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Handbook of industrial chemistry organic chemicals (2005)

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Handbook of
Industrial
Chemistry
Organic Chemicals

Mohammad Farhat AIi, Ph.D.
King Fahd University of Petroleum & Minerals
Dhahran, Saudi Arabia

Bassam M. El AIi, Ph.D.
King Fahd University of Petroleum & Minerals
Dhahran, Saudi Arabia

James G. Speight, Ph.D.
CD&Wlnc.
Laramie, Wyoming

McGraw-Hill
New York

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CIP Data is on file with the Library of Congress

Copyright © 2005 by The McGraw-Hill Companies, Inc. AU rights
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under the United States Copyright Act of 1976, no part of this publication
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in a data base or retrieval system, without the prior written permission
of the publisher.
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DOC/DOC

010987654

ISBN 0-07-141037-6
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production supervisor was Pamela A. Pelton. It was set in Century
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If such services are required, the assistance of an appropriate professional should be sought.



To our wives and families, and to all scientists
and engineers who preceded us in such work


ABOUTTHE EDITORS

is Professor of Industrial and
Petroleum Chemistry at King Fahd University of Petroleum
& Minerals in Saudi Arabia. An expert in characterization
studies of heavy ends, residues, and asphalt, he is also knowledgeable about crude oils and products, refining process
technology, waste oil recycling, and stability characteristics
of jet fuels.

MOHAMMAD FARHAT ALI, PH.D.,

BASSAM M. EL ALI, PH.D.,

is Professor of Industrial
Chemistry at King Fahd University of Petroleum &
Minerals in Saudi Arabia. His specialties include
homogenous and heterogeneous catalysis using transition
metal complexes in hydrocarboxylation, hydroformylation,
oxidation, coupling, hydrogenation, and other important
processes; investigation of the organometallic intermediates
and the mechanisms of various homogenous reactions; and
synthesis, characterization, and application of various
supported catalytic systems in the production of fine
chemicals. He has taught many industrial chemistry

courses including Industrial Catalysis, Industrial Organic
Chemistry, Industrial Inorganic Chemistry, and Petroleum
Processes.
G. SPEIGHT, PH.D., has more than 35 years' experience
in fields related to the properties and processing of conventional and synthetic fuels. He has participated in, and led,
significant research in defining the uses of chemistry with
heavy oil and coal. The author of well over 400 professional
papers, reports, and presentations detailing his research
activities, he has taught more than 50 related courses.
Dr. Speight is the author, editor, or compiler of a total of
25 books and bibliographies related to fossil fuel processing
and environmental issues. He lives in Laramie, Wyoming.
JAMES


Contributors

Hasan A. Al-Muallem, Ph.D.
Department of Chemistry
King Fahd University of
Petroleum & Minerals
Dhahran, Saudi Arabia
Mohammad Farhat AIi, Ph.D.
Professor of Chemistry
Department of Chemistry
King Fahd University of
Petroleum & Minerals
Dhahran, Saudi Arabia
Bassam M. ElAIi, Ph.D.
Professor of Chemistry

Department of Chemistry
King Fahd University of
Petroleum & Minerals
Dhahran, Saudi Arabia

Manfred J. Mirbach, Ph.D.
Landis Kane Consulting
R&D Management
Fuellinsdorf, Switzerland
Ahsan Shemsi
Department of Chemistry
King Fahd University of
Petroleum & Minerals
Dhahran, Saudi Arabia
James G. Speight, Ph.D.
CD&W Inc.
Laramie, Wyoming


Preface

The organic chemical industry is an important branch of industry and
its structure usually centers on petroleum and hydrocarbon derived
chemicals. The volume text of available books is generally lacking in covering other very important nonpetroleum-based organic industries such
as paints, dyes, edible oils, fats and waxes, soaps and detergents, sugars,
fermentation, chemical explosives, and agrochemical industries.
This book focuses primarily on the chemical processing of raw materials other than petroleum and hydrocarbons. These materials are usually converted into useful and profitable products that are, in general,
used as consumer goods. The book addresses the needs of both students
and practicing chemists and chemical engineers. It is intended to be a
primary source of information for the young practicing professionals

