US4248735A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Treatment of silica
Assignee: Phillips Petroleum Co
•
Filing: 1979-06-01
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Granted: 1981-02-03
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Expires: 1999-06-01
Abstract
Abstract A silica-containing composition suitable for supporting chromium to produce a catalyst capable of giving high melt flow olefin polymers for such applications as injection molding and the like requiring a narrow molecular weight distribution, is produced by treating a silica-containing material at an elevated temperature with either (1) CO, (2) a bromine or iodine component, or (3) an oxygen-containing sulfur component, more specifically a carbon, oxygen and sulfur-containing component. Thereafter, anhydrous chromium can be added, for instance, by means of a hydrocarbon solution of a soluble chromium compound, and the resulting composition activated in air to produce a catalyst. The bromine or iodine treated silica contains bound bromine or iodine if the treating agent is HBr, HI, an organic halide of Br or I or elemental Br or I used in conjunction with a reducing agent. This material is a novel composition of matter and is suitable for use as a reinforcing agent in rubber or plastics and as a support for a chromatographic column in addition to being suitable for supporting a chromium compound to produce a catalyst.
Inventors
- 👤 Max P. McDaniel
- 👤 Melvin B. Welch
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 03:02
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/16; B01J23/24; B01J23/26; B01J37/00; B01J37/12
Claims Analysis
Total Claims: 54
Claim 1
Independent Claim
81 words
A method for producing a catalyst comprising subjecting a silica-containing support at an elevated temperature to a treating ambient selected from (1) carbon monoxide, (2) a halogen-containing component selected from bromine, iodine, HBr, HI, organic bromides, and organic iodides, which halogen-containing component also either contains air or is followed by air or (3) a carbon, oxygen and sulfur-containing composition, thereafter incorporating a chromium compound under anhydrous conditions to thus form said catalyst and thereafter activating said catalyst in an oxygen ambient.
Claim 2
Independent Claim
81 words
A method for producing a catalyst comprising subjecting a silica-containing support at an elevated temperature to a treating ambient selected from (1) carbon monoxide, (2) a halogen-containing component selected from bromine, iodine, HBr, HI, organic bromides, and organic iodides, which halogen-containing component also either contains air or is followed by air or (3) a carbon, oxygen and sulfur-containing composition, thereafter incorporating a chromium compound under anhydrous conditions to thus form said catalyst and thereafter activating said catalyst in an oxygen ambient.
Claim 3
Dependent Claim
39 words
A method according to claim 1 wherein after said incorporation of said chromium compound said catalyst is activated in an oxygen ambient at a temperature within the range of 15°-870° C. for a time of at least 5 minutes.
Claim 4
Dependent Claim
14 words
A method according to claim 1 wherein said silica is a coprecipitated silica-titania cogel.
Claim 5
Dependent Claim
30 words
A method according to claim 1 wherein said chromium is incorporated in an amount sufficient to give 0.1 to 5 weight percent chromium based on the weight of said support.
Claim 6
Dependent Claim
43 words
A method according to claim 1 wherein said support is a silica-titania cogel containing 0.5 to 5 weight percent titanium based on the weight of said cogel. tion conditions after being subjected to said ambient and prior to incorporation of said chromium compound.
Claim 7
Dependent Claim
22 words
A method according to claim 1 wherein said chromium compound is incorporated by means of an inert liquid hydrocarbon diluent or solvent.
Claim 8
Dependent Claim
31 words
A method according to claim 1 wherein said support is preoxidized by being subjected to oxidation conditions after being subjected to said ambient and prior to incorporation of said chromium compound.
Claim 9
Dependent Claim
9 words
A catalyst produced by the method of claim 1.
Claim 10
Dependent Claim
13 words
A method according to claim 5 wherein said treating ambient is carbon monoxide.
Claim 11
Dependent Claim
13 words
A method according to claim 5 wherein said treating ambient is bromine vapor.
Claim 12
Dependent Claim
12 words
A method according to claim 5 wherein said treating ambient is HBr.
