Industrial Organic Chemicals

By Harold A. Wittcoff, Bryan G. Reuben and Jeffery S. Plotkin

An essential introduction to the organic chemicals industry—in the context of globalization, advances in technology, and environmental concerns

Providing 95 percent of the 500 billion pounds of organic chemicals produced in the world, the petroleum and natural gas industries are responsible for products that ensure our present quality of life. Products as diverse as gasoline, plastics, detergents, fibers, pesticides, tires, lipstick, shampoo, and sunscreens are based on seven raw materials derived from petroleum and natural gas. In an updated and expanded Third Edition, Industrial Organic Chemicals examines why each of these chemical building blocks—ethylene, propylene, C4 olefins (butenes and butadiene), benzene toluene, the xylenes, and methane—is preferred over another in the context of an environmental issue or manufacturing process, as well as their individual chemistry, derivatives, method of manufacture, uses, and economic significance.

The new edition details the seismic shifts in the world's chemistry industry away from the United States, Western Europe and Japan, transforming the Middle East and Asia-Pacific region, especially China, into major players. The book also details:

• The impact of globalization on the patterns of worldwide transportation of chemicals, including methods of shipping chemicals
• The technological advances in the area of polymerization and catalysis, including catalyst design and single-site catalysts
• Chemicals for electronics, with much new material on conducting polymers, photovoltaic cells, and related materials
• The discovery of vast reserves of shale gas and shale oil, altering long-term predictions of resource depletion in the United States and other countries
• Commercial and market aspects of the chemical industry, with coverage of emerging new companies such as INEOS, Formosa Plastics, LyondellBasell, and SABIC

With expanded coverage on the vital role of green chemistry, renewables, chemicals and fuels on issues of sustainability and climate change, Industrial Organic Chemicals offers an unparalleled examination of what is at the heart of this multi-billion dollar industry, how globalization has transformed it, and its ever growing role in preserving the Earth and its resources.

• Language: English
• Publisher: Wiley
• Release date: Dec 10, 2012
• ISBN: 9781118229873

Book preview

Preface

This third edition of Industrial Organic Chemicals is prompted by the impact of globalization and of threats to the environment. This is not to say that industrial chemistry has stood still – very much the reverse, and we have featured much new chemistry. All the same, our earlier books were about the exciting new world of petrochemical feedstocks and the ingenious new products that could be made from them. In this edition, the exciting new processes have become the dull traditional ones. Well-established processes of technology transfer have carried them to developing countries, especially those that produce petrochemical feedstocks. In addition, humankind's activities are seen both as depleting the resources of the planet and of polluting it to the point at which humankind will drown in its own effluvia. The extent of these threats is hotly contested; nonetheless, the chemical industry both contributes to the problems and is instrumental in trying to solve them.

There have been many developments since the second edition, and the following topics have gained especially in significance:

The world chemical industry has migrated from the United States, Western Europe, and Japan to the Middle East and to Asia-Pacific, especially China. Will shale oil and gas bring it back? (See Appendix D).

There is increased emphasis on environmental issues, with pressure on companies to clean up polluting processes or replace them with environmentally friendly ones.

Globalization has changed patterns of transportation of chemicals with, for example, solid polymers rather than petrochemical feedstocks being shipped from the Middle East.

The discovery of vast reserves of shale gas has altered the long-term predictions of resource depletion in the United States and other countries.

Considerations of sustainability and the threat of climate change have prompted research into processes (including electricity generation) that produce less or no carbon dioxide, or come from renewable resources.

We have retained some material that is now largely of historical interest, partly for sentimental reasons, but partly because the three authors have watched the meteoric rise of the chemical industry from its early days to its present-day maturity. We think there is a value in our readers observing how technology has developed, and the social, technological, and economic changes that have brought it to its present position.

Harold A. Wittcoff

Preface to the First Edition

In the early 1970s, one of us (BGR) wrote a book celebrating the rapid growth of the adolescent chemical industry. The organic chemicals industry at the time was growing at four times the rate of the economy. It was indicated nonetheless that trees do not grow to the sky. In 1980, in another book, we both declared the industry to be middle-aged with slow or zero growth. In this totally revised and expanded version of our earlier book, we reflect that the industry, at any rate in the developed world, is showing many of the illnesses of late middle-age.

The problems have arisen first from the undisciplined building of excess capacity with consequent fierce competition and low prices. Second, the entry of numerous developing countries into the industry has exacerbated the situation (Section 1.3.6), and third, there has been much stricter government legislation (Section 1.3.7). There is massive worldwide restructuring and continual shifting of commodity chemical manufacturing to areas other than the United States, Western Europe, and Japan. The Middle East and Southeast Asia are the principal new players in the game. Perhaps this trend will continue and the present developed world will in the future confine itself to the manufacture of specialties, but the economic and political forces at work are more complex than that. We hope to be able to discuss their resolution in another edition in about 10 years' time.

Meanwhile, some things have not changed. The organic chemicals industry is still based on seven basic raw materials all deriving from petroleum and natural gas. The wisdom of teaching about the chemical industry on the basis of these seven building blocks has been confirmed by the fact that, since the publication of our first book, one of us (HAW) has delivered by invitation 300 courses in 28 countries on the fundamentals of the industry based on this pattern. Most of these courses are for industrial personnel but academia has not been neglected.

Furthermore, some changes have been positive. For example, there have been exciting new processes such as the development of metallocene catalysts (Section 15.3.12). Section 4.6.1 describes new methyl methacrylate processes that give a potentially cheaper product, that do not produce ecologically undesirable ammonium hydrogen sulfate by-product or (in another process) that eliminate the use of dangerous hydrogen cyanide.

In this book, our main objective is still to present the technology of the organic chemicals industry as an organized body of knowledge, so that both the neophyte and the experienced practitioner can see the broad picture. Nonetheless, we have expanded its scope to include not only new processes but many apparently less important reactions that are significant because they give rise to the more profitable specialty chemicals. The lesser volume chemicals have been clearly delineated as such and the reader who wishes to see the industry on the basis of its large tonnage products can omit these sections.

We hope this book will be useful both to college students who have studied organic chemistry and to graduates and industrial chemists who work in or are interested in the chemical industry. Even though much of the chemistry has remained the same, the change in the way the industry looks at its problems provides ample justification for our offering this edition as a fresh perspective on industrial organic chemicals.

