Standard Oil of Ohio

In 1957 Standard Oil of Ohio (Sohio) discovered bismuth molybdate catalysts capable of producing high yields of acrolein at high propylene conversions (>90%) and at low pressures (12). Over the next 30 years much industrial and academic research and development was devoted to improving these catalysts, which are used in the production processes for acrolein, acryUc acid, and acrylonitrile. AH commercial acrolein manufacturing processes known today are based on propylene oxidation and use bismuth molybdate based catalysts. 

Invented and developed independently in the late 1950s by D.G. Stewart in the Distillers Company, and R. Grasselli in Standard Oil of Ohio. The former used a tin/antimony oxide catalyst the latter bismuth phosphomolybdate on silica. Today, a proprietary catalyst containing depleted uranium is used. See also Erdolchemie, OSW, Sohio. 

Support of the Department of Energy, National Science Foundation (CPE-82-01216), Amoco Production, Chevron Oil Field Research, Exxon Research and Engineering, Gulf Research and Development, Marathon Oil, Shell Developmmt, Standard Oil of Ohio, Texaco, and Union Oil, is gratefully acknowledged. 

Acrolein is needed industrially on a great scale, and to obtain it selectively from propene and O2 various different heterogeneous catalysts have been investigated. In 1957-1962 Standard Oil of Ohio (SOHIO) developed the Mo03/Bi203-catalyst system [1,2], that did not lead to a high propene conversion but yielded a fairly good selectivity. Furthermore, acrylonitrile can be obtained instead of acrolein if NH3 is added to the system (ammonoxidation of propene, Eq. 1). 

In 1959, Idol (2), and in 1962, Callahan et al. (2) reported that bismuth/molybdenum catalysts produced acrolein from propylene in higher yields than that obtained in the cuprous oxide system. The authors also found that the bismuth/molybdenum catalysts produced butadiene from butene and, probably more importantly, observed that a mixture of propylene, ammonia, and air yielded acrylonitrile. The bismuth/molybdenum catalysts now more commonly known as bismuth molybdate catalysts were brought to commercial realization by the Standard Oil of Ohio Company (SOHIO), and the vapor-phase oxidation and ammoxidation processes which they developed are now utilized worldwide. 

Although obviously not a coal liquefaction product, shale oil represents another synthetic fuel option. During the last quarter of 1979, the Department of Defense arranged with Standard Oil of Ohio through the Paraho Development Corporation to refine 100,000 barrels of raw shale oil. EPRI arranged for delivery of 4,500 barrels of the hydrotreated 700°F residue. 

The oxidation of propene to acrolein has been applied in industry since 1958, when Shell introduced a gas-phase oxidation based on a Cu20/SiC/l2 catalyst system. This process made acrolein a commodity product. A more efficient technology, still state-of-the-art, was subsequently developed by Standard Oil of Ohio (from 1957 onward), using bismuth molybdate and bismuth phosphatecatalysts... 

The timing of the petroleum companies entry into the chemical industry determined their long-term position in the industry. The four that commercialized petrochemicals before the Japanese attack on Pearl Harbor— Standard Oil of New Jersey (Exxon by 1993), Shell, Standard Oil of California (Chevron by 1993), and Phillips—were the first movers. By the 1950s they had become the leaders in the basic feedstocks and commodity polymers such as polystyrene, polyvinyl chloride, polyethylene, and polypropylene. Those companies that entered after 1941 achieved success by focusing on specific niche products in the manner of the smaller U.S. companies. As shown in Table 1.1, these include Arco (Atlantic Refining Company), Amoco (Standard Oil of Indiana), Ashland, and BP America (acquirer of Standard Oil of Ohio). 

SOHIO (BP AMERICA AFTER 1970) The specialty that Standard Oil of Ohio commercialized was developed by another SEP, the Badger Company, which, in Spitz s words, was the most experienced U.S. contractor in the application of fluid bed technology. Mastering that technology, Sohio so lowered the cost of acrylonitrile that it became the dominant American producer and world licenser, but made no attempt to go into acrylic fiber manufacturing. In the United States, its strength continued to rest on the intermediate acrylonitrile.23... 

British Petroleum (in Standard Oil of Ohio and Amoco and ARCO) Unilever (in Lever Brothers)... 

SCM Corporation Seagrave Corporation Searle, G. D., Company Shell Oil Company Skelly Oil Company Squibb Corporation Staley, A.E., Manufacturing Standard Brands Paint Standard Oil of California Standard Oil of Indiana Standard Oil of Ohio Stauffer Chemical Company Sterling Drug, Inc. 

The process used by the former Standard Oil of Ohio (SOHIO currently BP America) involved electrolytic conversion of HCN to cyanogen bromide, and subsequent conversion to cyanamide by ammonolysis, then to melamine by trimerization ... 

Carbon dioxide, acetaldehyde, and acrylic acid are formed as side products. A technical breakthrough was achieved by Standard Oil of Ohio (SOHIO) with the discovery of the bimetallic bismuth molybdate and bismuth phosphomolybdate catalysts. Propene is oxidized with air on a Bi203/Mo03 catalyst at 300-400 °C and 1-2 bar in a fixed-bed tubular reactor, which allows effective removal of heat from the exothermic reaction [15]. 

This process is known as the SOHIO (Standard Oil of Ohio Company) process. The bismuth-molybdate catalyst functions by providing intimately associated Bi—O and Mo=0 sites. The Bi—O sites are involved in abstracting a-hydrogen (see structure 24.47) while the Mo=0 sites interact with the incoming alkene, and are involved in activation of NH3 and in C—N bond formation. 

American Cyanamid Co., 3) Amoco Production Co., 4) Atlantic Richfield Co., 5) BASF-Wyandotte Co., 6) British Petroleum Co., England, 7). Calgon Corp., 8) Cities Service Oil Co., 9) Continental Oil Co., 10) Ethyl Corp., 11) Exxon Production Research Co., 12) Getty Oil Co., 13) Gulf Research and Development Co., 14) Marathop Oil Co., 15) Mobil Research and Development Co., 16) Nalco Chemical Co., 17) Phillips Petroleum Co., 18) Shell Development Co., 19) Standard Oil of Ohio Co., 20) Stepan Chemical Co., 21) Sun Oil Chemical Co., 22) Texaco Inc., 23) Union Carbide Corp., 24) Union Oil Co., 25) Westvaco Inc., 26) Witco Chemical Co., and the University of Florida. 

Acrylonitrile is produced today almost exclusively by ammonoxidation of propylene using the so-called Sohio process. Sohio stands for Standard Oil of Ohio, the first company to demonstrate successfully the process in 1960. The Sohio process reacts propylene, ammonia, and oxygen in a highly exothermic process (AH = —502 kj mol ) at 400-500 °C to acrylonitrile and water. The process uses a fluidized bed reactor to operate the reactor as isothermally as possible. The catalyst is a Fe-modified bismuth-phosphorous molybdate contact. The Sohio process has... 

Thirty-five years ago a young engineer from Standard Oil of Ohio asked me to define a step wise approach to troubleshooting process plant problems. Honestly, I didn t know how to answer her question. 

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