;Superphosphoric Acid;1146
2.9.4;WET PROCESS ACID BY-PRODUCTS
;1147
2.9.4.1;Phosphogypsum;1147
2.9.4.2;Fluorine Recovery;1148
2.9.4.3;Uranium Recovery from Wet Process Phosphoric Acid
;1148
2.9.4.4;Animal Feed Supplements;1148
2.9.4.5;Purified Phosphoric Acid;1148
2.9.4.6;Environmental Aspects;1150
2.9.5;REFERENCES;1150
2.10;24 Fertilizers and Food Production
;1152
2.10.1;INTRODUCTION;1152
2.10.2;OVERVIEW OF THE FERTILIZER INDUSTRY
;1155
2.10.3;RAW MATERIALS FOR FERTILIZER PRODUCTION
;1158
2.10.4;NITROGEN FERTILIZERS;1159
2.10.4.1;Natural Organics;1160
2.10.4.2;Nitrogen Fertilizers from Synthetic Ammonia
;1160
2.10.4.3;Miscellaneous Low-Volume Nitrogen Fertilizers
;1164
2.10.5;PHOSPHATE FERTILIZERS;1165
2.10.5.1;Natural Organic Phosphate Fertilizers;1165
2.10.5.2;Fertilizers from Mineral Phosphates;1166
2.10.5.3;Miscellaneous Low-Volume Phosphate Fertilizers
;1173
2.10.6;POTASSIUM SALTS;1175
2.10.6.1;Potassium Minerals;1177
2.10.6.2;Potassium Sulfate;1177
2.10.6.3;Potassium Nitrate;1178
2.10.6.4;Potassium Phosphates;1178
2.10.7;COMPOUND FERTILIZERS;1179
2.10.7.1;Nongranular Mixtures;1180
2.10.7.2;Compound Granulars;1180
2.10.7.3;Bulk Blends;1184
2.10.7.4;Fluid Mixtures;1186
2.10.7.5;Controlled-Release Fertilizers;1190
2.10.7.6;Physical Quality of Fertilizers;1194
2.10.8;REFERENCES;1195
2.11;25 Sulfur and Sulfuric Acid
;1198
2.11.1;SULFUR;1198
2.11.1.1;Transportation and Storage;1199
2.11.1.2;Solidification and Melting;1200
2.11.1.3;Development of the Sulfur Industry;1202
2.11.1.4;Sulfur Production Processes;1203
2.11.1.5;Recovered Sulfur;1204
2.11.1.6;Production and Consumption of Sulfur;1206
2.11.2;SULFURIC ACID;1209
2.11.2.1;Uses of Sulfuric Acid;1210
2.11.2.2;Development of the Sulfuric Acid Industry
;1210
2.11.2.3;Manufacture of Sulfuric Acid by the Contact Process
;1213
2.11.2.4;Sulfur Dioxide Production;1213
2.11.2.5;Single vs. Double Contact Process;1217
2.11.2.6;Oxidation of SO2
;1217
2.11.2.7;Absorption of SO3
;1218
2.11.2.8;Acid Cooling;1218
2.11.2.9;Other Modifications to the Sulfuric Process36
;1218
2.11.2.10;Other Sources of Sulfuric Acid;1220
2.11.2.11;Production and Consumption of Sulfuric Acid
;1220
2.11.3;REFERENCES;1222
2.12;26 Salt, Chlor-Alkali, and Related Heavy Chemicals
;1224
2.12.1;SODIUM CHLORIDE
;1224
2.12.2;SODA ASH;1226
2.12.3;SODIUM BICARBONATE;1230
2.12.4;SODIUM SULFATE;1230
2.12.5;SODIUM SULFIDES;1233
2.12.6;SODIUM THIOSULFATE;1233
2.12.7;SODIUM SULFITE;1234
2.12.8;SODIUM BISULFITE;1234
2.12.9;SODIUM HYPOSULFITE (HYDROSULFITE)
;1234
2.12.10;SODIUM PHOSPHATES;1235
2.12.11;SODIUM SILICATE;1235
