US4000211A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Dimerization of monoolefins with catalysts on solid supports
Assignee: Phillips Petroleum Co
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Filing: 1973-12-26
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Granted: 1976-12-28
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Expires: 1993-12-26
Abstract
Abstract Ethylene and/or propylene is dimerized by contacting the monoolefin with a catalyst formed by depositing a nickel complex such as bis(3-picoline)dichloronickel or bis(tributylphosphine)dichloronickel on a solid support such as silica-alumina. Preferably, an aluminum compound such as diethylaluminum chloride is also used in preparing the catalyst.
Inventors
- 👤 Clifford E. Smith
- 👤 Edward L. Czenkusch
- 👤 Grant C. Bailey
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 09:38
CPC Classifications
C; C07; C07C; C07C2/00; C07C2/02; C07C2/04; C07C2/06; C07C2/08; C07C2/26; C07C2/36; B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/14; B01J31/143; B01J31/16; B01J31/1616; B01J31/18; B01J31/1805; B01J31/181; B01J31/24; C07C2/32; B01J2531/00; B01J2531/80; B01J2531/84; B01J2531/847; C07C2521/00; C07C2521/06; C07C2521/08; C07C2521/12; C07C2531/00; C07C2531/02; C07C2531/12; C07C2531/14; C07C2531/16; C07C2531/22; C07C2531/24
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
199 words
A process for dimerizing at least one monoolefin selected from the group consisting of ethylene and propylene which comprises contacting said monoolefin with a catalyst under suitable reaction conditions, said catalyst having been prepared by: A. heat treating a solid catalyst support consisting essentially of silica, silica-alumina, or mixtures thereof, with flowing air at a temperature in the range of 800 to 1500° F. for a time in the range of 0.1 to 24 hours, said solid catalyst support being characterized by a pH value of less than 6 when slurried with distilled and decarbonated water, and B. contacting the thus heat treated solid catalyst support with (a) a nickel complex selected from the group consisting of compounds having the formula ##SPC2## (R 3 P) 2 NiCl 2 , wherein each R is individually selected from alkyl radicals having up to 20 carbon atoms; and n is zero or an integer in the range of 1 to 5; and (b) an aluminum compound having the formula R x AlCl y , wherein R is as previously defined, and x and y are integers in the range of 0 to 3 with the sum of x and y being 3.
Claim 2
Dependent Claim
199 words
A process for dimerizing at least one monoolefin selected from the group consisting of ethylene and propylene which comprises contacting said monoolefin with a catalyst under suitable reaction conditions, said catalyst having been prepared by: A. heat treating a solid catalyst support consisting essentially of silica, silica-alumina, or mixtures thereof, with flowing air at a temperature in the range of 800 to 1500° F. for a time in the range of 0.1 to 24 hours, said solid catalyst support being characterized by a pH value of less than 6 when slurried with distilled and decarbonated water, and B. contacting the thus heat treated solid catalyst support with (a) a nickel complex selected from the group consisting of compounds having the formula ##SPC2## (R 3 P) 2 NiCl 2 , wherein each R is individually selected from alkyl radicals having up to 20 carbon atoms; and n is zero or an integer in the range of 1 to 5; and (b) an aluminum compound having the formula R x AlCl y , wherein R is as previously defined, and x and y are integers in the range of 0 to 3 with the sum of x and y being 3.
Claim 3
Dependent Claim
20 words
A process in accordance with claim 1 wherein each of x and y has a value of at least 1.
Claim 4
Dependent Claim
12 words
A process in accordance with claim 2 wherein said support is silica-alumina.
Claim 5
Dependent Claim
15 words
A process in accordance with claim 1 wherein said pH value is less than 4.
Claim 6
Dependent Claim
25 words
A process in accordance with claim 4 wherein said nickel complex is selected from the group consisting of bis(2-picoline oxide)dichloronickel, bis(3-picoline)dichloronickel, bis(4-picoline)dichloronickel, bis(4-ethylpyridine)dichloronickel, and bis(tri-n-butylphosphine)dichloronickel.
Claim 7
Dependent Claim
12 words
A process in accordance with claim 1 wherein said support is silica.
Claim 8
Dependent Claim
21 words
A process in accordance with claim 5 wherein said aluminum compound is diethyl aluminum chloride, ethyl aluminum dichloride, or triethyl aluminum.
Claim 9
Dependent Claim
25 words
A process in accordance with claim 7 wherein said nickel complex is bis(tri-n-butylphosphine)dichloronickel, said support is silica, and said aluminum compound is diethyl aluminum chloride.
Claim 10
Dependent Claim
25 words
A process in accordance with claim 1 wherein said nickel complex is bis(tri-n-butylphosphine)dichloronickel, said support is silica-alumina, and said aluminum compound is diethyl aluminum chloride.
Claim 11
Dependent Claim
13 words
A process in accordance with claim 1 wherein said nickel complex is bis(tri-n-butylphosphine)dichloronickel.
Claim 12
Dependent Claim
12 words
A process in accordance with claim 8 wherein said monoolefin is ethylene.
Claim 13
Dependent Claim
12 words
A process in accordance with claim 8 wherein said monoolefin is propylene.
Claim 14
Dependent Claim
13 words
A process in accordance with claim 1 wherein said nickel compound is ##SPC3##
Claim 15
Dependent Claim
13 words
A process in accordance with claim 1 wherein said nickel compound is ##SPC4##
Claim 16
Dependent Claim
19 words
A process in accordance with claim 1 wherein said nickel compound is (R 3 P) 2 NiCl 2 .
Claim 17
Dependent Claim
81 words
A process in accordance with claim 1 wherein said reaction conditions comprise temperatures in the range of from -50 to 225° F., a pressure in the range of 20 to 500 psig, a reaction time in the range of from about 0.1 minute to about 20 hours, the mole ratio of said aluminum compound to said nickel complex ranges from 0.1:1 to 20:1, and the mole ratio of said nickel complex to said monoolefins ranges from about 0.00001 to about 0.1:1.
References Cited (Backward Citations)
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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) | 1979-12-28 | 1980-06-28 | 1980-12-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-12-28 | 1984-06-28 | 1984-12-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-12-28 | 1988-06-28 | 1988-12-28 | $7700.00 | Window Closed / Lapsed |