Fluid Catalytic Cracking - History

History

The first commercial use of catalytic cracking occurred in 1915 when Almer M. McAfee of 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 m3/d) of petroleum oil. Because of the economic depression of the early 1930s, 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 (320 m3/d) of petroleum oil.

In 1937, Sun Oil began operation of a new Houdry unit processing 12,000 barrels per day (1,900 m3/d) in their Marcus Hook refinery in Pennsylvania. 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 (22,000 m3/d).

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 Thermofor 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 semicommercial demonstration TCC unit was built in Socony-Vacuum's Paulsboro refinery in 1941 and operated successfully, producing 500 barrels per day (79 m3/d). Then a full-scale commercial TCC unit processing 10,000 barrels per day (1,600 m3/d) 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 (48,000 m3/d).

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. The first air-lift TCC unit began operation in October 1950 at the Beaumont, Texas refinery.

This fluid catalytic cracking process had first been investigated in the 1920s by Standard Oil of New Jersey, but research on it was abandoned during the economic depression years of 1929 to 1939. In 1938, when the success of Houdry’s process had become apparent, Standard Oil of New Jersey resumed the project as part of a consortium of that include five oil companies (Standard Oil of New Jersey, Standard Oil of Indiana, Anglo-Iranian Oil, Texas Oil and Dutch Shell), two engineering-construction companies (M.W. Kellogg and Universal Oil Products) and a German chemical company (I.G. Farben). The consortium was called Catalytic Research Associates (CRA) and its purpose was to develop a catalytic cracking process which would not impinge on Houdry's patents.

Chemical engineering professors Warren K. Lewis and Edwin R. Gilliland of the Massachusetts Institute of Technology (MIT) suggested to the CRA researchers that a low velocity gas flow through a powder might "lift" it enough to cause it to flow in a manner similar to a liquid. Focused on that idea of a fluidized catalyst, researchers Donald Campbell, Homer Martin, Eger Murphree and Charles Tyson of the Standard Oil of New Jersey (now Exxon-Mobil Company) developed the first fluidized catalytic cracking unit. Their U.S. Patent No. 2,451,804, A Method of and Apparatus for Contacting Solids and Gases, describes their milestone invention. Based on their work, M. W. Kellogg Company constructed a large pilot plant in the Baton Rouge, Louisiana refinery of the Standard Oil of New Jersey. The pilot plant began operation in May 1940.

Based on the success of the pilot plant, the first commercial fluid catalytic cracking plant (known as the Model I FCC) began processing 13,000 barrels per day (2,100 m3/d) of petroleum oil in the Baton Rouge refinery on May 25, 1942, just four years after the CRA consortium was formed and in the midst of World War II. A little more than a month later, in July 1942, it was processing 17,000 barrels per day (2,700 m3/d). In 1963, that first Model I FCC unit was shut down after 21 years of operation and subsequently dismantled.

In the many decades since the Model I FCC unit began operation, the fixed bed Houdry units have all been shut down as have most of the moving bed units (such as the TCC units) while hundreds of FCC units have been built. During those decades, many improved FCC designs have evolved and cracking catalysts have been greatly improved, but the modern FCC units are essentially the same as that first Model I FCC unit.

Note: All of the refinery and company names in this history section (with the exception of Universal Oil Products) have changed over time by mergers and buyouts. Some have changed a number of times.