2.12.12;CHLOR-ALKALI (CHLORINE AND CAUSTIC SODA)
;1237
2.12.13;HYDROCHLORIC ACID;1249
2.12.14;BROMINE AND BRINE CHEMICALS
;1249
2.12.15;BLEACHES;1252
2.12.16;SODIUM CHLORATE;1254
2.12.17;REFERENCES;1254
2.13;27 Industrial Gases
;1256
2.13.1;OVERVIEW;1256
2.13.2;NITROGEN;1262
2.13.3;OXYGEN;1262
2.13.4;ARGON;1263
2.13.5;HYDROGEN;1263
2.13.6;HELIUM;1268
2.13.7;CARBON DIOXIDE;1268
2.13.8;LIQUEFIED NATURAL GAS;1270
2.13.9;ACETYLENE;1271
2.13.10;NITROUS OXIDE;1273
2.13.11;REFERENCES;1274
2.14;28 Wood and Wood Products
;1275
2.14.1;INTRODUCTION;1275
2.14.2;WOOD STRUCTURE;1276
2.14.3;CHEMICAL COMPOSITION AND FIBER STRUCTURE
;1279
2.14.4;PULP AND PAPER;1281
2.14.4.1;Wood Preparation;1285
2.14.4.2;Mechanical Pulping;1286
2.14.4.3;Chemical Pulping;1286
2.14.4.4;Biomechanical Pulping;1293
2.14.4.5;Screening and Cleaning of Wood Pulp;1294
2.14.4.6;Bleaching of Wood Pulp;1294
2.14.4.7;Biotechnology-Biopulping and Biobleaching
;1295
2.14.4.8;Recycling;1296
2.14.4.9;Stock Preparation;1296
2.14.4.10;Papermaking Process;1297
2.14.4.11;Finishing and Converting;1301
2.14.4.12;Environmental Protection;1301
2.14.5;BOARD AND STRUCTURAL MATERIALS;1302
2.14.5.1;Lumber;1302
2.14.5.2;Plywood;1303
2.14.5.3;Fiberboard;1303
2.14.5.4;Particleboard and Oriented Strandboard (OSB)
;1303
2.14.5.5;Modified Wood and Wood Composites;1305
2.14.6;PRESERVATIVE TREATMENT OF WOOD;1309
2.14.6.1;Preservative Chemicals;1309
2.14.6.2;Preservation Process;1310
2.14.6.3;Preservative Retention;1311
2.14.6.4;Nonconventional Wood Preservation;1312
2.14.7;FIRE-RETARDANT TREATMENT OF WOOD;1313
2.14.7.1;Fire-Retardant Formulations;1313
2.14.8;CONVERSION OF WOOD TO ENERGY, FUELS, AND CHEMICALS
;1314
2.14.8.1;Direct Combustion;1315
2.14.8.2;Saccharification-Fermentation;1316
2.14.8.3;Thermal Decomposition;1320
2.14.8.4;Thermochemical Liquefaction;1325
2.14.9;NAVAL STORES;1326
2.14.9.1;Gum Naval Stores;1327
2.14.9.2;Wood Naval Stores;1328
2.14.9.3;Sulfate Naval Stores;1328
2.14.9.4;Uses of Naval Stores Products;1329
2.14.10;ADDITIONAL CHEMICALS FROM WOOD;1330
2.14.10.1;Tannins and Other Extractives;1330
2.14.10.2;Furfural;1330
2.14.10.3;Vanillin;1331
2.14.10.4;Dimethyl Sulfide and DMSO;1331
2.14.10.5;Medicinals;1331
2.14.10.6;Biotechnology Chemicals;1331
2.14.11;REFERENCES;1332
2.14.12;SELECTED REFERENCES;1333
2.15;29 Pigments, Paints, Polymer Coatings, Lacquers, and Printing Inks
;1335
2.15.1;INTRODUCTION;1335
2.15.2;VOC REGULATIONS;1337
2.15.2.1;Southwest;1338
2.15.2.2;Midwest;1338
2.15.2.3;East;1339
2.15.3;HAZARDOUS WASTE REGULATIONS;1339
2.15.4;TECHNICAL TRENDS IN COATINGS;1339
2.15.5;POWDER COATINGS;1341
