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US5510550A Expired / Lapsed US ⏱️ 0.0 years remaining

Selective acetylene hydrogenation

Assignee: Phillips Petroleum Co
•
Filing: 1995-05-19
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Granted: 1996-04-23
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Expires: 2015-05-19
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Abstract

Abstract A catalyst composition comprising palladium, silver and a support material (preferably alumina) is contacted at a relatively low temperature (of up to about 60° C.) with a liquid composition comprising an effective reducing agent (preferably an alkali metal borohydride, hydrazinc, formaldehyde, formic acid, ascorbic acid, dextrose, aluminum powder). Preferably, at least one alkali metal compound (more preferably KOH, RbOH, CsOH, KF) is also present in the liquid composition. An improved process for selectively hydrogenating acetylene (to ethylene) employs this wet-reduced catalyst composition.

Inventors

  • 👤 Tin-Tack P. Cheung
  • 👤 Marvin M. Johnson
  • 👤 Scott H. Brown
  • 👤 Stan A. Zisman
  • 👤 James B. Kimble

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-25 23:06
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/38; B01J23/40; B01J23/44; C; C07; C07C; C07C5/00; C07C5/02; C07C5/08; C07C5/09; B01J23/48; B01J23/50; B01J23/54; B01J23/66; B01J37/00; B01J37/16; B01J37/18; C07C7/00; C07C7/148; C07C7/163; C07C7/167; C07C2521/00; C07C2521/02; C07C2521/04; C07C2521/06; C07C2523/00; C07C2523/02; C07C2523/04; C07C2523/38; C07C2523/40; C07C2523/44; C07C2523/48; C07C2523/50; C07C2523/54; C07C2523/66; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/52

