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Patent US4003933A successfully refreshed from Google Patents.
US4003933A
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Hydrogenation of nitriles in absence of secondary reaction suppressant
Assignee: Phillips Petroleum Co
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Filing: 1975-07-16
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Granted: 1977-01-18
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Expires: 1995-07-16
Abstract
Abstract Nitriles are converted to primary amines in the absence of a secondary amine formation suppressant by hydrogenation of the nitriles in the presence of a catalyst comprising at least one Group VIII metal promoted by at least one Group IVB metal. The process is applicable to the hydrogenation of nitriles having the formula (A) x R(C.tbd.N) y wherein x is zero or an integer and y is an integer, R is a hydrocarbyl radical having from 2 to 30 carbons and a valence of x + y and each A is selected from the group consisting of --OR' and --NR' 2 wherein R' is hydrogen or a hydrocarbyl radical having from 1 to 10 carbon atoms. The process is particularly applicable to the hydrogenation of olefinically unsaturated dinitriles. The complete hydrogenation of olefinically unsaturated nitriles can be carried out in two sequential stages, utilizing a Group IVB metal promoted Group VIII metal catalyst in the first stage to achieve a reduction of the nitrile unsaturation and a suitable catalyst, e.g. ruthenium, in the second stage to achieve a reduction of the olefinic unsaturation.
Inventors
- 👤 Charles A. Drake
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 16:11
CPC Classifications
C; C07; C07C; C07C209/00; C07C209/44; C07C209/48
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
183 words
A process for the catalytic hydrogenation of at least one nitrile having the formula (A) x R(C.tbd.N) y wherein x is zero or an integer and y is an integer, R is a hydrocarbyl radical having a valence of x+y, and each A is selected from the group consisting of --OR' and --NR' 2 wherein each R' is individually selected from the group consisting of hydrogen and hydrocarbyl radicals having from 1 to 10 carbon atoms, to produce primary amines; comprising contacting said at least one nitrile with hydrogen and a catalyst under first suitable hydrogenation conditions in the at least substantial absence of any secondary amine formation suppressant; said catalyst comprising at least one first component selected from the group consisting of elemental Group VIII metals and compounds of Group VIII metals which are reducible by hydrogen to the corresponding elemental metal at said hydrogenation conditions, and at least one second component selected from the group consisting of elemental Group IVB metals and compounds of Group IVB metals which are reducible by hydrogen to the corresponding elemental metal at said hydrogenation conditions.
Claim 2
Dependent Claim
183 words
A process for the catalytic hydrogenation of at least one nitrile having the formula (A) x R(C.tbd.N) y wherein x is zero or an integer and y is an integer, R is a hydrocarbyl radical having a valence of x+y, and each A is selected from the group consisting of --OR' and --NR' 2 wherein each R' is individually selected from the group consisting of hydrogen and hydrocarbyl radicals having from 1 to 10 carbon atoms, to produce primary amines; comprising contacting said at least one nitrile with hydrogen and a catalyst under first suitable hydrogenation conditions in the at least substantial absence of any secondary amine formation suppressant; said catalyst comprising at least one first component selected from the group consisting of elemental Group VIII metals and compounds of Group VIII metals which are reducible by hydrogen to the corresponding elemental metal at said hydrogenation conditions, and at least one second component selected from the group consisting of elemental Group IVB metals and compounds of Group IVB metals which are reducible by hydrogen to the corresponding elemental metal at said hydrogenation conditions.
Claim 3
Dependent Claim
41 words
A process in accordance with claim 1 wherein x is zero or an integer in the range of 1 to 4, y is an integer in the range of 1 to 4, and R contains from 2 to 30 carbon atoms.
Claim 4
Dependent Claim
20 words
A process in accordance with claim 2 further comprising recovering at least a portion of the primary amines thus produced.
Claim 5
Dependent Claim
35 words
A process in accordance with claim 2 wherein the weight ratio of said at least one second component to said at least one first component is in the range of about 0.001:1 to about 0.2:1.
