US4981831A
Expired / Lapsed
US
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Twice-aged porous inorganic oxides, catalysts, and polymerization processes
Assignee: Phillips Petroleum Co
•
Filing: 1988-07-25
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Granted: 1991-01-01
•
Expires: 2008-07-25
Abstract
Abstract A silica-titania cogel or silica-titania-chromium tergel is first aged at a substantially neutral pH, then aged at an alkaline pH, and then spray dried or azeotrope dried to form a xerogel. Optionally, a pore-preserving agent can be added prior to drying. The cogel can be impregnated with a chromium compound. The chromium-containing catalyst is activated by calcination. The activated catalyst can be used as a polymerization catalyst to polymerize mono-1-olefins.
Inventors
- 👤 Ronald D. Knudsen
- 👤 Max P. McDaniel
- 👤 Elizabeth A. Boggs
- 👤 F. Wallace Bailey
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 17:32
CPC Classifications
B; B01; B01J; B01J21/00; B01J21/06; B01J21/063; B01J23/00; B01J23/16; B01J23/24; B01J23/26; B01J37/00; B01J37/02; B01J37/03; C; C01; C01B; C01B33/00; C01B33/113; C01B33/12; C01B33/16; C08; C08F; C08F10/00; C08F10/02
Claims Analysis
Total Claims: 44
Claim 1
Independent Claim
84 words
A process to make a porous inorganic oxide comprising the steps of: (a) forming a silica-titania cogel hydrogel; (b) aging said cogel under substantially neutral pH conditions; (c) aging the thus neutral-aged cogel under alkaline pH conditions in an aqueous solution at a sufficient pH, for a sufficient time and at a sufficient temperature to accomplish at least one of decreasing surface area, increasing pore volume, and increasing pore radius of the xerogel; and (d) spray-drying the thus twice-aged cogel to form a xerogel.
Claim 2
Dependent Claim
84 words
A process to make a porous inorganic oxide comprising the steps of: (a) forming a silica-titania cogel hydrogel; (b) aging said cogel under substantially neutral pH conditions; (c) aging the thus neutral-aged cogel under alkaline pH conditions in an aqueous solution at a sufficient pH, for a sufficient time and at a sufficient temperature to accomplish at least one of decreasing surface area, increasing pore volume, and increasing pore radius of the xerogel; and (d) spray-drying the thus twice-aged cogel to form a xerogel.
Claim 3
Dependent Claim
32 words
A process according to claim 1 further comprising the step of adding a pore-preserving agent selected from the group consisting of surfactants, organic silicon compounds, and mixtures thereof to said twice-aged cogel.
Claim 4
Dependent Claim
55 words
A process according to claim 2 wherein said pore-preserving agent is an organic silicon compound, and wherein said organic silicon compound is selected from the group consisting of tri-t-butylsilanol, tri-t-octylsilanol, tricyclohexylsilanol, triphenylsilanol, tribenzylsilanol, tri-1-naphthylsilanol, tri-4-phenanthrylsilanol, tri-o-tolylsilanol, tri-p-cumenylsilanol, tris(4-pentyl-1-naphthyl)silanol, tris(10-decyl-9-anthryl)silanol, tris(3-cycloheptylphenyl)silanol, tris(7-phenyl-1-naphthyl)silanol, diphenylsilanediol, di-1-naphthylsilanediol, dicyclododecylsilanediol, di-t-octylsilanediol, triphenylchlorosilane, tri-1-naphthylbromosilane, dicyclohexyl dichlorosilane, diphenyldiethoxysilane, phenylcyclohexylsilanediol, diphenyl-t-butylchlorosilane, and mixtures thereof.
Claim 5
Dependent Claim
17 words
A process according to claim 1 further comprising incorporating a chromium compound into said porous inorganic oxide.
Claim 6
Dependent Claim
27 words
A process according to claim 4 wherein said chromium compound is incorporated by adding an aqueous solution of a chromium compound to said hydrogel, prior to spray-drying.
Claim 7
Dependent Claim
29 words
A process according to claim 1 wherein said cogel contains titanium in the range of about 0.1 to about 10 weight percent, based on the weight of the cogel.
Claim 8
Dependent Claim
52 words
A process according to claim 1 wherein said substantially neutral pH aging is in an aqueous solution with a pH in the range of about 6 to about 7 pH units, for a time of at least 2 hours, at a temperature in the range of about 15° to about 95° C.
Claim 9
Dependent Claim
57 words
A process according to claim 1 wherein said alkaline pH aging is in an aqueous solution with a pH in the range of about 8 to about 10 pH units, for a time in the range of about 1 minute to about 50 hours, at a temperature in the range of about 70° to about 120° C.
Claim 10
Dependent Claim
33 words
A process according to claim 1 wherein said aqueous solution comprises water and at least one compound selected from the group consisting of alkali metal hydroxides, alkali metal silicates, ammonia, and mixtures thereof.