who wish to broaden their knowledge of the organic process industry as
a whole. The book may also serve as a textbook for advanced undergraduate students in industrial chemistry.
Chapter 1 describes the development of the chemical industry and its
role in welfare and employment around the world. This chapter shows
how raw materials are procured and converted to consumer products.
Chapter 2 discusses safety aspects in organic industries and methods
to protect the workers from hazards such as exposure to dangerous
chemicals, heat, pressures, high electric fields, accelerating objects, and
other sources of hazards.
Chapter 3 deals with the sources of pollution caused by raw materials, products, and wastes in petroleum, petrochemicals, pharmaceuticals, food, and other industries. The growing public concerns over the
safety of chemicals in the environment, and the efforts by the governments and industries for their control, are discussed.
Chapter 4 presents the chemistry and technology of edible oil, fat, and wax
processing including refining, recovery, crystallization, interesterification,
and hydrogenation. The key oxidation reactions of lipids leading to quality
deterioration of processed and unprocessed foods, and the mechanism of


the action of the antioxidants in improving oxidation stability of foods are
discussed.
Chapter 5 highlights the soap and detergent industry. The raw materials, important processes of production, and economic importance of the
soap and detergent industry are elaborated.
Chapter 6 covers one of the most widely distributed and abundant
organic chemicals—the sugars. The chemistry of saccharides, historical
survey, and world production of sugar are presented. The sugar recovery from the two principal sources—sugar cane and sugar beets—are
discussed. The chemistry and uses of nonsugar sweetening agents is
also presented.
Chapter 7 describes paints, pigments, and industrial coatings. The
major paint components, namely, pigments, binders, additives, and solvents are discussed in separate sections. These are followed by the principles of formulation, application techniques, durability, and testing of
paints.
Chapter 8 is devoted to the industrially produced dyes with their classification, manufacture, properties, and main applications, as well as

environmental and health aspects.
Chapter 9 presents an overview of modern fermentation processes and
their application in food, pharmaceutical, and industrial chemical industries. The social and economic importance of fermentation processes is
discussed.
The pharmaceutical industry is presented in Chapter 10 as one of the
most important sectors of healthcare worldwide. The discovery, the
development, and the production of drugs are covered in this chapter.
The chapter also includes the correlation between the growth in the
worldwide market for Pharmaceuticals and the increase of the world
population as a result of higher life expectancy and changes in lifestyle.
Chapter 11 presents an overview of the agrochemical industry.
Beginning with the introduction and historical background, it leads to
the modern trends in agriculture, chemical pest control, herbicides,
fungicides, insecticides, and biological pest control agents. Social and
economic aspects of pesticides use are also discussed.
Chapter 12 presents the chemistry of explosives. Chemical explosives
and propellants are well-covered in this book because of their importance
for peaceful uses. They are considered chemical compounds in pure form
or mixtures that rapidly produce a large volume of hot gases when
properly ignited. The destructive effects of explosives are much more
spectacular than their peaceful uses. However, it appears that more
explosives have been used by industries for peaceful purposes than in
all the wars.
Chapter 13 covers the conversion of crude oil into desired products in
an economically feasible and environmentally acceptable manner.


Descriptions are provided for (1) desalting and dewatering; (2) separation processes, of which distillation is the prime example; (3) conversion
processes, of which coking and catalytic cracking are prime examples;
and (4) finishing processes, of which hydrotreating to remove sulfur is

a prime example. Descriptions of the various petroleum products (from
fuel gas to asphalt and coke) are also given.
This chapter also includes a description of the petrochemical industry, and the production of the chemicals and compounds in a refinery that
are destined for further processing, and used as raw material feedstocks
for the fast-growing petrochemical industry.
Chapter 14 provides the basic principles of polymer science, and
addresses the importance of this subject. This chapter aims to give a
broad and unified description of the subject matter—describing the
polymerization reactions, structures, properties, and applications of
commercially important polymers, including those used as plastics,
fibers, and elastomers. This chapter focuses on synthetic polymers
because of the great commercial importance of these materials. The
chemical reactions by which polymer molecules are synthesized are
addressed along with the process conditions that can be used to carry
them out. This chapter also discusses topics on degradation, stability,
and environmental issues associated with the use of polymers.
This book is intended for university and college students who have
studied organic chemistry, as well as for scientists and technicians who
work in the organic chemical industry, and senior executives and specialists who wish to broaden their knowledge of the industrial organic
processes as a whole.
At the end, we gratefully acknowledge the financial aid, facilities,
and support provided by the Deanship of Scientific Research at King
Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia.
Mohammad Farhat AU, Ph.D.
Bassam M. ElAIi, Ph.D.
James G. Speight, Ph.D.