2.15.5.1;Electron Beam (EBI and Ultraviolet (UV) Curable Coatings
;1341
2.15.5.2;Current Automotive Coating Trends;1342
2.15.5.3;Coatings for Plastics;1343
2.15.5.4;New Cross-Linking Technologies;1344
2.15.6;PRINTING INKS;1344
2.15.7;PIGMENTS;1346
2.15.7.1;Inorganic Pigments;1346
2.15.7.2;Organic Pigments;1348
2.15.7.3;Pearlescent Pigments;1349
2.15.7.4;Aluminum Pigments;1350
2.15.8;LACQUERS;1350
2.15.9;REFERENCES;1351
2.16;30 Industrial Biotechnology: Discovery to Delivery
;1352
2.16.1;INTRODUCTION;1352
2.16.2;DISCOVERY OF ORGANISMS AND MOLECULES
;1353
2.16.2.1;Microbial Diversity;1353
2.16.2.2;Screening and Selection;1355
2.16.2.3;Cell Engineering;1356
2.16.2.4;Molecular Engineering;1358
2.16.3;DEVELOPMENT OF A PRODUCTION PROCESS
;1359
2.16.3.1;Strain;1359
2.16.3.2;Fermentation Process;1360
2.16.3.3;Sterilization;1360
2.16.3.4;Microbial Kinetics;1361
2.16.3.5;Ideal Types of Fermentors;1362
2.16.3.6;Oxygen Transfer Considerations;1365
2.16.3.7;Scale-Up/Down and Control;1365
2.16.3.8;Instrumentation and Control;1367
2.16.4;RECOVERY OF FERMENTATION PRODUCTS
;1368
2.16.4.1;Separation of Proteins and Peptides;1371
2.16.4.2;Fermentor Harvest and Primary Recovery
;1372
2.16.4.3;Formulation;1376
2.16.4.4;Whole Cell Recovery;1381
2.16.4.5;Separation of Small Molecules and Metabolites
;1381
2.16.4.6;Regulatory Considerations;1383
2.16.5;DELIVERY OF PRODUCTS;1383
2.16.5.1;Organic Acids and Polymers;1383
2.16.5.2;Amino Acids;1399
2.16.5.3;Vitamins and Neutraceuticals;1405
2.16.5.4;Antibiotics;1407
2.16.5.5;Biopharmaceuticals;1410
2.16.5.6;Enzymes;1412
2.16.6;FUTURE: BIOREFINERIES;1412
2.16.6.1;Acknowledgment;1413
2.16.7;REFERENCES;1413
2.17;31 Industrial Enzymes and Biocatalysis
;1416
2.17.1;INTRODUCTION;1416
2.17.2;INDUSTRIAL ENZYMES-PRODUCTION AND APPLICATIONS
;1417
2.17.2.1;Amylases;1419
2.17.2.2;Glucose Isomerase;1421
2.17.2.3;Proteases;1422
2.17.2.4;Cellulases;1424
2.17.2.5;Lipases;1426
2.17.3;INDUSTRIAL BIOCATALVSIS;1426
2.17.3.1;Biocatalyst Discovery and Engineering;1428
2.17.3.2;Biocatalytic Processes;1432
2.17.3.3;Immobilized Enzymes;1433
2.17.3.4;Whole Cell Biocatalysis;1437
2.17.4;BIOREACTOR CONFIGURATIONS;1439
2.17.4.1;Nonaqueous Biocatalysis;1442
2.17.4.2;Products of Biocatalysis;1443
2.17.4.3;Future Trends in Biocatalysis;1456
2.17.5;SUMMARY AND CONCLUSION;1459
2.17.6;REFERENCES;1459
2.18;32 Industrial Production of Therapeutic Proteins: Cell Lines, Cell Culture, and Purification
;1462
2.18.1;Cells Used For Industrial Production;1468
2.18.2;Expression Systems;1468
2.18.3;HOST CELL LINES;1468
2.18.3.1;Identifying High-Expressing Cells;1469
2.18.3.2;Cell Banking;1470
