US4750987A
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US
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Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion
Assignee: Ashland LLC
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Filing: 1986-11-07
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Granted: 1988-06-14
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Expires: 2006-11-07
Abstract
Abstract A process is disclosed for the conversion of a hydrocarbon oil feed having a significant content of vanadium to lighter oil products by contacting the feed under conversion conditions in a conversion zone with a catalyst containing a metal additive to immobilize vanadium compounds. Conversion conditions are such that coke and vanadium are deposited on the catalyst in the conversion zone. Coked catalyst is regenerated in the presence of an oxygen containing gas at a temperature sufficient to remove the coke and regenerated catalyst is recycled to the conversion zone for contact with fresh feed. The metal additive is present on the catalyst in an amount sufficient to immobilize the vanadium compounds in the presence of oxygen containing gas at the catalyst regeneration temperature. A catalyst composition comprises a crystalline alumino-silicate zeolite dispersed in an amorphous inert solid matrix containing the metal additive, which may be introduced into the catalyst during the conversion process or during catalyst manufacture. Metal additives include water soluble inorganic metal salts and hydrocarbon soluble inorganic metal salts and hydrocarbon soluble organometallic 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
2026-10-29 03:51
CPC Classifications
C; C10; C10G; C10G11/00; C10G11/14; C10G11/18; C10G11/02; C10G11/04; C10G11/05; Y; Y10; Y10S; Y10S502/00; Y10S502/521
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
197 words
A process for the cracking of a hydrocarbon oil feed having a significant content of at least 0.1 ppm vanadium to lighter oil products, said process comprising contacting said feed under conversion conditions in a conversion zone with a catalyst containing a precipitated metal additive to immobilize vanadium compounds by forming compounds therewith that have melting points above temperatures found in regenerating a coked catalyst; and having catalytic cracking characteristics, coke and vanadium being deposited on said catalyst by said contact; regenerating said coked catalyst in the presence of an oxygen containing gas at a temperature sufficient to remove at least some of said coke, and, recycling said regenerated catalyst to said conversion zone for contact with fresh feed; said metal additive being present on said catalyst in an amount sufficient to immobilize at least a portion of said vanadium compound in the presence of said oxygen containing gas at said catalyst regeneration temperature; wherein said metal additive to immobilize vanadium compounds deposited on the catalyst is selected from the group consisting of Sr, Sc, Y, Nb, and Ta elements, and an element in the actinide series, or a combination of two or more of said elements.
Claim 2
Dependent Claim
197 words
A process for the cracking of a hydrocarbon oil feed having a significant content of at least 0.1 ppm vanadium to lighter oil products, said process comprising contacting said feed under conversion conditions in a conversion zone with a catalyst containing a precipitated metal additive to immobilize vanadium compounds by forming compounds therewith that have melting points above temperatures found in regenerating a coked catalyst; and having catalytic cracking characteristics, coke and vanadium being deposited on said catalyst by said contact; regenerating said coked catalyst in the presence of an oxygen containing gas at a temperature sufficient to remove at least some of said coke, and, recycling said regenerated catalyst to said conversion zone for contact with fresh feed; said metal additive being present on said catalyst in an amount sufficient to immobilize at least a portion of said vanadium compound in the presence of said oxygen containing gas at said catalyst regeneration temperature; wherein said metal additive to immobilize vanadium compounds deposited on the catalyst is selected from the group consisting of Sr, Sc, Y, Nb, and Ta elements, and an element in the actinide series, or a combination of two or more of said elements.
Claim 3
Dependent Claim
40 words
The process of claim 1 wherein the oil feed is a reduced crude or crude oil containing 200 ppm or less of metal consisting of nickel, vanadium, iron and copper and having a Conradson carbon value of 5-15 or less.
Claim 4
Dependent Claim
34 words
The process of claim 1 wherein the oil feed is a reduced crude or crude oil containing 200 ppm or less of vanadium and having a Conradson carbon value of 12 wt% or less.
Claim 5
Dependent Claim
33 words
The process of claim 1 wherein the oil feed is a reduced crude or crude oil containing 100 ppm or less of vanadium and having a carbon value of 10 wt% or less.
Claim 6
Dependent Claim
34 words
The process of claim 1 wherein said oil feed is a reduced crude or crude oil containing 75 ppm or less of vanadium and having a Conradson carbon value of 10 wt% or less.
Claim 7
Dependent Claim
33 words
The process of claim 1 wherein said catalyst comprises 10 to 40 wt% of a crystalline alumino-silicate zeolite dispersed in an amorphour inert solid matrix containing said metal additive to immobilize vanadium compounds.
Claim 8
Dependent Claim
32 words
The process of claim 1 wherein metal of said metal additive prior to incorporation into said catalyst is part of a water soluble inorganic metal salt or a hydrocarbon soluble organo-metallic compound.
Claim 9
Dependent Claim
32 words
The process of claim 1 wherein said metal additive reacts with vanadium compounds to form binary metal vanadates or mixtures of said vanadates to form ternary or quaternary compounds, complexes, or alloys.
