Union Carbide Corporation

Secondary alcohols (C q—for surfactant iatermediates are produced by hydrolysis of secondary alkyl borate or boroxiae esters formed when paraffin hydrocarbons are air-oxidized ia the presence of boric acid [10043-35-3] (19,20). Union Carbide Corporation operated a plant ia the United States from 1964 until 1977. A plant built by Nippon Shokubai (Japan Catalytic Chemical) ia 1972 ia Kawasaki, Japan was expanded to 30,000 t/yr capacity ia 1980 (20). The process has been operated iadustriaHy ia the USSR siace 1959 (21). Also, predominantiy primary alcohols are produced ia large volumes ia the USSR by reduction of fatty acids, or their methyl esters, from permanganate-catalyzed air oxidation of paraffin hydrocarbons (22). The paraffin oxidation is carried out ia the temperature range 150—180°C at a paraffin conversion generally below 20% to a mixture of trialkyl borate, (RO)2B, and trialkyl boroxiae, (ROBO). Unconverted paraffin is separated from the product mixture by flash distillation. After hydrolysis of residual borate esters, the boric acid is recovered for recycle and the alcohols are purified by washing and distillation (19,20). 

The search for catalyst systems which could effect the 0x0 reaction under milder conditions and produce higher yields of the desired aldehyde resulted in processes utilizing rhodium. Oxo capacity built since the mid-1970s, both in the United States and elsewhere, has largely employed tertiary phosphine-modified rhodium catalysts. For example, over 50% of the world s butyraldehyde (qv) is produced by the LP Oxo process, technology Hcensed by Union Carbide Corporation and Davy Process Technology. 

Ligand-Modified Rhodium Process. The triphenylphosphine-modified rhodium oxo process, termed the LP Oxo process, is the industry standard for the hydroformylation of ethylene and propylene as of this writing (ca 1995). It employs a triphenylphosphine [603-35-0] (TPP) (1) modified rhodium catalyst. The process operates at low (0.7—3 MPa (100—450 psi)) pressures and low (80—120°C) temperatures. Suitable sources of rhodium are the alkanoate, 2,4-pentanedionate, or nitrate. A low (60—80 kPa (8.7—11.6 psi)) CO partial pressure and high (10—12%) TPP concentration are critical to obtaining a high (eg, 10 1) normal-to-branched aldehyde ratio. The process, first commercialized in 1976 by Union Carbide Corporation in Ponce, Puerto Rico, has been ficensed worldwide by Union Carbide Corporation and Davy Process Technology. 

Darlene M. Back Elke M. Clark Ramesh Ramach dran Union Carbide Corporation... 

Aluminum Acetates" in ECT 1st ed. under "Aluminum Compounds," Vol. 1, pp. 626 —627, "Aluminum Formates" in ECT 1st ed. under "Aluminum Compounds," Vol. 1, pp. 630—632, by Benjamin Toubes, Victor Chemical Works, "Aluminum Acetate" in ECT 2nd ed. under "Aluminum Compounds," Vol. 2, pp. 11—13, by Albert Stewart, MaUinckrodt Chemical Works, "Aluminum Formate" in ECT 2nd ed. under "Aluminum Compounds," Vol. 2, pp. 14—17, by Benjamin Toubes, Victor Chemical Works, a Division of Stauffer Chemical Company, "Aluminum Carboxylates" in ECT 3rd ed. under "Aluminum Compounds," Vol. 2, pp. 202—209, by Glenn H. Warner, Union Carbide Corporation. 

Company (Bayway, New Jersey). This was followed in 1921, by the start-up of isopropyl alcohol production in Clendenin, West Virginia, by the Carbide and Carbon Chemicals (Union Carbide) Corporation. The Shell Oil Company began production in the 1930s at Dominguez, California (55). These three companies are the principal domestic manufacturers as of the mid-1990s. 

Flame plating (D-gun) employs oxygen and fuel gas. In this method, developed by the Union Carbide Corporation, the gas mixture is detonated by an electric spark at four detonations per second. The powders, mixed with the gas, are fed under control into a chamber from which they are ejected when detonation occurs. The molten, 14—16-pm particles are sprayed at a velocity of 732 m/s at distances of 5.1—10.2 cm from the surface. The substrate is moved past the stationary gun. 

Dimethyl and diethyl sulfate are available in a vahety of containers from 0.5-kg glass botdes to tank cars. Diethyl sulfate is somewhat less toxic than dimethyl sulfate and is considered noncorrosive, but dimethyl sulfate is classified as a corrosive Hquid and ICC regulations must be observed. Mild steel to 306 stainless steel is used for large-volume storage. Dimethyl sulfate is manufactured by E. I. du Pont de Nemours Co., Inc., and diethyl sulfate by Union Carbide Corporation. Other producers are Rhc ne-Poulenc and Hoechst-Celanese. 

The solvent can be tailored to provide selective acid gas removal based on the Hquid—gas solubiHties. For example, the Selexol process, Hcensed by Union Carbide Corporation, uses the dimethyl ether of polyethylene glycol (DMPEG) to provide high hydrogen sulfide selectivity. The solubiHty of hydrogen sulfide in DMPEG is 8—10 times that of carbon dioxide. 

The Cansolv process, Hcensed by Union Carbide Corporation, features an aqueous solution of a proprietary amine to absorb the sulfur dioxide. 

In the late 1980s, Brodie crystalHsers were installed in the United Kingdom and in France for upgrading phthaHc-grade naphthalene to 99% purity or better. This apparatus, developed by Union Carbide Corporation, AustraHa, for separating o- and -dichlorobensene, was adapted for naphthalene refining. The one installed in the United Kingdom, however, has been closed (21) (see Naphthalene). 

Prestone II Physical Properties Data Bulletin, 7th ed.. Union Carbide Corporation, Tarrytown, N.Y., 1974. 

Union Carbide Corporation, Chemicals and Plastics Division, New York, 1965, unpubUshed physical property data. 

Glenn W. Baldwin, M.S., P.E., Staff Engineer, Union Carbide Corporation Member, American Institute of Chemical Engineers (Section 12, Psyclirometry Evaporative Cooling, and Solids Drying)... 

Laurence G. Britton, Ph.D., Research Scientist, Union Carbide Corporation (Section 26, Process Safety)... 

Evan Buck, M.S.Ch.E., Manager, Tliermopliysical Property Skill Center, Central Technology, Union Carbide Corporation (Section 2, Physical and Chemical Data)... 

From published data, Chemicals Division, Union Carbide Corporation. Used hypermission. The paper describing these data is by Shank, ASHRAE7 (1965) 94-101. c = critical temperature. 

Values converted from tables of Sbank, Theimodynarmc Propeities of UCON 245 Refiigerant, Union Carbide Corporation, New York, 1966. See also Sbank, ] Chem. Eng. Data, 12, 474 80 (1967). c = critical point. Tbe notation 6.46.—4 signifies 6.46 X 10" ... 

Courtesy Union Carbide Corporation, Carbon Products Division. 

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