US4053515A
Expired / Lapsed
US
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Catalytic hydrogenation of unsaturated dinitriles employing high purity alumina
Assignee: Phillips Petroleum Co
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Filing: 1975-07-21
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Granted: 1977-10-11
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Expires: 1995-07-21
Abstract
Abstract The catalytic hydrogenation of an unsaturated dinitrile reactant of the formula ##STR1## wherein each R is an alkylene or an alkylidene radical, and each R' is an alkyl radical, is carried out in the presence of a secondary amine formation suppressant, hydrogen, a suitable diluent, and a catalyst composed of a catalytic component supported on high purity alumina, the catalytic component being selected from ruthenium, rhodium, palladium, cobalt and nickel in element form or in the form of a compound which is reducible by hydrogen to the elemental metal.
Inventors
- 👤 Charles A. Drake
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 03:49
CPC Classifications
C; C07; C07C; C07C209/00; C07C209/44; C07C209/48
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
181 words
A process for the catalytic hydrogenation of an unsaturated dinitrile feedstock comprising at least one unsaturated dinitrile compound of the formula ##STR8## wherein each R is individually selected from the group consisting of an alkylene radical and an alkylidene radical, R' is an alkyl radical, and the number of carbon atoms in said compound is in the range of 7 to 30; which comprises contacting said feedstock under suitable hydrogenation conditions with a secondary amine formation suppressant, hydrogen, a suitable diluent, and a supported catalyst to thereby effect the at least substantially complete hydrogenation of said at least one unsaturated dinitrile compound to the corresponding branched-chain saturated aliphatic diamine; said supported catalyst comprising a catalytic component and a catalyst support, said catalyst support consisting essentially of alumina having a purity of at least 99.5 weight percent after calcination, said catalytic component being selected from the group consisting of elemental ruthenium, elemental rhodium, elemental palladium, elemental cobalt, elemental nickel and compounds of ruthenium, rhodium, palladium, cobalt or nickel which are reducible by hydrogen to the respective elemental metal at said hydrogenation conditions.
Claim 2
Dependent Claim
181 words
A process for the catalytic hydrogenation of an unsaturated dinitrile feedstock comprising at least one unsaturated dinitrile compound of the formula ##STR8## wherein each R is individually selected from the group consisting of an alkylene radical and an alkylidene radical, R' is an alkyl radical, and the number of carbon atoms in said compound is in the range of 7 to 30; which comprises contacting said feedstock under suitable hydrogenation conditions with a secondary amine formation suppressant, hydrogen, a suitable diluent, and a supported catalyst to thereby effect the at least substantially complete hydrogenation of said at least one unsaturated dinitrile compound to the corresponding branched-chain saturated aliphatic diamine; said supported catalyst comprising a catalytic component and a catalyst support, said catalyst support consisting essentially of alumina having a purity of at least 99.5 weight percent after calcination, said catalytic component being selected from the group consisting of elemental ruthenium, elemental rhodium, elemental palladium, elemental cobalt, elemental nickel and compounds of ruthenium, rhodium, palladium, cobalt or nickel which are reducible by hydrogen to the respective elemental metal at said hydrogenation conditions.
Claim 3
Dependent Claim
57 words
A process in accordance with claim 1, wherein said feedstock further comprises at least one unsaturated dinitrile reactant of the formula ##STR9## wherein each R" is independently selected from the group consisting of an alkylene radical and an alkylidene radical, and the number of carbon atoms in said reactant is in the range of 7 to 30.
Claim 4
Dependent Claim
33 words
A process in accordance with claim 1 wherein the content of the metal of said catalytic component is in the range of about 0.5 to about 50 weight percent of said supported catalyst.
Claim 5
Dependent Claim
27 words
A process in accordance with claim 1 wherein each of said alkylene radical, said alkylidene radical and said alkyl radical has from 1 to 15 carbon atoms.
Claim 6
Dependent Claim
17 words
A process in accordance with claim 1 wherein said at least one unsaturated dinitrile compound comprises 5-methyl-4-nonenedinitrile.