2.18.3.3;Cell Stability;1471
2.18.4;MEDIA;1471
2.18.4.1;Commercial Serum-Free Media;1471
2.18.4.2;Approaches for Serum-Free Medium Development
;1472
2.18.4.3;Serum-Free Adaptation;1474
2.18.5;BIOREACTOR SYSTEMS;1475
2.18.5.1;Stirred-Tank Systems;1475
2.18.5.2;Disposable Bioreactors;1476
2.18.5.3;Modes of Bioreactor Operation;1477
2.18.6;CELL CULTURE PROCESS AND CONTROL
;1477
2.18.6.1;Process Parameters;1478
2.18.6.2;Mitigating Effects of Physical and Chemical Stress
;1478
2.18.6.3;Fed-Batch Process Control and Optimization
;1480
2.18.6.4;Perfusion Process Control and Optimization
;1480
2.18.6.5;Scale-Up of Mammalian Cell Bioreactors
;1480
2.18.7;PURIFICATION PROCESS;1481
2.18.7.1;Generic Processes;1482
2.18.7.2;Clarification of Broth;1482
2.18.7.3;Capture of Product;1483
2.18.7.4;Removal of Impurities;1484
2.18.7.5;Strategies for Scaling Up Purification Processes
;1485
2.18.8;ACKNOWLEDGMENTS;1486
2.18.9;REFERENCES;1486
2.19;33 Biomass Conversion
;1490
2.19.1;AN INTRODUCTION TO BIOMASS AND THE BIOREFINERY
;1490
2.19.1.1;WHAT IS BIOMASS?;1490
2.19.1.1.1;The Structure and Composition of Biomass
;1491
2.19.1.2;CONVERTING BIOMASS INTO ENERGY AND OTHER PRODUCTS
;1492
2.19.1.2.1;Biological Versus Thermochemical Processing
;1492
2.19.1.3;THE BIOREFINERV;1495
2.19.1.4;BIOMASS, FOSSIL ENERGY SAVINGS, AND GREENHOUSE GAS MITIGATION
;1496
2.19.1.4.1;Life-Cycle Assessments of Biopower;1496
2.19.1.4.2;Life-Cycle Assessments of Biofuels;1497
2.19.1.5;COST PROJECTIONS FOR FUELS AND POWER FROM BIOMASS
;1497
2.19.1.5.1;The Competitiveness of Biopower;1497
2.19.1.5.2;The Competitiveness of Biofuels;1499
2.19.1.6;BIOMASS AS A SUSTAINABLE AND SUBSTANTIAL ENERGY SOURCE
;1499
2.19.1.6.1;Biomass as a Substantial Source of Energy-Balancing the Demands on our Land
;1499
2.19.1.7;MICROBIAL BIOETHANOL PRODUCTION;1503
2.19.1.8;ETHANOL FERMENTATION SCHEMES;1503
2.19.1.9;METABOLIC PATHWAY ENGINEERING;1504
2.19.1.10;PERFORMANCE ASSESSMENT;1505
2.19.1.11;FUTURE DIRECTIONS;1505
2.19.2;BIOMASS ANALYSIS AND COMPOSITIONAL VARIABILITY
;1506
2.19.2.1;INTRODUCTION;1506
2.19.2.1.1;The Importance of Reliable Compositional Methods for Biomass Analysis
;1506
2.19.2.1.2;The Need for Accurate, Real-Time Biomass Analysis Methods
;1507
2.19.2.1.3;Heterogeneity and Biomass Analysis;1507
2.19.2.1.4;Genetic Factors That May Contribute to Cell Wall Compositional Variability
;1508
2.19.2.1.5;Environmental Factors That May Contribute to Variance
;1510
2.19.2.1.6;Analytical Variance;1511
2.19.2.2;PORTFOLIO METHODS;1511
2.19.2.2.1;Wet Chemical Methods;1511
2.19.2.3;EXTRACTIVES DETERMINATION;1514