Claim 6
Dependent Claim
36 words
A process in accordance with claim 4 wherein said first component is elemental cobalt particles or a compound of cobalt which is reducible by hydrogen to finely divided particles of elemental cobalt at said hydrogenation conditions.
Claim 7
Dependent Claim
35 words
A process in accordance with claim 5 wherein said second component is elemental zirconium or a compound of zirconium which is reducible by hydrogen to finely divided particles of elemental zirconium at said hydrogenation conditions.
Claim 8
Dependent Claim
29 words
A process in accordance with claim 6 wherein the weight ratio of said elemental zirconium to said elemental cobalt is in the range of about 0.005:1 to about 0.1:1.
Claim 9
Dependent Claim
62 words
A process in accordance with claim 7 wherein said at least one nitrile comprises at least one olefinically unsaturated dinitrile of the formula ##STR5##wherein such R" has from 1 to 15 carbon atoms and is individually selected from the group consisting of an alkylene radical and an alkylidene radical, and R"' is an alkyl radical having from 1 to 15 carbon atoms.
Claim 10
Dependent Claim
27 words
A process in accordance with claim 8 wherein each R" has from 1 to 6 carbon atoms, and wherein R"' has from 1 to 3 carbon atoms.
Claim 11
Dependent Claim
103 words
A process in accordance with claim 9 further comprising recovering at least a portion of the resulting olefinically unsaturated primary diamines and contacting the thus recovered unsaturated primary diamines with hydrogen and a second catalyst under second suitable hydrogenation conditions to produce a primary diamine product at least substantially free of olefinic unsaturation, said second catalyst comprising particles of at least one member of the group consisting of elemental cobalt, elemental nickel, elemental ruthenium, elemental rhodium, elemental palladium and compounds of cobalt, nickel, ruthenium, rhodium or palladium which are reducible by hydrogen to the corresponding elemental metal at said second suitble hydrogenation conditions.
Claim 12
Dependent Claim
74 words
A process in accordance with claim 10 wherein said first suitable hydrogenation conditions comprise a temperature in the range of about 30° to about 300° C and a hydrogen pressure in the range of about 500 to about 5000 psig, and wherein said second suitable reaction conditions comprise a temperature in the range of about 100° to about 250° C and a hydrogen pressure in the range of about 500 to about 5000 psig.
Claim 13
Dependent Claim
61 words
A process in accordance with claim 11 wherein each of said first and second reaction conditions further comprise the presence of a diluent selected from the group consisting of unsubstituted alkanols having from 1 to 12 carbon atoms per molecule, saturated hydrocarbons having from 4 to 12 carbon atoms per molecule, and unsubstituted ethers having from 4 to 12 carbon atoms.
Claim 14
Dependent Claim
36 words
A process in accordance with claim 2 wherein said first component is elemental cobalt particles or a compound of cobalt which is reducible by hydrogen to finely divided particles of elemental cobalt at said hydrogenation conditions.
Claim 15
Dependent Claim
35 words
A process in accordance with claim 13 wherein said second component is elemental zirconium or a compound of zirconium which is reducible by hydrogen to finely divided particles of elemental zirconium at said hydrogenation conditions.
Claim 16
Dependent Claim
35 words
A process in accordance with claim 2 wherein said second component is elemental zirconium or a compound of zirconium which is reducible by hydrogen to finely divided particles of elemental zirconium at said hydrogenation conditions.
Claim 17
Dependent Claim
73 words
A process in accordance with claim 2 wherein said at least one nitrile comprises at least one olefinically unsaturated nitrile, further comprising recovering at least a portion of the resulting olefinically unsaturated primary amine and contacting the thus recovered olefinically unsaturated primay amine with hydrogen and a suitable catalyst under suitable hydrogenation conditions to convert the thus contacted olefinically unsaturated primary amine to a primary amine at least substantially free of olefinic unsaturation.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-01-18 | 1980-07-19 | 1981-01-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-01-18 | 1984-07-19 | 1985-01-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-01-18 | 1988-07-19 | 1989-01-18 | $7700.00 | Window Closed / Lapsed |