Contents


About the Editors .............................................................

vi

Contributors .....................................................................

vii

Preface ............................................................................

ix

1. Introduction: an Overview of the Chemical
Process Industry and Primary Raw Materials .......

1

1.1

The Chemical Process Industry .................................

1

1.2

Development of the Chemical Industry ......................

2

1.3


Characteristics of the Chemical Industry ...................

3

1.4

Raw Materials, Manufacturing, and
Engineering ................................................................

5

Environmental Aspects ..............................................

8

References ............................................................................

9

2. Safety Considerations in Process Industries ........

11

1.5

2.1

Introduction .................................................................


12

2.2

OSHA (Occupational Safety and Health
Administration) and PSM (Process Safety
Management) .............................................................

14

2.3

Incident Statistics and Financial Aspects ..................

16

2.4

Safety Decision Hierarchy ..........................................

16

2.5

Hazard Analysis and Risk Assessment
(HARA) .......................................................................

17

Types of Hazards in Industries ..................................


18

2.6.1

18

2.6

Heat and Temperature .............................

This page has been reformatted by Knovel to provide easier navigation.

v


vi

Contents
2.6.2

Pressure Hazards .....................................

19

2.6.3

Electrical Hazards ....................................

21


2.6.4

Mechanical Hazards .................................

23

2.6.5

Toxic Materials .........................................

24

2.6.6

Fire and Explosion ...................................

27

2.6.7

Accelerator and Falling Objects ................

30

2.6.8

Confined Space ........................................

31


2.6.9

Radiation ..................................................

33

2.6.10 Noise and Vibrations ................................

37

2.6.11 Ergonomics ..............................................

39

Risk Management Plan ..............................................

40

2.7.1

The Role of Safety Personnel ...................

40

2.7.2

Personal Protective Equipment
(PPE) .......................................................


41

Appraising Plant Safety and
Practices ..................................................

44

Planning for Emergencies ........................

45

References ............................................................................

47

3. Industrial Pollution Prevention ...............................

49

2.7

2.7.3
2.7.4

3.1

Definition of Industrial Waste .....................................

50


3.2

Types of Industrial Wastes .........................................

51

3.2.1

Classification of Industrial Waste ..............

52

3.3

Public Concern over Pollution ....................................

54

3.4

Legislation to Waste Management ............................

56

3.5

Industrial Pollution Prevention ...................................

57


3.6

Assessment of Industrial Pollution Prevention ..........

58

3.6.1

Assessment of Waste Generation ............

58

3.6.2

Feasibility of the Industrial Pollution
Prevention ................................................

59

Feasibility Implementation ........................

59

3.6.3

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Contents


vii

Waste Management ...................................................

61

3.7.1

Procedural Change ..................................

61

3.7.2

Technology Change .................................

63

3.7.3

Input Material Change ..............................

64

3.7.4

Product Change .......................................

64


Recycling ....................................................................

64

3.8.1

Options in Recycling .................................

65

3.8.2

Recycling Technologies ...........................

66

Waste Treatment ........................................................

69

3.9.1

Physical Treatment ...................................

70

3.9.2

Chemical Treatment .................................


73

3.9.3

Biological Treatment .................................

75

3.10 Waste Disposal by Incineration .................................

77

3.10.1 Rotary Kiln Incinerators ............................

78

3.10.2 Liquid Injection Incinerators (LII) ..............

79

3.10.3 Fluidized Bed Incinerators ........................

81

3.10.4 Multiple-Hearth Incinerators .....................

81

3.11 Ultimate Disposal .......................................................


81

3.11.1 Land-Farming ...........................................

81

3.11.2 Landfilling .................................................

82

3.11.3 Deep-Well Injection ..................................

83

3.11.4 Ocean Dumping .......................................

83

References ............................................................................

84

4. Edible Oils, Fats, and Waxes ..................................

85

3.7

3.8


3.9

4.1

Introduction .................................................................

86

4.2

Fatty Acids ..................................................................

88

4.3

Glycerides ..................................................................

92

4.4

Physical Properties of Triglycerides ...........................

94

4.4.1

94


Melting Point ............................................

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viii

Contents

4.5

4.4.2

Specific Heat ............................................

94

4.4.3

Viscosity ...................................................

94

4.4.4

Density .....................................................

96

4.4.5


Refractive Index .......................................

96

4.4.6

Polymorphism ..........................................

96

4.4.7

Other Physical Properties .........................

96

Chemical Properties of Triglycerides .........................

98

4.5.1

Hydrolysis ................................................

