US4083882A — Production of 1,4-butanediol

Claim 1

Independent Claim 176 words

A process for producing 1,4-butanediol which comprises (1) reacting acrolein with hydrogen in the vapor phase in acrolein/hydrogen molar ratio between 1:1 and 1:1000 at a temperature between about 75° C and 250° C and a pressure between about 75 and 5000 psi in the presence of a catalyst comprising a silver-cadmium alloy to yield a hydrogenation product mixture containing alcohol, wherein the automic ratio of silver to cadmium in the alloy is in the range of between about 0.1 and 3 to 1, and the alloy exhibits an X-ray diffraction pattern which is substantially free of detectable unalloyed metal crystallite lines; (2) contacting the allyl alcohol product mixture with hydrogen and carbon monoxide in a hydrogen carbon monoxide ratio between 1:2 and 2:1 under hydroformylation conditions at a temperature between about 20° C and 120° C and a pressure between about 15 and 150 psi in the presence of a hydroformylation catalyst to yield a product mixture containing 4-hydroxybutanal; (3) separating the 4-hydroxybutanal from the product mixture; and (4) hydrogenating the 4-hydroxybutanal to product 1,4-butanediol.

Claim 2

Dependent Claim 176 words

A process for producing 1,4-butanediol which comprises (1) reacting acrolein with hydrogen in the vapor phase in acrolein/hydrogen molar ratio between 1:1 and 1:1000 at a temperature between about 75° C and 250° C and a pressure between about 75 and 5000 psi in the presence of a catalyst comprising a silver-cadmium alloy to yield a hydrogenation product mixture containing alcohol, wherein the automic ratio of silver to cadmium in the alloy is in the range of between about 0.1 and 3 to 1, and the alloy exhibits an X-ray diffraction pattern which is substantially free of detectable unalloyed metal crystallite lines; (2) contacting the allyl alcohol product mixture with hydrogen and carbon monoxide in a hydrogen carbon monoxide ratio between 1:2 and 2:1 under hydroformylation conditions at a temperature between about 20° C and 120° C and a pressure between about 15 and 150 psi in the presence of a hydroformylation catalyst to yield a product mixture containing 4-hydroxybutanal; (3) separating the 4-hydroxybutanal from the product mixture; and (4) hydrogenating the 4-hydroxybutanal to product 1,4-butanediol.

Claim 3

Dependent Claim 20 words

A process in accordance with claim 1 wherein the silver-cadmium alloy in step (1) is supported on a carrier substrate.

Claim 4

Dependent Claim 13 words

A process in accordance with claim 18 wherein the carrier substrate is silica.

Claim 5

Dependent Claim 26 words

A process in accordance with claim 1 wherein in step (2) the hydrogen and carbon monoxide are in a molar ratio between about 1:2 and 2:1.

Claim 6

Dependent Claim 23 words

A process in accordance with claim 1 wherein in step (2) the hydroformylation catalyst is a complex of rhodium metal and phosphine ligand.

Claim 7

Dependent Claim 30 words

A process in accordance with claim 1 wherein in the step (2) hydroformylation reaction the allyl alcohol is converted to 4-hydroxybutanal in a yield of at least 75 weight percent.

Claim 8

Dependent Claim 28 words

A process in accordance with claim 1 wherein in step (3) the separation of 4-hydroxybutanal from the product mixture is achieved by aqueous extraction of the product mixture.

Claim 9

Dependent Claim 42 words

A process in accordance with claim 7 wherein in step (3) the 4-hydroxybutanal product is separated from the reaction mixture by aqueous extraction, and the resultant aqueous extract phase is subjected to hydrogenation conditions in step (4) to convert 4-hydroxybutanal to 1,4-butanediol.

