Patent US4513093A successfully refreshed from Google Patents.
US4513093A
Expired / Lapsed
US
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Immobilization of vanadia deposited on sorbent materials during treatment of carbo-metallic oils
Assignee: Ashland LLC
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Filing: 1981-03-19
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Granted: 1985-04-23
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Expires: 2001-03-19
Abstract
Abstract A process is disclosed for the treatment of a hydrocarbon oil feed having a significant content of vanadium to provide a higher grade of oil products by contacting the feed under treatment conditions in a treatment zone with sorbent material containing a metal additive to immobilize vanadium compounds. Treatment conditions are such that coke and vanadium are deposited on the sorbent in the treatment zone. Coked sorbent is regenerated in the presence of an oxygen containing gas at a temperature sufficient to remove the coke, and regenerated sorbent is recycled to the treatment zone for contact with fresh feed. The metal additive is present on the sorbent in an amount sufficient to immobilize the vanadium compounds in the presence of oxygen containing gas at the sorbent regeneration temperature. A sorbent composition disclosed comprises a kaolin clay containing the metal additive, which may be introduced into the clay during the treatment process or during sorbent manufacture. Metal additives include water soluble inorganic metal salts and hydrocarbon soluble organo-metallic compounds of select metals.
Inventors
- 👤 H. Wayne Beck
- 👤 James D. Carruthers
- 👤 Edward B. Cornelius
- 👤 William P. Hettinger, Jr.
- 👤 Stephen M. Kovach
- 👤 James L. Palmer
- 👤 Oliver J. Zandona
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 19:04
CPC Classifications
C; C10; C10G; C10G25/00; C10G25/003; C10G25/06; C10G25/09; Y; Y10; Y10S; Y10S502/00; Y10S502/521
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
52 words
A sorbent material wherein the composition of said sorbent comprises kaolin clay, a titania gel in an amount in the range of about 1 to about 8 weight percent of sorbent, and a metal additive sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperatures.
Claim 2
Dependent Claim
52 words
A sorbent material wherein the composition of said sorbent comprises kaolin clay, a titania gel in an amount in the range of about 1 to about 8 weight percent of sorbent, and a metal additive sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperatures.
Claim 3
Dependent Claim
53 words
A sorbent wherein the composition of said sorbent comprises a kaolin clay, an alumina gel in an amount in the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperatures.
Claim 4
Dependent Claim
53 words
A sorbent wherein the composition of said sorbent comprises a kaolin clay, an alumina gel in an amount in the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperatures.
Claim 5
Dependent Claim
53 words
A composition of matter for use as a sorbent comprising kaolin clay, a zirconia gel in an amount of the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature.
Claim 6
Dependent Claim
53 words
A composition of matter for use as a sorbent comprising kaolin clay, a zirconia gel in an amount of the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature.
Claim 7
Dependent Claim
57 words
A composition of matter for use as a sorbent comprised of microspherical particles each containing clay, a titania gel in an amount in the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature.
Claim 8
Dependent Claim
57 words
A composition of matter for use as a sorbent comprised of microspherical particles each containing clay, a titania gel in an amount in the range of about 1 to about 8 weight percent, and a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature.
Claim 9
Dependent Claim
51 words
A sorbent comprised of microspherical particles each containing a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature, microspherical clay, and an alumina gel in an amount in the range of about 1 to about 8 weight percent.
Claim 10
Dependent Claim
51 words
A sorbent comprised of microspherical particles each containing a metal additive in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature, microspherical clay, and an alumina gel in an amount in the range of about 1 to about 8 weight percent.
Claim 11
Dependent Claim
67 words
A sorbent comprised of microspherical particles each containing a metal additive, in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature, kaolin clay, a titania gel or a zirconia gel or a combination of titania gel and zirconia gel with an alumina gel, said gel material comprising about 1 to about 8 weight percent of said sorbent.
Claim 12
Dependent Claim
67 words
A sorbent comprised of microspherical particles each containing a metal additive, in an amount sufficient to immobilize vanadium compounds in the presence of an oxygen containing gas at sorbent regeneration temperature, kaolin clay, a titania gel or a zirconia gel or a combination of titania gel and zirconia gel with an alumina gel, said gel material comprising about 1 to about 8 weight percent of said sorbent.
Claim 13
Dependent Claim
31 words
A composition of claim 1 wherein said sorbent comprises a clay and has a surface area below 50 m 2 /g and a pore volume of about 0.2 cc/g or greater.
