Industrial Organic Chemistry / Edition 5

by Hans-Jürgen Arpe, Stephen Hawkins

Overview

This bestselling standard, now in its fifth, completely revised English edition, is an excellent source of technological and economic information on the most important precursors and intermediates used in the chemical industry. Both a handbook and ready reference, this volume has a uniform structure for ease of use, with a number of fold-out flow charts illustrating complex chemical processes, plus summaries and relevant statistical data in the margins. The text is rounded off by a comprehensive list of references and a detailed subject index.


From reviews of previous editions (authored by K. Weissermel/H.-J. Arpe)

"This book is an immensely comprehensive and practical work. University chemistry students would benefit from reading this book as it provides a valuable insight into chemical technology, which is often lacking in undergraduate chemistry courses. The university lecturer can obtain examples of applied organic syntheses and keep up to date with the constant changes in chemical manufacturing. It should appeal most to chemists and engineers in the chemical industry, who should benefit from the technological, scientific and economic interrelationships and their potential developments." (Synthesis - Journal of Synthetic Organic Chemistry)

"It would be unkind and misleading to call this book a poor man's Kirk Othmer, but it could almost be described as an encyclopedia... it is easy to read and one has to admire the authors' dedication and endeavor in getting so much into a single volume. They have provided a book that is interesting reading as well as being an excellent reference. It is a highly recommended book, which I hope the authors will find the energy to continue updating on a regular basis." (Chemistry in Britain)

"...it should be ready to hand to every chemist or process engineer involved directly or indirectly with industrial organic chemistry. It should be in the hand of every higher-graduate student, especially if chemical technology is not part of the study, like in many college universities..." (Tenside-Surfactants-Detergents)

"Whether student or scientist, theorist or practician - everybody interested in industrial organic chemistry will appreciate this work. ..." (farbe + lack)

Product Details

ISBN-13:	9783527320028
Publisher:	Wiley
Publication date:	10/18/2010
Edition description:	Revised
Pages:	525
Product dimensions:	6.90(w) x 9.60(h) x 1.30(d)

About the Author

Professor Hans-Jürgen Arpe studied chemistry at the Christian-Albert-University in Kiel, Germany and where he also received his PhD under guidance of Professor R. Grewe. Hans-Jürgen Arpe commenced his career at the Koninklijke/ Shell-Laboratory in Amsterdam, The Netherlands. He then moved to the Shell Research Laboratories near Bonn, Germany, followed by his appoint as Head of the Research Department Aliphatic Intermediates at Hoechst AG, Frankfurt, Germany and Head of the scientific library of Hoechst AG. Professor Arpe was an Honorary Professor at the Friedrich-Alexander-University Erlangen, Germany.