2.19.2.3.1;Carbohydrate Determination;1514
2.19.2.3.2;Lignin Determination;1514
2.19.2.3.3;Protein Determination;1515
2.19.2.3.4;Other Feedstock Constituents;1515
2.19.2.3.5;Degradation Products;1515
2.19.2.3.6;Reconstructing the Composition of the Original Biomass Sample
;1515
2.19.2.4;APPLICATION OF METHODS;1517
2.19.2.4.1;Biomass Process Monitoring and Improvement
;1517
2.19.2.4.2;Survey of Corn Stover Compositional Diversity
;1517
2.19.2.4.3;Genetic Screening and Cell-Wall Genomics
;1521
2.19.2.5;FUTURE APPLICATIONS;1521
2.19.2.6;SUMMARY AND CONCLUSIONS;1522
2.19.3;BIOCATALYSTS FOR BIOMASS DECONSTRUCTION
;1522
2.19.3.1;SUMMARY OF PLANT CELL WALL STRUCTURE
;1522
2.19.3.2;ENZYMATIC HYDROLYSIS OF PLANT CELL WALL COMPONENTS
;1523
2.19.3.3;CELLULASES;1525
2.19.3.3.1;Endoglucanases;1526
2.19.3.3.2;Exoglucanases;1526
2.19.3.3.3;Endoglucanases and ß-Glucosidases
;1526
2.19.3.4;TOTAL CELLULASE ACTIVITY MEASUREMENTS
;1526
2.19.3.4.1;The IUPAC Filter Paper Assay;1526
2.19.3.4.2;General Non-IUPAC Cellulases Assays;1528
2.19.3.4.3;Mathematical Modeling;1529
2.19.3.4.4;Endocellulase Activity Measurement;1529
2.19.3.4.5;Viscometric Assays;1529
2.19.3.4.6;Exocellulase Activity Measurements;1530
2.19.3.4.7;ß-Glucosidase Activity Measurements
;1530
2.19.3.5;HEMICELLULASES;1531
2.19.3.5.1;General Hemicellulase Assays;1531
2.19.3.5.2;Hemicellulose Debranching Enzymes;1532
2.19.3.5.3;Hemicellulose Depolymerization Enzymes
;1533
2.19.3.6;PECTINASES;1535
2.19.4;CHEMICAL CATALYSIS FOR BIOMASS DECONSTRUCTION
;1536
2.19.4.1;INTRODUCTION;1536
2.19.4.2;SCOPE OF THE REVIEW;1538
2.19.4.3;SEPARATION OF BIOPOLYMERS FROM BIOMASS RAW MATERIALS
;1539
2.19.4.3.1;Dilute Acid Pretreatments;1539
2.19.4.3.2;Solvent Separation Processes;1539
2.19.4.3.3;Steam Explosion and Related Processes;1540
2.19.4.3.4;The Kraft Process;1540
2.19.4.4;DECONSTRUCTION OF BIOREFINERY RAW MATERIALS AND BIOPOLYMERS TO MONOMERIC PRODUCTS
;1542
2.19.4.4.1;Polymeric Carbohydrate Hydrolysis Processes
;1542
2.19.4.4.2;Carbohydrate Pyrolysis;1542
2.19.4.4.3;Carbohydrate Oxidation;1543
2.19.4.4.4;Carbohydrate Dehydration;1543
2.19.4.4.5;Lignin Deconstruction;1546
2.19.4.5;CONCLUSIONS;1547
2.19.5;THERMOCHEMICAL BIOMASS CONVERSION
;1547
2.19.5.1;INTRODUCTION;1547
2.19.5.2;PYROLYSIS;1550
2.19.5.2.1;Fast Pyrolysis;1551
2.19.5.2.2;Slow Pyrolysis;1552
2.19.5.3;GASIFICATION;1553
2.19.5.3.1;Gasifier Reactor Designs;1554
2.19.5.3.2;Biomass-Gasification Product Gas;1555
2.19.5.3.3;Syngas Cleanup and Conditioning;1556
2.19.5.3.4;Integrated Gasification Combined Cycle;1558
2.19.5.3.5;Fuel Cell Applications;1559