Claim 13
Dependent Claim
12 words
A method according to claim 5 wherein said treating ambient is bromine+air.
Claim 14
Dependent Claim
13 words
A method according to claim 5 wherein said treating ambient is iodine vapor.
Claim 15
Dependent Claim
12 words
A method according to claim 5 wherein said treating ambient is HI.
Claim 16
Dependent Claim
12 words
A method according to claim 5 wherein said treating ambient is iodine+air.
Claim 17
Dependent Claim
32 words
A method according to claim 5 wherein said treating ambient is said halogen-containing component of (2) and wherein said halogen-containing component is bromine and wherein said ambient contains in addition carbon monoxide.
Claim 18
Dependent Claim
32 words
A method according to claim 5 wherein said treating ambient is said halogen-containing component of (2) and wherein said halogen-containing component is iodine and wherein said ambient contains in addition carbon monoxide.
Claim 19
Dependent Claim
13 words
A method according to claim 5 wherein said treating ambient is carbonyl sulfide.
Claim 20
Dependent Claim
17 words
A method according to claim 5 wherein said elevated temperature is within the range of 750°-925° C.
Claim 21
Dependent Claim
24 words
A method according to claim 6 wherein said chromium compound is one of a π-bonded organochromium compound, esters of chromic acid, and chromium acetylacetonate.
Claim 22
Dependent Claim
87 words
A method according to claim 7 wherein said support is a silica-titania cogel containing about 2 weight percent titanium, said elevated temperature is within the range of 750°-925° C., said chromium compound is selected from tertiary butyl chromate, and dicumene chromium carried in normal hexane, and wherein said preoxidation is carried out at a temperature within the range of 525°-925° C., and wherein after said incorporation of said chromium compound said catalyst is activated by heating in air at a temperature within the range of 315°-760° C.
Claim 23
Dependent Claim
9 words
A catalyst produced by the method of claim 21.
Claim 24
Independent Claim
58 words
A method for producing an iodinated or brominated silica comprising subjecting a silica-containing composition at a temperature within the range of 500°-1000° C. under reducing conditions to a treating ambient selected from at least one of (a) elemental iodine or elemental bromine plus a reducing agent; (b) HI or HBr or (c) an organic iodide or organic bromide.
Claim 25
Independent Claim
58 words
A method for producing an iodinated or brominated silica comprising subjecting a silica-containing composition at a temperature within the range of 500°-1000° C. under reducing conditions to a treating ambient selected from at least one of (a) elemental iodine or elemental bromine plus a reducing agent; (b) HI or HBr or (c) an organic iodide or organic bromide.
Claim 26
Dependent Claim
32 words
A method according to claim 23 wherein said treating ambient comprises 0.1 to 10 mole percent of iodine or bromine, the remainder being said reducing agent, said reducing agent comprising carbon monoxide.
Claim 27
Dependent Claim
17 words
A method according to claim 24 wherein said elevated temperature is within the range of 750°-925° C.
Claim 28
Dependent Claim
17 words
A method according to claim 24 wherein said treating ambient consists essentially of iodine vapor plus CO.
Claim 29
Dependent Claim
17 words
A method according to claim 24 wherein said treating agent consists essentially of bromine plus carbon monoxide.
Claim 30
Dependent Claim
37 words
A composition comprising silica containing 0.01-20 weight percent of a halogen selected from bromine and iodine based on the weight of said silica, said composition being further characterized by said halogen being bound directly to silicon atoms.
Claim 31
Dependent Claim
37 words
A composition comprising silica containing 0.01-20 weight percent of a halogen selected from bromine and iodine based on the weight of said silica, said composition being further characterized by said halogen being bound directly to silicon atoms.
Claim 32
Dependent Claim
31 words
A composition according to claim 28 wherein said halogen is iodine and is present in an amount within the range of 3-10 weight percent based on the weight of said silica.
Claim 33
Dependent Claim
31 words
A composition according to claim 28 wherein said halogen is bromine and is present in an amount within the range of 3-10 weight percent based on the weight of said silica.
