Patent US4397761A successfully refreshed from Google Patents.
US4397761A
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Phosphate containing support for vanadium catalyst
Assignee: Phillips Petroleum Co
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Filing: 1980-12-31
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Granted: 1983-08-09
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Expires: 2000-12-31
Abstract
Abstract A supported vanadium catalyst comprising a vanadium compound on a phosphate-containing base. This catalyst in conjunction with an organoaluminum cocatalyst is capable of giving good activity and producing a polymer having broad molecular weight distribution. The catalyst system is sufficiently sensitive to hydrogen to allow broad leeway in controlling the molecular weight of the resulting polymers.
Inventors
- 👤 Max P. McDaniel
- 👤 Marvin M. Johnson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 11:57
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/14; B01J31/143; C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 44
Claim 1
Independent Claim
53 words
A catalyst system comprising: (a) a catalyst comprising an activated vanadium compound on a phosphate-containing support; and (b) an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 2
Dependent Claim
53 words
A catalyst system comprising: (a) a catalyst comprising an activated vanadium compound on a phosphate-containing support; and (b) an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 3
Dependent Claim
20 words
A catalyst system according to claim 1 wherein said cocatalyst is one of diethylaluminum chloride, ethylaluminum dichloride, or ethylaluminum sesquichloride.
Claim 4
Dependent Claim
36 words
A catalyst system according to claim 1 wherein said cocatalyst is present in an amount sufficient to given an atom ratio of metal of said organometal cocatalyst to vanadium within the range of 2:1 to 75:1.
Claim 5
Dependent Claim
35 words
A catalyst system according to claim 1 wherein said cocatalyst is present in an amount sufficient to give 50 to 250 parts by weight per million parts by weight of solvent in a polymerization reaction.
Claim 6
Dependent Claim
36 words
A catalyst system according to claim 1 wherein the vanadium of said vanadium compound is present in an amount within the range of 0.1 to 5 weight percent based on the weight of said phosphate-containing support.
Claim 7
Dependent Claim
16 words
A catalyst according to claim 1 wherein said vanadium compound is vanadium acetylacetonate or vanadyl trichloride.
Claim 8
Independent Claim
123 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by forming an aluminum phosphate hydrogel, converting said hydrogel to a xerogel, introducing a vanadium compound by one of coprecipitating with said aluminum phosphate, adding an aqueous solution of a vanadium compound to said hydrogel or adding a non-aqueous solution of a vanadium compound to said xerogel, and activating said xerogel containing said vanadium compound by heating to a temperature of 150°-800° C. to produce said supported catalyst; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 9
Independent Claim
123 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by forming an aluminum phosphate hydrogel, converting said hydrogel to a xerogel, introducing a vanadium compound by one of coprecipitating with said aluminum phosphate, adding an aqueous solution of a vanadium compound to said hydrogel or adding a non-aqueous solution of a vanadium compound to said xerogel, and activating said xerogel containing said vanadium compound by heating to a temperature of 150°-800° C. to produce said supported catalyst; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 10
Dependent Claim
30 words
A method according to claim 7 wherein said aluminum phosphate is produced by combining an aqueous solution containing aluminum and boron ions with a source of phosphate ions and neutralizing.
Claim 11
Dependent Claim
23 words
A method according to claim 8 wherein said aluminum ions are from aluminum nitrate and said source of phosphate ions is phosphoric acid.
Claim 12
Dependent Claim
20 words
A method according to claim 7 wherein said aluminum phosphate is produced by combining an aluminum alkoxide with phosphoric acid.
Claim 13
Dependent Claim
12 words
A method according to claim 10 wherein said alkoxide is aluminum ethoxide.
Claim 14
Independent Claim
138 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by forming an aluminum phosphate hydrogel by combining a source of phosphate ions with a melt of an aluminum salt and neutralizing, converting said hydrogel to a xerogel, introducing a vanadium compound by one of coprecipitating with said aluminum phosphate, adding an aqueous solution of a vanadium compound to said hydrogel or adding a non-aqueous of a vanadium compound to said xerogel, and activating said xerogel containing said vanadium compound by heating to a temperature of 150°-800° C. to produce said supported catalyst; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 15
Independent Claim
138 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by forming an aluminum phosphate hydrogel by combining a source of phosphate ions with a melt of an aluminum salt and neutralizing, converting said hydrogel to a xerogel, introducing a vanadium compound by one of coprecipitating with said aluminum phosphate, adding an aqueous solution of a vanadium compound to said hydrogel or adding a non-aqueous of a vanadium compound to said xerogel, and activating said xerogel containing said vanadium compound by heating to a temperature of 150°-800° C. to produce said supported catalyst; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 16
Dependent Claim
23 words
A method according to claim 11 wherein said aluminum salt is hydrated aluminum nitrate and said source of phosphate ions is phosphoric acid.
Claim 17
Dependent Claim
21 words
A method according to claim 7 wherein said activating is carried out in an ambient comprising either air or carbon monoxide.
Claim 18
Independent Claim
107 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by treating a silica-containing material with a phosphating agent selected from phosphate ions and vaporized phosphorus compounds so as to give 0.001 to 0.2 gram atoms of phosphorus per mole of silica, incorporating a vanadium compound to produce said supported catalyst, and activating the resulting catalyst at a temperature of 150°-800° C.; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 19
Independent Claim
107 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by treating a silica-containing material with a phosphating agent selected from phosphate ions and vaporized phosphorus compounds so as to give 0.001 to 0.2 gram atoms of phosphorus per mole of silica, incorporating a vanadium compound to produce said supported catalyst, and activating the resulting catalyst at a temperature of 150°-800° C.; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 20
Dependent Claim
43 words
A method according to claim 15 wherein said silica is produced by one of spray drying, tray drying, or oven drying and wherein said phosphating agent is phosphoric acid, and wherein said treating is carried out on said silica in the hydrogel stage.
