Petroleum and Downstream Products Oil products, from feedstocks to plastics, created the modern world.

MICHAEL J. FELTON

etroleum has been the fuel for the dramatic of Ohio and changes that occurred during most of the Atlantic Richfield P20th century. Ever since it began to be (ARCO), formerly exploited, that dark liquid found so abundantly in Atlantic certain regions of the world has been both a fuel Storage Co., and and source of material product for the chemical merged with industry. In both transportation and chemical prod- (Standard Oil of Indiana). uct development, advances in petroleum processing Standard Oil also exported its refined and crude were made for the same reason—the replacement oils, which led to industry development in other of natural products. countries. In 1892, a British seashell importer’s son Starting in 1854, George Bissell became fasci- commissioned a tanker ship to transport Russian nated with “rock oil” that was demonstrated at his kerosene to China and Singapore. This tanker was alma mater, Dartmouth College. Bissell the first for a new company, called saw the commercial potential of this Shell, which ended up merging with product to address the dependence its competitor, the Royal Dutch on whale or coal oil for illuminating Company of the Netherlands, in lamps. He organized a company and 1907. commissioned a Yale chemist to Using petroleum for lamp oil and analyze the oil, which indicated that lubricants left much of the crude oil lubricants and waxes could also be unused. Fractions such as gasoline produced. Other individuals primari- and naphtha were often dumped. ly sold rock oil as a medicine, and However, they would later provide some was sold as lamp oil. The inexpensive fuel for two inventions company now had to obtain the oil, that would change the world: the car and Bissell hired Edwin Drake to drill and plastics. a well to extract oil. Most other rock oils were either collected at the surface or were Plastics and Synthetic Polymers Top: Oil refinery, Photodisc obtained from wells drilled for salt extraction. The first truly synthetic plastic, Bakelite, was Center: Wallace Carothers in 1935, Drake struck oil on August 27, 1859, and combined made in 1907 by Leo Baekeland. He combined Chemical & Engineering News with refining technology invented in Britain by phenol and formaldehyde to produce a hard plas- James Young, the oil industry was officially started. tic—the first of what are known today as phenolic Many small oil companies started as commer- resins. The condensation reaction between cial oil production spread, and by 1869, Cleveland, phenol and formaldehyde produced a ther- OH, was the oil capital of the world. There, in moset plastic that could be molded but 1870, John D. Rockefeller formed the Standard could also be heated again and remolded. Oil Company from several oil companies in which Unlike shellac, it would not burn, boil, melt he was involved. Rockefeller’s negotiation talent, easily, or dissolve in solvents, but its most along with his various partners’ strengths, allowed important use was as an electrical insulator. Standard Oil to become so dominant that it In 1927, the patent on Bakelite expired, and the inspired the Sherman Anti-Trust Act, which was Bakelite Company was eventually acquired by used to divide the company in 1911. The various Union Carbide. parts of Standard Oil are still well known today. Although natural rubber was being supplied For instance, ExxonMobil was formed from Stan- from Asia and South America, the price of raw dard Oil of (Esso and ) and natural rubber was highly volatile, which led to the Standard Oil of New York () years after they search for a replacement. In 1901, Russian Ivan were separated. Other Standard Oil progeny Kondakov produced rubber by reacting include ChevronTexaco (Chevron was formerly dimethylbutadiene with potash. In 1909, Fritz Standard Oil of California) and BP. BP purchased Hofmann used a process similar to Kondakov’s at