98

4.5.2

Methanolysis ............................................


98

4.5.3

lnteresterification ......................................

98

4.5.4

Hydrogenation ..........................................

99

4.5.5

Isomerization ............................................ 100

4.5.6

Polymerization .......................................... 100

4.5.7

Autoxidation ............................................. 100

4.6

Sources of Edible Oils and Main Fats .......................


102

4.7

Oils and Fats: Processing and Refining ....................

103

4.8

Fats and Oils Stability and Antioxidants ....................

115

4.9

Methods of Analysis and Testing of Fats
and Oils ......................................................................

118

4.9.1

Identification and Compositional
Analysis .................................................... 118

4.9.2

Quality Control Tests ................................ 120


References ............................................................................

121

5. Soaps and Detergents ............................................. 123
5.1

Soap ...........................................................................

123

5.1.1

Introduction .............................................. 123

5.1.2

History ...................................................... 124

5.1.3

Raw Materials .......................................... 125

5.1.4

Chemistry of Soaps .................................. 125

5.1.5


Classification of Soaps ............................. 126

This page has been reformatted by Knovel to provide easier navigation.


Contents

5.2

5.3

5.4

ix

5.1.6

Manufacturing of Soaps ........................... 127

5.1.7

Environmental Aspects ............................. 130

Detergent ....................................................................

130

5.2.1

Introduction and History ........................... 130


5.2.2

Principle Groups of Synthetic
Detergents ............................................... 132

5.2.3

Surfactants ............................................... 133

5.2.4

Inorganic Builders .................................... 144

5.2.5

Sundry Organic Builders .......................... 149

5.2.6

Manufacturing of Detergents .................... 153

Environmental Aspects ..............................................

156

5.3.1

Emissions and Controls ............................ 156


5.3.2

Wastewater and the Environment ............. 157

5.3.3

Biodegradation ......................................... 158

Economic Aspects ......................................................

159

References ............................................................................

160

6. Sugar ......................................................................... 163
6.1

Introduction .................................................................

163

6.2

The Chemistry of Saccharides ...................................

164

6.3


Properties of Sucrose ................................................

167

6.4

Historical Survey and World Production ....................

168

6.5

Cane Sugar ................................................................

170

6.5.1

Raw Sugar Manufacture ........................... 170

6.5.2

Refining of Raw Sugar ............................. 180

6.6

Beet Sugar .................................................................

184


6.7

Other Sugars ..............................................................

189

6.8

By-Products of the Sugar Industry .............................

191

6.9

Other Sweeteners ......................................................

192

6.9.1

Acesulfame-K ........................................... 194

This page has been reformatted by Knovel to provide easier navigation.


x

Contents
6.9.2


Alitame ..................................................... 194

6.9.3

Aspartame ................................................ 195

6.9.4

Cyclamate ................................................ 195

6.9.5

Saccharin ................................................. 196

6.9.6

Sucralose ................................................. 197

6.10 Sugar Analysis ...........................................................

197

References ............................................................................

198

7. Paints, Pigments, and Industrial Coatings ............ 201
7.1


Introduction .................................................................

201

7.2

Constituents of Paints ................................................

204

7.2.1

Pigments .................................................. 204

7.2.2

Inorganic Pigments ................................... 209

7.2.3

Organic Pigments ..................................... 217

7.2.4

Binders ..................................................... 221

7.2.5

Solvents ................................................... 226


7.2.6

Additives .................................................. 227

7.3

Paint Formulation .......................................................

231

7.4

Paint Manufacture ......................................................

234

7.5

7.4.1

Pigment Dispersion .................................. 234

7.4.2

Processing Operations ............................. 237

7.4.3

Classification and Types of Paints ............ 238


7.4.4

Varnishes ................................................. 245

7.4.5

Lacquers .................................................. 245

Paint Application and Causes for Paint Failure .........

246

7.5.1

Techniques of Paint Application ............... 246

7.5.2

Causes for Paint Failure ........................... 248

7.6

Testing and Quality Control .......................................

254

7.7

Environmental Impacts and Risks .............................


255

References ............................................................................

256

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Contents

xi

8. Dyes: Chemistry and Applications ......................... 259
8.1

Introduction .................................................................

259

8.2

Colorants ....................................................................

260

8.3

Classification of Dyes .................................................


261

8.4

Textile Fibers ..............................................................

268

8.5

The Application of Dyes .............................................

272

8.6

Intermediates ..............................................................