Claim 11
Dependent Claim
44 words
A process according to claim 4 wherein said chromium compound is incorporated by impregnating said spray-dried xerogel with a chromium compound, wherein said xerogel contains chromium in the range of about 0.1 to about 20 weight percent, based on the weight of the xerogel.
Claim 12
Dependent Claim
47 words
A process according to claim 10 further comprising the step of heating said chromium impregnated xerogel at a temperature in the range of about 300° to about 1000° C., for a time in the range of about 30 minutes to about 50 hours, in an oxidizing atmosphere.
Claim 13
Dependent Claim
14 words
A process according to claim 1 wherein said silica-titania cogel is a silica-titania-chromium tergel.
Claim 14
Dependent Claim
32 words
A process according to claim 12 further comprising the step of adding a pore-preserving agent selected from the group consisting of surfactants, organic silicon compounds, and mixtures thereof to said twice-aged hydrogel.
Claim 15
Dependent Claim
55 words
A process according to claim 13 wherein said pore-preserving agent is said organic silicon compound, and wherein said organic silicon organisilicon compound is selected from the group consisting of tri-t-butylsilanol, tri-t-octylsilanol, tricyclohexylsilanol, triphenylsilanol, tribenzylsilanol, tri-1-naphthylsilanol, tri-4-phenanthrylsilanol, tri-o-tolylsilanol, tri-p-cumenylsilanol, tris(4-pentyl-1-naphthyl)silanol, tris(10-decyl-9-anthryl)silanol, tris(3-cycloheptylphenyl)silanol, tris(7-phenyl-1-naphthyl)silanol, diphenylsilanediol, di-1-naphthylsilanediol, dicyclododecylsilanediol, di-t-octylsilanediol, triphenylchlorosilane, tri-1-naphthylbromosilane, dicyclohexyldichlorosilane, diphenyldiethoxysilane, phenylcyclohexylsilanediol, diphenyl-t-butylchlorosilane, and mixtures thereof.
Claim 16
Dependent Claim
31 words
A process according to claim 12 wherein said silica-titania chromium tergel contains titanium in the range of about 0.1 to about 10 weight percent, based on the weight of the tergel.
Claim 17
Dependent Claim
31 words
A process according to claim 12 wherein said spray-dried silica-titania-chromium xerogel contains chromium in the range of about 0.1 to about 20 weight percent, based on the weight of the xerogel.
Claim 18
Dependent Claim
51 words
A process according to claim 12 wherein said neutral pH aging is in an aqueous solution with a pH in the range of about 6 to about 7 pH units, for a time of at least 2 hours, at a temperature in the range of about 15° to about 95° C.
Claim 19
Dependent Claim
48 words
A process according to claim 12 wherein said alkaline pH aging is in an aqueous solution at a sufficient pH, for a sufficient time and at a sufficient temperature to accomplish at least one of decreasing surface area, increasing pore volume, and increasing pore radius of the xerogel.
Claim 20
Dependent Claim
57 words
A process according to claim 12 wherein said alkaline pH aging is in an aqueous solution with a pH in the range of about 8 to about 10 pH units, for a time in the range of about 1 minute to about 50 hours, at a temperature in the range of about 70° to about 120° C.
Claim 21
Dependent Claim
33 words
A process according to claim 19 wherein said aqueous solution comprises water and at least one compound selected from the group consisting of alkali metal hydroxides, alkali metal silicates, ammonia, and mixtures thereof.
Claim 22
Dependent Claim
48 words
A process according to claim 12 further comprising the step of heating said silica-titania-chromium spray dried xerogel at a temperature in the range of about 300° to about 1000° C., for a time in the range of about 30 minutes to about 50 hours, in an oxidizing atmosphere.
Claim 23
Dependent Claim
10 words
A catalyst support produced by the process of claim 1.
Claim 24
Dependent Claim
10 words
A catalyst support produced by the process of claim 2.
Claim 25
Dependent Claim
9 words
A catalyst produced by the process of claim 10.
Claim 26
Dependent Claim
50 words
A catalyst according to claim 24 with a pore volume in the range of about 0.7 to about 1.1 cc/gm, an average pore radius in the range of about 30 to about 60 Å, and a surface area in the range of about 300 to about 400 m 2 /gm.
Claim 27
Dependent Claim
9 words
A catalyst produced by the process of claim 12.
Claim 28
Dependent Claim
9 words
A catalyst produced by the process of claim 13.
Claim 29
Dependent Claim
88 words
A process to make a porous inorganic oxide comprising the steps of: (a) forming a silica-titania cogel hydrogel; (b) aging said cogel under substantially neutral pH conditions; (c) aging the thus neutral-aged cogel under alkaline pH conditions in an aqueous solution at a sufficient pH, for a sufficient time and at a sufficient temperature to accomplish at least one of decreasing surface area, increasing pore volume, and increasing pore radius of the xerogel; and (d) azeotrope drying the thus twice-aged hydrogel to convert said hydrogel to a xerogel.