Preface to the Second Edition

In the preface to the first edition, we expressed the hope that we could comment on the chemical industry's evolution in 10 years' time. Dramatic changes have motivated us to compress this time frame. There have been unprecedented restructuring, severe and complicated feedstock problems, and massive shifts of capacity to developing countries, whose economic and political stability is in doubt. Possible terrorist activity dictates elaborate safety and security procedures and the design of plants with small inventories is a priority.

To increase our cover, particularly of the patent literature, we have invited Dr. Jeffrey S. Plotkin, Director of the Process Evaluation and Research Planning program at Nexant ChemSystems to join us as co-author.

Acknowledgments

We are grateful to the many friends and colleagues with whom we spoke often during the revision of this book. Much knowledge and clarification evolved in this way. Nexant ChemSystems Inc.'s numerous multiclient reports provided detailed information on both reaction conditions and production economics.

We thank Prof. Maurice Kreevoy for his review of the catalyst chapter and his many helpful suggestions. We also thank librarians Mrs. Denise Phillips and Ms Lorraine Moneypenny who searched the literature diligently for us. Ms Pat Cairns cheerfully did many things to make the revision easier, and we thank her sincerely. We also thank Mr. Ted Wittcoff who good naturedly compensated for his father's computer shortcomings.

Bryan Godel Reuben 1934–2012

Bryan was one of the UK's first mass-spectometrists and a pioneering teacher in industrial chemistry. His early love of chemistry was developed with experiments—many of them explosive—in his father's pharmacy. Bryan won a scholarship to the Queen's College, Oxford, to study chemistry. With his PhD he went onto a post-doctoral fellowship at Brookhaven National Laboratory in New York, where he worked with Lewis Friedman on the kinetics of gas-phase ion-molecule reactions. Bryan found living in the U.S. both exciting and stimulating and was always pleased to return there for work and for holidays.

Bryan returned to the UK to work for Distillers as a physical chemist but after only a year moved to sales development. This led to a career determining lifelong interest in the relationship between chemistry and economics. In 1963 he moved from commerce to academia at Battersea College of Advanced Technology (soon to become the University of Surrey) where he first met his great friend Michael L. Burstall. Together they developed a ground breaking industrial chemistry course and wrote one of the standard works in the field, The Chemical Economy (1973). In 1977 Bryan moved to the chemical engineering department of Borough Polytechnic (later London South Bank University) as principal lecturer responsible for organizing and developing research. He was appointed Professor of Chemical Technology in 1990.

Bryan was a teacher with a gift for explaining complex problems with clarity and wit, which is probably why he had many invitations to work abroad. In 1972 he spent a sabbatical year at the Hebrew University, Jerusalem, where he helped to set up the Master's program in applied chemistry and lectured on industrial processes and catalysis. He later taught at the Weizmann Institute and at the universities of Bar Ilan and Ben Gurion and acted as a consultant for the Israel Ministry of Development. In 1979 he taught at the Universities of Texas, Oregon, Michigan, and Missouri and in 1981 was visiting professor and consultant at the University of Campinas, Brazil.

Apart from his scientific work, Bryan had a life long interest in the arts. At Oxford he wrote comedy revues and sketches and at Brookhaven he directed the local amateur dramatic society in several revues and plays and also took to the stage as an actor, a hobby which he continued on his return to England. His journalism continued until 2012. He delighted in writing satirical articles and book reviews on a wide variety of subjects. However it was always his wish to write a book for the popular market (such as people might buy at airports as he used to say) and in 2008 he wrote Bread–a Slice of History, together with John Marchant and Joan Alcock, colleagues from South Bank University. He enjoyed appearing as an authority on bread on the BBC4 program In Search of the Perfect Loaf.

Since his early twenties, Bryan had been an enthusiastic and expert skier. He delighted in taking his family and later also his grandchildren, on skiing holidays. He continued to do this until 2011, despite a catastrophic ski accident in 1987 in which he broke many bones and tore his aortic valve. In the preface to Pharmaceutical Chemicals in Perspective, which he wrote with Harold Wittcoff in 1988, Bryan thanked the doctors in Grenoble who had saved his life. He was also grateful to the pharmaceutical industry, whose drugs allowed him to survive for many more years and two further open heart operations.

Professionally, Bryan published more than 140 papers on the chemical, pharmaceutical and process industries, as well as 13 books, many of which became standard works, including Industrial Organic Chemicals in Perspective (1980) with Harold Wittcoff. Harold met Bryan after the publication of The Chemical Economy (1973). In the years to come, Bryan and Harold worked together on many projects and they became close friends as well as colleagues. Their collaboration was a source of great joy not only to Bryan but to his entire family. Bryan was planning to work on the proofs of this third edition of Industrial Organic Chemicals the week before he died. He would be delighted and proud to know that all their hard work has come to fruition.

List of Acronyms and Abbreviations

Introduction

How to Use Industrial Organic Chemicals, Third Edition

This new edition is the latest in a series of books by the authors on the technology and economics of the chemical industry. It is justified by the rapid rate of change in the industry. We discuss many new processes and improvements in many older ones. There have also been extensive changes in the economics of the industry, in its location and in issues of green chemistry and sustainability.

This introductory chapter was originally intended to show, first, the origin of our information and, second, where you may follow up topics that arouse your interest. These aims have been retained, but we have revised our approach to information gathering to reflect the influence of the Internet. Indeed, for all we know, you are reading this on an e-book reader or have downloaded it onto your mainframe.

The answer to the question Where did we get our information from? is We sort of picked it up in fifty years or so associated with the industry. A 2010 book on a topic related to ours has run to several editions. Its general bibliography contains 20 books of which 13 were published before 1980. These sources are long out of print and inaccessible to the general reader. This has prompted us to delete all references before 1990 and most before 2000, apart from a few books and articles of emotional or historical significance. Readers interested in the earlier bibliographies should consult our earlier editions. Much of our information also accrued during courses on the chemical industry given over many years by the authors, most recently under the auspices of Nexant/ChemSystems. One author (HAW) has presented this course in 28 countries (many several times) to over 1000 students and we have drawn on information and illustrations from it.