274

8.6.1

Miscellaneous Reactions .......................... 285

8.7

Manufacture of Dyes ..................................................

286


8.8

Environmental and Health Aspects ...........................

287

References ............................................................................

288

9. Industrial Fermentation ........................................... 289
9.1

Introduction and History .............................................

290

9.2

Biochemical and Processing Aspects ........................

292

9.3

9.4

9.2.1

Overview .................................................. 292


9.2.2

Microorganisms ........................................ 293

9.2.3

Culture Development ................................ 296

9.2.4

Process Development .............................. 298

9.2.5

Bioreactors ............................................... 300

9.2.6

Downstream Processing ........................... 303

9.2.7

Animal and Plant Cell Cultures ................. 304

Food and Feed Treatment by Fermentation ..............

304

9.3.1


Food Conservation ................................... 304

9.3.2

Feed and Agriculture ................................ 309

9.3.3

Single Cell Protein (SCP) ......................... 309

Industrial Chemicals by Fermentation .......................

311

9.4.1

Ethanol ..................................................... 311

9.4.2

Other Industrial Alcohols .......................... 312

9.4.3

Organic Acids ........................................... 313

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xii

Contents

9.5

9.4.4

Amino Acids ............................................. 314

9.4.5

Vitamins ................................................... 316

9.4.6

Industrial Enzymes ................................... 317

Pharmaceutical Products by Fermentation ...............

318

9.5.1

Pharmaceuticals by Direct
Fermentation ............................................ 318

9.5.2

Pharmaceuticals via

Biotransformation ..................................... 319

9.5.3

Biopolymers ............................................. 322

9.6

Environmental Biotechnology ....................................

323

9.7

Social and Economic Aspects ...................................

327

Bibliography ..........................................................................

328

10. The Pharmaceutical Industry .................................. 331
10.1 Introduction .................................................................

332

10.2 Use and Economic Aspects .......................................

332


10.3 Discovery and Development of Drugs .......................

337

10.3.1 Introduction .............................................. 337
10.3.2 Classical Drug Discovery and Early
Development ............................................ 339
10.3.3 Modern Drug Discovery ............................ 341
10.3.4 Preclinical Testing .................................... 344
10.3.5 Clinical Testing ......................................... 345
10.4 Classification and the Chemistry of
Pharmaceutical Products ...........................................

347

10.4.1 The Analgesics ......................................... 347
10.4.2 Antiallergy and Antiasthmatic Drugs ......... 351
10.4.3 Antibacterials and Antibiotics .................... 353
10.4.4 Antidepressants ....................................... 357
10.4.5 Antiepileptics ............................................ 359
10.4.6 Antihypertensives ..................................... 359
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Contents

xiii

10.4.7 Antiulcers ................................................. 361

10.4.8 Antipsychotic Agents ................................ 362
10.4.9 Diuretics ................................................... 363
10.4.10 Contraceptives ......................................... 364
10.4.11 Vitamins ................................................... 364
10.5 Industrial Processes in Pharmaceutical
Industry .......................................................................

365

10.5.1 Research and Development ..................... 366
10.5.2 Chemical Manufacturing ........................... 366
10.6 Manufacturing of Pharmaceutical Products ...............

370

10.6.1 The Manufacturing of Aspirin .................... 370
10.6.2 The Manufacture of Pyribenzamine .......... 371
10.6.3 Formulation, Mixing, and
Compounding ........................................... 372
10.7 Quality Control ............................................................

378

References ............................................................................

379

11. Agrochemicals ......................................................... 381
11.1 Introduction and History .............................................


381

11.2 Chemical Pest Control ...............................................

385

11.2.1 Herbicides ................................................ 386
11.2.2 Insecticides .............................................. 390
11.2.3 Fungicides ................................................ 392
11.2.4 Miscellaneous Compounds ...................... 396
11.2.5 Chemical Synthesis of Pesticides ............. 401
11.3 Formulated Products ..................................................

403

11.4 Biological Pest Control ...............................................

407

11.5 Testing Requirements for New Pesticides ................

410

11.5.1 General Information and Physical and
Chemical Properties ................................. 410
11.5.2 Toxicity ..................................................... 413
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xiv


Contents
11.5.3 Residues in Food ..................................... 414
11.5.4 Human Safety Risk Assessment .............. 415
11.5.5 Environmental Fate and
Environmental Toxicology ........................ 417
11.6 Social and Economic Aspects ...................................

