Houdry

Butadiene. Although butadiene was produced in the United States in the eady 1920s, it was not until the start of Wodd War 11 that significant quantities were produced to meet the war effort. A number of processes were investigated as part of the American Synthetic Rubber Program. Catalytic dehydrogenation of / -butenes and / -butanes (Houdry process) and thermal cracking of petroleum hydrocarbons were chosen (12). 

Toluene Hydrodeall lation. Benzene is produced from the hydrodemethylation of toluene under catalytic or thermal conditions. The main catalytic hydrodealkylation processes are Hydeal (UOP) and DETOL (Houdry) (49). Two widely used thermal processes are HD A (Arco and Hydrocarbon Research Institute) and THD (Gulf). These processes contribute 25—30% of the world s total benzene supply. 

Dehydrogenation of /i-Butane. Dehydrogenation of / -butane [106-97-8] via the Houdry process is carried out under partial vacuum, 35—75 kPa (5—11 psi), at about 535—650°C with a fixed-bed catalyst. The catalyst consists of aluminum oxide and chromium oxide as the principal components. The reaction is endothermic and the cycle life of the catalyst is about 10 minutes because of coke buildup. Several parallel reactors are needed in the plant to allow for continuous operation with catalyst regeneration. Thermodynamics limits the conversion to about 30—40% and the ultimate yield is 60—65 wt % (233). 

The Catofin process, which was formerly the property of Air Products (Houdry Division), uses a proprietary chromium catalyst in a fixed-bed reactor operating under vacuum. There are actually multiple reactors operating in cycHc fashion. In sequence, these reactors process feed for about nine minutes and are then regenerated for nine minutes. The chromium catalyst is reduced from Cr to Cr during the regeneration cycle. 

Dehydrogenation. The dehydrogenation of paraffins is equihbrium-limited and hence requites high temperatures. Using this approach and conventional separation methods, both Houdry and UOP have commercialized the dehydrogenation of propane to propylene (92). A similar concept is possible for ethane dehydrogenation, but an economically attractive commercial reactor has not been built. 

Figure 19. Moving bed catalytic crackers (A) Thermoform moving bed process (B) Houdry catalytic cracking process.

Remarkably, seventy years after Houdry s utilization of the catalytic properties of activated clay and the subsequent development of ci ystalline aluminosilicate catalysts that arc a magnitude more catalytically active, the same fundamental principles remain the basis for the modern manufacture of gasoline, heating oils, and petrochemicals. 

Houdry concentrated his personal efforts on developing a viable processing scheme, solving the engineering problems, scaling the process to commercial size, and developing requisite equipment. In 1930,... 

II. F. Sheets of Vacuum Oil Company, who learned of Houdi y s work and shared his vision for converting vaporized petroleum to gasoline catalytically, invited him to the United States. After a successful trial run, Houdry moved his laboratory and associates from France to Paulsboro, New Jersey, to form a joint venture, Iloudiy Process Corporation, with Vacuum Oil Company. In that year Vacuum Oil Company merged with Standard Oil of New York to become Socony-Vacuum Company (much later Mobil Oil Corporation). 

The Houdry fixed-bed cyclic units were soon displaced in the 1940s by the superior Fluid Catalytic Cracking process pioneered by Warren K. Lewis of MIT and Eger Murphree and his team of engineers at Standard Oil of Newjersey (now Exxon). Murphree and his team demonstrated that hundreds of tons of fine catalyst could be continuously moved like a fluid between the cracking reactor and a separate vessel for... 

American Chemical. Society. (1996). A Mational Histone Chemical Landmark The Houdry Process for the Catalytic Conversion of Crude Petroleum to I ligh-Octane Gasoline. Washington, DC American Chemical Society. Buonora, P. T. (1998). Aimer IVicAfee at Gulf Oil. Chemical Heritage 16(2) 5-7, 44—4G. 

Enos, J. L. (1962). Petroleum Progress and Protits Allistoiy of Process Innovation. Cambridge, MA MIT Press. Mosely, C. G. (1984). Eugene Houdry, Catalytic Cracking and World War II Aviation Gasoline. Journal of Chemical Education 61 655—656. 