The answer to how you follow up your interests today is also different. Two generations ago, the conscientious worker would read the professional journals, sift through the learned journals, and check with Chemical Abstracts or one of its associated services. On an occasional visit to a large library, he or she would browse the open shelves around a Dewey decimal number of interest and see what new books there were. Business information was like gold dust. Marketing people hung around bars that employees of rival companies frequented and tried to piece together what was actually happening from the fragments of information that were dropped.

Today, one types keywords into Google and gets, at a conservative estimate, a million hits. We have passed from information famine to information overload. The problem is to sort the correct information from the speculative and the mistaken. The press has reported indignantly that Google keeps records of one's previous searches and places items it thinks will be of interest high on its listings. That seems a blessing rather than a curse. The drawback of citing URLs (internet addresses, known as Uniform Resource Locators) is that some of them disappear with time, and also that the URL copied from one's browser is sometimes accessible only through the home page of the organization producing the information. We recommend readers who get error messages when following our URL citations to try to address the home page of the organization concerned and to navigate from there.

Wikipedia is a treasure house of information and is much more reliable on scientific than on political matters. It is the starting point for many searches and provides references to more detailed sources. We have cited it unashamedly. Furthermore, we have reduced direct references to the scientific literature and have preferred to cite URLs, chemical industry journals, and professional magazines. These report novel developments and provide threads that lead to the more solid literature. We are not sure how user-friendly this will turn out to be, but we feel that it is at least some sort of response to changes in the way people search for information.

I.1 Why this Book was Written and How it is Structured

The petrochemical industry provides well over 90% by tonnage of all organic chemicals. It grew rapidly in the 1950s and 1960s. Many new processes and products were introduced. Large economies of scale proved possible. The prices of chemicals and polymers dropped so that they could compete with traditional materials. Cheerfully colored plastic housewares, highly functional packaging, shampoos that tolerated hard water, and easy care garments of synthetic fibers were no longer exciting new technology but had become an accepted and routine part of modern life.

By the 1970s growth was leveling off. The first and second oil shocks increased the price of crude oil and hence of its downstream products. Economies of scale suffered a hiatus to rise again in the late 1990s with the construction of 1 million metric tons of ethylene per year steam crackers and 1.6 million metric tons per year methanol plants. The industry had matured. As its technology became better known and more available, developing countries started their own petrochemical industries, competing with the developed countries and thus depressing profitability. In the early 2000s the trickle of the industry to the Middle East and Asia-Pacific became a flood. For many products today, production in Asia-Pacific is greater than the United States and Western Europe combined. The industry in the West has rationalized. Of the world's twenty leading chemical companies in 1990, only eight were flourishing in 2008.

Furthermore, the impact of the industry on the environment has become evident, and it stands accused of everything from promoting global warming to changing the sex of fish. While many in the industry think that much of this is motivated by anti-industry hype, there is still an important and widespread movement toward greener chemistry.

New products are no longer the name of the game partly because expensive toxicity testing is required before a new compound can be introduced. Thus, rather than developing bigger, better plants to manufacture novel chemicals, the industry is concerned with lessening pollution, improving processes, and developing specialty chemical formulations and niche products that can be sold at higher profit margins. Research and development has become highly process-oriented, in part to find less 1polluting processes, and in part to combat maturity and to gain an edge over competition with money-saving technology. Examples are given throughout the book.

Chapter 1 deals with the characteristics of the chemical industry and its place in the U.S. economy.

Chapter 2 deals with globalization – the spread of the chemical industry from the places it originated, namely, Western Europe and the United States, to Asia-Pacific and the Middle East.

Chapter 3 concerns the movement of chemicals from wherever they are produced – often from countries that had no chemical industry a generation ago – to wherever they are consumed. Transport is crucial in a globalized world and accounts for perhaps 10% of the cost of the average chemical.

Chapter 4 describes where organic chemicals come from and then shows how the major sources, petroleum and natural gas, provide seven basic chemicals or chemical groups from which most petrochemicals are made. The basic building blocks comprise olefins – ethylene, propylene, and the C4 olefins (butadiene, isobutene, 1- and 2-butenes) – plus the aromatics, benzene, toluene, and the xylenes (ortho, meta, para) – and one alkane, methane. The chapter explains how the olefins derive primarily from steam cracking and secondarily from catalytic cracking, and how the aromatics derive primarily from catalytic reforming in the United States but from steam cracking in Europe. Methane occurs as such in natural gas, and reserves of this have recently been augmented by the supplies from abundant shale. The important interface between the refinery and the petrochemical industry is described as is the relationship between feedstock flexibility and profitability.

Chapters 5 and 6 describe the chemistry of ethylene and propylene. They are the most important of the seven building blocks and are treated accordingly.

Chapters 7 and 8 deal with the C4 and C5 olefins. The C5 compounds and their derivatives are only used in low volume and are not included in the seven basic building blocks. They are nonetheless an important source of isoprene for a synthetic analog of natural rubber (Section 17.3.10) and for thermoplastic elastomers (Section 17.3.8).

Chapters 9, 10, and 11 describe the chemistry of the aromatics – benzene, toluene, and the xylenes. Benzene has been overshadowed by ethylene and propylene since the 1960s but is still the third most important of the building blocks.

Chapter 12 describes the chemistry of methane, a relatively unreactive molecule, which nonetheless is the source of synthesis gas (CO + H2) for ammonia and methanol manufacture. Stranded natural gas is a methane source that needs to be exploited. Acetylene is discussed here, since it may be made from methane. Very important fifty years ago, its significance has been steadily decreased by newer chemistry based on ethylene and propylene, but it has recently made a comeback in the fast-developing Chinese chemical industry with its strong emphasis on coal.

Chapter 13 is devoted to the growing industrial chemistry based on alkanes other than methane. The substitution of alkanes for olefins, which depends on sophisticated catalyst development, could change industrial chemistry profoundly in the future.

Chapters 14, 15, and 16 deal with nonpetroleum sources of chemicals – coal, fats and oils, and carbohydrates. The chemical industry in the nineteenth and early twentieth centuries was based on chemicals derived from coal tar or coke oven distillate. Today, this is a specialty area, and our major interest in coal focuses on its conversion to synthesis gas. This would be the first stage in building a coal-based chemical industry should petroleum and natural gas become depleted, and it is already being revived in China.