Claims Analysis

Total Claims: 28
Claim 1
Independent Claim 206 words
In a process for the selective hydrogenation of acetylene to ethylene which comprises mixing (a) a feed gas comprising acetylene and (b) hydrogen gas and contacting the mixture of (a) and (b) with (c) an effective catalyst composition, the improvement which comprises employing a catalyst composition which has been prepared by a method consisting essentially of the steps of: (1) contacting a solid composition comprising palladium, silver and an inorganic support material with a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of alkali metal borohydrides, hydrazine, aldehydes containing 1-6 carbon atoms per molecule, ketones containing 1-6 carbon atoms per molecule, carboxylic acids containing 1-6 carbon atoms per molecule, aluminum metal and zinc metal, (ii) at least one non-reducing liquid component, and (iii) at least one dissolved alkali metal compound selected from the group consisting of alkali metal hydroxides and alkali metal fluorides, at a temperature of up to about 60° C. for a time period of at least about 1 second, so as to produce a wet-reduced solid composition; (2) substantially separating said wet-reduced solid composition produced in step (1) from said liquid reduction composition; and (3) drying the substantially separated, wet-reduced solid composition obtained in step (2).
Claim 2
Dependent Claim 206 words
In a process for the selective hydrogenation of acetylene to ethylene which comprises mixing (a) a feed gas comprising acetylene and (b) hydrogen gas and contacting the mixture of (a) and (b) with (c) an effective catalyst composition, the improvement which comprises employing a catalyst composition which has been prepared by a method consisting essentially of the steps of: (1) contacting a solid composition comprising palladium, silver and an inorganic support material with a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of alkali metal borohydrides, hydrazine, aldehydes containing 1-6 carbon atoms per molecule, ketones containing 1-6 carbon atoms per molecule, carboxylic acids containing 1-6 carbon atoms per molecule, aluminum metal and zinc metal, (ii) at least one non-reducing liquid component, and (iii) at least one dissolved alkali metal compound selected from the group consisting of alkali metal hydroxides and alkali metal fluorides, at a temperature of up to about 60° C. for a time period of at least about 1 second, so as to produce a wet-reduced solid composition; (2) substantially separating said wet-reduced solid composition produced in step (1) from said liquid reduction composition; and (3) drying the substantially separated, wet-reduced solid composition obtained in step (2).
Claim 3
Dependent Claim 116 words
A process in accordance with claim 1, wherein said inorganic support material is selected from the group consisting of alumina, titania, zirconia and mixtures thereof; said at least one reducing agent is selected from the group consisting of sodium borohydride, potassium borohydride, hydrazine, formaldehyde, formic acid, ascorbic acid and aluminum metal; said at least one non-reducing liquid component is selected from the group consisting of water, methanol and mixtures thereof; said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide, rubidium fluoride, cesium hydroxide and cesium fluoride; said temperature is about 10°-60° C.; and said time period is about 10 seconds to about 10 hours.
Claim 4
Dependent Claim 36 words
A process in accordance with claim 2, wherein said temperature in step (1) is about 20°-50° C., said time period of step (1) is about 0.02-2 hours, and the pressure in step (1) is approximately atmospheric.
Claim 5
Dependent Claim 31 words
A process in accordance with claim 2 wherein said solid composition used in step (1) contains about 0.01-0.2 weight-% palladium, about 0.02-2 weight-% silver, and alumina as the inorganic support material.
Claim 6
Dependent Claim 30 words
A process in accordance with claim 4, wherein said at least one reducing agent used in step (1) is selected from the group consisting of sodium borohydride and potassium borohydride.
Claim 7
Dependent Claim 41 words
A process in accordance with claim 4, wherein said at least one reducing agent is hydrazine, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 8
Dependent Claim 45 words
A process in accordance with claim 4, wherein said at least one reducing agent used in step (1) is formaldehyde, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 9
Dependent Claim 55 words
A process in accordance with claim 4, wherein said at least one reducing agent used in step (1) is selected from the group consisting of formic acid and ascorbic acid, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 10
Dependent Claim 47 words
A process in accordance with claim 4, wherein said at least one reducing agent used in step (1) is aluminum metal powder, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 11
Dependent Claim 32 words
A process in accordance with claim 1, wherein the weight percentage of said at least one reducing agent in said liquid reduction composition is employed in step (1) is about 0.5-50 weight-%.
Claim 12
Dependent Claim 28 words
A process in accordance with claim 1, wherein said feed gas comprises acetylene as an impurity in an ethylene stream, at an acetylene concentration of about 1-50,000 ppm.
Claim 13
Dependent Claim 35 words
A process in accordance with claim 1, wherein said selective hydrogenation is carried out at a temperature of about 0° C. to about 150° C. and a pressure of about 100 to about 1,000 psig.
Claim 14
Dependent Claim 251 words