Claim 7
Dependent Claim
152 words
A process in accordance with claim 1 wherein said hydrogenation conditions comprise a weight ratio of the total catalytic component metal present to the unsaturated dinitriles in the range of about 0.01:100 to about 30:100, a mol ratio of secondary amine formation suppressant to cyano groups in the range of about 1:1 to about 25:1, a hydrogen pressure in the range of about 500 to about 5000 psig, a weight ratio of the unsaturated dinitriles to the diluent in the range of about 0.001:100 to about 15:100, a temperature in the range of about 30° to about 250° C, and a reaction time in the range of about 15 minutes to about 10 hours if conducted as a batch process and a liquid hourly space velocity rate in the range of about 0.1 to about 10 volumes of unsaturated dinitrile plus diluent per volume of catalyst if conducted as a continuous process.
Claim 8
Dependent Claim
125 words
A process in accordance with claim 2 wherein said hydrogenation conditions comprise a weight ratio of the total catalytic component metal present to the unsaturated dinitriles in a batch hydrogenation process in the range of about 0.1:100 to about 20:100 or a liquid hourly space velocity in the range of about 0.1 to about 10 volumes of unsaturated dinitrile reactant plus diluent per volume of total catalyst composition per hour in a continuous hydrogenation process; a mol ratio of ammonia to cyano groups in the range of about 7:1 to about 15:1, a hydrogen pressure in the range of about 1000 to about 3000 psig; and a weight ratio of the unsaturated dinitriles to the diluent in the range of about 0.1:100 to about 12:100.
Claim 9
Dependent Claim
37 words
A process in accordance with claim 7 wherein said catalytic component is selected from the group consisting of elemental ruthenium, ruthenium compounds which are reducible by hydrogen to elemental ruthenium at said hydrogenation conditions, and mixures thereof.
Claim 10
Dependent Claim
25 words
A process in accordance with claim 8 wherein said diluent is at least one member of the group consisting of tertiary alkanols and saturated hydrocarbons.
Claim 11
Dependent Claim
37 words
A process in accordance with claim 7 wherein said catalytic component is selected from the group consisting of elemental nickel, nickel compounds which are reducible by hydrogen to elemental nickel at said hydrogenation conditions, and mixtures thereof.
Claim 12
Dependent Claim
33 words
A process in accordance with claim 10 wherein said supported catalyst has been calcined, then treated with an alkali metal hydroxide, and the thus treated catalyst has been calcined before contacting said feedstock.
Claim 13
Dependent Claim
15 words
A process in accordance with claim 11 wherein said alkali metal hydroxide comprises sodium hydroxide.
Claim 14
Dependent Claim
33 words
A process in accordance with claim 1 wherein said supported catalyst has been calcined, then treated with an alkali metal hydroxide, and the thus treated catalyst has been calcined before contacting said feedstock.
Claim 15
Dependent Claim
15 words
A process in accordance with claim 13 wherein said alkali metal hydroxide comprises sodium hydroxide.
Claim 16
Dependent Claim
19 words
A process in accordance with claim 14 wherein said alumina has a purity of at least 99.8 weight percent.
Claim 17
Dependent Claim
19 words
A process in accordance with claim 1 wherein said alumina has a purity of at least 99.9 weight percent.
Claim 18
Dependent Claim
17 words
A process in accordance with claim 1 further comprising recovering a diamine product essentially free of unsaturation.
Claim 19
Dependent Claim
14 words
A process in accordance with claim 1 wherein said feedstock comprises 5-methylenenonanedinitrile and 5-methyl-4-nonenedinitrile.
Claim 20
Dependent Claim
79 words
A process in accordance with claim 1 wherein said catalyst support has been prepared by the preparation of triethyl aluminum by the reaction of high purity aluminum, hydrogen and ethylene; the reaction of the resulting triethyl aluminum with additional ethylene molecules to form higher aluminum alkyls; oxidation of the aluminum alkyls to aluminum alkoxide; hydrolysis of the aluminum alkoxide to form an alumina slurry and alcohols; extraction of residual alcohols from the alumina slurry; and drying of the alumina.
Claim 21
Dependent Claim
14 words
A process in accordance with claim 19 wherein said feedstock comprises 5-methylenenonanedinitrile and 5-methyl-4-nonenedinitrile.
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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) | 1980-10-10 | 1981-04-11 | 1981-10-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-10-10 | 1985-04-11 | 1985-10-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-10-10 | 1989-04-11 | 1989-10-11 | $7700.00 | Window Closed / Lapsed |