The chemistry of fats and oils (Chapter 15) is reflected in the surfactant area and in numerous specialty performance products. Carbohydrate-based chemicals (Chapter 16) are also largely specialties. These two groups are nonetheless sources of renewable raw materials and their conversion often employs biotechnology. As these materials are primarily agricultural products, their use competes with foodstuffs production and is attracting not only research interest but also debate as to its wisdom.

Since the overwhelming majority of all organic chemicals manufactured end up in polymers, Chapter 17 is devoted to polymerization processes and polymer properties. Recent developments in metallocene catalysts, dendrimers, and conducting polymers are included. Chapter 18 deals with the all-important subject of catalysis without which there would hardly be a chemical industry. Chapter 19 deals with the emergence of green chemistry, a topic that dominates the books published on industrial chemistry since 1990. Finally, Chapter 20 deals with the vital issue of sustainability, both in terms of individual problems (air pollution, waste disposal, electricity from solar cells, etc.) and global issues such as international competition and resource depletion.

It is the new processes and attitudes that provided the incentives for this third edition, but we have also expanded its scope to include many apparently less important reactions, which are significant because they give rise to the more profitable specialty chemicals. We have also retained details of some obsolete processes, not only because they may one day be revived, but also because it is crucial to understand why one process might supplant another.

We hope this book will be useful both to university students who have studied organic chemistry, and to graduates, industrial chemists, and managers who work in or are interested in one of the most remarkable industries of the twentieth century and, even though we have only experienced a decade of it, the twenty-first century.

We intend each chapter to be self-sufficient; hence there is inevitably a degree of repetition. We have tried to minimize this by extensive cross-referencing and hope the reader will be tolerant of what remains.

I.2 North American Industry Classification System

The U.S. government provides statistics on all branches of industry, dividing them according to the North American Industry Classification system (NAICS) (http://www.census.gov/cgi-bin/sssd/naics/naicsrch?chart_code=31&search=2007 NAICS Search). The 2002 revisions were further revised in 2007. Each major segment of the economy is classified under a number between 1 and 99 (see Table 1.1). Manufacturing industries are classified under numbers 31–33 and the chemical and allied products industry falls within this category at 325. Statistics for subsegments of the industry are provided under four-, five-, or six-digit numbers. Thus 3252 is Resins, synthetic rubbers & artificial & synthetic fibers and filaments, 325211 is Plastics materials and resins, 325212 is Synthetic rubber, and 32522 is Artificial & synthetic fibers and filaments. We have relied on these data for our book, although it is never possible to obtain up-to-date figures. Thus the material published in 2010 contains information for 2008. The more detailed figures from the 2010 census are appearing piecemeal. Statistics from other sources are often more up-to-date but are less authoritative (Section I.4.5).

The industries that form the chemical and allied products industries are shown in Table 1.2. Although at times one might wish for even more detailed information, the North American Industry Classification provides a wealth of it. Other countries do not have comparable databases; many have Standard Industrial Classifications, but none is so detailed. The classifications in other countries rarely correspond to those in the United States or to each other, and analysts wishing to tackle official statistics should be aware of the pitfalls.

I.3 Units and Nomenclature

The widespread adoption of the SI (Système international d'unités) system of units based on the meter, the kilogram, and the second has worsened rather than improved the plethora of units used in the chemical industry. Three kinds of tons are in common use – the short ton (2000 lb), the metric ton or tonne (1000 kg or 2204.5 lb), and the long ton (2240 lb). U.S. statistics are frequently given in millions of pounds, which are at least unambiguous, but we give most of our figures in metric tons. In addition, we try to quote figures in the units actually used by industry – petroleum is measured in barrels, benzene in gallons, mixed xylenes in gallons, and (incredibly) p-xylene in pounds – and to give conversions into better known units. A table of conversion factors is given in Appendixes B and C.

Similarly, in naming chemicals, we tend to use the names conventional in industry rather than the more academic nomenclature of the International Union of Pure and Applied Chemistry (IUPAC). Thus we write hydrogen not dihydrogen; ethylene, acetylene, and acetic acid; not ethene, ethyne, and ethanoic acid.

Industry makes no effort to use consistent nomenclature. Ethene and propene are universally known as ethylene and propylene and would scarcely be recognized by their IUPAC names. The C4 olefins, however, are frequently referred to as butenes rather than butylenes, and we have followed this style. We use trivial names where industry does. Thus we refer to C6H5CH(CH3)2 as cumene, the name by which it isbought and sold, rather than the more informative names of isopropylbenzene, 2-phenylpropane, or (1-methylethyl)benzene. The term ethanal would be likely to be misread or misheard in industry as ethanol, and the compound is known as acetaldehyde. So important is trivial nomenclature that the pharmaceutical industry could not exist without it.

We regret the lack of consistency that the use of trivial nomenclature entails, but we feel it best serves our aim of communicating with chemical industry personnel and preparing students to enter the industry.

I.4 General Bibliography

As noted above, we have cleaned up our bibliography to reflect the influence of the Internet. A rapid search of the Amazon website will provide lists of books on any conceivable topic. We assume that readers have access to background articles on most topics and we have provided endnotes to each chapter that replace the notes and references in earlier editions. These refer specifically to the information to which they are attached, even where anecdotal material is appended.

I.4.1 Encyclopedias

The most important single reference work is R. E. Kirk and D. F. Othmer, Kirk–Othmer's Encyclopedia of Chemical Technology, Volumes 1–27, 5th ed., J. I. Kroschwitz and M. Howe-Grant, editors, Hoboken NJ: Wiley-Interscience; 2004–2007. Kirk–Othmer provides comprehensive and well-referenced coverage of almost every aspect of industrial chemistry. There is access to registered users (via a university or other subscriber) at www.mrw.interscience.wiley.com/uric or www.mrw.interscience.wiley.com/kirk, and these sites will also search the whole of the Wiley-Interscience collection. The earlier volumes of the first to fourth editions are inevitably dated but provide information not readily available from other sources. If a subject is not treated in the new edition, it is always worth consulting the older one.

The only encyclopedia to rival Kirk–Othmer is Ullmann's Encyclopedia of Industrial Chemistry, M. Bohnett and F. Ullmann editors, Weinheim: Wiley-VCH. It was first published in 1914 and this, the sixth edition, appeared as a 40-volume set in 2003. It has a more international approach than Kirk–Othmer and is available online to subscribers.