In a process for the selective hydrogenation of acetylene to ethylene which comprises mixing (a) a feed gas comprising acetylene and (b) hydrogen gas and contacting the mixture of (a) and (b) with (c) an effective catalyst composition, the improvement which comprises employing a catalyst composition which has been prepared by a method consisting essentially of the steps of: (1) contacting (a) a solid composition comprising palladium, silver and an inorganic support material with (b) a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of alkali metal borohydrides, hydrazine, aldehydes containing 1-6 carbon atoms per molecule, ketones containing 1-6 carbon atoms per molecule, carboxylic acids containing 1-6 carbon atoms per molecule, sugars containing an aldehyde group, sugars containing an α-hydroxyketone group, aluminum metal and zinc metal, (ii) at least one non-reducing liquid component, and (iii) at least one dissolved alkali metal compound selected from the group consisting of alkali metal hydroxides and alkali metal fluorides, at a temperature of up to about 60° C. for a time period of at least about 1 second, so as to produce a wet-reduced, solid composition; (2) substantially separating the wet-reduced solid composition produced in step (1) from said liquid reduction composition; (3) drying the substantially separated, wet-reduced solid composition obtained in step (2); and (4) heating the dried, wet-reduced solid composition obtained in step (3) in an oxidizing gas atmosphere at a temperature of about 300°-700° C. for a time period of at least about 10 minutes.
Claim 15
Dependent Claim 251 words
In a process for the selective hydrogenation of acetylene to ethylene which comprises mixing (a) a feed gas comprising acetylene and (b) hydrogen gas and contacting the mixture of (a) and (b) with (c) an effective catalyst composition, the improvement which comprises employing a catalyst composition which has been prepared by a method consisting essentially of the steps of: (1) contacting (a) a solid composition comprising palladium, silver and an inorganic support material with (b) a liquid reduction composition comprising (i) at least one reducing agent selected from the group consisting of alkali metal borohydrides, hydrazine, aldehydes containing 1-6 carbon atoms per molecule, ketones containing 1-6 carbon atoms per molecule, carboxylic acids containing 1-6 carbon atoms per molecule, sugars containing an aldehyde group, sugars containing an α-hydroxyketone group, aluminum metal and zinc metal, (ii) at least one non-reducing liquid component, and (iii) at least one dissolved alkali metal compound selected from the group consisting of alkali metal hydroxides and alkali metal fluorides, at a temperature of up to about 60° C. for a time period of at least about 1 second, so as to produce a wet-reduced, solid composition; (2) substantially separating the wet-reduced solid composition produced in step (1) from said liquid reduction composition; (3) drying the substantially separated, wet-reduced solid composition obtained in step (2); and (4) heating the dried, wet-reduced solid composition obtained in step (3) in an oxidizing gas atmosphere at a temperature of about 300°-700° C. for a time period of at least about 10 minutes.
Claim 16
Dependent Claim 120 words
A process in accordance with claim 13, wherein said inorganic support material is selected from the group consisting of alumina, titania and zirconia; said at least one reducing agent is selected from the group consisting of sodium borohydride, potassium borohydride, hydrazine, formaldehyde, formic acid, ascorbic acid, dextrose and aluminum metal; said at least one non-reducing liquid component is selected from the group consisting of water, methanol and mixtures thereof; said at least one dissolved alkali metal is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide, rubidium fluoride, cesium hydroxide and cesium fluoride; said temperature in step (1) is about 10°-60° C.; and said time period in step (1) is about 10 seconds to about 10 hours.
Claim 17
Dependent Claim 36 words
A process in accordance with claim 14, wherein said temperature in step (1) is about 20°-50° C., said time period of step (1) is about 0.02-2 hours, and the pressure in step (1) is about atmospheric.
Claim 18
Dependent Claim 31 words
A process in accordance with claim 14, wherein said solid composition used in step (1) contains about 0.01-0.2 weight-% palladium, about 0.02-2 weight-% silver, and alumina as the inorganic support material.
Claim 19
Dependent Claim 26 words
A process in accordance with claim 16, wherein said at least one reducing agent is selected from the group consisting of sodium borohydride and potassium borohydride.
Claim 20
Dependent Claim 41 words
A process in accordance with claim 16, wherein said at least one reducing agent is hydrazine, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 21
Dependent Claim 41 words
A process in accordance with claim 16, wherein said at least one reducing agent is formaldehyde, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 22
Dependent Claim 51 words
A process in accordance with claim 16, wherein said at least one reducing agent is selected from the group consisting of formic acid and ascorbic acid, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 23
Dependent Claim 41 words
A process in accordance with claim 16 wherein said at least one reducing agent is dextrose, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide, potassium fluoride, rubidium hydroxide and cesium hydroxide.
Claim 24
Dependent Claim 39 words
A process in accordance with claim 16, wherein said at least one reducing agent is aluminum metal powder, and said at least one dissolved alkali metal compound is selected from the group consisting of potassium hydroxide and potassium fluoride.
Claim 25
Dependent Claim 31 words
A process in accordance with claim 13, wherein the weight percentage of said at least one reducing agent in said liquid reduction composition employed in step (1) is about 0.5-50 weight-%.
Claim 26
Dependent Claim 28 words
A process in accordance with claim 13, wherein said feed gas comprises acetylene as an impurity in an ethylene stream at an acetylene concentration of about 1-50,000 ppm.
Claim 27
Dependent Claim 35 words
A process in accordance with claim 13, wherein said selective hydrogenation is carried out at a temperature of about 0° C. to about 150° C. and a pressure of about 100 to about 1,000 psig.
Claim 28
Dependent Claim 30 words
A process in accordance with claim 13, wherein step (4) is carried out in air at a temperature of about 400°-600° C. for a time period of about 0.2-20 hours.

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