2.19.5.3.6;Syngas to Liquid Fuels;1559
2.19.5.4;COMBUSTION;1560
2.19.5.4.1;Co-Firing;1563
2.19.5.5;ACKNOWLEDGMENT;1564
2.19.6;REFERENCES;1564
2.20;34 Animal and Vegetable Fats, Oils, and Waxes
;1590
2.20.1;BIOTECHNOLOGY IN AGRICULTURE AND PROCESSING
;1590
2.20.1.1;Human Survival Is Biotechnology;1590
2.20.1.2;Genetic Messages;1592
2.20.1.3;Water Activity;1593
2.20.1.4;Herbicide- and Insect-Resistant Oilseed Crops
;1594
2.20.1.5;Concerns About Transgenic Crops;1596
2.20.1.6;Drivers and Tools for the Future;1598
2.20.1.7;Biotechnology Practices in Soybean Production and Processing
;1599
2.20.2;INTRODUCTION TO LIPIDS;1601
2.20.2.1;Recent Fats and Oils Industry Changes;1601
2.20.2.2;AOCS, an Information Source;1602
2.20.2.3;Nutrition and Health Implications;1603
2.20.3;NOMENCLATURE AND MOLECULAR STRUCTURES
;1603
2.20.3.1;General;1603
2.20.3.2;Fatty Acids;1604
2.20.3.3;Triacylglycerols;1610
2.20.3.4;Oxidation;1610
2.20.3.5;Biohydrogenation and Conjugated Linoleic Acids
;1611
2.20.3.6;Fatty Acid and Triacylglycerol Melting Characteristics
;1612
2.20.3.7;Polymorphism and Crystal Types;1612
2.20.4;OTHER LIPIDS;1615
2.20.4.1;Waxes;1615
2.20.4.2;Terpenes;1615
2.20.4.3;Sterols;1618
2.20.4.4;Fat-Soluble Vitamins;1618
2.20.4.5;Phosphatides;1621
2.20.5;FATS AND OILS SOURCES AND CONSUMPTION
;1622
2.20.5.1;Production;1622
2.20.5.2;Changes in Sources;1623
2.20.5.3;Consumption;1625
2.20.6;EXTRACTION OF FATS AND OILS;1626
2.20.6.1;Basic Processes;1626
2.20.7;SCREW PRESS OPERATIONS;1626
2.20.7.1;Decanters and Centrifuges;1627
2.20.7.2;Olive Oil;1629
2.20.7.3;Coconut Oil;1629
2.20.7.4;Palm Oil;1629
2.20.8;ANIMAL FATS AND FISH OilS;1630
2.20.8.1;Extraction of lards and Tallows;1630
2.20.8.2;Inedible Animal Products;1631
2.20.8.3;Restaurant Greases;1631
2.20.8.4;Animal Fat Specifications, Production, and Utilization
;1632
2.20.8.5;Fish Oils;1632
2.20.8.6;Feeding Animal and Marine Fats;1632
2.20.9;ROW CROP OILSEEDS PROCESSING;1634
2.20.9.1;Extraction Plants;1634
2.20.9.2;Seed Preparation for Extraction;1636
2.20.9.3;Solvent Extractors;1641
2.20.9.4;Solvents;1641
2.20.9.5;Desolventizing-Toasting;1644
2.20.9.6;Miscella Refining;1645
2.20.10;REFINING OF VEGETABLE FATS AND OILS
;1645
2.20.10.1;Oil Receiving and Handling;1645
2.20.10.2;Phosphatides Degumming, Lecithin Uses
;1647
2.20.10.3;Alkali Neutralization;1649
2.20.10.4;Silica Gel Adsorption;1651
2.20.10.5;Bleaching;1651
2.20.11;OILS AND FATS MODIFICATION;1652
2.20.11.1;Solid Fat Index/Solid Fat Content;1652
2.20.11.2;Thermal Fractionation;1654
2.20.11.3;Hydrogenation;1656
2.20.11.4;Interesterification;1659