The Encyclopedia of Polymer Science and Engineering, 3rd ed., J. I. Kroschwitz, editor (12 volumes plus supplement and an index volume), Interscience, New York: 2003-2004, provides comprehensive coverage of polymer chemistry.

The Encyclopedia of Chemical Processing and Design, J. J. McKetta and R. G. Anthony, editors, New York: Dekker; has a chemical engineering orientation. It had run to 69 volumes by 2002 but the publication process seems to have run out of steam. As it started in 1976, it is perhaps inevitable that the approach is inconsistent. Individual articles are worthwhile but the content is unpredictable.

R. D. Ashford, Dictionary of Industrial Chemicals, 2nd ed., London: Wavelength; 2002, and A. Comyns, Encyclopedic Dictionary of Named Processes in Chemical Technology, Boca Raton, FL: CRC Press; 3rd ed., 2007 are useful reference works.

Some consulting companies publish reports on a continuing basis that contain a wealth of up-to-date information on chemistry, engineering, and markets of numerous industrial chemicals. These are quite expensive, however, and are usually found only in industrial libraries, the subscriber agreeing to keep the information confidential. One such program is entitled Process Evaluation and Research Planning (PERP Program) Nexant Inc./ChemSystems, 44 South Broadway, White Plains, NY 10601-4425 USA, which covers in depth the chemistry, engineering, and market data for many of the basic petrochemicals as well as important specialty chemicals. We used to have great respect for the Chemical Economics Handbook, Stanford Research Institute, Menlo Park, CA, but since it was taken over by IHS (Information Handling Services) we confess we have not seen a copy. It is available by annual subscription or individual report.

I.4.2 Books

Before the spectacular growth of the chemical industry after World War II, three classic books appeared that encompassed much of what was done at that time. These books have been repeatedly revised and updated and, although they seem old-fashioned in some ways, they are certainly worthy of mention. The oldest and also, because it has been updated, the newest is, J. A. Kent and E. R. Riegel, Kent and Riegel's Handbook of Industrial Chemistry and Biotechnology, 11th ed., New York: Springer; 2007. Riegel first appeared in 1928 as Riegel's Handbook of Industrial Chemistry and is now a multi-author survey of the chemical and allied products industry.

Chemicals are discussed from the point of view of the consumer in an interesting and original book, B. Selinger, Chemistry in the Market-Place, 5th ed., Sydney: Harcourt Brace; 1998. Selinger is a pioneer of the Australian consumer movement and chaired a committee on toxic waste disposal. He describes the formulation of many domestic products together with the reasons for the various additives and the theory behind them.

P. J. Chenier, Survey of Industrial Chemistry, 3rd ed., New York: Kluwer Academic-Plenum; 2002, contains well-written thumbnail sketches of about a hundred industrial organic chemicals plus a few inorganics. It describes some economic aspects of the industry but is strongly United States oriented. Handbook of Petrochemicals Production Processes, R. A. Meyers, editor, New York: McGraw Hill; 2005, is described as a handbook, but is more a multi-author encyclopedic description of 53 industrial process technologies for producing 18 different petrochemicals.

S. Matar and L. F. Hatch, Chemistry of Petrochemical Processes, Boston: Gulf Professional Publishing, 2nd ed., 2001, is a competent exposition of petrochemistry, weak on social and economic implications but redeemed by excellent flow diagrams. Regrettably the second edition is changed only slightly from the first. Some will prefer R. A. Meyers, Handbook of Petroleum Refining Processes, 3rd ed., New York: McGraw Hill; 2003.

The University of York (UK) Chemical Education Centre publishes regular editions of D. Waddington et al., The Essential Chemical Industry, 5th ed. 2010. Each chapter deals effectively with a different chemical.

On the historical side, P. Spitz, Petrochemicals: The Rise of an Industry, New York: Wiley; 1988, contains fascinating detail of the early petrochemicals industry. P. J. T. Morris, editor, has complied From Classical to Modern Chemistry: The Instrumental Revolution, Royal Society of Chemistry, London, 2002, which deals with the impact that advances in instrumentation, especially in environmental analysis and process control, have made on what chemists and chemical engineers do and how they think about their subject. The UK Chemical Industries Association has produced Development of the UK Chemical Industry: A Historical Review, CIA, London, 2000. Tony Travis et al. have recently published in paperback Determinants in the Evolution of the European Chemical Industry, 1900–1939: New Technologies, Political Frameworks, Markets and Companies, Heidelberg: Springer; 2010.

I.4.3 Journals

A serious student of the chemical industry must follow the trade press whose range of interests includes new products and processes, changes in the structure and prospects of the industry, takeovers and trades, mergers and demergers, as well as economic trends.

A selection of news magazines for English-speaking readers includes Chemical and Engineering News (weekly, ACS, Washington DC); Hydrocarbon Processing (monthly, Gulf Publishing, Houston, TX), Chemistry and Industry (fortnightly, Society of Chemical Industry, London), and Chemistry World (Royal Society of Chemistry, London). European Chemical News has died but its daughter publication, Asian Chemical News (Reed Business Information, UK), started in 1994 and appears to be thriving. IHS (Information Handling Services) has acquired two important journals, Chemical Week (weekly, IHS Inc., 140 East 45th Street, 40th Floor, New York, NY 10017; 133 Houndsditch, London EC3A 7BX) and ICIS Chemical Business, which formerly was Chemical Market Reporter. This last carried a comprehensive list of U.S. prices of almost all widely sold chemicals, but the last list appeared in 2006. Present prices can be obtained from Chemical Week by subscription. For those who are financially challenged, there is an ICIS weekly newsletter that can be e-mailed free, and this can be strongly recommended.

I.4.4 Patents

Patents are a device whereby the government grants inventors the sole right to exploit their inventions for a period of 20 years in the United States and the European Community, and similar periods in other countries. In return, the inventors disclose details of their inventions in their patent specifications. Recent legislation in the United States has extended the life of a pharmaceutical patent to 22 years under certain circumstances and similar patent term restoration has been enacted in Europe.

