US5587348A
Expired / Lapsed
US
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Alkyne hydrogenation catalyst and process
Assignee: Phillips Petroleum Co
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Filing: 1995-04-19
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Granted: 1996-12-24
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Expires: 2015-04-19
Abstract
Abstract A catalyst composition comprises palladium, at least one chemically bound alkali metal (preferably potassium), chemically bound fluorine and an inorganic support material (preferably alumina), wherein the atomic ratio of fluorine to alkali metals about 1.3:1 to about 4:1. Preferably, silver is also present in the catalyst composition. The above-described catalyst is employed as a catalyst in the selective hydrogenation of C 2 -C 10 alkynes (preferably acetylene) to the corresponding alkenes in the presence of sulfur impurities.
Inventors
- 👤 Scott H. Brown
- 👤 Stan A. Zisman
- 👤 James B. Kimble
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 23:26
CPC Classifications
C; C07; C07C; C07C7/00; C07C7/148; C07C7/163; C07C7/167; B; B01; B01J; B01J23/00; B01J23/38; B01J23/54; B01J23/56; B01J23/58; B01J23/66; B01J27/00; B01J27/06; B01J27/08; B01J27/12; B01J27/128; B01J27/13; C07C5/00; C07C5/02; C07C5/08; C07C5/09; 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; C07C2523/56; C07C2523/58; C07C2523/66
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
62 words
A catalyst composition which comprises about 0.01-1 weight-% palladium, about 0.05-5 weight-% of at least one alkali metal, about 0.03-10 weight-% fluorine, and an inorganic support material selected from the group consisting of alumina, titania, zirconia and mixtures thereof, wherein the atomic ratio of fluorine to said at least one alkali metal is in the range of about 1.3:1 to about 4:1.
Claim 2
Dependent Claim
62 words
A catalyst composition which comprises about 0.01-1 weight-% palladium, about 0.05-5 weight-% of at least one alkali metal, about 0.03-10 weight-% fluorine, and an inorganic support material selected from the group consisting of alumina, titania, zirconia and mixtures thereof, wherein the atomic ratio of fluorine to said at least one alkali metal is in the range of about 1.3:1 to about 4:1.
Claim 3
Dependent Claim
33 words
A catalyst composition in accordance with claim 1, wherein said at least one alkali metal is selected from the group consisting of potassium, rubidium and cesium, and said inorganic support material is alumina.
Claim 4
Dependent Claim
17 words
A catalyst composition in accordance with claim 2, wherein said at least one alkali metal is potassium.
Claim 5
Dependent Claim
26 words
A catalyst composition in accordance with claim 3, wherein the weight ratio of potassium to palladium is in the range of about 0.2:1 to about 100:1.
Claim 6
Dependent Claim
22 words
A catalyst composition in accordance with claim 3, comprising about 0.01-0.2 weight-% palladium, about 0.1-1 weight-% potassium and about 0.2-1 weight-% fluorine.
Claim 7
Dependent Claim
22 words
A catalyst composition in accordance with claim 5, wherein the atomic ratio of fluorine to potassium is about 1.4:1 to about 3:1.
Claim 8
Dependent Claim
28 words
A catalyst composition in accordance with claim 6, further comprising about 0.02-2 weight-% silver, at a weight ratio of silver to palladium of about 2:1 to about 10:1.
Claim 9
Dependent Claim
22 words
A catalyst composition in accordance with claim 3, wherein the atomic ratio of fluorine to potassium is about 1.4:1 to about 3:1.
Claim 10
Dependent Claim
14 words
A catalyst composition in accordance with claim 3, further comprising about 0.01-10 weight-% silver.
Claim 11
Dependent Claim
24 words
A catalyst composition in accordance with claim 5, wherein said at least one alkali metal is potassium, and said inorganic support material is alumina.
Claim 12
Independent Claim
125 words
A method of preparing a catalyst composition which comprises about 0.01-1 weight-% palladium, about 0.05-5 weight-% of at least one alkali metal, about 0.03-10 weight-% fluorine, and an inorganic support material selected from the group consisting of alumina, titania, zirconia, and mixtures thereof, wherein the atomic ratio of fluorine to said at least one alkali metal is in the range of about 1.3:1 to about 4:1; said method comprising contacting a solid composition which comprises palladium and said inorganic support material with (a) at least one dissolved alkali metal compound selected from the group consisting of hydroxides, bicarbonates, carbonates, nitrates, bisulfates and fluorides and with (b) at least one dissolved fluorine compound selected from the group consisting of hydrogen fluoride, ammonium fluoride and ammonium bifluoride.
Claim 13
Independent Claim
125 words
A method of preparing a catalyst composition which comprises about 0.01-1 weight-% palladium, about 0.05-5 weight-% of at least one alkali metal, about 0.03-10 weight-% fluorine, and an inorganic support material selected from the group consisting of alumina, titania, zirconia, and mixtures thereof, wherein the atomic ratio of fluorine to said at least one alkali metal is in the range of about 1.3:1 to about 4:1; said method comprising contacting a solid composition which comprises palladium and said inorganic support material with (a) at least one dissolved alkali metal compound selected from the group consisting of hydroxides, bicarbonates, carbonates, nitrates, bisulfates and fluorides and with (b) at least one dissolved fluorine compound selected from the group consisting of hydrogen fluoride, ammonium fluoride and ammonium bifluoride.
