US4293725A
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US
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Use of metal modified refractory metal oxide/silica supported nickel cluster catalyst to oligomerize ethylene
Assignee: Chevron USA Inc
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Filing: 1980-05-21
•
Granted: 1981-10-06
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Expires: 2000-05-21
Abstract
Abstract Ethylene is oligomerized by intimately contacting ethylene with a metal modified catalyst. The catalyst is produced by contacting (a) a refractory metal oxide/silica support, such as alumina/silica wherein the silica content of the support is from about 2 to about 95 weight percent and the metal oxide content of the support is from about 5 to about 98 percent with (b) a solution of a basic metal and then (c) contacting the resulting metal modified support with a tris(cyclopentadienyl)trinickel dicarbonyl.
Inventors
- 👤 David L. Beach
- 👤 Thaddeus P. Kobylinski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 04:41
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/26; B01J31/16; B01J31/1616; B01J31/20; B01J31/22; B01J31/2282; B01J31/2295; C; C07; C07C; C07C2/00; C07C2/02; C07C2/04; C07C2/06; C07C2/08; C07C2/26; C07C2/32; C07C2/34; B01J21/00; B01J21/12; B01J2231/00; B01J2231/20; B01J2531/00; B01J2531/001; B01J2531/002; B01J2531/007; B01J2531/02; B01J2531/0202; B01J2531/0211; B01J2531/80; B01J2531/84; B01J2531/847; B01J31/02; B01J31/04; B01J31/2204; B01J31/2208; B01J31/2226; B01J31/223; B01J31/2234; C07C2521/00; C07C2521/02; C07C2521/04; C07C2521/06; C07C2521/08; C07C2521/12; C07C2531/00; C07C2531/16; C07C2531/22; Y; Y02; Y02P; Y02P20/00; Y02P20/50
Claims Analysis
Total Claims: 86
Claim 1
Independent Claim
115 words
A process for oligomerizing ethylene which comprises contacting ethylene with a catalyst composition obtained by contacting (1) a refractory metal oxide/silica support wherein the silica content of said support is from about 2 to about 95 weight percent and the metal oxide content of said support is from about 5 to about 98 weight percent with (2) a solution of a soluble salt whose cationic portion is selected from the group consisting of an alkali metal, an alkaline earth metal and a lanthanide and whose anionic portion is selected from the group consisting of a halide, a nitrate, an acetate and an acetylacetonate and (3) then contacting the metal modified support with a tris(cyclopentadienyl)trinickel dicarbonyl.
Claim 2
Dependent Claim
115 words
A process for oligomerizing ethylene which comprises contacting ethylene with a catalyst composition obtained by contacting (1) a refractory metal oxide/silica support wherein the silica content of said support is from about 2 to about 95 weight percent and the metal oxide content of said support is from about 5 to about 98 weight percent with (2) a solution of a soluble salt whose cationic portion is selected from the group consisting of an alkali metal, an alkaline earth metal and a lanthanide and whose anionic portion is selected from the group consisting of a halide, a nitrate, an acetate and an acetylacetonate and (3) then contacting the metal modified support with a tris(cyclopentadienyl)trinickel dicarbonyl.
Claim 3
Dependent Claim
49 words
A process as defined in claim 1 wherein said tris(cyclopentadienyl)trinickel dicarbonyl has the structure: ##STR4## wherein R, R' and R" are the same or different C 1 to C 20 hydrocarbon radicals and n, n' and n" can be the same or different integers of 0 to 5, inclusive.
Claim 4
Dependent Claim
50 words
A process as defined in claim 2 wherein the metal oxide component of said support has the formula M x O y , wherein M is aluminum, magnesium, zirconium or thorium, x is an integer of from 1 to 2 and y is an integer of from 1 to 3.
Claim 5
Dependent Claim
16 words
A process as defined in claim 3 wherein the metal oxide in said support is alumina.
Claim 6
Dependent Claim
40 words
A process as defined in claim 1 wherein the silica content in said support is from about 15 to about 92 weight percent and the metal oxide content in said support is from about 10 to about 85 weight percent.
Claim 7
Dependent Claim
40 words
A process as defined in claim 1 wherein the silica content in said support is from about 80 to about 92 weight percent and the metal oxide content in said support is from about 10 to about 20 weight percent.
Claim 8
Dependent Claim
39 words
A process as defined in claim 4 wherein the silica content in said support is from about 15 to about 92 weight percent and the alumina content in said support is from about 10 to about 85 weight percent.