Claim 21
Dependent Claim
18 words
A method according to claim 15 wherein said activating is carried out in either air or carbon monoxide.
Claim 22
Independent Claim
78 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by forming a silica/phosphate composition containing a vanadium compound, and activating said thus-produced vanadium-containing composition by heating at a temperature of 150°-800° C.; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 23
Independent Claim
78 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by forming a silica/phosphate composition containing a vanadium compound, and activating said thus-produced vanadium-containing composition by heating at a temperature of 150°-800° C.; and (b) combining said supported catalyst with an organoaluminum cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 24
Dependent Claim
32 words
A method according to claim 18 wherein said silica/phosphate composition is produced by coprecipitating silica and aluminum phosphate to form a hydrogel, and removing water from said hydrogel to form a xerogel.
Claim 25
Dependent Claim
26 words
A method according to claim 19 wherein said hydrogel is formed by contacting tetrahydrocarbyl orthosilicate with an aluminum salt and a phosphoric acid and thereafter neutralizing.
Claim 26
Dependent Claim
60 words
A method according to claim 18 wherein said silica/phosphate composition is produced by impregnating a silica hydrogel or xerogel with aluminum phosphate by adding a source of aluminum ions and phosphate ions to a slurry of a silica hydrogel or xerogel in a diluent and thereafter forming said aluminum phosphate by either evaporating off the diluent or adding a base.
Claim 27
Dependent Claim
49 words
A method according to claim 21 wherein said silica xerogel is produced by one of spray drying, tray drying, or oven drying, said source of aluminum ions is an aluminum salt, said source of phosphate ions is phosphoric acid and said phosphate is produced by evaporating off the solid.
Claim 28
Dependent Claim
49 words
A method according to claim 18 wherein said silica/phosphate composition is produced by impregnating a silica xerogel with boron phosphate by adding a source of boron ions and a source of phosphate ions to a slurry of a silica xerogel in a diluent and thereafter evaporating off the diluent.
Claim 29
Dependent Claim
38 words
A method according to claim 23 wherein said silica is produced by one of tray drying, spray drying, or ove drying, said source of boron ions is boric acid and said source of phosphate ions is phosphoric acid.
Claim 30
Dependent Claim
35 words
A method according to claim 18 wherein said silica/phosphate composition is produced by precipitating aluminum phosphate in the presence of a silica hydrogel or xerogel and removing water to convert said hydrogel to a xerogel.
Claim 31
Dependent Claim
38 words
A method according to claim 25 wherein sodium silicate is added to an acid to form said silica hydrogel and wherein an aluminum salt and phosphoric acid are added thereto and the resulting mixture neutralized with a base.
Claim 32
Dependent Claim
32 words
A method according to claim 23 wherein said silica/phosphate composition is produced by physically mixing a silica xerogel and aluminum phosphate xerogel either prior to said activating or subsequent to said activating.
Claim 33
Dependent Claim
17 words
A method according to claim 27 wherein said silica xerogel and aluminum phosphate xerogel are separately activated.
Claim 34
Independent Claim
119 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by phosphating an alumina-containing composition by treating same with a phosphating agent selected from (1) phosphate ions, and (2) vaporous phosphorus compounds to give a surface composition having a 0.2:1 to 1.8:1 P/Al atom ratio, said composition having a vanadium compound incorporated therein, activating the thus phosphated alumina composition containing said vanadium compound by heating at a temperature within the range of 150°-800° C.; and (b) combining said supported catalyst with an organometal cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 35
Independent Claim
119 words
A method of producing a catalyst system comprising: (a) forming a supported catalyst by phosphating an alumina-containing composition by treating same with a phosphating agent selected from (1) phosphate ions, and (2) vaporous phosphorus compounds to give a surface composition having a 0.2:1 to 1.8:1 P/Al atom ratio, said composition having a vanadium compound incorporated therein, activating the thus phosphated alumina composition containing said vanadium compound by heating at a temperature within the range of 150°-800° C.; and (b) combining said supported catalyst with an organometal cocatalyst of the formula R n AlX 3-n wherein R is a 1 to 12 carbon atom alkyl radical, n is a number between 1 and 2 inclusive, and X is a halogen.
Claim 36
Dependent Claim
24 words
A method according to claim 29 wherein said alumina is in the hydrogel stage during said phosphating and said phosphating agent is phosphoric acid.
Claim 37
Dependent Claim
17 words
A method according to claim 29 wherein said activating is carried out in air or carbon monoxide.
Claim 38
Dependent Claim
9 words
A catalyst produced by the method of claim 7.
Claim 39
Dependent Claim
9 words
A catalyst produced by the method of claim 15.
Claim 40
Dependent Claim
9 words
A catalyst produced by the method of claim 18.
Claim 41
Dependent Claim
9 words
A catalyst produced by the method of claim 29.
Claim 42
Dependent Claim
14 words
A method according to claim 7 wherein said activating is carried out in air.
Claim 43
Dependent Claim
15 words
A method according to claim 7 wherein said activating is carried out in carbon monoxide.
Claim 44
Dependent Claim
12 words
A method according to claim 7 wherein said cocatalyst is diethylaluminum chloride.
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) | 1986-08-08 | 1987-02-07 | 1987-08-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-08 | 1991-02-07 | 1991-08-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-08 | 1995-02-07 | 1995-08-09 | $7700.00 | Window Closed / Lapsed |