Table of Contents

Preface to the First Edition xiii

Preface to the Second Edition xvii

Preface to the Third Edition xix

Preface to the Fourth Edition xxi

1 Various Aspects of the Energy and Raw Material Supply 1

1.1 Present and Predictable Energy Requirements 2

1.2 Availability of Individual Sources 3

1.2.1 Oil 3

1.2.2 Natural Gas 4

1.2.3 Coal 5

1.2.4 Nuclear Fuels 5

1.3 Prospects for the Future Energy Supply 7

1.4 Present and Anticipated Raw Material Situation 8

1.4.1 Petrochemical Primary Products 8

1.4.2 Coal Conversion Products 11

2 Basic Products of Industrial Syntheses 15

2.1 Synthesis Gas 15

2.1.1 Generation of Synthesis Gas 15

2.1.1.1 Synthesis Gas via Coal Gasification 16

2.1.1.2 Synthesis Gas from Cracking of Natural Gas and Oil 19

2.1.2 Synthesis Gas Purification and Use 21

2.2 Production of the Pure Synthesis Gas Components 24

2.2.1 Carbon Monoxide 24

2.2.2 Hydrogen 26

2.3 C₁ Units 29

2.3.1 Methanol 29

2.3.1.1 Manufacture of Methanol 30

2.3.1.2 Applications and Potential Applications of Methanol 32

2.3.2 Formaldehyde 37

2.3.2.1 Formaldehyde from Methanol 38

2.3.2.2 Uses and Potential Uses of Formaldehyde 40

2.3.3 Formic Acid 42

2.3.4 Hydrocyanic Acid 46

2.3.5 Methylamines 51

2.3.6 Halogen Derivatives of Methane 52

3 Olefins 59

3.1 Historical Development of Olefin Chemistry 59

3.2 Olefins from Cracking of Hydrocarbons 60

3.3 Special Manufacturing Processes for Olefins 63

3.3.1 Ethylene, Propene 63

3.3.2 Butenes 67

3.3.3 Higher Olefins 75

3.3.3.1 Unbranched Higher Olefins 75

3.3.3.2 Branched Higher Olefins 83

3.4 Olefin Metathesis 86

4 Acetylene 91

4.1 Present Significance of Acetylene 91

4.2 Manufacturing Processes for Acetylene 93

4.2.1 Manufacture Based on Calcium Carbide 93

4.2.2 Thermal Processes 94

4.3 Utilization of Acetylene 98

5 1,3-Diolefins 107

5.1 1,3-Butadiene 107

5.1.1 Historical Syntheses of 1,3-Butadiene 108

5.1.2 1,3-Butadiene from C₄ Cracking Fractions 109

5.1.3 1,3-Butadiene from C₄ Alkanes and Alkenes 111

5.1.4 Utilization of 1,3-Butadiene 114

5.2 Isoprene 117

5.2.1 Isoprene from C₅ Cracking Fractions 118

5.2.2 Isoprene from Synthetic Reactions 119

5.3 Chloroprene 122

5.4 Cyclopentadiene 125

6 Syntheses involving Carbon Monoxide 127

6.1 Hydroformylation of Olefins 127

6.1.1 Chemical Basis of Hydroformylation 128

6.1.2 Industrial Operation of Hydroformylation 131

6.1.3 Catalyst Modifications in Hydroformylation 134

6.1.4 Utilization of oxo Products 136

6.1.4.1 Oxo Alcohols 136

6.1.4.2 Oxo Carboxylic Acids 138

6.1.4.3 Aldol and Condensation Products of the Oxo Aldehydes 139

6.2 Carbonylation of Olefins 141

6.3 Koch Carboxylic Acid Synthesis 143

7 Oxidation Products of Ethylene 147

7.1 Ethylene Oxide 147

7.1.1 Ethylene Oxide by the Chlorohydrin Process 148

7.1.2 Ethylene Oxide by Direct Oxidation 149

7.1.2.1 Chemical Principles 149

7.1.2.2 Process Operation 150

7.1.2.3 Potential Developments in Ethylene Oxide Manufacture 152

7.2 Secondary Products of Ethylene Oxide 153

7.2.1 Ethylene Glycol and Higher Ethylene Glycols 154

7.2.1.1 Potential Developments in Ethylene Glycol Manufacture 155

7.2.1.2 Uses of Ethylene Glycol 158

7.2.1.3 Secondary Products: Glyoxal, Dioxolane, 1,4-Dioxane 158

7.2.2 Polyethoxylates 160

7.2.3 Ethanolamines and Secondary Products 161

7.2.4 Ethylene Glycol Ethers 164

7.2.5 Additional Products from Ethylene Oxide 167

7.3 Acetaldehyde 168

7.3.1 Acetaldehyde via Oxidation of Ethylene 169

7.3.1.1 Chemical Basis 169

7.3.1.2 Process Operation 171

7.3.2 Acetaldehyde from Ethanol 172

7.3.3 Acetaldehyde by C₃/C₄ Alkane Oxidation 173

7.4 Secondary Products of Acetaldehyde 173

7.4.1 Acetic Acid 174

7.4.1.1 Acetic Acid by Oxidation of Acetaldehyde 175

7.4.1.2 Acetic Acid by Oxidation of Alkanes and Alkenes 177

7.4.1.3 Carbonylation of Methanol to Acetic Acid 180

7.4.1.4 Potential Developments in Acetic Acid Manufacture 182

7.4.1.5 Use of Acetic Acid 183

7.4.2 Acetic Anhydride and Ketene 185

7.4.3 Aldol Condensation of Acetaldehyde and Secondary Products 189

7.4.4 Ethyl Acetate 191