Claim 9
Dependent Claim
39 words
A process as defined in claim 4 wherein the silica content in said support is from about 80 to about 92 weight percent and the alumina content in said support is from about 10 to about 20 weight percent.
Claim 10
Dependent Claim
31 words
A process as defined in claim 4 wherein the silica content in said support is about 87 weight percent and the alumina content in said support is about 12 weight percent.
Claim 11
Dependent Claim
31 words
A process as defined in claim 4 wherein the silica content in said support is about 75 weight percent and the alumina content is said support is about 25 weight percent.
Claim 12
Dependent Claim
30 words
A process as defined in claim 1 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 13
Dependent Claim
30 words
A process as defined in claim 2 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 14
Dependent Claim
30 words
A process as defined in claim 3 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 15
Dependent Claim
30 words
A process as defined in claim 4 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 16
Dependent Claim
30 words
A process as defined in claim 5 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 17
Dependent Claim
30 words
A process as defined in claim 6 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 18
Dependent Claim
30 words
A process as defined in claim 7 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 19
Dependent Claim
30 words
A process as defined in claim 8 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 20
Dependent Claim
30 words
A process as defined in claim 9 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 21
Dependent Claim
30 words
A process as defined in claim 10 wherein said tris(cyclopentadienyl)trinickel dicarbonyl is defined by the chemical formula (η 5 --C 5 H 5 ) 3 Ni 3 (CO) 2 .
Claim 22
Dependent Claim
37 words
A process as defined in claim 1 wherein said support is calcined, prior to said contact with said tris(cyclopentadienyl)trinickel dicarbonyl at a temperature from about 200° to about 800° C. for about one to about 24 hours.
Claim 23
Dependent Claim
34 words
A process as defined in claim 1 wherein said contact between said support and said tris(cyclopentadienyl)trinickel dicarbonyl is conducted in the absence of air at a temperature of about 20° to about 200° C.
Claim 24
Dependent Claim
19 words
A process as defined in claim 1 wherein a solution of said tris(cyclopentadienyl)trinickel dicarbonyl is contacted with said support.
Claim 25
Dependent Claim
14 words
A process as defined in claim 23 wherein said solution is a benzene solution.
Claim 26
Dependent Claim
14 words
A process as defined in claim 23 wherein said solution is a cyclohexane solution.
Claim 27
Dependent Claim
24 words
A process as defined in claim 1 wherein the nickel content of said catalyst composition is from about 0.001 to about five weight percent.
Claim 28
Dependent Claim
24 words
A process as defined in claim 1 wherein the nickel content of said catalyst composition is from about 0.05 to about two weight percent.
Claim 29
Dependent Claim
24 words
A process as defined in claim 14 wherein the nickel content of said catalyst composition is from about 0.001 to about five weight percent.
Claim 30
Dependent Claim
24 words
A process as defined in claim 14 wherein the nickel content of said catalyst composition is from about 0.05 to about two weight percent.
Claim 31
Dependent Claim
37 words
A process as defined in claim 1 wherein said contact between said support and said tris(cyclopentadienyl)trinickel dicarbonyl is effected at a temperature from about 20° to about 200° C. for about 10 minutes to about 12 hours.
Claim 32
Dependent Claim
37 words
A process as defined in claim 1 wherein said contact between said support and said tris(cyclopentadienyl)trinickel dicarbonyl is effected at a temperature from about 20° to about 100° C. for about 15 minutes to about one hour.
Claim 33
Dependent Claim
37 words
A process as defined in claim 14 wherein said contact between said support and said tris(cyclopentadienyl)trinickel dicarbonyl is effected at a temperature from about 20° to about 200° C. for about 10 minutes to about 12 hours.
Claim 34
Dependent Claim
37 words
A process as defined in claim 14 wherein said contact between said support and said tris(cyclopentadienyl)trinickel dicarbonyl is effected at a temperature from about 20° to about 100° C. for about 15 minutes to about one hour.
Claim 35
Dependent Claim
24 words
A process as defined in claim 1 wherein the solid tris(cyclopentadienyl)trinickel dicarbonyl is contacted with said support and a hydrocarbon solvent is then added.
Claim 36
Dependent Claim
13 words
A process as defined in claim 34 wherein said hydrocarbon solvent is benzene.
Claim 37
Dependent Claim
13 words
A process as defined in claim 34 wherein said hydrocarbon solvent is cyclohexane.