Claim 10

Dependent Claim 130 words

A process for producing 1,4-butanediol which comprises (1) reacting acrolein with hydrogen in the vapor phase at a temperature between about 75° C and 250° C and a pressure between about 75 and 5000 psi in the presence of a catalyst comprising a silver-cadmium alloy on a carrier substate to yield a hydrogenation product mixture containing allyl alcohol, wherein the atomic ratio of silver to cadmium in the alloy is in the range of between about 0.1 and 3 to 1, and the alloy exhibits an X-ray diffraction pattern which is substantially free of detectable unalloyed metal crystallite lines; and (2) contacting the allyl alcohol product mixture with hydrogen and carbon monoxide under hydroformylation conditions in the presence of cobalt metal-ligand complex catalyst to yield a product mixture containing 1,4-butanediol.

Claim 11

Dependent Claim 130 words

A process for producing 1,4-butanediol which comprises (1) reacting acrolein with hydrogen in the vapor phase at a temperature between about 75° C and 250° C and a pressure between about 75 and 5000 psi in the presence of a catalyst comprising a silver-cadmium alloy on a carrier substate to yield a hydrogenation product mixture containing allyl alcohol, wherein the atomic ratio of silver to cadmium in the alloy is in the range of between about 0.1 and 3 to 1, and the alloy exhibits an X-ray diffraction pattern which is substantially free of detectable unalloyed metal crystallite lines; and (2) contacting the allyl alcohol product mixture with hydrogen and carbon monoxide under hydroformylation conditions in the presence of cobalt metal-ligand complex catalyst to yield a product mixture containing 1,4-butanediol.

Claim 12

Dependent Claim 64 words

A process in accordance with claim 9 wherein in step (2) the hydroformylation reaction is conducted in series at a temperature between about 80° C and 120° C and a pressure between about 300 and 3000 psi in a first zone, and a temperature between about 150° C and 225° C and a pressure between about 300 and 3000 psi in a second zone.

Claim 13

Dependent Claim 158 words

A process for producing 1,4-butanediol which comprises (1) reacting acrolein with hydrogen in the vapor phase at a temperature between about 75° C and 250° C and a pressure between about 75 and 5000 psi in the presence of a catalyst comprising a silver-cadmium-zinc alloy to yield a hydrogenation product mixture containing allyl alcohol, wherein the atomic ratio of silver to cadmium in the alloy is in the range of between about 0.1 and 3 to 1 and the zinc is contained in the alloy in a quantity between about 0.001 and 30 weight percent based on the total weight of alloy, and the alloy exhibits and X-ray diffraction pattern which is substantially free of detectable unalloyed metal crystallite lines; (2) contacting the allyl alcohol product mixture with hydrogen and carbon monoxide under hydroformylation to yield a product mixture containing a 4-hydroxybutanal; (3) separating the 4-hydroxybutanal from the product mixture; and (4) hydrogenating the 4-hydroxybutanal to product 1,4-butanediol.

Claim 14

Dependent Claim 158 words

A process for producing 1,4-butanediol which comprises (1) reacting acrolein with hydrogen in the vapor phase at a temperature between about 75° C and 250° C and a pressure between about 75 and 5000 psi in the presence of a catalyst comprising a silver-cadmium-zinc alloy to yield a hydrogenation product mixture containing allyl alcohol, wherein the atomic ratio of silver to cadmium in the alloy is in the range of between about 0.1 and 3 to 1 and the zinc is contained in the alloy in a quantity between about 0.001 and 30 weight percent based on the total weight of alloy, and the alloy exhibits and X-ray diffraction pattern which is substantially free of detectable unalloyed metal crystallite lines; (2) contacting the allyl alcohol product mixture with hydrogen and carbon monoxide under hydroformylation to yield a product mixture containing a 4-hydroxybutanal; (3) separating the 4-hydroxybutanal from the product mixture; and (4) hydrogenating the 4-hydroxybutanal to product 1,4-butanediol.

Claim 15

Dependent Claim 20 words

A process in accordance with claim 11 wherein the silver-cadmium-zinc alloy in step (1) is supported on a carrier substrate.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1981-04-10	1981-10-10	1982-04-11	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1985-04-10	1985-10-10	1986-04-11	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1989-04-10	1989-10-10	1990-04-11	$7700.00	Window Closed / Lapsed

Production of 1,4-butanediol

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