7.4.5 Pyridine and Alkyl Pyridines 193

8 Alcohols 197

8.1 Lower Alcohols 197

8.1.1 Ethanol 197

8.1.2 2-Propanol 202

8.1.3 Butanols 205

8.1.4 Amyl Alcohols 209

8.2 Higher Alcohols 209

8.2.1 Oxidation of Paraffins to Alcohols 213

8.2.2 Alfol Synthesis 214

8.3 Polyhydric Alcohols 216

8.3.1 Pentaerythritol 216

8.3.2 Trimethylolpropane 217

8.3.3 Neopentyl Glycol 218

9 Vinyl Halogen and Vinyl Oxygen Compounds 221

9.1 Vinyl Halogen Compounds 221

9.1.1 Vinyl Chloride 221

9.1.1.1 Vinyl Chloride from Acetylene 222

9.1.1.2 Vinyl Chloride from Ethylene 223

9.1.1.3 Potential Developments in Vinyl Chloride Manufacture 226

9.1.1.4 Uses of Vinyl Chloride and 1,2-Dichloroethane 227

9.1.2 Vinylidene Chloride 229

9.1.3 Vinyl Fluoride and Vinylidene Fluoride 229

9.1.4 Trichloro- and Tetrachloroethylene 231

9.1.5 Tetrafluoroethylene 233

9.2 Vinyl Esters and Ethers 234

9.2.1 Vinyl Acetate 234

9.2.1.1 Vinyl Acetate Based on Acetylene or Acetaldehyde 234

9.2.1.2 Vinyl Acetate Based on Ethylene 236

9.2.1.3 Possibilities for Development of Vinyl Acetate Manufacture 238

9.2.2 Vinyl Esters of Higher Carboxylic Acids 240

9.2.3 Vinyl Ethers 241

10 Components for Polyamides 243

10.1 Dicarboxylic Acids 245

10.1.1 Adipic Acid 246

10.1.2 1,12-Dodecanedioic Acid 249

10.2 Diamines and Aminocarboxylic Acids 251

10.2.1 Hexamethylenediamine 251

10.2.1.1 Manufacture of Adiponitrile 251

10.2.1.2 Hydrogenation of Adiponitrile 255

10.2.1.3 Potential Developments in Adiponitrile Manufacture 256

10.2.2 ω-Aminoundecanoic Acid 257

10.3 Lactams 258

10.3.1 Є-Caprolactam 258

10.3.1.1 Є-Caprolactam from the Cyclohexanone Oxime Route 258

10.3.1.2 Alternative Manufacturing Processes for Є-Caprolactam 263

10.3.1.3 Possibilities for Development in Є-Caprolactam Manufacture 265

10.3.1.4 Uses of Є-Caprolactam 266

10.3.2 Laurolactam 268

11 Propene Conversion Products 273

11.1 Oxidation Products of Propene 274

11.1.1 Propylene Oxide 274

11.1.1.1 Propylene Oxide from the Chlorohydrin Process 274

11.1.1.2 Indirect Oxidation Routes to Propylene Oxide 275

11.1.1.3 Possibilities for Development in the Manufacture of Propylene Oxide 279

11.1.2 Secondary Products of Propylene Oxide 283

11.1.3 Acetone 285

11.1.3.1 Direct Oxidation of Propene 286

11.1.3.2 Acetone from 2-Propanol 287

11.1.4 Secondary Products of Acetone 288

11.1.4.1 Acetone Aldolization and Secondary Products 289

11.1.4.2 Methacrylic Acid and Ester 290

11.1.5 Acrolein 295

11.1.6 Secondary Products of Acrolein 296

11.1.7 Acrylic Acid and Esters 299

11.1.7.1 Traditional Acrylic Acid Manufacture 299

11.1.7.2 Acrylic Acid from Propene 301

11.1.7.3 Possibilities for Development in Acrylic Acid Manufacture 303

11.2 Allyl Compounds and Secondary Products 304

11.2.1 Allyl Chloride 304

11.2.2 Allyl Alcohol and Esters 307

11.2.3 Glycerol from Allyl Precursors 309

11.3 Acrylonitrile 312

11.3.1 Traditional Acrylonitrile Manufacture 313

11.3.2 Ammoxidation of Propene 314

11.3.2.1 Sohio Acrylonitrile Process 315

11.3.2.2 Other Propene/Propane Ammoxidation Processes 316

11.3.3 Possibilities for Development of Acrylonitrile Manufacture 317

11.3.4 Uses and Secondary Products of Acrylonitrile 318

12 Aromatics — Production and Conversion 321

12.1 Importance of Aromatics 321

12.2 Sources of Feedstocks for Aromatics 322

12.2.1 Aromatics from Coking of Hard Coal 323

12.2.2 Aromatics from Reformate and Pyrolysis Gasoline 324

12.2.2.1 Isolation of Aromatics 327

12.2.2.2 Special Separation Techniques for Non-Aromatic/Aromatic and Aromatic Mixtures 328

12.2.3 Possibilities for Development of Aromatics Manufacture 333

12.2.4 Condensed Aromatics 334

12.2.4.1 Naphthalene 335

12.2.4.2 Anthracene 336

12.3 Conversion Processes for Aromatics 339

12.3.1 Hydrodealkylation 339

12.3.2 m-Xylene Isomerization 341

12.3.3 Disproportionation, Transalkylation, and Methylation 343

13 Benzene Derivatives 347

13.1 Alkylation and Hydrogenation Products of Benzene 348

13.1.1 Ethylbenzene 348

13.1.2 Styrene 351

13.1.3 Cumene 354

13.1.4 Higher Alkylbenzenes 356

13.1.5 Cyclohexane 357