ENTERPRISE OF THE CHEMICAL SCIENCES 11 Germany’s Bayer to produce polyisoprene, but it using sodium to form polybutadiene. I.G. Farben was not marketed because it proved to be too called its rubber “Buna” (butadiene and Na) and expensive. A year later, another Russian, Sergey V. soon began producing Buna S and Buna N, which Lebedev, made polybutadiene from ethyl alcohol. contained styrene and nitrile, respectively. Buna N Hofmann finally succeeded in 1912 in making was an economic success—even during the depres- PETROLEUM AND an economic rubber. Polymethylisoprene, or sion—because it was oil resistant, unlike most DOWNSTREAM PRODUCTS “methyl rubber,” was less expensive because it other natural and synthetic rubbers. could be made from acetone. Rubber prices DuPont provided two major stepping-stones crashed the following year, halting production of during the 1930s. First, in 1931, researchers at the methyl rubber, but Germany revamped its manu- DuPont Research Station in , led by facture during World War I when both Bayer and Wallace Hume Carothers, synthesized neoprene. BASF collaborated in its production. Second, Paul Flory—who in 1974 was awarded the Nobel Prize in Chemistry—created a mathemati- I.G. Farben, ICI, DuPont, and the Soviet Union cal theory of how polymerization and cross-linking In spite of Germany’s defeat in World War I, ties occur. Carothers’ group at DuPont went on to between its chemical companies remained, and in synthesize other forms of neoprene (polychlorobu- 1925, a conglomerate was formed called Inter- tadiene) and polyester, and in 1934 the group essen-Gemeinschaft Farbenindustrie AG, better discovered nylon. Neoprene was eyed for rubber known as I.G. tire production but proved unsuccessful; however, Farben, from it was one of the first polymers produced from GLOBALIZATION companies such as petroleum sources. Petroleum and petrochemicals have always been a Agfa, Casella, In the late 1930s, ICI developed two new poly- global industry as demand and supply have shifted BASF, Bayer, mers, polyethylene and poly(methyl methacrylate). around the world. One region where demand is increas- Hoechst, Hüls, Although polyethylene could not be used to insu- ing very rapidly is Asia. and Kalle. The late high-voltage wires, it was an excellent insulator Japan has led the region in economic development, British followed of high-frequency cables, such as those used in but as the economies of South Korea, Thailand, Malaysia, suit, merging long-distance communications, and even radar. Singapore, Indonesia, and Taiwan have developed over Nobel Explosives, DuPont and ICI had a cross-licensing agreement the past 30 years, demand for petrochemicals has risen Brunner Mond, allowing DuPont to develop and market these new in kind. United Alkali, and polymers in the while ICI gained The rapid increase in demand has many companies British Dyestuff access to nylon and other DuPont polymers. investing in increased capacity, with most of it located in Corp. into Imperial DuPont began commercial production, but not China. Foreign companies investing in China are required Chemical Indus- mass production, of neoprene in 1933. This and to have local partners; BASF is building an ethylene tries (ICI) in 1926. other polymer plants depended on feedstock from cracker with Yangzi Petrochemical, BP has partnered Although the various sources, but most used coal tar or other with Sinopec, and Shell is working with CNOOC. Other United States did coal by-products. Soviet synthetic rubber factories companies are increasing production in order to export not merge its used an alcohol-based process, but in 1936, the to China. Formosa Plastics Corp. (Taiwan), Mitsui chemical compa- Soviets built a petroleum-based polybutadiene Chemicals (Japan), and Nippon Petrochemicals (Japan) nies into a plant, providing a glimpse of the future. are all expanding propylene production for domestic and conglomerate, it export demand. had DuPont—one War and the Rise of Petrochemicals With the increased demand in Asia and throughout of the few U.S. The German government funded rubber research the world, oil-rich regions such as the Persian Gulf will chemical compa- as well as coal liquefaction research during the continue to supply the extra demand for crude oil, but nies expending 1930s in an aim to become self-sufficient. The they are also working on supplying higher-value products significant United States was less prepared and accelerated such as petrochemicals. For example, countries like resources on R&D. its synthetic rubber plan after the Japanese cut off Saudi Arabia are investing more resources into producing These three major access to natural rubber from Asia. higher-value products than crude oil. The Saudi company companies, and the The United States assigned cooperative SABIC (Saudi Basic Industries Corp.), started in 1976, Soviet Union, work to key industries as part of the war effort. has rapidly grown to become a major producer of petro- made many of the Research into synthetic rubber production was chemicals. SABIC is now the third-largest ethylene pro- advances in poly- to be conducted jointly by the four major rubber ducer in the world. Outside companies are also working mer chemistry manufacturers—Goodyear, B.F. Goodrich, the with the state oil companies in this region. Japan’s between World U.S. Rubber Company (Uniroyal), and Fire- Sumitomo Chemical is working with Saudi Aramco War I and World stone—as well as the Standard Oil companies (Saudi Arabia’s state oil company) on a large refinery War II. and several chemical companies. Before the war, petrochemical project. The first chal- Standard Oil of New Jersey (Exxon) had devel- lenge after World oped technologies to produce butadiene from War I was the devel- petroleum instead of coal. opment of a better synthetic rubber. I.G. Farben The Rubber Reserve Company determined began research into synthetic rubber in 1926, but that I.G. Farben’s Buna S would be the material

Above: Polystyrene plant in China, the Soviet Union built the first pilot plant in 1930. used for the bulk of rubber production, made possi- Chemical & Engineering News The German and Soviet rubbers were similar, ble by seized patents. Dow Chemical was placed in