420

11.6.1 Social Consequences of Pesticide
Use .......................................................... 420
11.6.2 Economic Aspects .................................... 422
Bibliography ..........................................................................

426

12. Chemical Explosives and Propellants .................... 429
12.1 Chemical Explosives ..................................................

430

12.1.1 Introduction .............................................. 430
12.1.2 Development of Explosives ...................... 430
12.1.3 Classification of Explosives ...................... 435
12.1.4 Chemistry of Explosives ........................... 444
12.2 Propellants .................................................................

449


12.2.1 Gun Propellants ....................................... 449
12.2.2 Rocket Propellants ................................... 453
12.3 Pyrotechnics ...............................................................

455

12.3.1 Sound Producers ..................................... 456
12.3.2 Light Producers ........................................ 456
12.3.3 Heat Producers ........................................ 457
12.3.4 Smoke Producers ..................................... 457
12.4 Manufacturing of Explosives ......................................

458

12.4.1 TNT Production ........................................ 458
12.4.2 Black Powder Production ......................... 459
12.4.3 RDX and HMX Production ........................ 461
12.5 Thermochemistry of Explosives .................................

462

12.5.1 Oxygen Balance ....................................... 463
12.5.2 Heat of Formation .................................... 464
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Contents

xv


12.5.3 Heat of Explosion ..................................... 465
12.5.4 Explosive Power and Power Index ........... 467
12.6 Safety and Environmental Considerations ................

467

12.7 Classification, Transportation, and Storage of
Explosives ..................................................................

469

12.7.1 Explosives Classification .......................... 469
12.7.2 Transportation of Explosives .................... 470
12.7.3 Storage of Explosives ............................... 470
References ............................................................................

471

13. Petroleum and Petrochemicals ............................... 473
13.1 Introduction .................................................................

473

13.2 Desalting and Dewatering ..........................................

477

13.3 Evaluation ...................................................................

478


13.4 Distillation ...................................................................

478

13.5 Cracking, Coking, Hydrocracking, and
Reforming ...................................................................

481

13.6 Treating Processes ....................................................

497

13.7 Petroleum Products ....................................................

499

13.8 Fuel Gas (Refinery Gas) and Liquefied
Petroleum Gas ...........................................................

499

13.9 Gasoline .....................................................................

499

13.10 Solvents ......................................................................

501


13.11 Kerosene ....................................................................

502

13.12 Fuel Oil .......................................................................

502

13.13 Lubricating Oil ............................................................

503

13.14 Petroleum Wax ...........................................................

504

13.15 Asphalt ........................................................................

505

13.16 Coke ...........................................................................

506

13.17 Petrochemicals ...........................................................

507

Bibliography ..........................................................................


509

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xvi

Contents

14. Synthetic Polymers .................................................. 511
14.1 Basic Concepts and Definitions .................................

511

14.2 Classification of Polymers ..........................................

513

14.3 Polymers Industry ......................................................

520

14.4 Polymer Structure ......................................................

520

14.5 Polymer Structure-Property Relationships ................

541


14.5.1 Thermal Properties ................................... 541
14.5.2 Mechanical Properties .............................. 546
14.5.3 Solubility ................................................... 548
14.5.4 Viscosity ................................................... 554
14.6 Rheology ....................................................................

556

14.7 Molecular Weight of Polymers ...................................

560

14.8 The Synthesis of High Polymers ................................

564

14.8.1 Condensation or Step-Reaction
Polymerization .......................................... 569
14.8.2 Addition or Chain-Reaction
Polymerization .......................................... 572
14.8.3 Free Radical Polymerization ..................... 573
14.8.4 Ionic Polymerization ................................. 582
14.9 Polymerization Techniques ........................................

594

14.10 Copolymerization .......................................................

600


14.11 Modification of Synthetic Polymers ............................

607

14.12 Degradation, Stability, and Environmental
Issues .........................................................................

611

14.13 Polymer Additives ......................................................

616

References ............................................................................

