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Fischer Tropsch Synthesis

Fischer Tropsch Synthesis

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Published by: rafaeldesmonteiro on Sep 28, 2009
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06/28/2013

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Foreword
In general, there are two approaches to the production of substitutes for crude petroleum.In one of these, the organic material is heated at high temperatures under a high pressure of hydrogen. In the other approach, the organic material is converted to a mixture of hydrogen andcarbon monoxide (syngas) and this syngas is converted to hydrocarbons by conversion oversuitable catalysts. The papers included in the present volume are concerned with the indirectliquefaction approach.The introduction of the catalytic synthesis of ammonia was widely recognized. TheNobel Prize in 1918 for chemistry was awarded to Fritz Haber for his developments that led tothe synthesis of ammonia from the elements. The development of the very high pressureammonia synthesis and its commercial success gave Germany a decided leadership position inhigh pressure process during the early part of the twentieth century. Rapidly following theammonia synthesis, the commercial production of methanol from synthesis gas was a commercialsuccess. After much work, Bergius finally was able to show that heating coal at hightemperatures under high pressures of hydrogen led to the production of liquid products. FritzFischer, director of the coal research laboratory, worked to develop a coal conversion process thatcould compete with the direct process developed by Bergius. During the 1920s, the work byFischer and coworkers led to what is now known as the Fischer-Tropsch process. The advancesin high pressure process technology led to the Nobel Prize being awarded in 1932 to Bergius andCarl Bosch; however, the Fischer-Tropsch scientific advances were not afforded this honor. TheFischer-Tropsch process also lost out to the direct coal liquefaction process in the production of synfuels in Germany during the 1935-1945 period, for both technological and political reasons.During the energy crisis of the 1970s the direct and indirect coal liquefaction processesreceived much attention. During this period the direct coal liquefaction process received moreattention in the U.S., with four large scale demonstration plants being operated. At that time, themajor goal of producing synfuels was to provide a source of gasoline and the direct liquefactionprocess provided high octane gasoline due to its high aromatics content. Today the direct coalliquefaction process is out of favor, primarily because of the high aromatics content and thereduction of the high heteroatom content which greatly exceed today’s environmentalrequirements. This, plus the advances in Fischer-Tropsch technology during the interveningthirty years, leads to the concentration of the effort to produce commercial quantities of synfuelsupon the Fischer-Tropsch technology. In addition to the fifty year efforts by Sasol that nowproduces about 150,000 bbl/day, Shell Oil (15,000 bbl/d) and PetroSA (formerly Mossgas;40,000 bbl/d) became commercial producers in the early 1990s. Sasol has brought on line a35,000 bbl/d plant in Qatar in mid-2006.The present book addresses four major areas of interest in Fischer-Tropsch synthesis(FTS). The first three contributions address the development of FTS during the early years inGermany and Japan and more recently by BP. The next section includes eight contributions thatrelate to the development of catalysts for FTS, their structure and changes that occur during use.The third section contains six contributions that relate to impact of various process conditionsupon the productivity and selectivity of the FTS operation. The final section consists of sixcontributions relating to the FTS process and the conversion of the primary products to usefulfuels. Most of these contributions are based on presentations at the 2005 Spring NationalMeeting of the American Chemical Society, held in San Diego in 2005.
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A History of the Fischer-Tropsch Synthesis in Germany 1926-45
Anthony N. Stranges
 Department of History, Texas A&M University, College Station, TX 77843-4236 
1.Introduction: twentieth-century synthetic fuels overview
The twentieth-century coal-to-petroleum, or synthetic fuel, industry evolved in threestages: (1) invention and early development of the Bergius coal liquefaction (hydrogenation) andFischer-Tropsch (F-T) synthesis from 1910 to 1926; (2) Germany’s industrialization of theBergius and F-T processes from 1927 to 1945; and (3) global transfer of the German technologyto Britain, France, Japan, Canada, the United States, South Africa, and other nations from the1930s to the 1990s.Petroleum had become essential to the economies of industrialized nations by the 1920s.The mass production of automobiles, the introduction of airplanes and petroleum-powered ships,and the recognition of petroleum’s high energy content compared to wood and coal, required ashift from solid to liquid fuels as a major energy source. Industrialized nations responded indifferent ways. Germany, Britain, Canada, France, Japan, Italy, and other nations having little orno domestic petroleum continued to import petroleum. Germany, Japan, and Italy also acquiredby force the petroleum resources of other nations during their 1930s-40s World War IIoccupations in Europe and the Far East. In addition to sources of naturally-occurring petroleum,Germany, Britain, France, and Canada in the 1920s-40s synthesized petroleum from theirdomestic coal or bitumen resources, and during the 1930s-40s war years Germany and Japansynthesized petroleum from the coal resources they seized from occupied nations. A much morefavorable energy situation existed in the United States, and it experienced few problems inmaking an energy shift from solid to liquid fuels because it possessed large resources of bothpetroleum and coal.Germany was the first of the industrialized nations to synthesize petroleum whenFriedrich Bergius (1884-1949) in Rheinau-Mannheim in 1913 and Franz Fischer (1877-1947) andHans Tropsch (1889-1935) at the Kaiser Wilhelm Institute for Coal Research (KWI) in Mülheim,Ruhr, in 1926 invented processes for converting coal to petroleum. Their pioneering researchesenabled IG Farben, Ruhrchemie, and other German chemical companies to develop atechnologically-successful synthetic fuel industry that grew from a single commercial-size coalliquefaction plant in 1927 to twelve coal liquefaction and nine F-T commercial-size plants that in1944 reached a peak production of 23 million barrels of synthetic fuel.Britain’s synthetic fuel program evolved from post-World War I laboratory and pilot-plant studies that began at the University of Birmingham in 1920 on the F-T synthesis and in1923 on coal liquefaction. The Fuel Research Station in East Greenwich also began research oncoal liquefaction in 1923, and the program reached its zenith in 1935 when Imperial ChemicalIndustries (ICI) constructed a coal liquefaction plant at Billingham that had the capacity tosynthesize annually 1.28 million barrels of petroleum. British research and development matched
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© 2007 Elsevier B.V. All rights reserved.B.H. Davis and M.L. Occelli (Editors)Fischer-Tropsch Synthesis, Catalysts and Catalysis
 