12 ENTERPRISE OF THE CHEMICAL SCIENCES charge of styrene production, which also involved withstand the heat of pasteurization, leading to use Monsanto, Union Carbide, and Koopers. The U.S. in consumer products such as food containers. By government provided about $700 million for the 1961, there were at least nine North American construction of plants. producers of polypropylene, but the Italian compa- Other plastics were also seen as essential to the ny Montecatini sued Phillips Petroleum for patent war effort. Polyethylene from ICI became the infringement. Phillips Petroleum won patent PETROLEUM AND secret that allowed the Allies to build lightweight protection in 1983. Since then, polyethylene and DOWNSTREAM PRODUCTS radar systems that could be loaded onto a plane or polypropylene have become the most widely used ship. Plexiglas and Lexan (acrylics) provided plane plastics in the petrochemical trade. canopies that were stronger and lighter than glass. Poly(vinyl chloride) (PVC) was finally perfected The Ethylene and Propylene Kings by Waldo Semon at B.F. Goodrich and used to Production of plastics reached more than 107 make raincoats and bug nets, and in the form of billion pounds in 2003 in North America, and Saran made by Dow Chemical, although not final products, 51 it protected planes during billion pounds of ethylene transport. Teflon was essen- and 35 billion pounds of tial in the separation of propylene were produced, uranium-235 from uranium- accounting for a large seg- 238 under extremely corro- ment of the industry. Ethyl- sive conditions for the ene and propylene have Manhattan Project. become the predominate The oil industry was feedstocks because they can pushed to dramatically be used to produce a large increase production to meet array of plastics. the demand for motor and More than half of ethyl- aviation fuel as well as new ene is used to make polyeth- petrochemicals needed for ylene for everything from rubber (butadiene and pipes to milk jugs, but it can styrene) and other polymers. The demand for avia- also be converted to ethylene oxide to produce tion fuel and butadiene overlapped because detergents and to ethylene glycol for food packag- butylene and butane were needed to make high- ing and textiles. Ethylene is also used to make octane aircraft fuel. styrene monomers, which can be polymerized to The oil industry turned to technology it had make polystyrenes like Styrofoam and styrene- developed in the 1920s and 1930s to meet the butadiene rubber for automobile tires. Propylene is expanded demand. Catalytic cracking, alkylation, used to make polypropylene plastics and to make and catalytic reforming were all applied to increase acrylonitrile for producing acrylic polymers, pro- usable products from a given amount of crude oil. pylene oxide for polyurethanes, oxo alcohols (PVC After the war, U.S. refining capacity increased plasticizers), cumene for epoxy resins and polycar- 29%, and the products from refineries had become bonate, and isopropyl alcohol. significantly more valuable. Benefiting from the In 2003, Dow was the largest producer of ethyl- fact that before the war the United States had ene in the world. The chemical company first 71% of the world’s refining capacity, U.S. compa- entered the plastics market in 1935, and in 2000, it nies were clear leaders in oil refining and the new acquired another key chemical company, Union field of petrochemicals. Carbide. ExxonMobil comes in second, producing more than 16.6 million pounds of ethylene. In Commercial Explosion addition, many producers of ethylene and propyl- After World War II, new uses for plastics and a ene manufacture some of their products as joint dramatic increase in consumer demand for plastics ventures with other companies, including many created an extremely healthy petrochemical state oil companies. For instance, Dow operates industry. In the early 1950s, Amoco, Phillips joint ventures with Petrochemical Industries Petroleum, and DuPont began working on devel- Company, the state oil company of Kuwait, and oping new polymers. In 1953, Karl Ziegler at the with NOVA Chemicals, a Canadian ethylene Max Planck Institute for Coal Research discov- producer. ered that polyethylene could be made at much The volume and variety of manufactured poly- lower pressures using an organometallic catalyst mers have increased dramatically since 1907, and than the very high pressures that ICI was using. the trend should continue for the foreseeable The resulting polymer also had a higher density future. While production of feedstocks has and higher melting point. matured, new polymers and new uses for existing Polypropylene was discovered around the same polymers will continue to drive the industry. time, but its central patents were bogged down in Human history is categorized by the materials used—the Stone Age, the Iron Age, the Bronze Center: Dow Chemical Co. ad, litigation. However, in 1957, Hercules began 1950, Chemical & Engineering making polypropylene to use in bottles that could Age—are we in the Plastic Age? ◆ News

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