Through the 1920s Houdry had experimented in France on a number of possible catalytic routes to higher octane fuel. Finding little success in France, he came to the United States to further develop his process. After initial attempts at commercialization under the sponsorship of Sacony-Vacuum Company (currently Mobil) in Paulsboro, New Jersey, failed, I loudly and his development company, Houdiy Process Corporation, moved to Sun. 

Over the next four years, Houdry, working closely with Sun s engineering team headed by Clarence Thayer, worked to build a commercial plant. The limitations imposed by a static catalyst bed design imposed a major obstacle, particularly in the formation of carbon deposits that fouled the catalyst mass and impeded a continuous system of production. 

Fluid catalytic cracking rapidly overtook its competitors as both a source of fuel and of critical organic intermediates. Prior to 1942, the Houdry Process controlled 90 percent of the catalytic fuel market. But only three years later, in 1945, fluid cracking led all other catalytic cracking processes in market share (40 percent). At this time Thermofor technology stood at 31 percent, and Houdry at less chan 30 percent. 

The Houdry Process is used in the catalytic cracking of petroleum. 

Tucci, E., Dufallo, J. M. and Feldman, R. J., Commercial Performance of the Houdry CATOFIN Process for Isobutylene Production for MTBE, Catalysts, and Catalytic Processes Used in Saudi Arabia Workshop, KFUPM, Nov. 6, 1991. 

Serious research in catalytic reduction of automotive exhaust was begun in 1949 by Eugene Houdry, who developed mufflers for fork lift trucks used in confined spaces such as mines and warehouses (18). One of the supports used was the monolith—porcelain rods covered with films of alumina, on which platinum was deposited. California enacted laws in 1959 and 1960 on air quality and motor vehicle emission standards, which would be operative when at least two devices were developed that could meet the requirements. This gave the impetus for a greater effort in automotive catalysis research (19). Catalyst developments and fleet tests involved the partnership of catalyst manufacturers and muffler manufacturers. Three of these teams were certified by the California Motor Vehicle Pollution Control Board in 1964-65 American Cyanamid and Walker, W. R. Grace and Norris-Thermador, and Universal Oil Products and Arvin. At the same time, Detroit announced that engine modifications by lean carburation and secondary air injection enabled them to meet the California standard without the use of catalysts. This then delayed the use of catalysts in automobiles. 

Catadiene [Catalytic butadiene] Also spelled Catadien. A version of the Houdry process for converting mixtures of butane isomers into butadiene by dehydrogenation over an alumina/chromia catalyst. Another version converts propane to propylene. Rapid coking of the catalyst necessitates use of several reactors in parallel, so that reactivation can be carried out continuously. Developed by Houdiy and first operated at El Segundo, CA, in 1944. By 1993, 20 plants had been built worldwide. Now licensed by ABB Lummus Crest. 

CATOFIN [CATalytic OleFIN] A version of the Houdry process for converting mixtures of C3 - C5 saturated hydrocarbons into olefins by catalytic dehydrogenation. The catalyst is chromia on alumina in a fixed bed. Developed by Air Products Chemicals owned by United Catalysts, which makes the catalyst, and licensed through ABB Lummus Crest. Nineteen plants were operating worldwide in 1991. In 1994, seven units were used for converting isobutane to isobutylene for making methyl /-butyl ether for use as a gasoline additive. 

Cycloversion A petroleum treatment process which combined catalytic reforming with hydrodesulfurization. The catalyst was bauxite. The process differed from the Houdry process in that the catalyst bed temperature was controlled by injecting an inert gas. Developed by the Phillips Petroleum Company and used in the United States in the 1940s. Pet. Refin., 1960, 39(9), 205. 

Houdry The first catalytic petroleum cracking process, based on an invention by E. J. Houdiy in 1927, which was developed and commercialized by the Houdry Process Corporation. The process was piloted by the Vacuum Oil Company, Paulsboro, NJ, in the early 1930s. The catalyst was contained in a fixed bed. The first successful catalyst was an aluminosilicate mineral. Subsequently, other related catalysts were developed by Houdry in the United States, by I. G. Farbenindustrie in Germany, and by Imperial Chemical Industries in England. After World War II, the clay-based catalysts were replaced by a variety of synthetic catalysts, many based on alumino-silicates. Later, these too were replaced by zeolites. U.S. Patents 1,837,963 1,957,648 1,957,649. 

Hypotreating A process for desulfurizing and hydrogenating petroleum fractions. Developed by the Houdry Process and Chemical Company. 

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