2.20.11.5;Deodorization/Physical Refining;1663
2.20.12;NOTES ON MAJOR ROW CROP OILSEEDS
;1666
2.20.12.1;Soybean;1666
2.20.12.2;Cottonseed;1667
2.20.12.3;Rapeseed/Canola;1668
2.20.12.4;Sunflowerseed;1668
2.20.12.5;Peanut;1669
2.20.13;TRANS FATS NUTRITIONAL LABELING;1669
2.20.14;EDIBLE USES OF FATSAND OILS;1671
2.20.14.1;Antioxidants;1671
2.20.14.2;Nonionic Surfactants and Emulsifiers;1673
2.20.14.3;Table Oils;1673
2.20.14.4;Frying Oils;1674
2.20.14.5;Specialty Oils;1676
2.20.14.6;Margarines And Spreads;1677
2.20.14.7;Shortenings;1681
2.20.14.8;Other Edible Applications;1681
2.20.15;INDUSTRIAL USES OF FATS AND OILS;1682
2.20.15.1;Timeline;1682
2.20.15.2;Chemurgy Revisited;1683
2.20.15.3;Industrial Oils Utilization;1683
2.20.15.4;Fatty Acid Methyl Esters, Biodiesel;1684
2.20.15.5;Other Industrial Applications;1687
2.20.16;ANALYTICAL METHODS;1688
2.20.17;REFERENCES;1691
2.21;35 Sugar and Other Sweeteners
;1698
2.21.1;INTRODUCTION;1698
2.21.2;SUGAR;1699
2.21.2.1;History8
;1699
2.21.3;RAW SUGAR PRODUCTION;1699
2.21.3.1;Crystal Quality;1709
2.21.3.2;Bagasse;1709
2.21.3.3;Direct Consumption Sugar;1711
2.21.3.4;Edible Products from the Mill;1711
2.21.3.5;New Technology;1711
2.21.4;CANE SUGAR REFINING;1712
2.21.4.1;Affination and Melting;1712
2.21.4.2;Purification;1713
2.21.4.3;Crystallization;1715
2.21.4.4;Remelt Sugar;1716
2.21.4.5;Packaging and Storing Refined Granulated Sugar
;1716
2.21.4.6;Specialty Sugars;1716
2.21.5;BEET SUGAR;1717
2.21.6;AGRICULTURE;1718
2.21.6.1;Harvesting and Beet Handling;1718
2.21.6.2;Extraction of the Juice;1719
2.21.6.3;Juice Purification;1719
2.21.6.4;Evaporation and Standard Liquor;1720
2.21.6.5;Extending the Processing Cycle-Thick Juice Storage
;1721
2.21.6.6;Crystallization, Centrifuging, and Drying;1721
2.21.7;MOLASSES DESUGARIZATION;1721
2.21.7.1;Sugar Recovery from Beet Molasses;1721
2.21.7.2;Desugarization of Cane Molasses;1722
2.21.8;PROCESS CONTROL AND INSTRUMENTATION
;1722
2.21.9;CANE AND BEET SUGAR PRODUCTION;1723
2.21.10;SUGAR CONSUMPTION AND USAGE;1723
2.21.11;DERIVATIVES OF SUCROSES - UCROCHEMISTRY
;1723
2.21.12;SWEETENERS DERIVED FROM STARCH;1724
2.21.12.1;Starch Conversion;1725
2.21.12.2;Acid Hydrolysis of Starch;1725
2.21.12.3;Acid-Enzyme Hydrolysis;1726
2.21.12.4;Enzyme-Enzyme Hydrolysis;1726
2.21.12.5;Crystalline Dextrose;1727
2.21.12.6;Crystalline Fructose;1727
2.21.12.7;High Fructose Corn Syrup (HFCS);1727
2.21.13;MOLASSES;1727
2.21.14;OTHER SWEETENERS;1728
2.21.15;REGULATION AND TRADE IN SUGAR;1729
2.21.16;ENVIRONMENTAL CONCERNS;1730
2.21.16.1;Issues of Genetic Engineering;1730
2.21.17;REFERENCES;1731
