Texaco reactions

The first anhydride plant in actual operation using methyl acetate carbonylation was at Kingsport, Tennessee (41). A general description has been given (42) indicating that about 900 tons of coal are processed daily in Texaco gasifiers. Carbon monoxide is used to make 227,000 t/yr of anhydride from 177,000 t/yr of methyl acetate 166,000 t/yr of methanol is generated. Infrared spectroscopy has been used to foUow the apparent reaction mechanism (43). 

In addition to the nitrile and alcohol routes for fatty amine preparation, processes have been described by Unocal and Pennwalt Corporation, using an olefin and secondary amine (14—16) by Texaco Inc., hydrogenation of nitroparaffins (17—20) by Onyx Corporation, reaction of an alkyl haUde with secondary amines (21,22) by Henkel Cie, GmbH, reduction of an ester in the presence of a secondary amine (23) by catalytic hydroammonolysis of carboxyhc acids (24) and by the Hofmann rearrangement (25). 

The Texaco gasifier and a similar unit developed by The Dow Chemical Company are pressurized entrained gasifiers. At the top pulverized coal is mixed with reaction gas and is blown down into the gasifier. The reaction products leave from the side, and ash is blown down to a water pool where it is quenched. These units have operated at an Eastman Kodak facUity in Kingsport, Tennessee and at the Coolwater power station in California for an integrated combined cycle power plant. 

A new route to ethylene glycol from ethylene oxide via the intermediate formation of ethylene carbonate has recently been developed by Texaco. Ethylene carbonate may be formed by the reaction of carbon monoxide, ethylene oxide, and oxygen. Alternatively, it could be obtained by the reaction of phosgene and methanol. 

Methylacrylate and ethylenediamine were obtained from the Merck. Jeffamine T-3000 was purchased from Texaco Chemical Company. Other chemicals were used as obtained from the Fluka without further purification unless otherwise noted. Solvents were dried and distilled according to literature procedures prior to use. Reactions were controlled by thin layer chromatography (TLC) on silica gel 60 F254 and spots were detected either by UV-visible light or by charging with vapor. 

The 2-butanol feedstock is conventionally obtained by the sulfuric acid-catalyzed addition of water to -butenes. This is a two-step reaction involving sulfation and hydrolysis in which the conversion of -butenes is 90% and selectivity to 2-butanol is 95% (15). During operation the sulfuric acid becomes diluted and must be reconcentrated before reuse. In 1983 Deutsche Texaco commercialized a single-step route in which 2-butanol is formed by the hydration of -butenes in the presence of a strongly acidic ion-exchange resin containing sulfonic acid groups (16—18). The direct reaction is carried out at 150—160°C and 7 MPa. Virtually anhydrous 2-butanol is recovered in this process (19). Direct hydration requires lower utilities and investment costs, operates at 99% selectivity to 2-butanol, but is hindered by low (5—15%) -butene conversion per pass. 

The reaction occurs rapidly at alkaline pH (7—10), with higher pH values resulting in better yields due to faster Schiff base formation. To ensure complete conversion of available aldehydes to amines, add the ammonia or diamine compound to the reaction in at least a 10-fold molar excess over the expected number of formyl groups present, Diamines that are commonly used for this process include ethylene diamine, diamino-dipropylamine (3,3 -iminobispropylamine), 1,6-diaminohexane, and the Jeffamine derivative EDR-148 containing a hydrophilic, 10-atom chain (Texaco Chemical Co.). 

Figure 384 A PEG—amine compound, such as the Jeffamine polymers from Texaco, may be reacted with this heterobifunctional cross-linker to form amide bond derivatives terminating in maleimide groups. This results in a homobifunctional reagent capable of cross-linking thiol molecules. Subsequent reaction with sulfhydryl-containing molecules yields thioether linkages.

The Entrained system is a high temperature, high reaction rate process in which coal, oxygen (or air) and steam combine rapidly to produce LBG or MBG. The commercial processes aim primarily at the use of oxygen. Several developmental processes use oxygen or air. The most widely used commercial process (Koppers-Totzek) is operated at atmospheric pressure. The Texaco partial oxidation process used with oil and gas is under development for use with coal. Shell and Koppers are developing a pressurized version of the current Koppers-Totzek process. The advantages of the entrained... 

In 1981, Texaco announced the rutheiuum/H2/CO-catalyzed homologation of carboxyhc acids. Homologation refers to a chain-extension reaction that increases the carbon number of the carboxyhc acid see Homologation Reactions). The particular reaction that was initially studied was the conversion of acetic acid to propioiuc acid. The proposed mechanism shown in Scheme 22 is based on a Ru /Ru cycle, similar to that suggested by Knifton and coworkers at Texaco. 

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