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US4632747A Expired / Lapsed US ⏱️ 0.0 years remaining

Hydrotreating process employing catalysts comprising a supported, mixed metal sulfide iron promoted Mo and W

Assignee: ExxonMobil Technology and Engineering Co
•
Filing: 1984-12-28
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Granted: 1986-12-30
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Expires: 2004-12-28
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Abstract

Abstract This invention relates to the preparation and use of catalysts useful for hydroprocessing processes, such as hydrotreating, wherein said catalysts are formed by heating, at elevated temperature, in the presence of sulfur and under oxygen-free conditions, a composite of support material and one or more catalyst precursor salts containing a thiometallate anion of Mo, W or mixture thereof and a cation comprising one or more divalent promoter metals at least one of which is iron, wherein said promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, and wherein said additional divalent promoter metal, if any, is selected from the group consisting of Ni, Co, Mn, Zn, Cu and mixture thereof.

Inventors

  • 👤 Teh C. Ho
  • 👤 II Archie R. Young
  • 👤 Allan J. Jacobson
  • 👤 Russell R. Chianelli

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-05 20:50
CPC Classifications
B; B01; B01J; B01J27/00; B01J27/02; B01J27/04; B01J27/047; B01J27/051; B01J27/0515; B01J23/00; B01J23/70; B01J23/76; B01J23/84; B01J23/85; B01J27/049; C; C10; C10G; C10G49/00; C10G49/02; C10G49/04

