US4288648A
Expired / Lapsed
US
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Process for the oligomerization of ethylene
Assignee: Chevron USA Inc
•
Filing: 1980-05-21
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Granted: 1981-09-08
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Expires: 2000-05-21
Abstract
Abstract Ethylene is oligomerized by contacting ethylene with a catalyst 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 tris(cyclopentadienyl)trinickel dicarbony. This process is characterized by a relatively high reaction rate at moderate temperatures and pressures and results in the production of relatively high proportions of desirable trimer, tetramer, pentamer, and higher olefinic products.
Inventors
- 👤 David L. Beach
- 👤 Thaddeus P. Kobylinski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 18:49
CPC Classifications
B; B01; B01J; B01J31/00; 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; B01J2531/02; B01J2531/0202; B01J2531/0211; B01J2531/80; B01J2531/84; B01J2531/847; 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: 68
Claim 1
Independent Claim
60 words
A process for oligomerizing ethylene which comprises contacting ethylene with a catalyst composition obtained by contacting (a) 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 (b) a tris(cyclopentadienyl)trinickel dicarbonyl.
Claim 2
Dependent Claim
60 words
A process for oligomerizing ethylene which comprises contacting ethylene with a catalyst composition obtained by contacting (a) 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 (b) 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 in 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 (ρ 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 (ρ 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 (ρ 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 (ρ 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 (ρ 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 (ρ 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 (ρ 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 (ρ 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 (ρ 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 (ρ 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
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 43
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 44
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 45
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 46
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 47
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 48
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 49
Dependent Claim
14 words
A process as defined in claim 47 wherein said solvent is an aromatic solvent.
Claim 50
Dependent Claim
14 words
A process as defined in claim 47 wherein said solvent is an aliphatic solvent.
Claim 51
Dependent Claim
14 words
A process as defined in claim 47 wherein said solvent is an alicyclic solvent.
Claim 52
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 53
Dependent Claim
14 words
A process as defined in claim 51 wherein said solvent is an aromatic solvent.
Claim 54
Dependent Claim
14 words
A process as defined in claim 51 wherein said solvent is an aliphatic solvent.
Claim 55
Dependent Claim
14 words
A process as defined in claim 51 wherein said solvent is an alicyclic solvent.
Claim 56
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 57
Dependent Claim
14 words
A process as defined in claim 55 wherein said solvent is an aromatic solvent.
Claim 58
Dependent Claim
14 words
A process as defined in claim 55 wherein said solvent is an aliphatic solvent.
Claim 59
Dependent Claim
14 words
A process as defined in claim 55 wherein said solvent is an alicyclic solvent.
Claim 60
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 61
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 62
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 63
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 64
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 65
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 66
Dependent Claim
61 words
A process as defined in claim 47 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 67
Dependent Claim
61 words
A process as defined in claim 51 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 68
Dependent Claim
61 words
A process as defined in claim 55 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) | 1984-09-07 | 1985-03-09 | 1985-09-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-09-07 | 1989-03-09 | 1989-09-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-09-07 | 1993-03-09 | 1993-09-08 | $7700.00 | Window Closed / Lapsed |