Claim 38
Dependent Claim
34 words
A process as defined in claim 1 wherein said catalyst is activated or preactivated by heating at a temperature of about 70° to about 200° C. for about five minutes to about four hours.
Claim 39
Dependent Claim
34 words
A process as defined in claim 1 wherein said catalyst is activated or preactivated by heating at a temperature of about 100° to about 170° C. for about twenty minutes to about one hour.
Claim 40
Dependent Claim
34 words
A process as defined in claim 14 wherein said catalyst is activated or preactivated by heating at a temperature of about 70° to about 200° C. for about five minutes to about four hours.
Claim 41
Dependent Claim
34 words
A process as defined in claim 14 wherein said catalyst is activated or preactivated by heating at a temperature of about 100° to about 170° C. for about twenty minutes to about one hour.
Claim 42
Dependent Claim
18 words
A process as defined in claim 1 wherein said solution of a soluble salt is an aqueous solution.
Claim 43
Dependent Claim
18 words
A process as defined in claim 1 wherein said solution of a soluble salt is an alcoholic solution.
Claim 44
Dependent Claim
19 words
A process as defined in claim 1 wherein the cationic portion of said soluble salt is an alkali metal.
Claim 45
Dependent Claim
20 words
A process as defined in claim 1 wherein the cationic portion of said soluble salt is an alkaline earth metal.
Claim 46
Dependent Claim
18 words
A process as defined in claim 1 wherein the cationic portion of said soluble salt is a lanthanide.
Claim 47
Dependent Claim
18 words
A process as defined in claim 1 wherein the anionic portion of said soluble salt is a halide.
Claim 48
Dependent Claim
18 words
A process as defined in claim 1 wherein the anionic portion of said soluble salt is a nitrate.
Claim 49
Dependent Claim
18 words
A process as defined in claim 1 wherein the anionic portion of said soluble salt is an acetate.
Claim 50
Dependent Claim
18 words
A process as defined in claim 1 wherein the anionic portion of said soluble salt is an acetylacetonate.
Claim 51
Dependent Claim
13 words
A process as defined in claim 43 wherein said alkali metal is potassium.
Claim 52
Dependent Claim
14 words
A process as defined in claim 44 wherein said alkaline earth metal is magnesium.
Claim 53
Dependent Claim
12 words
A process as defined in claim 45 wherein said lanthanide is lanthanum.
Claim 54
Dependent Claim
12 words
A process as defined in claim 46 wherein said halide is chloride.
Claim 55
Dependent Claim
14 words
A process as defined in claim 1 wherein said soluble salt is potassium acetate.
Claim 56
Dependent Claim
14 words
A process as defined in claim 1 wherein said soluble salt is magnesium nitrate.
Claim 57
Dependent Claim
14 words
A process as defined in claim 1 wherein said soluble salt is lanthanum chloride.
Claim 58
Dependent Claim
27 words
A process as defined in claim 1 wherein said soluble salt is present in said solution in a concentration of from about 0.01 to about 1.0 molar.
Claim 59
Dependent Claim
45 words
A process as defined in claim 1 wherein the amount of metal on said support after said support is contacted with said solution of a water soluble salt is within the range of about 0.1 to about 5.0 weight percent based on the final support.
Claim 60
Dependent Claim
45 words
A process as defined in claim 1 wherein said ethylene and catalyst composition are contacted at a temperature of from about 20° to about 250° C. and a pressure of from about one to about 70 atmospheres for about 10 minutes to about 12 hours.
Claim 61
Dependent Claim
44 words
A process as defined in claim 1 wherein said ethylene and catalyst composition are contacted at a temperature of from about 50° to about 170° C. and a pressure of from about six to about 60 atmospheres for about 0.5 to about four hours.
Claim 62
Dependent Claim
45 words
A process as defined in claim 4 wherein said ethylene and catalyst composition are contacted at a temperature of from about 20° to about 250° C. and a pressure of from about one to about 70 atmospheres for about 10 minutes to about 12 hours.
Claim 63
Dependent Claim
44 words
A process as defined in claim 4 wherein said ethylene and catalyst composition are contacted at a temperature of from about 50° to about 170° C. and a pressure of from about six to about 60 atmospheres for about 0.5 to about four hours.
Claim 64
Dependent Claim
45 words
A process as defined in claim 14 wherein said ethylene and catalyst composition are contacted at a temperature of from about 20° to about 250° C. and a pressure of from about one to about 70 atmospheres for about 10 minutes to about 12 hours.