Patents lie at the heart of a developed society. It is difficult to see how innovation could take place if innovators were not rewarded for their efforts. I knew that a country without a patent office ... was just a crab, said Mark Twain, and couldn't travel any way but sideways or backwards. Meanwhile, the patent literature has grown exponentially. In the United States, it took about 200 years to amass four million patents, the four millionth having been issued in 1976. It took only 15 years to accumulate one million more patents, and U.S. Patent 5,000,000 was issued on 19 March 1991 to L. O. Ingram et al. It described the use of modern biotechnology to produce one of the oldest synthetic organic chemicals – ethanol. Patent 7,000,000 was issued in 2006, and by 17 May 2011 the number had reached 7,950,000.

Patent specifications are a major source of technical information. They often disclose information at a much earlier date than the scientific literature; sometimes they are the only source of such information. Negative results often appear in patents but not in scientific journals, and knowledge of what has been tried without success may save the working scientist much time.

Academic scientists shun patents because the introductions and claims are written in legal jargon with long convoluted sentences. Librarians shun them because they are published as individual items and are difficult to collect and bind. They have, however, one overwhelming advantage. They are classified by subject and can be subscribed to in this way, a copy of a U.S. patent costing $3.00.

Patent applications are numbered consecutively as they are received by the U.S. Patent Office (U.S. serial number) and, when the patent is granted, it is assigned another number (U.S. patent number). Other patent offices do the same.

Brief accounts of patents appear in the chemical trade literature. Chemical Abstracts publishes a numerical patent index that lists each patent number together with its corresponding Chemical Abstracts abstract number, country of origin, and serial number. It also provides a worldwide list of major patent offices and their addresses. Chemisches Zentralblatt (Akademie Verlag, Berlin) offers a similar service together with a guide to its use (Chemisches Zentralblatt: das System). Derwent (Thomson/Derwent, 14 Great Queen Street, London WC2 5DF, UK) publishes analyses and abridgements of patents from every country classified by subject, and provides monthly bulletins, for example, Organic Patents Bulletin and Pharmaceutical Patents Bulletin. Derwent has contributed greatly to making patent literature available.

The Official Gazette, copies of patents, coupon books (a convenient way to pay for copies), listings of patents by subject, copies of foreign patents, and much other information may be obtained from the Commissioner of Patents and Trademarks, Washington DC 20231. Although many official and commercial organizations exist to help the student of the patent literature, a thorough search can be conducted only at the National Patent Library, Washington DC.

In the United Kingdom, the equivalent of the Official Gazette is the Patents and Design Journal (PDJ), and it and other information are available from the Patent Office, Concept House, Cardiff Road, Newport, NP10 8QQ. The departure of the Office from London has been compensated for by a Central Inquiry Unit, telephone [phone], website www.patent.gov.uk. A thorough search can be carried out at the British Library (Patents Section), 96 Euston Road, London NW1 2DB.

Information on subject codes and many other aids to patent searching may be found in Kirk–Othmer (Section I.4.1). Highly praised for its clarity and sound advice is The Business of Invention, P. Bissel and G. Barker, Wordbase, Halifax, West Yorkshire, UK.

Access to patents has been simplified greatly by computerized searching of patent databases of which Derwent, Chemical Abstracts, Inpadoc, and esp@cenet are the most important. The United States (www.uspto.gov), European (www.european-patent-office.org/inpadoc), and British Patent Offices (gb.espacenet.com) are all online. Delphion Research, founded in 2000, has established an intellectual property network that can be subscribed to at a variety of levels ranging from full premier membership to a one-day pass. It enables one to perform text searches of United States, European, and Japanese patents, plus other intellectual property resources. Searching can be done by patent number or subject. WIPO, the World Intellectual Property Organization, based in Geneva, produces many CD-ROM and online publications dealing with the state-of-play of patents throughout the world. This has become more important as more countries have come into line with the GATT (General Agreement of Trade and Tariffs) regulations.

Although use of these databases requires skill, the user is rewarded by the access these bases provide to vast amounts of information. It is said that the Japanese have been able to accomplish a great deal in the chemical industry because of their skill in reading and interpreting patents. As the industry becomes more and more competitive, it is important to monitor trends, to know what other companies are doing, and to avoid duplication. The patent literature can contribute more than any other source to knowing what your neighbor is doing, an important concept in today's technical world where an inventor can bring a new frame of reference to someone else's invention to create new and unanticipated goods and services.

I.4.5 Statistics and Internet Sources of Information

Students of the commercial side of the chemical industry will require access to statistics of production and consumption. We have given sample statistics in this new edition but have been hindered by the fact that most of the revision was performed before the appearance of data for 2010. However, 2009 was a year of recession, so that the use of 2009 figures gives a misleading impression. In general, therefore, we have used 2008 as a base year, although we have updated in various areas.

Comprehensive U.S. statistics were formerly published annually by the United States International Trade Commission as Synthetic Organic Chemicals: United States Production and Sales. Publication ceased after 1994 on the spurious grounds that the data were available from other sources. The National Petroleum Refiners' Association (NPRA) took over some of the operation and makes the information, mainly on petrochemicals, available to member companies.

Various publications appear annually. The Chemical Manufacturers Association produces the handbook. It contains general information about the chemical industry including sales, volumes, pollution and environmental problems, and trends. The U.S. Business and Defense Services Administration publishes the Chemical Statistics Directory and the United States Office of Domestic Commerce, Chemical and Drugs Section, publishes its Industry Report.

The American Chemical Society has a website, www.chemistry.org, that gives links to sources of industrial data, usually, let it be said, to the relevant issues of Chemical & Engineering News (see below), which is an ACS publication.

Figures for the major chemicals plus much information about companies, employment, and related topics are published more rapidly in Chemical & Engineering News at the end of June or the beginning of July of the subsequent year. Thus the data for 2009 were published in the 5 July 2010 edition. An important major source is the Guide to the Business of Chemistry, American Chemistry Council, 1300 Wilson Blvd., Arlington, VA 22209. The United States Bureau of the Census (www.census.gov/compendia/statab/) has statistics for the NAICS group 325 and its subgroups (see Section I.2) at http://factfinder.census.gov/servlet/IBQTable?_bm=y&-_skip=300&-ds_name=AM0831GS101&-_lang=en. The results of the more detailed 2010 census should be available soon. The Statistical Abstract of the United States is produced by the U.S. Census Bureau and has heavily aggregated data about chemicals.