Claim 34
Dependent Claim
16 words
A composition according to claim 29 wherein said silica is produced by coprecipitating silica and titanium.
Claim 35
Dependent Claim
41 words
A composition comprising silica containing 0.001 to 1 millimoles of a halogen selected from bromine and iodine per 100 square meters of surface area of said silica, said composition being further characterized by said halogen being bound directly to silicon atoms.
Claim 36
Dependent Claim
41 words
A composition comprising silica containing 0.001 to 1 millimoles of a halogen selected from bromine and iodine per 100 square meters of surface area of said silica, said composition being further characterized by said halogen being bound directly to silicon atoms.
Claim 37
Dependent Claim
24 words
A composition according to claim 32 containing 0.03 to 0.3 millimoles of said halogen per 100 square meters of surface area of said silica.
Claim 38
Dependent Claim
16 words
A composition according to claim 32 wherein said silica is produced by coprecipitating silica and titanium.
Claim 39
Dependent Claim
23 words
A composition according to claim 32 further characterized by said halogen not coming off at 871° C. in CO or N 2 .
Claim 40
Dependent Claim
11 words
A composition according to claim 32 wherein said halogen is iodine.
Claim 41
Dependent Claim
11 words
A composition according to claim 32 wherein said halogen is bromine.
Claim 42
Dependent Claim
43 words
A composition comprising silica containing 0.01-20 weight percent of a halogen selected from bromine and iodine based on the weight of said silica, said composition being further characterized by said halogen not coming off at 871° C. in CO or N 2 .
Claim 43
Dependent Claim
43 words
A composition comprising silica containing 0.01-20 weight percent of a halogen selected from bromine and iodine based on the weight of said silica, said composition being further characterized by said halogen not coming off at 871° C. in CO or N 2 .
Claim 44
Dependent Claim
11 words
A composition according to claim 38 wherein said halogen is iodine.
Claim 45
Dependent Claim
11 words
A composition according to claim 38 wherein said halogen is bromine.
Claim 46
Independent Claim
63 words
A method of making a free radical containing silica composition comprising subjecting a silica-containing composition at a temperature within the range of 500°-1000° C. under reducing conditions to a treating ambient selected from (a) elemental iodine plus a reducing agent; (b) HI or (c) an organic iodide and thereafter treating the resulting halogen-containing silica in an oxygen-containing ambient to burn off surface halogen.
Claim 47
Independent Claim
63 words
A method of making a free radical containing silica composition comprising subjecting a silica-containing composition at a temperature within the range of 500°-1000° C. under reducing conditions to a treating ambient selected from (a) elemental iodine plus a reducing agent; (b) HI or (c) an organic iodide and thereafter treating the resulting halogen-containing silica in an oxygen-containing ambient to burn off surface halogen.
Claim 48
Dependent Claim
19 words
A method according to claim 41 wherein said treatment to burn off surface halogen is carried out in air.
Claim 49
Dependent Claim
10 words
A silica composition produced by the method of claim 41.
Claim 50
Dependent Claim
37 words
A method according to claim 42 wherein said treatment to burn off surface halogen is carried out at a temperature within the range of 525°-925° C. for a time within the range of 1 to 5 hours.
Claim 51
Dependent Claim
16 words
A method according to claim 42 wherein said treating ambient is elemental iodine plus carbon monoxide.
Claim 52
Dependent Claim
19 words
A method according to claim 42 wherein said silica is a silica-titania cogel containing about 2 weight percent titanium.
Claim 53
Dependent Claim
18 words
A composition according to claim 43 having an ESR g value within the range of 1.8 to 2.2.
Claim 54
Dependent Claim
20 words
A composition according to claim 43 wherein said silica is a silica-titania containing cogel containing about 2 weight percent titanium.
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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) | 1984-02-03 | 1984-08-04 | 1985-02-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-02-03 | 1988-08-04 | 1989-02-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-02-03 | 1992-08-04 | 1993-02-03 | $7700.00 | Window Closed / Lapsed |