13.2 Oxidation and Secondary Products of Benzene 359

13.2.1 Phenol 359

13.2.1.1 Manufacturing Processes for Phenol 360

13.2.1.2 Potential Developments in Phenol Manufacture 368

13.2.1.3 Uses and Secondary Products of Phenol 370

13.2.2 Dihydroxybenzenes 374

13.2.3 Maleic Anhydride 378

13.2.3.1 Maleic Anhydride from Oxidation of Benzene 379

13.2.3.2 Maleic Anhydride from Oxidation of Butene 380

13.2.3.3 Maleic Anhydride from Oxidation of Butane 382

13.2.3.4 Uses and Secondary Products of Maleic Anhydride 383

13.3 Other Benzene Derivatives 386

13.3.1 Nitrobenzene 386

13.3.2 Aniline 387

13.3.3 Diisocyanates 390

14 Oxidation Products of Xylene and Naphthalene 397

14.1 Phthalic Anhydride 397

14.1.1 Oxidation of Naphthalene to Phthalic Anhydride 397

14.1.2 Oxidation of o-Xylene to Phthalic Anhydride 399

14.1.3 Esters of Phthalic Acid 401

14.2 Terephthalic Acid 404

14.2.1 Manufacture of Dimethyl Terephthalate and Terephthalic Acid 405

14.2.2 Fiber Grade Terephthalic Acid 407

14.2.3 Other Manufacturing Routes to Terephthalic Acid and Derivatives 409

14.2.4 Uses of Terephthalic Acid and Dimethyl Terephthalate 413

15 Appendix 417

15.1 Process and Product Schemes 417

15.2 Definitions of Terms used in Characterizing Chemical Reactions 459

15.3 Abbreviations for Companies 461

15.4 Sources of Information 462

15.4.1 General Literature 462

15.4.2 More Specific Literature (publications, monographs) 464

Index 487

Editorial Reviews

"The fourth edition of this established work follows in the excellent tradition of the previous three editions. It retains the concept of the original, providing technological and economic information on the key building blocks of the chemical industry.
The book is packed with information, much of which cannot easily be found elsewhere, and certainly not in such a readily digestible form. The companies and innovators responsible for the chemistry described are clearly credited, and indeed this volume provides an excellent history of the worldwide bulk organic chemicals industry. Throughout the book the authors indicate potential future developments in the manufacture of these important precursors and intermediates.
The reader friendly format seen in the previous editions is retained, wherein each chapter or subsection is provided with a chemical flow diagram illustrating the interrelationship of the products, these flow diagrams folding out such that they can be constantly referred to whilst reading the text. In addition, the main text is accompanied by a synopsis in the margin, which concisely presents all of the essential points, thus facilitating browsing. The contents are logically and clearly organized, and there are detailed reference lists for each chapter, together with an extensive index. This latest edition also includes updated statistics and adopts the new IUPAC nomenclature guidelines.(...) This book will be a positive addition to the libraries and bookshelves of chemists and chemical engineers working in the organic sector, including those to whom many of the molecules describes are considered to be "commercially available starting materials". Non-scientists (e.g. industrial economists, lawyers) will also gain an appreciation of the complex technological, scientific and economic inter-relationships (and potential developments) which characterize industrial organic chemistry."
Organic Process Research & Development, Peter Spargo

"This book is an immensely comprehensive and practical work. University chemistry students would benefit from reading this book as it provides a valuable insight into chemical technology, which is often lacking in undergraduate chemistry courses. The university lecturer can obtain examples of applied organic syntheses and keep up to date with the constant changes in chemical manufacturing. It should appeal most to chemists and engineers in the chemical industry, who should benefit from the technological, scientific and economic interrelationships and their potential developments."
Synthesis - Journal of Synthetic Organic Chemistry

From the Publisher