US4294724A
Expired / Lapsed
US
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Titanium impregnated silica-chromium catalysts
Assignee: Phillips Petroleum Co
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Filing: 1980-02-06
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Granted: 1981-10-13
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Expires: 2000-02-06
Abstract
Abstract In accordance with one embodiment of this invention, a silica hydrogel is prepared and dried in the presence of a pore preserving agent after which a titanium compound is anhydrously incorporated therewith. In accordance with the second embodiment of this invention, a silica hydrogel or a silica xerogel is impregnated with an aqueous organic acid solution of a substituted or unsubstituted titanium acetylacetonate. The invention allows the use of conventional drying to produce a silica exhibiting characteristics associated with azeotrope dried titanium-silica for use as a support for chromium catalysts. The resulting catalysts are broadly applicable in the polymerization of olefins and are of particular utility in the slurry polymerization of olefins, particularly predominantly ethylene monomer.
Inventors
- 👤 Max P. McDaniel
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 20:54
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
206 words
A process for producing a chromium-containing catalyst comprising forming a silica hydrogel containing a pore preserving agent selected from (1) organic silicon compounds having the structure R n SiA 4-n wherein n is an integer of 2 or 3, and wherein each R is a saturated or unsaturated hydrocarbon group wherein each R can be the same or different and wherein A is selected from the group consisting of hydroxy radicals, halides and alkoxy radicals in which the alkyl group therein contains from 1 to about 10 carbon atoms, (2) water soluble inorganic acids which are sufficiently ionized to produce a pH of 0 to 3.5, (3) organic acids having an acid strength equal to or greater than that of acetic acid, and (4) anionic, cationic or non-ionic surfactants; drying said hydrogel by means of air oven drying, spray drying, tray drying, vacuum oven drying or drying under a heat lamp to form a xerogel; and anhydrously incorporating a titanium compound into said xerogel, and wherein said chromium is introduced by either coprecipitating same with said silica hydrogel, by combining an aqueous solution of a water-soluble chromium compound with said hydrogel, or adding anhydrous solution of a chromium compound soluble in non-aqueous solvents to said xerogel.
Claim 2
Dependent Claim
206 words
A process for producing a chromium-containing catalyst comprising forming a silica hydrogel containing a pore preserving agent selected from (1) organic silicon compounds having the structure R n SiA 4-n wherein n is an integer of 2 or 3, and wherein each R is a saturated or unsaturated hydrocarbon group wherein each R can be the same or different and wherein A is selected from the group consisting of hydroxy radicals, halides and alkoxy radicals in which the alkyl group therein contains from 1 to about 10 carbon atoms, (2) water soluble inorganic acids which are sufficiently ionized to produce a pH of 0 to 3.5, (3) organic acids having an acid strength equal to or greater than that of acetic acid, and (4) anionic, cationic or non-ionic surfactants; drying said hydrogel by means of air oven drying, spray drying, tray drying, vacuum oven drying or drying under a heat lamp to form a xerogel; and anhydrously incorporating a titanium compound into said xerogel, and wherein said chromium is introduced by either coprecipitating same with said silica hydrogel, by combining an aqueous solution of a water-soluble chromium compound with said hydrogel, or adding anhydrous solution of a chromium compound soluble in non-aqueous solvents to said xerogel.
Claim 3
Dependent Claim
25 words
A process according to claim 1 wherein said chromium in the form of a compound soluble in nonaqueous solvents is anhydrously impregnated onto said xerogel.
Claim 4
Dependent Claim
22 words
A method according to claim 1 wherein said hydrogel is washed and after said washing said pore preserving agent is admixed therewith.
Claim 5
Dependent Claim
24 words
A method according to claim 3 wherein said chromium is added as an aqueous solution of a water soluble chromium compound to said hydrogel.
Claim 6
Dependent Claim
24 words
A method according to claim 4 wherein said chromium is incorporated in the form of a compound selected from CrO 3 and chromium acetate.
Claim 7
Dependent Claim
38 words
A method according to claim 3 wherein said chromium-containing catalyst contains from about 0.5 to about 4 weight percent chromium and from 1.5 to 5.5 weight percent titanium based on the total weight of the final dried catalyst.
Claim 8
Dependent Claim
23 words
A method according to claim 3 wherein said titanium is incorporated by impregnating said xerogel with a nonaqueous solution of a titanium compound.
Claim 9
Dependent Claim
16 words
A method according to claim 7 wherein said titanium compound is added in a hydrocarbon solution.
Claim 10
Dependent Claim
13 words
A method according to claim 8 wherein said titanium compound is titanium tetraisopropoxide.
Claim 11
Dependent Claim
21 words
A method according to claim 3 wherein said titanium compound is added neat to said xerogel during a subsequent activation process.
Claim 12
Dependent Claim
25 words
A method according to claim 1 wherein said pore preserving agent is selected from a polysiloxane-polyoxyalkylene copolymer, a polyethoxylated sorbitol monolaurate, and a polyethoxylated t-octylphenol.