Claim 65
Dependent Claim
44 words
A process as defined in claim 14 wherein said ethylene and catalyst composition are contacted at a temperature of from about 50° to about 170° C. and a pressure of from about six to about 60 atmospheres for about 0.5 to about four hours.
Claim 66
Dependent Claim
21 words
A process as defined in claim 1 wherein said ethylene and catalyst composition are contacted in the presence of a solvent.
Claim 67
Dependent Claim
14 words
A process as defined in claim 65 wherein said solvent is an aromatic solvent.
Claim 68
Dependent Claim
14 words
A process as defined in claim 65 wherein said solvent is an aliphatic solvent.
Claim 69
Dependent Claim
14 words
A process as defined in claim 65 wherein said solvent is an alicyclic solvent.
Claim 70
Dependent Claim
21 words
A process as defined in claim 4 wherein said ethylene and catalyst composition are contacted in the presence of a solvent.
Claim 71
Dependent Claim
14 words
A process as defined in claim 69 wherein said solvent is an aromatic solvent.
Claim 72
Dependent Claim
14 words
A process as defined in claim 69 wherein said solvent is an aliphatic solvent.
Claim 73
Dependent Claim
14 words
A process as defined in claim 69 wherein said solvent is an alicyclic solvent.
Claim 74
Dependent Claim
21 words
A process as defined in claim 14 wherein said ethylene and catalyst composition are contacted in the presence of a solvent.
Claim 75
Dependent Claim
14 words
A process as defined in claim 73 wherein said solvent is an aromatic solvent.
Claim 76
Dependent Claim
14 words
A process as defined in claim 73 wherein said solvent is an aliphatic solvent.
Claim 77
Dependent Claim
14 words
A process as defined in claim 73 wherein said solvent is an alicyclic solvent.
Claim 78
Dependent Claim
32 words
A process as defined in claim 1 wherein said catalyst composition is present in an amount sufficient to provide about 0.1 mg. to about 1.0 g. of nickel per mole of ethylene.
Claim 79
Dependent Claim
32 words
A process as defined in claim 1 wherein said catalyst composition is present in an amount sufficient to provide about 1.0 mg. to about 0.1 g. of nickel per mole of ethylene.
Claim 80
Dependent Claim
32 words
A process as defined in claim 4 wherein said catalyst composition is present in an amount sufficient to provide about 0.1 mg. to about 1.0 g. of nickel per mole of ethylene.
Claim 81
Dependent Claim
32 words
A process as defined in claim 4 wherein said catalyst composition is present in an amount sufficient to provide about 1.0 mg. to about 0.1 g. of nickel per mole of ethylene.
Claim 82
Dependent Claim
32 words
A process as defined in claim 14 wherein said catalyst composition is present in an amount sufficient to provide about 0.1 mg. to about 1.0 g. of nickel per mole of ethylene.
Claim 83
Dependent Claim
32 words
A process as defined in claim 14 wherein said catalyst composition is present in an amount sufficient to provide about 1.0 mg. to about 0.1 g. of nickel per mole of ethylene.
Claim 84
Dependent Claim
61 words
A process as defined in claim 65 wherein said ethylene and catalyst composition are contacted in a reaction chamber to which ethylene is continuously or intermittently added, addition of ethylene to said reaction chamber is ceased after about 0.4 to about four hours, and the product olefins obtained in said process are allowed to continue to react at an elevated temperature.
Claim 85
Dependent Claim
61 words
A process as defined in claim 69 wherein said ethylene and catalyst composition are contacted in a reaction chamber to which ethylene is continuously or intermittently added, addition of ethylene to said reaction chamber is ceased after about 0.4 to about four hours, and the product olefins obtained in said process are allowed to continue to react at an elevated temperature.
Claim 86
Dependent Claim
61 words
A process as defined in claim 73 wherein said ethylene and catalyst composition are contacted in a reaction chamber to which ethylene is continuously or intermittently added, addition of ethylene to said reaction chamber is ceased after about 0.4 to about four hours, and the product olefins obtained in said process are allowed to continue to react at an elevated temperature.
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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) | 1984-10-05 | 1985-04-06 | 1985-10-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-10-05 | 1989-04-06 | 1989-10-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-10-05 | 1993-04-06 | 1993-10-06 | $7700.00 | Window Closed / Lapsed |