Claim 14
Dependent Claim
29 words
A method in accordance with claim 11 further comprising the steps of drying and then calcining, at a temperature of about 300°-700° C., the material produced by said contacting.
Claim 15
Dependent Claim
32 words
A method in accordance with claim 11, wherein said at least one alkali metal is selected from the group consisting of potassium, rubidium and cesium, and said inorganic support material is alumina.
Claim 16
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 13.
Claim 17
Dependent Claim
26 words
A method in accordance with claim 13, wherein said at least one alkali metal is potassium and said at least one fluorine compound is ammonium fluoride.
Claim 18
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 15.
Claim 19
Dependent Claim
27 words
A method in accordance with claim 13, wherein said solid composition further comprises silver, and the catalyst composition prepared by said method comprises about 0.01-10 weight-% silver.
Claim 20
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 17.
Claim 21
Dependent Claim
33 words
A method in accordance with claim 17, wherein the catalyst composition prepared by said method comprises about 0.01-0.2 weight-% palladium, about 0.02-2 weight-% silver, about 0.1-1 weight-% potassium and about 0.2-1 weight-% fluorine.
Claim 22
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 19.
Claim 23
Dependent Claim
35 words
A method in accordance with claim 19, wherein the weight ratio of silver to palladium is about 2:1 to about 10:1 and the weight ratio of potassium to palladium is about 0.2:1 to about 100:1.
Claim 24
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 11.
Claim 25
Independent Claim
187 words
A method of preparing a catalyst composition which comprises about 0.01-1 weight-% palladium, about 0.01-10 weight-% silver, about 0.05-5 weight-% of at least one alkali metal, about 0.03-10 weight-% fluorine, and an inorganic support material selected from the group consisting of alumina, titania, zirconia and mixtures thereof, wherein the atomic ratio of fluorine to said at least one alkali metal is in the range of about 1.3:1 to about 4:1; said method comprising impregnating a solid material which comprises palladium, silver and said inorganic support material with: (a) an aqueous solution comprising (i) at least one reducing agent selected from the group consisting of hydrazine, alkali metal borohydrides, 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, reducing sugars containing an aldehyde group and reducing sugars containing an alpha-hydroxyketone group and (ii) at least one at least one dissolved alkali metal compound selected from the group consisting of hydroxides and fluorides, and thereafter with (b) at least one dissolved fluorine compound selected from the group consisting of hydrogen, fluoride, ammonium fluoride and ammonium bifluoride.
Claim 26
Independent Claim
187 words
A method of preparing a catalyst composition which comprises about 0.01-1 weight-% palladium, about 0.01-10 weight-% silver, about 0.05-5 weight-% of at least one alkali metal, about 0.03-10 weight-% fluorine, and an inorganic support material selected from the group consisting of alumina, titania, zirconia and mixtures thereof, wherein the atomic ratio of fluorine to said at least one alkali metal is in the range of about 1.3:1 to about 4:1; said method comprising impregnating a solid material which comprises palladium, silver and said inorganic support material with: (a) an aqueous solution comprising (i) at least one reducing agent selected from the group consisting of hydrazine, alkali metal borohydrides, 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, reducing sugars containing an aldehyde group and reducing sugars containing an alpha-hydroxyketone group and (ii) at least one at least one dissolved alkali metal compound selected from the group consisting of hydroxides and fluorides, and thereafter with (b) at least one dissolved fluorine compound selected from the group consisting of hydrogen, fluoride, ammonium fluoride and ammonium bifluoride.
Claim 27
Dependent Claim
29 words
A method in accordance with claim 23, further comprising the steps of drying and then calcining, at a temperature of about 300°-700° C., the material obtained after said contacting.
Claim 28
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 23.
Claim 29
Dependent Claim
63 words
A method in accordance with claim 23, wherein said inorganic support material is alumina, said at least one reducing agent is selected from the group consisting of hydrazine, formaldehyde, formic acid, ascorbic acid and dextrose, said at least one alkali metal is selected from the group consisting of potassium, cesium and rubidium, and said at least one dissolved fluorine compound is ammonium fluoride.
Claim 30
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 26.
Claim 31
Dependent Claim
27 words
A method in accordance with claim 26, wherein said at least one reducing agent is formaldehyde or dextrose and said at least one alkali metal is potassium.
Claim 32
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 28.
Claim 33
Dependent Claim
33 words
A method in accordance with claim 26, wherein the catalyst composition prepared by said method comprises about 0.01-0.2 weight-% palladium, about 0.02-2 weight-% silver, about 0.1-1 weight-% potassium and about 0.2-1 weight-% fluorine.
Claim 34
Dependent Claim
35 words
A method in accordance with claim 30, wherein the weight ratio of silver to palladium is about 2:1 to about 10:1 and the weight ratio of potassium to palladium is about 0.2:1 to about 100:1.
Claim 35
Dependent Claim
10 words
A catalyst composition prepared by the method of claim 30.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1999-12-24 | 2000-06-24 | 2000-12-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2003-12-24 | 2004-06-24 | 2004-12-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2007-12-24 | 2008-06-24 | 2008-12-24 | $7700.00 | Window Closed / Lapsed |