User:Milton Beychok/Sandbox

The first commercial use of catalytic cracking occurred in 1915 when Almer M. McAfee of the Gulf Refining Company developed a batch process using aluminum chloride (a Friedel Crafts catalyst known since 1877) to catalytically crack heavy petroleum oils. However, the prohibitive cost of the catalyst prevented the widespread use of McAfee's process at that time.

In 1922, a French mechanical engineer named Eugene Jules Houdry and a French pharmacist named E.A. Prudhomme set up a laboratory near Paris to develop a catalytic process for converting lignite coal to gasoline. Supported by the French government, they built a small demonstration plant in 1929 that processed about 60 tons per day of lignite coal. The results indicated that the process was not economically viable and it was subsequently shutdown.

Houdry had found that Fuller's Earth, a clay mineral containing aluminosilicate (Al₂SiO₆), could convert oil derived from the lignite to gasoline. He then began to study the catalysis of petroleum oils and had some success in converting vaporized petroleum oil to gasoline. In 1930, the Vacuum Oil Company invited him to come to the United States and he moved his laboratory to Paulsboro, New Jersey.

In 1931, the Vacuum Oil Company merged with Standard Oil of New York (Socony) to form the Socony-Vacuum Oil Company. In 1933, a small Houdry process unit processing 200 barrels per day (32,000 litres per day) of petroleum oil. Because of the economic depression of the early 1930's, Socony-Vacuum was no longer able to support Houdry's work and gave him permission to seek help elsewhere.

In 1933, Houdry and Socony-Vacuum joined with Sun Oil Company in developing the Houdry process. Three years later, in 1936, Socony-Vacuum converted an older thermal cracking unit in their Paulsboro refinery in New Jersey to a small demonstration unit using the Houdry process to catalytically crack 2,000 barrels per day (318,000 litres per day) of petroleum oil.

In 1937, Sun Oil began operation of a new Houdry unit processing 12,000 barrels per day (2,390,000 litres per day) in their Marcus Hook refinery in New Jersey. The Houdry process at that time used reactors with a fixed bed of catalyst and was a semi-batch operation involving multiple reactors with some of the reactors in operation while other reactors were in various stages of regenerating the catalyst. Motor-driven valves were used to switch the reactors between online operation and offline regeneration and a cycle timer managed the switching. Almost 50 percent of the cracked product was gasoline as compared with about 25 percent from the thermal cracking processes.

By 1938, when the Houdry process was publicly announced, Socony-Vacuum had eight additional units under construction. Licensing the process to other companies also began and by 1940 there were 14 Houdry units in operation processing 140,000 barrels per day (22,300,000 litres per day).

The next major step was to develop a continuous process rather than the semi-batch Houdry process. That step was implemented by advent of the moving-bed process known as the Thermafor Catalytic Cracking (TCC) process which used a bucket conveyor-elevator to move the catalyst from the regeneration kiln to the separate reactor section. A small demonstration TCC unit was built in Socony-Vacuum's Paulsboro refinery in 1941 and operated successfully. Then a full-scale commercial TCC unit processing 10,000 barrels per day (1,590,000 litres per day) began operation in 1943 at the Beaumont, Texas refinery of Magnolia Oil Company, an affiliate of Socony-Vacuum. By the end of World War II in 1945, the processing capacity of the TCC units in operation was about 300,000 barrels per day (47,700,000 litres per day).

It is said that the Houdry and TCC units were a major factor in the winning of World War II by supplying the high-octane gasoline needed by the air forces of Great Britain and the United States.

In the years immediately after World War II, the Houdriflow process and the air-lift TCC process were developed as improved variations on the moving-bed theme. Just like Houdry's fixed-bed reactors, the moving-bed designs were prime examples of good engineering by developing a method of continuously moving the catalyst between the reactor and regeneration sections.

FCC

When the war ended, demand for aviation fuel plummeted, but the postwar hegemony of the automobile ensured a future for catalytic cracking. By that time a fluid catalytic-cracking process had made the original Houdry method obsolete

This process had first been investigated in the 1920s by Standard Oil of New Jersey, but research on it was abandoned during the Depression. In the late 1930s and early 1940s, when the success of Houdry’s process became apparent, Standard of New Jersey resumed the project as part of a consortium with Standard of Indiana, Texaco, Shell, Universal Oil Products, and other firms (including, in the early days, I. G. Farben of Germany, which had great expertise in catalysis).

In 1938, Jersey formed a consortium of eight companies, Jersey, M.W. Kellogg Co., Standard Oil Co. of Indiana, Anglo-iranian Oil Co., Universal Oil Products Co., The Texas Corp. (now Texaco Inc.), Royal Dutch Shell, and 1. G. Farben (which was dropped in 1940), called Catalytic Research Associates, or CRA. CRA's purpose was to develop a catalytic cracking process which would operate outside Houdry's patents.

Following its successful start-up in May 1942, the first Model I cracker (Fig. 13) performance was gradually improved.14 By July 1942 its feed rate was already over 17,000 b/d

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Donald Campbell, Homer Martin, Eger Murphree and Charles Tyson, who were known for their development of a process still used today to produce more than half of the world's gasoline. These "Four Horsemen" were part of the Exxon Research Co. The world's first commercial Fluid Catalytic Cracking facility began production for Exxon in 1942. The Fluid Catalytic Cracking process revolutionized the petroleum industry by more efficiently transforming higher boiling oils into lighter, usable products.

Their notable US Patent No. 2,451,804: A Method of and Apparatus for Contacting Solids and Gases describes their milestone invention. Over half the world's gasoline is currently produced by a process developed in 1942 by the "Four Horsemen" of Exxon Research and Engineering Company. The world's first commercial Fluid Catalytic Cracking facility began production for Exxon on May 25, 1942

By the 1930s, Exxon began looking for a way to increase the yield of high-octane gasoline from crude oil. Researchers discovered that a finely powdered catalyst behaved like a fluid when mixed with oil in the form of vapor. During the cracking process, a catalyst will split hydrocarbon molecule chains into smaller pieces. These smaller, or cracked, molecules then go through a distillation process to retrieve the usable product. During the cracking process, the catalyst becomes covered with carbon; the carbon is then burned off and the catalyst can be re-used. Campbell, Martin, Murphree, and Tyson began thinking of a design that would allow for a moving catalyst to ensure a steady and continuous cracking operation. The four ultimately invented a fluidized solids reactor bed and a pipe transfer system between the reactor and the regenerator unit in which the catalyst is processed for re-use. In this way, the solids and gases are continuously brought in contact with each other to bring on the chemical change. This work culminated in a 100 barrel-per-day demonstration pilot plant located at Exxon's Baton Rouge facility. The first commercial production plant processed 13,000 barrels of heavy oil daily, making 275,000 gallons of gasoline.