Claim 30
Dependent Claim
88 words
A process to make a porous inorganic oxide comprising the steps of: (a) forming a silica-titania cogel hydrogel; (b) aging said cogel under substantially neutral pH conditions; (c) aging the thus neutral-aged cogel under alkaline pH conditions in an aqueous solution at a sufficient pH, for a sufficient time and at a sufficient temperature to accomplish at least one of decreasing surface area, increasing pore volume, and increasing pore radius of the xerogel; and (d) azeotrope drying the thus twice-aged hydrogel to convert said hydrogel to a xerogel.
Claim 31
Dependent Claim
32 words
A process according to claim 28 further comprising the step of adding a pore-preserving agent selected from the group consisting of surfactants, organic silicon compounds, and mixtures thereof to said twice-aged cogel.
Claim 32
Dependent Claim
17 words
A process according to claim 28 further comprising incorporating a chromium compound into said porous inorganic oxide.
Claim 33
Dependent Claim
44 words
A process according to claim 30 wherein said chromium compound is incorporated by impregnating said azeotrope-dried xerogel with a chromium compound, wherein said xerogel contains chromium in the range of about 0.1 to about 20 weight percent, based on the weight of the xerogel.
Claim 34
Dependent Claim
47 words
A process according to claim 31 further comprising the step of heating said chromium impregnated xerogel at a temperature in the range of about 300° to about 1000° C., for a time in the range of about 30 minutes to about 50 hours, in an oxidizing atmosphere.
Claim 35
Dependent Claim
14 words
A process according to claim 28 wherein said silica-titania cogel is a silica-titania-chromium tergel.
Claim 36
Dependent Claim
32 words
A process according to claim 33 further comprising the step of adding a pore-preserving agent selected from the group consisting of surfactants, organic silicon compounds, and mixtures thereof to said twice-aged hydrogel.
Claim 37
Dependent Claim
48 words
A process according to claim 33 further comprising the step of heating said silica-titania-chromium azeotrope dried xerogel at a temperature in the range of about 300° to about 1000° C., for a time in the range of about 30 minutes to about 50 hours in an oxidizing atmosphere.
Claim 38
Dependent Claim
10 words
A catalyst support produced by the process of claim 28.
Claim 39
Dependent Claim
50 words
A catalyst according to claim 36 with a pore volume in the range of about 2.0 to about 2.8 cc/gm, an average pore radius in the range of about 100 to about 200 Å, and a surface area in the range of about 300 to about 400 m 2 /gm.
Claim 40
Dependent Claim
9 words
A catalyst produced by the process of claim 32.
Claim 41
Dependent Claim
9 words
A catalyst produced by the process of claim 35.
Claim 42
Dependent Claim
149 words
A process to make a catalyst comprising: (a) forming a silica-titania-chromium tergel; (b) aging said tergel under substantially neutral pH conditions, said conditions comprising a pH of about 7, for a time of about 2 hours, and a temperature in the range of about 80° to about 95° C.; (c) aging the thus neutral-aged tergel under alkaline pH conditions, said conditions comprising using ammonium hydroxide to achieve and maintain a pH in the range of about 8 to about 10, for a time in the range of about 5 to about 30 hours, and a temperature in the range of about 80° to about 95° C.; (d) spray-drying the thus twice-aged tergel to form a xerogel; and (e) calcining said xerogel under air at a temperature in the range of about 300° to about 800° C., for a time in the range of about 2 to about 10 hours.
Claim 43
Dependent Claim
149 words
A process to make a catalyst comprising: (a) forming a silica-titania-chromium tergel; (b) aging said tergel under substantially neutral pH conditions, said conditions comprising a pH of about 7, for a time of about 2 hours, and a temperature in the range of about 80° to about 95° C.; (c) aging the thus neutral-aged tergel under alkaline pH conditions, said conditions comprising using ammonium hydroxide to achieve and maintain a pH in the range of about 8 to about 10, for a time in the range of about 5 to about 30 hours, and a temperature in the range of about 80° to about 95° C.; (d) spray-drying the thus twice-aged tergel to form a xerogel; and (e) calcining said xerogel under air at a temperature in the range of about 300° to about 800° C., for a time in the range of about 2 to about 10 hours.
Claim 44
Dependent Claim
9 words
A catalyst produced by the process of claim 40.
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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) | 1993-12-31 | 1994-07-02 | 1995-01-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-12-31 | 1998-07-02 | 1999-01-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-12-31 | 2002-07-02 | 2003-01-01 | $7700.00 | Window Closed / Lapsed |