2.22;36 Soap, Fatty Acids, and Synthetic Detergents
;1735
2.22.1;SOAP AND FATTY ACIDS;1735
2.22.1.1;Introduction;1735
2.22.1.2;Chemistry;1735
2.22.1.3;Manufacturing Technology;1736
2.22.1.4;Raw Materials;1737
2.22.1.5;Functional Properties of Soap;1738
2.22.1.6;Manufacturing Processes;1738
2.22.1.7;Fatty Acids;1745
2.22.1.8;Fractionation and Physical Separation;1745
2.22.1.9;Fat Refining;1746
2.22.1.10;Fat Splitting Processes;1746
2.22.1.11;Fatty Acid Distillation;1751
2.22.1.12;Special Separation Methods;1754
2.22.2;SYNTHETIC DETERGENTS;1755
2.22.2.1;Characteristic Features of Surfactants;1756
2.22.2.2;Raw Materials for Surfactant Production;1757
2.22.2.3;Intermediates for Surfactant Production;1759
2.22.2.4;World Surfactant Consumption;1763
2.22.2.5;Anionic Surfactants;1763
2.22.2.6;Nonionic Surfactants;1769
2.22.2.7;Amphoteric Surfactants;1771
2.22.2.8;Cationic Surfactants;1771
2.22.2.9;Detergent Additives;1772
2.22.2.10;Production of Synthetic Detergents;1775
2.22.2.11;Agglomeration;1778
2.22.2.12;Liquid Detergent Processing;1779
2.22.2.13;Detergent Trends;1780
2.22.3;LIST OF ABBREVIATIONS USED IN THE TEXT
;1781
2.22.4;REFERENCES;1781
2.23;37 Chemical Explosives and Rocket Propellants
;1783
2.23.1;PART I. CHEMICAL EXPLOSIVES;1783
2.23.1.1;INTRODUCTION;1783
2.23.1.2;COMMERCIAL EXPLOSIVES MARKET;1783
2.23.1.3;CHEMISTRY OF COMBUSTION AND EXPLOSION
;1785
2.23.1.4;HISTORICAL DEVELOPMENT;1788
2.23.1.5;CLASSIFICATION OF EXPLOSIVES;1790
2.23.1.6;STRUCTURAL CHARACTERISTICS OF EXPLOSIVES
;1793
2.23.1.7;EXPLOSIVES MANUFACTURING AND USE
;1793
2.23.1.7.1;TNT 12,4,6-Trinitrotoluene);1794
2.23.1.7.2;RDX and HMX;1794
2.23.1.7.3;HNS 12,2',4,4',6,6'-Hexanitrostilbene);1794
2.23.1.7.4;TATB (1,3,5-Triamino-2,4,6-trinitrobenzenel
;1796
2.23.1.7.5;DDNP (2-Diazo-4,6-dinitrophenol)
;1796
2.23.1.7.6;PETN (Pentaerythritol Tetranitrate)
;1797
2.23.1.7.7;NG (Nitroglycerin or Glyercol Trinitrate)
;1797
2.23.1.7.8;Dynamite;1798
2.23.1.7.9;Packaged Explosives;1798
2.23.1.7.10;Ammonium Nitrate and ANFO;1800
2.23.1.7.11;Bulk Emulsions;1801
2.23.1.8;INITIATION SYSTEMS;1806
2.23.1.8.1;Non-Electric Initiation;1808
2.23.2;PART II. ROCKET PROPELLANTS;1809
2.23.2.1;PRINCIPLES OF ROCKET PROPULSION;1810
2.23.2.2;TYPES OF PROPELLANTS;1811
2.23.2.3;SOLID PROPELLANTS;1812
2.23.2.3.1;Composite Propellants;1814
2.23.2.3.2;Liquid Propellants;1819
2.23.2.3.3;Liquid Fuels;1825
2.23.2.4;ADVANCED MONOPROPELLANT STUDIES
;1827
2.23.2.5;BIPROPELLANT APPLICATIONS;1828
2.23.2.6;BIPROPELLANT FUELS;1828
2.23.2.7;IGNITION DELAY;1829
2.23.3;REFERENCES;1832
2.24;Index;1835
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