618

Index ............................................................................... 621

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T
Introduction: An Overview
of the Chemical Process
Industry and Primary
Raw Materials

Mohammad Farhat AIi

1.1

The Chemical Process Industry

1

1.2

Development of the Chemical Industry

2

1.3

Characteristics of the Chemical Industry

3

1.4

Raw Materials, Manufacturing, and Engineering

5

1.5

Environmental Aspects

8


References

9

1.1

The Chemical Process Industry

The chemical process industry includes those manufacturing facilities
whose products result from (a) chemical reactions between organic materials, or inorganic materials, or both; (b) extraction, separation, or purification of a natural product, with or without the aid of chemical reactions;
(c) the preparation of specifically formulated mixtures of materials, either
natural or synthetic. Examples of products from the chemical process
industry are plastics, resins, dyes, Pharmaceuticals, paints, soaps, detergents, petrochemicals, perfumes, inorganics, and synthetic organic materials. Many of these processes involve a number of unit operations of
chemical engineering depending on the size definition of a plant, as well
as such basic chemical reactions (processes) as polymerization, oxidation,
reduction, hydrogenation, and the like. The global chemical industry is


valued at one and a half trillion US dollars today with more than 70,000
commercial products. The total world trade in chemicals is valued at
US$400 billion, 10 percent of the value of global trade [I].
The three largest sectors within the world chemical industry are petrochemicals, Pharmaceuticals, and performance chemicals. Petrochemicals
dominate the global chemical industry with a share of 30 percent, followed by Pharmaceuticals (16.5 percent) and performance chemicals (16 percent). The European Union (EU), the United States, and
Germany are the three largest manufacturers followed by Japan,
France, the United Kingdom, Italy, and other Asian countries. However,
there has been a significant shift of global demand for chemicals from
industrialized to developing nations, and the movement of basic chemical manufacturing from industrialized regions to Asia-Pacific and China
[2].
The chemical industry as a whole makes a massive contribution to
welfare and employment around the world. The European Union (EU)

is the world's largest chemical producer, accounting for nearly a third
of the estimated world production. Throughout the EU, about 1.7 million
people are employed in some 25,000 chemical companies and the
industry provides further employment in a broad range of downstream
industries [2]. The U.S. chemical, petrochemical, and pharmaceutical
industries together had more than 13,000 establishments, more than one
million employees, and a total value of shipments worth approximately
US$406.9 billion [3]. Also, many of the Asian and Latin American countries have grown rapidly and have become international competitors in
the chemical industry. Consequently, the global chemical industry is
among the most competitive industries in the world. Being an intermediate input industry, the chemical industry has both forward and backward linkages with other segments of the manufacturing sector thereby
acting as a precursor for the good performance of the manufacturing
sector as a whole.
1.2

Development of the Chemical Industry

The oldest traces of a chemical industry were found in the Middle Age
and they were primarily based on the knowledge and skill in producing
candles, soaps, paints, and medicaments. Manufacturing these products,
at the very beginning, was a homemade affair that aimed to fulfill the
needs of just one or more households. Chemical production came of age
as an industry in the late 1700s but it remained small because many of
the manufacturers did not have the capabilities for continual and larger
production. The evolution of what we know as the modern chemical
industry started more recently. Over the nineteenth and the twentieth centuries, chemists played key roles in expanding the frontiers of


knowledge in advancing medicine and industry, and creating such products as aspirin, synthetic polymers, and rubbers. The discovery of the
first synthetic dyestuff, mauve, in the 1860s by W. H. Perkins proved to
be instrumental in the evolution of the organic chemical industry in the

United Kingdom and Germany. The dawn of the twentieth century
brought fundamental changes mainly as a result of the emphasis on
research on the applied aspects of chemistry in Germany and the United
States. Entrepreneurs took full advantage of the increasing scientific
knowledge to revolutionize the chemical industry as a whole.
The organic chemical industry has grown at a remarkable rate since
1940 as a result of the development and growth of the petroleum refining and petrochemical sectors. The rapid growth in petrochemicals in
the 1960s and 1970s was largely because of the enormous increase in
demand for synthetic polymers. The chemical industry today is highly
research and development (R&D) intensive while producing a high rate
of innovation, making significant contributions to the economy. Yet, the
chemical industry may be regarded as having become a mature manufacturing industry, following its rapid growth in the 1960s and 1970s,
dampening the returns from the high-risk R&D investments. Moreover,
many of the basic processes for producing key intermediate chemicals
have lost their patent protection over the years, enabling other countries
of the world, who wish to venture into this area, to buy their own manufacturing plants. As a result, petroleum-producing countries such as
Korea, Mexico, Saudi Arabia, and other Middle Eastern countries have
entered and rapidly expanded their production of the aromatic petrochemical intermediates together with the final polymer products such
as polyethylene, polypropylene, polyesters, and epoxy resins. There is
also a growing shift in the global chemical industry as a consequence of
both the rapidly growing population and the industrial development of
countries of southeast Asia. It is envisaged that China, with its enormous
population, will become both a major market and a major producer in
chemicals production during the twenty-first century.
1.3

