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Olefin polymerization catalyst and catalyst support

Assignee: Enron Chemical Co
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Filing: 1983-06-07
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Granted: 1984-10-09
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Expires: 2003-06-07
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Abstract

Abstract Catalysts prepared from large pore volume zirconia-silica catalyst supports and a method of polymerizing olefins comprising contacting an olefin or mixture of olefins with the catalysts. The supports are prepared by reacting a zirconium compound of the formula M 4 Zr(C 2 O 4 ) 4 .nH 2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A 2 SiO 3 , where A is an alkali metal, in an aqueous solution at a pH equal to at least 11, then adding an acidic solution to a pH of about 5-9 to produce a hydrocogel. The hydrocogel is then aged and washed free of soluble by-products with an aqueous liquid. Water is removed from the washed hydrocogel by azeotropic distillation or by washing with a water miscible solvent, then residual water is removed by chemically reacting this water with a ketal of the formula RC(OR) 2 R where R is the same or different and is an alkyl group of 1-5 carbon atoms, and then calcining the resulting xerocogel.

Inventors

  • 👤 Robert A. Dombro

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-26 14:15
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/16; B01J23/24; B01J23/26; B01J21/00; B01J21/06; B01J21/08; C; C08; C08F; C08F10/00

Claims Analysis

Total Claims: 18
Claim 1
Independent Claim 245 words
An olefin polymerization catalyst prepared by the steps of: a. reacting a zirconium compound of the formula M 4 Zr(C 2 O 4 ) 4 .nH 2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A 2 SiO 3 , where A is an alkali metal, in an aqueous solution at a pH of at least 11 and then adding an acidic material to a pH of about 5-9, to produce a hydrocogel; b. aging said hydrocogel at a temperature between about ambient to 90° C. for at least one hour; c. washing said hydrocogel of b with an aqueous liquid; d. partially dehydrating the resulting washed hydrocogel of c by azeotropic distillation by mixing with a compound capable of forming an azeotrope with water or by washing the hydrocogel with a water miscible solvent to produce a substantially water-free, large pore volume zirconia-silica catalyst support; e. removing residual water from the product of d by chemically reacting this water with a ketal of the formula RC(OR) 2 R in which R is the same or different and is hydrogen or an alkyl group of 1-5 carbon atoms; f. calcining the resulting zerocogel at a temperature of about 1000°-1850° F. preparatory to its use as an olefin polymerization catalyst support; g. introducting a chromium compound onto said calcined support of f; and h. activating to produce an active polymerization catalyst.
Claim 2
Dependent Claim 245 words
An olefin polymerization catalyst prepared by the steps of: a. reacting a zirconium compound of the formula M 4 Zr(C 2 O 4 ) 4 .nH 2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A 2 SiO 3 , where A is an alkali metal, in an aqueous solution at a pH of at least 11 and then adding an acidic material to a pH of about 5-9, to produce a hydrocogel; b. aging said hydrocogel at a temperature between about ambient to 90° C. for at least one hour; c. washing said hydrocogel of b with an aqueous liquid; d. partially dehydrating the resulting washed hydrocogel of c by azeotropic distillation by mixing with a compound capable of forming an azeotrope with water or by washing the hydrocogel with a water miscible solvent to produce a substantially water-free, large pore volume zirconia-silica catalyst support; e. removing residual water from the product of d by chemically reacting this water with a ketal of the formula RC(OR) 2 R in which R is the same or different and is hydrogen or an alkyl group of 1-5 carbon atoms; f. calcining the resulting zerocogel at a temperature of about 1000°-1850° F. preparatory to its use as an olefin polymerization catalyst support; g. introducting a chromium compound onto said calcined support of f; and h. activating to produce an active polymerization catalyst.
Claim 3
Dependent Claim 21 words
The catalyst of claim 1 wherein said acidic compound in said aqueous solution is sulfuric acid, hydrochloric acid or ammonium sulfate.
Claim 4
Dependent Claim 10 words
The catalyst of claim 1 wherein said ketal comprises 2,2-dimethoxypropane.
Claim 5
Dependent Claim 10 words