Publications by the United Nations and the UK Chemicals Industry Association are fairly light on statistics, but detailed figures may be obtained rather belatedly from government sources in most countries. In the United Kingdom, disaggregated figures appear relatively quickly in the Business Monitor, HMSO, London, and are summarized in, for example, Business Monitor, Report on the Census of Production, summary volumes published occasionally, HMSO, London.

In Europe, too, many useful data and some comments are published by the industry association CEFIC (Centre Européen des Fédérations de L'industrie Chimique) and by their subsidiary APPE, the Association of Petrochemicals Producers in Europe, who produce an annual Activity Review of exceptional interest. CEFIC material is most easily available online at www.cefic.org and www.petrochemistry.net. They have as members a range of associations dealing with lower olefins, aromatics, acetyls, acrylonitrile, amines, ethanol, acrylic monomers, plasticizers and intermediates, fuel oxygenates, ethylene oxide and derivatives, methanol, phenol, propylene oxide and glycols, oxygenated solvents, hydrocarbon solvents, styrene, and coal tar chemicals. Each contributes its own reports.

The most important academic database is that of the Institute of Scientific Information (ISI), known as the ISI Web of Knowledge (www.isinet.com/isi). Starting with a science citation index, they now also operate social science, and arts and humanities indexes. Membership of a subscribing institution is necessary. The NIST Chemistry Webbook (webbook.nist.gov/chemistry) is open to all and provides chemical and physical property data on over 40,000 compounds.

Finally and extremely useful are the Chemical Company Annual Reports that are published online. Among the color photographs of Chief Executive Officers, nuggets of valuable information are often to be found. They can all be accessed by search engine.

Chapter 1

The Evolution of the Organic Chemicals Industry

The United States, Western Europe, and Japan are the most complex societies that have ever existed. Division of labor has been carried to the point where most people perform highly specialized tasks and rely on many others to provide them with the goods and services they need. In return for these goods and services, they provide their outputs to satisfy the needs of others. All men are brothers in a material sense just as they should be in a moral sense.

The various segments of the economy are interrelated in a complex way. For example, manufacturing industry draws heavily on the output of the mining sector by buying iron ore from which to make steel. In turn, it may convert that steel to machinery to sell back to the mining industry where it will be used in mining operations.

1.1 The National Economy

The interdependence of a society's activities may be seen more clearly if its economy is divided into specific industries or groups of industries. Until 1997 this was done according to the standard industrial classification (SIC) of the U.S. Bureau of the Census, but this has now been revised as the North American Industry Classification System (NAICS). Table 1.1 shows the main sectors of a developed economy. The manufacturing sector is designated sections 31–33. Each industry within it is allocated a three-digit code number, chemical manufacturing being 325. Sectors, subsectors, and sub-subsectors of the industry are then allocated four-, five-, and six-digit numbers, For example, Basic Chemical Manufacturing is 3251, Dyes and Pigments are 32513, and Synthetic Organic Dyes and Pigments are 325132. Broadly speaking, the basic chemical industry (NAICS 3251) isolates or synthesizes chemicals, whereas the allied products industries (NAICS 3252–3259) modify, formulate, and package products based on those chemicals. The NAICS codes for the chemical industry are shown in Table 1.2.

Table 1.1 Main Sectors of a Developed Economy.

Source: United States Census Bureau, Annual Survey of Manufacturers 2010.

Table 1.2 Breakdown of Manufacturing Category NAICS 31–33 (2009a)

The combined value of shipments is the total sales of the industry. Value added is defined as the value of shipments less cost of raw materials and cost of manufacture (Appendix A). Value added per employee is the productivity. Among the specific items in the cost of manufacture are containers, fuels, purchased electricity, bought-in services, and contract work. It is thus the value added to all the inanimate inputs to an industry by the people working in it. The total value added throughout the economy is the gross national product (GNP), the sum of wealth produced by the nation, in this case about $14.35 trillion for the United States in 2009, amounting to $46,740 per person.

The manufacturing sector contributed about $2.3 trillion of value added, which was about a sixth of that year's GDP (gross disposable product = GNP − net income from abroad). The figure has dropped from about 40% in the past generation. This underscores the point that manufacturing, the traditional means for creating wealth, is no longer the major part of our national economy and has to some extent been replaced by services.¹ A similar shift has occurred in Europe and the data are shown in Figure 1.1.

Figure 1.1 Services make up almost half of the European Union GDP. Mnufacturing makes up 13.5% and chemicals 1.1%.

(Source: CEFIC.)

In 1991 the chemical industry provided the largest amount of value added among manufacturing industries and, while surrendering the position briefly, it was firmly in position by 2009 (a bad year). Its main competition has been from Food Manufacturing (311), Transportation Equipment (336) and Computers and Electronic Products (334). In shipments, in 2009, it tied with Food Manufacturing (311) and was followed by Transportation Equipment (336), Petroleum and Coal Products (324), and Computers and Electronic Products. The Chemical Industry ranks only sixth in the number of employees. Value added per employee is the usual measure of productivity, and here the chemical industry ranks third after Beverage and Tobacco Products and Petroleum and Coal Products.

These data are shown in Figure 1.2.

Figure 1.2 Shipments and value added in manufacturing industry, United States 2009.

(Source: U.S. Bureau of the Census.)

1.2 Size of the Chemical Industry

The world chemical industry produced sales of about $3 trillion in 2008 (1871 billion euros in 2009); the euro:dollar exchange rate varied between 1.2 and 1.4 over these years). It provided jobs directly for more than 7 million people and indirectly for 20 million. The division by product sector is shown in Figure 1.3 and by region in Figure 1.4. The United States accounted for about 21% of this business, the European Union (25 countries) for 24%, and Japan for about 6.4%. Asia-Pacific, a relative newcomer, accounted for 38% if Japan is excluded. Other regions are much less significant. Fourteen years ago, the United States accounted for a third and Japan for about 15%, so there has been a huge swing to Asia-Pacific. This will be discussed in Chapter 2. During the previous 10 years, world trade in chemicals grew more than 1.6 times faster than that of global output and has risen to an estimated €970 billion (US$ 1.2 trillion). Almost 45% of the value of the global chemical industry is traded, and more than 35% of this world trade is intracompany in nature.

Figure 1.3 World chemical market 2008: total $3 trillion.

Figure 1.4 World chemical market by region (2009); total 1871 billion euros.