Claim 10
Dependent Claim
26 words
The process of claim 1 wherein said metal additive is present in the catalyst in the range of about 1 to 20 wt%, of said catalyst.
Claim 11
Dependent Claim
21 words
The process of claim 1 wherein said vanadium compounds deposited on the catalyst include vanadium oxides, sulfides, sulfites, sulfates or oxysulfides.
Claim 12
Dependent Claim
19 words
The process of claim 1 wherein said metal additive is added to a spray dried catalyst by impregnation techniques.
Claim 13
Dependent Claim
23 words
The process of claim 1 wherein said catalyst comprises a crystalline silica-metallo zeolite and said metal additive is included in said zeolite composition.
Claim 14
Dependent Claim
24 words
The process of claim 1 wherein the concentration of vanadium deposited on said catalyst ranges from about 0.1 to 5 wt% of catalyst weight.
Claim 15
Dependent Claim
31 words
The process of claim 1 wherein said oil feed further contains nickel and the ratio of said vanadium to said nickel is in the range of from about 1:3 to 5:1.
Claim 16
Dependent Claim
30 words
The process of claim 1 wherein said oil feed has a significant content of heavy metals and the vanadium proportion of said total metals content is greater than fifty percent.
Claim 17
Dependent Claim
27 words
The process of claim 1 wherein the atomic ratio of metal in said metal additive to the vanadium present in said oil feed is at least 0.5.
Claim 18
Dependent Claim
38 words
The process of claim 1 wherein said metal additive is a water soluble inorganic metal salt selected from the group consisting of a halide, nitrate, sulfate, sulfite, carbonate and a combination of at least two of said salts.
Claim 19
Dependent Claim
41 words
The process of claim 1 wherein said metal additive is an organo-metallic compound selected from the group of compounds consisting of an alcoholate, ester, phenolate, naphthenate, carboxylate, dienyl sandwich compound and a combination of at least two of said group members.
Claim 20
Dependent Claim
34 words
The process of claim 1 wherein said catalyst comprises 0.1 to 20 wt. % of said metal additive incorporated in said catalyst as a gelatinous precipitate in the pores of a spray dried gel.
Claim 21
Dependent Claim
32 words
The process of claim 1 wherein said metal additive containing catalyst further comprises up to 40 wt. % of a crystalline alumino silicate zeolite component comprised of one or more different zeolites.
Claim 22
Dependent Claim
52 words
The process of claim 1 wherein said oil feed comprises residual stocks with significant metals content at least 0.1 ppm of and the composition of said catalyst comprises silica-alumina, kaolin clay, crystalline alumino silicate zeolite, and a titania gel in an amount in the range of about 1 to 8 weight percent.
Claim 23
Dependent Claim
50 words
The process of claim 1 wherein said oil feed comprises residual stocks with high metals content, and the composition of said catalyst comprises kaolin clay, crystalline alumino silicate zeolite, a zirconia gel in an amount in the range of about 1 to 8 wt. % and either silica or silica-alumina.
Claim 24
Dependent Claim
48 words
The process of claim 1 wherein said oil feed comprises residual stocks with high metals content, and the composition of said catalyst comprises silica or silica-alumina, kaolin clay, crystalline alumino silicate zeolite, and alumina gel in an amount in the range of about 1 to 8 weight percent.
Claim 25
Dependent Claim
31 words
The process of claim 1 wherein the oil feed is a gas oil containing more than 0.1 ppm vanadium and having a Conradson carbon value of less than 1.0 wt. %.
Claim 26
Dependent Claim
53 words
The process of claim 1 in which said oil feed is a crude oil or heavy fractions thereof, said catalyst has a micro-activity value of at least 50 volume percent, and said conversion zone comprises a riser transfer zone followed by rapid separation of coked catalyst from gaseous products produced by said process.
Claim 27
Dependent Claim
32 words
The process of claim 7 wherein said metal additive reacts with vanadium compounds to form binary metal vanadates, mixtures of said vanadates or to form ternary or quaternary compounds, complexes or alloys.
Claim 28
Dependent Claim
30 words
The process of claim 1 wherein said metal additive to immobilize vanadium compounds deposited on the catalyst is selected from the group consisting of Sr, Sc, Y, Nb, and Ta.
Claim 29
Dependent Claim
19 words
The process of claim 1, wherein said metal additive to immobilize vanadium compounds deposited on the catalyst comprises Sc.
Claim 30
Dependent Claim
19 words
The process of claim 27, wherein said metal additive to immobilize vanadium compounds deposited on the catalyst comprises Sr.
Claim 31
Dependent Claim
19 words
The process of claim 27, wherein said metal additive to immobilize vanadium compounds deposited on the catalyst comprises Y.
Claim 32
Dependent Claim
19 words
The process of claim 37, wherein said metal additive to immobilize vanadium compounds deposited on the catalyst comprises Nb.
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