Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1992-09-04
1996-04-09
Reamer, James H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568400, C07C 4534
Patent
active
055063632
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This invention relates generally to oxidation of olefins to carbonyl compounds. More specifically, it relates to oxidation of olefins to carbonyl compounds by polyoxoanion oxidants in aqueous solution, catalyzed by palladium. In another aspect, it relates to reoxidation of reduced polyoxoanions in aqueous solution by reaction with dioxygen. It further relates to an overall process for the oxidation of olefins to carbonyl compounds by dioxygen catalyzed by palladium and polyoxoanions in aqueous solution.
BACKGROUND OF THE INVENTION
The catalyst solutions and the processes of the present invention are useful for the production of aldehydes, ketones, and carboxylic acids, which are chemicals of commerce and/or feedstocks for the production of chemicals and materials of commerce. For example, acetone, methyl ethyl ketone and methyl isobutyl ketone are used as solvents. Acetaldehyde is used in the production of acetic acid, polyols, and pyridines. Acetic acid is used in the production of vinyl acetate, cellulose acetate, and various alkyl acetate esters which are used as solvents. Acetone is used in the production of methylmethacrylate for polymethylmethacrylate. Cyclohexanone is used in the production of caprolactam for nylon-6 and adipic acid for nylon-6,6. Other cyclic ketones can be used for the production of other nylon-type polymers.
Acetaldehyde is industrially produced by the Wacker oxidation of ethylene by dioxygen, which uses an aqueous catalyst system of palladium chloride, copper chloride, and hydrochloric acid to accomplish the following net conversion:
Reviews of the Wacker process chemistry and manufacturing processes for the direct oxidation of ethylene to acetaldehyde can be found in "The Oxidation of Olefins with Palladium Chloride Catalysts", Angew. Chem. internat. Edit., Vol. 1 (1962), pp. 80-88, and in Chapter 8 of Ethylene and its Industrial Derivatives, S. A. Miller ed., Ernest Benn Ltd., London, 1969, each of which is incorporated by reference entirely. Aspects of Wacker technology are also disclosed in U.S. Pat. Nos. 3,122,586, 3,119,875, and 3,154,586, each incorporated by reference entirely.
In the Wacker process chemistry, ethylene is oxidized by cupric chloride in aqueous solution, catalyzed by palladium: ##STR1##
In a typical manufacturing operation, copper is present in the aqueous solution at concentrations of about 1 mole per liter, total chloride is present at concentrations of about 2 moles per liter, and the palladium catalyst is present at concentrations of about 0.01 moles per liter. Under these conditions, palladium(II) exists predominantly as the tetrachloropalladate ion, PdCl.sub.4.sup.=. Cuprous chloride resulting from the oxidation of ethylene is solubilized in the aqueous solution by the co-produced hydrochloric acid, as the dichlorocuprate ion, Cu.sup.l Cl.sub.2.sup.-. In a subsequent Wacker chemistry step, this reduced copper is reoxidized by reaction with dioxygen: +H.sub.2 O (3)
Two acetaldehyde manufacturing processes, a two-stage process and a one-stage process, have been developed and operated using the Wacker system chemistry. In the two-stage process, ethylene oxidation by cupric chloride, reaction (2), and reoxidation of cuprous chloride by air, reaction (3), are conducted separately, with intermediate removal of the acetaldehyde product from the aqueous solution. The reoxidized aqueous solution is recycled to the ethylene oxidation stage. The reactions are conducted at temperatures of about 100 to 130.degree. C. in reactors which, by providing very efficient gas-liquid mixing, result in high rates of diffusion (mass transfer) of the reacting gas into the aqueous solution. Under these conditions, about 0.24 moles ethylene per liter of solution can be reacted within about 1 minute in the ethylene reactor, corresponding to an average ethylene reaction rate of about 4 (millimoles/liter)/second. With a typical palladium concentration of about 0.01 moles per liter, this corresponds to a palladium turnover frequency (a measure of catalys
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Grate John H.
Hamm David R.
Muraoka Mark T.
Saxton Robert J.
Catalytica Inc.
Grate John H.
Reamer James H.
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