(Source: CEFIC Chemdata International.)

EU 27 embraces the expanded European community including the 12 Eastern European countries recently admitted. NAFTA is the North America Free Trade Organization – the United States, Canada, and Mexico. Rest of Europe includes Switzerland, Norway, and the Central and East European countries not in the EU; Other is Oceania and Africa.

Figure 1.3 shows that commodity chemicals (inorganics plus petrochemicals) make up half the global market with specialties (life science and performance chemicals) making up the other half. Performance chemicals include specialty surfactants, electronic chemicals, specialty adhesives and sealants, explosives, catalysts, cosmetic additives, dyes and pigments, flavors and fragrances, specialty lubricants, oil field chemicals, paint additives, photographic chemicals, photovoltaic chemicals, plastics additives, and water treatment chemicals. Life science chemicals include pharmaceuticals, agrochemicals, fine chemicals, animal health products, nutritional products and vitamins, diagnostic substances, and biological products.

The division by sector, although the categories do not match NAICS categories precisely, suggests that the world pattern is close to the U.S. pattern. For example, NAICS 32532 + 32541 (pharmaceuticals and agrochemicals) comes to 27.7% compared with life science chemicals at 28%; inorganics (32512 + 32518 + 32534) comes to 9.1% compared with 9%; and petrochemicals + textiles (32511 + 32519+ 3252) comes to 39% compared with 40%. This is perhaps surprising in that one would expect the United States to have a higher proportion of sales of the higher value specialties.

The U.S. industry had sales of about $300 billion in 1992, $460 billion in 2000, and $751 billion in 2008. The division by shipments is shown in Figure 1.5 and Table 1.3, which also show the division by value added. Petrochemical manufacturing has easily the highest value added per employee, reflecting the small labor force required to operate the huge, semiautomatic cracking units. The same, but to a lesser extent, applies to fertilizer manufacturing, which is based on huge ammonia plants.

Figure 1.5 Subdivisions of the chemical industry by employees, sector, and value added.

Table 1.3 United States Chemical Industry 2008.

Source: U.S. Census Bureau, American Factfinder.

Comparison of the shipments and value added in Figure 1.5 shows that fine chemicals, such as pharmaceuticals, pesticides, and toilet preparations, make a larger contribution to the chemical industry's value added than they do to its shipments. They tend to be high-priced products with specialized markets, and their manufacture is less capital- and more labor-intensive than the manufacture of the run-of-the-mill general chemicals. Their importance to the chemical industry is best represented by the value-added figure, which, for example, emphasizes the overwhelming importance of the pharmaceutical sector, which accounts for 25.9% of shipments but 40.2% of value added.

The total chemicals sector in the United States grew by 3.5%/year between 1991 and 2001 but by only 0.9%/year between 1999 and 2009. The basic chemicals sector shrank by 0.4%/year between 1999 and 2000 and the organic chemicals sector shrank by 0.2%/year over the same period. Thus the organics chemicals sector showed lackluster performance over the 1990s and early 2000s. Production dipped dramatically in 2001 and recovered strongly, reaching a peak in 2007 but slumping by about 20% in the following two years. At the time of writing, a 2010 recovery is probable, but the chemical industries of the Western world and Japan have had a difficult two decades, in contrast to the vigorous growth of earlier years.

1.3 Characteristics of the Chemical Industry

The chemical industry has certain well-defined characteristics that govern its attitudes and performance. These are listed in Table 1.4; we shall discuss the first six in this chapter and the remainder in Chapter 2.

Table 1.4 Characteristics of the Chemical Industry.

1.3.1 Capital Intensity and Economies of Scale

The chemical industry is capital intensive. It produces huge quantities of homogeneous materials, frequently liquids or gases, which can be manufactured, processed, and shipped most economically on a large scale. This was less so through the nineteenth century until World War II. The early chemical industry used more general purpose equipment and operated batch processes that required little capital investment but had high labor costs. Typical of such processes were the Leblanc route to sodium carbonate and the benzenesulfonate route to phenol (Section 9.1).

The petroleum refining industry was the first to convert to continuous operation on a large scale. The engineering developed for the petroleum industry was applied to the chemical industry after World War II. Plant sizes escalated as dramatic economies of scale became possible. The capacity of a typical ethylene cracker rose from 32,000 metric tons per year in 1951 to 450,000 metric tons per year in 1972. This was regarded as an upper size limit until the early 1990s when plants with 680,000 metric tons per year capacity were built. Meanwhile, in 2001, BASF/Fina brought on stream a 900,000 metric ton ethylene plant in Port Arthur, Texas, and SABIC has built a 1,200,000 metric ton plant at Al Jubail on the Gulf Coast of Saudi Arabia. The Port Arthur plant will incorporate a metathesis unit described in Section 4.14. Even the residual butadiene/isobutene will make this the world's largest C4 olefins plant.

Currently there are few batch processes of any size in operation for commodity chemicals, and substantial economies of scale are a characteristic of the petrochemical industry. They arise not only from improved technology but also from purely geometric factors. The capacity of a great deal of chemical equipment (e.g., storage tanks and distillation columns) varies with its volume, that is, the cube of its linear dimensions. The cost, on the other hand, is the cost of a surface to enclose the volume and varies with the square of the linear dimensions. Consequently, cost is proportional to (capacity)²/³. This is called the square-cube law. It does not apply to all equipment. The capacity of a heat exchanger depends on its surface area so cost is proportional to (capacity)1 and there are no economies of scale. Control systems are not affected by capacity at all, so cost is proportional to (capacity)⁰ and economies are infinite. It is claimed that for a modern petrochemical plant overall, cost is proportional to (capacity)⁰.⁶.

Labor costs are a small proportion of petrochemical plant cash costs (HDPE 2.5%, benzene 3.5%, purified terephthalic acid 5.7%, acrylonitrile 7.3%) but they contribute to economies of scale, because they do not increase proportionately to increase in size of the plant. Doubling the size of a unit does not double labor cost. Indeed, because of automation, the labor cost may increase only 10–20%.²

The size and complexity of a modern chemical plant demand high capital investment. Although other industries invest more capital per dollar of sales, the chemical industry has the highest investment of current capital. That means that the chemical industry invests more each year than do other capital-intensive industries such as mining, where equipment once bought remains in service for many years.

Capital intensity has a number of