The catalyst of claim 1 wherein said ketal comprises 2,2-dimethoxybutane.
Claim 6
Dependent Claim 10 words
The catalyst of claim 1 wherein said ketal comprises 2,2-diethoxypropane.
Claim 7
Dependent Claim 10 words
The catalyst of claim 1 wherein said ketal comprises 2-methoxy-2-ethoxypropane.
Claim 8
Dependent Claim 32 words
The catalyst of claim 1 wherein said washing step (c) is carried out with an aqueous liquid comprising at least one of water and an aqueous solution of a thermally decomposible salt.
Claim 9
Dependent Claim 24 words
The catalyst of claim 7 wherein said thermally decomposible salt is selected from the group consisting of ammonium nitrate, ammonium carbonate, and ethylenediamine diacetate.
Claim 10
Dependent Claim 225 words
A catalyst support prepared by the steps of: a. reacting a zirconium compound of the formula M 4 Zr(C 2 O 4 ) 4 .nH 2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A 2 SiO 3 , where A is an alkali metal, in an aqueous solution at a pH of at least 11 and then adding an acidic material to a pH of about 5-9, to produce a hydrocogel; b. aging said hydrocogel at a temperature between about ambient to 90° C. for at least one hour; c. washing said hydrocogel of b with an aqueous liquid; d. partially dehydrating the resulting washed hydrocogel of c by azeotropic distillation by mixing with a compound capable of forming an azeotrope with water or by washing the hydrocogel with a water miscible solvent to produce a substantially water-free, large pore volume zirconia-silica catalyst support; e. removing residual water from the product of d by chemically reacting this water with a ketal of the formula RC(OR) 2 R in which R is the same or different and is hydrogen or an alkyl group of 1-5 carbon atoms; and, f. calcining the resulting zerocogel at a temperature of about 1000°-1850° F. prepatory to its use as an olefin polymerization catalyst support.
Claim 11
Dependent Claim 225 words
A catalyst support prepared by the steps of: a. reacting a zirconium compound of the formula M 4 Zr(C 2 O 4 ) 4 .nH 2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A 2 SiO 3 , where A is an alkali metal, in an aqueous solution at a pH of at least 11 and then adding an acidic material to a pH of about 5-9, to produce a hydrocogel; b. aging said hydrocogel at a temperature between about ambient to 90° C. for at least one hour; c. washing said hydrocogel of b with an aqueous liquid; d. partially dehydrating the resulting washed hydrocogel of c by azeotropic distillation by mixing with a compound capable of forming an azeotrope with water or by washing the hydrocogel with a water miscible solvent to produce a substantially water-free, large pore volume zirconia-silica catalyst support; e. removing residual water from the product of d by chemically reacting this water with a ketal of the formula RC(OR) 2 R in which R is the same or different and is hydrogen or an alkyl group of 1-5 carbon atoms; and, f. calcining the resulting zerocogel at a temperature of about 1000°-1850° F. prepatory to its use as an olefin polymerization catalyst support.
Claim 12
Dependent Claim 22 words
The catalyst support of claim 9 wherein said acidic compound in said aqueous solution is sulfuric acid, hydrochloric acid or ammonium sulfate.
Claim 13
Dependent Claim 11 words
The catalyst support of claim 9 wherein said ketal comprises 2,2-dimethoxypropane.
Claim 14
Dependent Claim 11 words
The catalyst support of claim 9 wherein said ketal comprises 2,2-dimethoxybutane.
Claim 15
Dependent Claim 11 words
The catalyst support of claim 9 wherein said ketal comprises 2,2-diethoxypropane.
Claim 16
Dependent Claim 11 words
The catalyst support of claim 9 wherein said ketal comprises 2-methoxy-2-ethoxypropane.
Claim 17
Dependent Claim 33 words
The catalyst support of claim 9 wherein said washing step c is carried out with an aqueous liquid comprising at least one of water and an aqueous solution of a thermally decomposible salt.
Claim 18
Dependent Claim 25 words
The catalyst support of claim 15 wherein said thermally decomposible salt is selected from the group consisting of ammonium nitrate, ammonium carbonate, and ethylenediamine diacetate.

References Cited (Backward Citations)

US3120483A Cited
US3950316A Cited
US4279780A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1987-10-09 1988-04-09 1988-10-09 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1991-10-09 1992-04-09 1992-10-09 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1995-10-09 1996-04-09 1996-10-09 $7700.00 Window Closed / Lapsed

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