Characteristics of the Chemical Industry

The chemical industry is essentially a science-based industry. The technologies applied in the chemical industry have their well-established scientific roots, and industry growth has been closely linked to scientific
discoveries. One of the main reasons for the enormous growth of the

chemical industry in the developed world has been its great commitment
to the investment in R&D. This traditional investment in R&D does
much to explain the outstanding growth rate of the industry in the
twentieth century and its superior record of increased productivity. The
industry's organized application of science to industrial problems has


produced a host of new products, new processes, and new applications
[4].
The chemical and drug companies in the United States now spend
about $US18 billion annually on R&D. The scientific and technical
research by these industries significantly contributes in making human
lives safer, longer, easier, and more productive [5].
Table 1.1 shows the chemical sales and R&D spending for the global
top 10 companies in the world [5].
The chemical industry produces many materials that are essential for
our most fundamental needs for food, shelter, and health. It also produces products of great importance to the high technology world of computing, telecommunications, and biotechnology. The U.S. government
uses the following eight standard industrial classification codes to
categorize chemical companies [6].









Industrial inorganic chemicals
Plastics, materials, and synthetics

Drugs
Soap, cleaners, and toilet goods
Paints and allied products
Industrial organic chemicals
Agricultural chemicals
Miscellaneous chemical products

According to an estimate by the U.S. Environmental Protection
Agency (EPA), there are 15,000 chemicals manufactured in the United

TABLE 1.1

Rank
1
2
3
4
5
6
7
8
9
10

Global Top 10 by Chemical Sales (2003-2004)

Company
Dow Chemicals
BASF
DuPont

Bayer
Total
ExxonMobil
BP
Shell
Mitsubishi Chemical
Degussa

Country

Chemical sales
($ millions)

R&D spending
($ millions)

U.S.A.
Germany
U.S.A.
Germany
France
U.S.A.
U.K.
U.K.
Japan
Germany

32,632.0
30,768.0
30,249.0

21,567.5
20,197.3
20,190.0
16,075.0
15,186.0
13,216.4
12,929.7

981.0
904.1
1,349.0
1,299.0
NA
NA
NA
NA
NA
401.7

NA: Not available.
SOURCE: Chemical & Engineering News, July 19, 2004, p. 11-13.


States in quantities greater than 10,000 pounds [7]. The organic chemical industry, which manufactures carbon-containing chemicals, accounts
for much of this diversity.
Chemical manufacturing has been undertaken by many different
types of companies largely because of its central role in industry.
Chemical products are made from raw materials supplied by a large
number of different industries including petroleum, agriculture, and
mines products. In turn, chemicals themselves are used as raw materials in almost all other types of manufacturing. The production of chemicals is thus attractive to companies that are seeking to upgrade their

low-value feedstock (raw materials required for an industrial process)
to a profitable chemical product. Petroleum companies, in particular, are
increasingly acquiring leading positions in the organic chemical industry. Of the top 10 leading producers listed in Table 1.1, four are petroleum companies including Total, ExxonMobil, BP, and Shell Oil.
Mergers and acquisitions (M&As) have performed a significant role in
the evolution of the chemical industry. Before World War II, the German
manufacturer, IG Farben, was the largest producer of organic chemicals
in the world. After the war, the Allied powers restructured German industry and IG Farben was broken into its major constituent firms: BASF,
Bayer, and Hoechst. At about the same time, the British government
enforced a merger of strong firms such as Brunner, Maud, and Nobel
with much weaker firms—United Alkali and the British Dyes, to establish one big firm, Imperial Chemical Industries (ICI). In the United States,
DuPont, during the 1980s, was involved in over 50 acquisitions, investing more than $10 billion. Total M&A activity in the United States in 1999
reached $45 billion. It is estimated that in the rest of the world M&As
totaled $1.2 trillion [8]. M&As have performed a number of important
roles in the chemical industry and enabled many U.S. firms to acquire foreign businesses to obtain the needed presence in the local world markets.
1.4 Raw Materials, Manufacturing,
and Engineering

Industrial chemistry procures raw materials from natural environments
to convert them into intermediates, which subsequently serve as base
materials to every other kind of industry. There are four sources of
natural environment:
a.
b.
c.
d.

The
The
The
The


earth's crust (lithosphere)
marine and oceanic environment (hydrosphere)
air (atmosphere)
plants (biosphere)


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