Claim 14
Dependent Claim
31 words
A composition of claim 2 wherein said sorbent comprieses a clay and has a surface area below 50 m 2 /g and a pore volume of about 0.2 cc/g or greater.
Claim 15
Dependent Claim
31 words
A composition of claim 3 wherein said sorbent comprises a clay and has a surface area below 50 m 2 /g and a pore volume of about 0.2 cc/g or greater.
Claim 16
Dependent Claim
34 words
A composition of claim 4, 5 and 6 wherein said sorbent comprises a clay and has a surface area below 50 m 2 /g and a pore volume of about 0.2 cc/g or greater.
Claim 17
Dependent Claim
33 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said sorbent is in spherical form and ranges in size from 10-200 microns for use in a riser fluidized transfer zone.
Claim 18
Dependent Claim
38 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said sorbent is in spherical form and ranges in size from greater than 200 microns to 1/4 inch for use in a moving bed treatment zone.
Claim 19
Dependent Claim
39 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said sorbent is prepared from materials selected from the group consisting of bentonite, kaolin, montmorillonites, smectites, 2-layered lamellar silicates, mullite, pumice, silica, laterite or pillared inter-layered clays.
Claim 20
Dependent Claim
28 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is a water soluble inorganic metal salt or a hydrocarbon soluble organo-metallic compound.
Claim 21
Dependent Claim
57 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive to immobilize vanadium compounds comprises Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Mi, In, Tl, Bi, Te, or an element in the lanthanide or actinide series, or an combination of two or more of said elements.
Claim 22
Dependent Claim
40 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive can react with vanadium compounds to form binary metal vanadates or mixtures of said vanadates or to form ternary or quaternary compounds, complexes, or alloys.
Claim 23
Dependent Claim
34 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is present in said sorbent in an amount in the range of about 1 to about 20 weight percent.
Claim 24
Dependent Claim
36 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is present in said sorbent in an amount in the range of about 1 to about 8 percent of said sorbent.
Claim 25
Dependent Claim
27 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said vanadium compounds deposited on said sodium include vanadium oxides, sulfides, sulfites, sulfates, or oxysulfates.
Claim 26
Dependent Claim
38 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is added to an aqueous slurry of the ingredients comprising said sorbent and said aqueous slurry containing said metal additive is spray dried.
Claim 27
Dependent Claim
25 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is added to a spray dried sorbent by impregnation techniques.
Claim 28
Dependent Claim
49 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is introduced into said sorbent by adding an aqueous solution of a metal salt or a hydrocarbon solution of an organo-metallic composition at any point in the processing cycle wherein said sorbent is used.
Claim 29
Dependent Claim
39 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein the concentration of vanadium deposited on said sorbent ranges from about 0.05 to about 5 weight percent of said sorbent based on the weight of said sorbent.
Claim 30
Dependent Claim
40 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is a water soluble inorganic metal salt comprising a halide, nitrate, sulfite, sulfate, or carbonate or a combination of two or more of said salts.
Claim 31
Dependent Claim
43 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is a hydrocarbon soluble metal compound comprised of an alcoholate, ester, phenolate, naphthenate, carboxylate, or dienyl sandwich compound or a combination of two or more of said compounds.
Claim 32
Dependent Claim
18 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is tetraisopropyl titanate.
Claim 33
Dependent Claim
18 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is titanium tetrachloride.
Claim 34
Dependent Claim
19 words
A composition of claims 1, 2, 3, 4, 5 or 6 wherein said metal additive is methylcyclopentadienyl manganese tricarbonyl.
Claim 35
Dependent Claim
18 words
A composition of claim 1, 2, 3, 4, 5 or 6 wherein said metal additive is zirconia acetate.
References Cited (Backward Citations)
US2258787A
Cited
US2308557A
Cited
US2374313A
Cited
US2344911A
Cited
US2454942A
Cited
US2471131A
Cited
US2579123A
Cited
US2862878A
Cited
US2901419A
Cited
US2886513A
Cited
US3471410A
Cited
US3546094A
Cited
US3696025A
Cited
US3746659A
Cited
US3977963A
Cited
US4141858A
Cited
US4101417A
Cited
US4111845A
Cited
US4264434A
Cited
US4264433A
Cited
US4208302A
Cited
US4283274A
Cited
US4268376A
Cited
US4256564A
Cited
US4244810A
Cited
US4331533A
Cited
US4332674A
Cited
US4336160A
Cited
US4428826A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-04-22 | 1988-10-22 | 1989-04-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-04-22 | 1992-10-22 | 1993-04-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-04-22 | 1996-10-22 | 1997-04-23 | $7700.00 | Window Closed / Lapsed |