Germany’s, but because of liquefaction’s high cost and the government’s decision to rely onpetroleum imports rather than price supports for an expanded domestic industry, Billinghamremained the only British commercial-size synthetic fuel plant. F-T synthesis in the 1930s-40snever advanced beyond the construction of four small experimental plants: Birmingham, the FuelResearch Station’s two plants that operated from 1935 to 1939, and Synthetic Oils Ltd. nearGlasgow [1].Britain and Germany had the most successful synthetic fuel programs. The others wereeither smaller-scale operations, such as France’s three demonstration plants (two coal liquefactionand one F-T), Canada’s bitumen liquefaction pilot plants, and Italy’s two crude petroleumhydrogenating (refining) plants, or technological failures as were Japan’s five commercial-sizeplants (two coal liquefaction and three F-T) that produced only about 360,000 barrels of liquidfuel during the World War II years [2].The US Bureau of Mines had begun small-scale research on the F-T synthesis in 1927and coal liquefaction in 1936, but did no serious work on them until the government expressedconsiderable concern about the country’s rapidly increasing petroleum consumption in theimmediate post-World War II years. At that time the Bureau began a demonstration program,and from 1949 to 1953 when government funding ended, it operated a small 200-300 barrel perday coal liquefaction plant and a smaller fifty barrel per day F-T plant at Louisiana, Missouri. Inaddition to the Bureau’s program, American industrialists constructed four synthetic fuel plants inthe late 1940s and mid-1950s, none of which achieved full capacity before shutdown in the 1950sfor economic and technical reasons. Three were F-T plants located in Garden City, Kansas;Brownsville, Texas; and Liberty, Pennsylvania. The fourth plant was a coal liquefaction plant inInstitute, West Virginia [3].Following the plant shutdowns in the United States and until the global energy crises of 1973-74 and 1979-81, all major synthetic fuel research and development ceased except for theconstruction in 1955 of the South African Coal, Oil, and Gas Corporation’s (SASOL) F-T plant inSasolburg, south of Johannesburg. South Africa’s desire for energy independence and the lowquality of its coal dictated the choice of F-T synthesis rather than coal liquefaction. ItsJohannesburg plant remained the only operational commercial-size synthetic fuel plant until the1970s energy crises and South Africa’s concern about hostile world reaction to its apartheidpolicy prompted SASOL to construct two more F-T plants in 1973 and 1976 in Secunda.The 1970s energy crises also revitalized synthetic fuel research and development in theUnited States and Germany and led to joint government-industry programs that quicklydisappeared once the crises had passed. Gulf Oil, Atlantic Richfield, and Exxon in the UnitedStates, Saarbergwerke AG in Saarbrüken, Ruhrkohle AG in Essen, and Veba Chemie inGelsenkirchen, Germany, constructed F-T and coal liquefaction pilot plants in the 1970s andearly 1980s only to end their operation with the collapse of petroleum prices a few years later [4].In the mid-1990s two developments triggered another synthetic fuel revival in the UnitedStates: (1) petroleum imports again reached 50 percent of total consumption, or what they wereduring the 1973-1974 Arab petroleum embargo, and (2) an abundance of natural gas, equivalentto 800,000,000,000 barrels of petroleum, but largely inaccessible by pipeline, existed.Syntroleum in Tulsa, Oklahoma; Exxon in Baytown, Texas; and Atlantic Richfield in Plano,Texas, developed modified F-T syntheses that produced liquid fuels from natural gas and therebyoffered a way of reducing the United States’s dependence on petroleum imports. TheDepartment of Energy (DOE) at its Pittsburgh Energy Technology Center through the 1980s-90salso continued small-scale research on improved versions of coal liquefaction. DOE pointed out
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