Claim 13
Dependent Claim
12 words
A method according to claim 3 wherein said hydrogel is spray dried.
Claim 14
Dependent Claim
42 words
A method according to claim 12 wherein said pore preserving agent is selected from a polysiloxane-polyoxyalkylene copolymer, a polyethoxylated sorbitol monolaurate, and a polyethoxylated t-octylphenol, said titanium compound is titanium tetraisopropoxide and wherein said titanium compound is added from a hydrocarbon solution.
Claim 15
Dependent Claim
15 words
A method according to claim 1 wherein said xerogel is activated by reduction and reoxidation.
Claim 16
Dependent Claim
9 words
A catalyst produced by the method of claim 14.
Claim 17
Dependent Claim
9 words
A catalyst produced by the method of claim 1.
Claim 18
Dependent Claim
137 words
A process for producing a chromium-containing catalyst comprising forming a silica hydrogel and thereafter removing water to form a xerogel, said silica in either the hydrogel stage or the xerogel stage being impregnated with an aqueous titanium-containing composition formed by mixing an essentially water-free organic acid and a titanium compound of the formula ##STR2## wherein the R and R' groups are the same or different and are selected from 1-7 carbon atom alkyl radicals to give a titanium-containing composition and thereafter diluting said titanium-containing composition with water to give said aqueous titanium-containing composition, and wherein said chromium is introduced by either coprecipitating same with said silica hydrogel, by combining an aqueous solution of a water-soluble chromium compound with said hydrogel, or adding an anhydrous solution of a chromium compound soluble in a non-aqueous solvent to said xerogel.
Claim 19
Dependent Claim
137 words
A process for producing a chromium-containing catalyst comprising forming a silica hydrogel and thereafter removing water to form a xerogel, said silica in either the hydrogel stage or the xerogel stage being impregnated with an aqueous titanium-containing composition formed by mixing an essentially water-free organic acid and a titanium compound of the formula ##STR2## wherein the R and R' groups are the same or different and are selected from 1-7 carbon atom alkyl radicals to give a titanium-containing composition and thereafter diluting said titanium-containing composition with water to give said aqueous titanium-containing composition, and wherein said chromium is introduced by either coprecipitating same with said silica hydrogel, by combining an aqueous solution of a water-soluble chromium compound with said hydrogel, or adding an anhydrous solution of a chromium compound soluble in a non-aqueous solvent to said xerogel.
Claim 20
Dependent Claim
34 words
A method according to claim 17 wherein said organic acid and said titanium compound are mixed in a ratio within the range of 1:1 to 10:1 of acid:titanium compound to form said titanium-containing composition.
Claim 21
Dependent Claim
33 words
A method according to claim 18 wherein said titanium-containing composition is diluted with said water in a ratio within the range of 1:1 to 10:1 water:titanium-containing composition to give said aqueous titanium-containing composition.
Claim 22
Dependent Claim
21 words
A method according to claim 17 wherein said aqueous titanium containing-containing composition is added to said silica at the hydrogel stage.
Claim 23
Dependent Claim
29 words
A method according to claim 17 wherein said aqueous titanium-containing composition is added to said silica in the xerogel stage and thereafter the thus titanium impregnated xerogel is dried.
Claim 24
Dependent Claim
31 words
A method according to claim 21 wherein said silica is formed from a hydrogel also containing a pore preserving agent selected from organic silicon compounds, oxygen-containing organic compounds, acids and surfactants.
Claim 25
Dependent Claim
12 words
A method according to claim 17 wherein said R groups are methyl.
Claim 26
Dependent Claim
62 words
A method according to claim 17 wherein said silica is made by adding an alkali metal silicate to an acid to form a hydrogel, washing the hydrogel with water, impregnating the thus washed hydrogel with an aqueous solution of a chromium compound selected from CrO 3 and chromium acetate and spray drying, said aqueous titanium-containing composition being added to the washed hydrogel.
Claim 27
Dependent Claim
58 words
A method according to claim 24 wherein said chromium-containing catalyst contains from about 0.5 to about 4 weight percent chromium and 1.5 to 5.5 weight percent titanium based on the total weight of the final dried catalyst and wherein the titanium compound is diisopropoxy titanium acetylacetonate and wherein said essentially water free organic acid is glacial acetic acid.
Claim 28
Dependent Claim
17 words
A method according to claim 25 wherein said thus impregnated silica is activated by reduction and reoxidation.
Claim 29
Dependent Claim
9 words
A catalyst produced by the method of claim 26.
Claim 30
Dependent Claim
9 words
A catalyst produced by the method of claim 17.
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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) | 1984-10-12 | 1985-04-13 | 1985-10-13 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-10-12 | 1989-04-13 | 1989-10-13 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-10-12 | 1993-04-13 | 1993-10-13 | $7700.00 | Window Closed / Lapsed |