Claims Analysis

Total Claims: 31
Claim 1
Independent Claim 170 words
A hydrocracking process comprising contacting a hydrocarbon feed at a temperature of at least about 100° C. and in the presence of hydrogen, with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material with one or more precursor salts and heating said composite at elevated temperature of at least about 150° C., in the presence of sulfur or sulfur bearing compounds and under oxygen-free conditions for a time sufficient to form said catalyst, wherein said precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising at least one promoter metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn wherein said divalent promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L, wherein said feed contacts said catalyst for a time sufficient to hydrocrack at least a portion of said feed.
Claim 2
Dependent Claim 170 words
A hydrocracking process comprising contacting a hydrocarbon feed at a temperature of at least about 100° C. and in the presence of hydrogen, with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material with one or more precursor salts and heating said composite at elevated temperature of at least about 150° C., in the presence of sulfur or sulfur bearing compounds and under oxygen-free conditions for a time sufficient to form said catalyst, wherein said precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising at least one promoter metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn wherein said divalent promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L, wherein said feed contacts said catalyst for a time sufficient to hydrocrack at least a portion of said feed.
Claim 3
Dependent Claim 90 words
The process of claim 1 wherein said tetrathiometallate salt has the formula (ML) (Mo y W 1-y S 4 ) wherein M comprises at least one metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn, wherein y is any value ranging from 0 to 1 and wherein L is one or more neutral, nitrogen-containing ligands, at least one of which is a chelating polydentate ligand.
Claim 4
Dependent Claim 19 words
The process of claim 2 wherein said salt is formed in the presence of a slurry of support material.
Claim 5
Dependent Claim 29 words
The process of any of claims 1, 2 or 3 wherein ligand L is selected from the group consisting of alkyl amines, aryl amines, nitrogen heterocycles and mixtures thereof.
Claim 6
Dependent Claim 32 words
The process of claim 4 wherein said precursor salt contains iron and at least one additional promoter metal selected from the group consisting of Ni, Co, Zn, Cu, Mn and mixture thereof.
Claim 7
Dependent Claim 12 words
The process of claim 5 wherein ligand L comprises an alkyl amine.
Claim 8
Dependent Claim 16 words
The process of claim 6 wherein said catalyst is formed in the presence of excess sulfur.
Claim 9
Dependent Claim 171 words
A process for hydrotreating a hydrocarbon feed which comprises contacting said feed at a temperature of at least about 150° C. and in the presence of hydrogen with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material with one or more precursor salts and heating said composite at elevated temperature of at least about 150° C., in the presence of sulfur or sulfur bearing compounds and under oxygen-free conditions for a time sufficient to form said catalyst, wherein said precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising at least one promoter metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn wherein said divalent promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L, said contacting occurring for a time sufficient to hydrotreat at least a portion of said feed.
Claim 10
Dependent Claim 171 words
A process for hydrotreating a hydrocarbon feed which comprises contacting said feed at a temperature of at least about 150° C. and in the presence of hydrogen with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material with one or more precursor salts and heating said composite at elevated temperature of at least about 150° C., in the presence of sulfur or sulfur bearing compounds and under oxygen-free conditions for a time sufficient to form said catalyst, wherein said precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising at least one promoter metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn wherein said divalent promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L, said contacting occurring for a time sufficient to hydrotreat at least a portion of said feed.
Claim 11
Dependent Claim 90 words
The process of claim 8 wherein said tetrathiometallate salt has the formula (ML) (Mo y W 1-y S 4 ) wherein M comprises at least one metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn, wherein y is any value ranging from 0 to 1 and wherein L is one or more neutral, nitrogen-containing ligands, at least one of which is a chelating polydentate ligand.
Claim 12
Dependent Claim 90 words
The process of claim 8 wherein said tetrathiometallate salt has the formula (ML) (Mo y W 1-y S 4 ) wherein M comprises at least one metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn, wherein y is any value ranging from 0 to 1 and wherein L is one or more neutral, nitrogen-containing ligands, at least one of which is a chelating polydentate ligand.
Claim 13
Dependent Claim 19 words
The process of claim 10 wherein said salt is formed in the presence of a slurry of support material.
Claim 14
Dependent Claim 29 words
The process of any of claims 8, 10 or 11 wherein ligand L is selected from the group consisting of alkyl amines, aryl amines, nitrogen heterocycles and mixtures thereof.
Claim 15
Dependent Claim 32 words
The process of claim 11 wherein said precursor salt contains iron and at least one additional promoter metal selected from the group consisting of Ni, Co, Zn, Cu, Mn and mixture thereof.
Claim 16
Dependent Claim 12 words
The process of claim 12 wherein said ligand comprises an alkyl amine.
Claim 17
Dependent Claim 16 words
The process of claim 14 wherein said catalyst is formed in the presence of excess sulfur.
Claim 18
Dependent Claim 13 words
The process of claim 15 wherein said feed is a lube oil fraction.
Claim 19
Dependent Claim 13 words
The process of claim 8 wherein said feed is a lube oil fraction.
Claim 20
Dependent Claim 13 words
The process of claim 13 wherein said feed is a lube oil fraction.
Claim 21
Dependent Claim 175 words
A process for removing nitrogen from a nitrogen-containing hydrocarbon feed which comprises contacting said feed at a temperature of at least about 150° C. and in the presence of hydrogen with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material with one or more precursor salts and heating said composite at elevated temperature of at least about 150° C., in the presence of sulfur or sulfur-bearing compounds and under oxygen-free conditions for a time sufficient to form said catalyst, wherein said precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising at least one promoter metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn wherein said divalent promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L, said contacting occurring for a time sufficient to remove at least a portion of nitrogen from said feed.
Claim 22
Dependent Claim 175 words
A process for removing nitrogen from a nitrogen-containing hydrocarbon feed which comprises contacting said feed at a temperature of at least about 150° C. and in the presence of hydrogen with a catalyst obtained by compositing a quantity of inorganic refractory oxide support material with one or more precursor salts and heating said composite at elevated temperature of at least about 150° C., in the presence of sulfur or sulfur-bearing compounds and under oxygen-free conditions for a time sufficient to form said catalyst, wherein said precursor salt contains a tetrathiometallate anion of Mo, W or mixture thereof and a cation comprising at least one promoter metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn wherein said divalent promoter metal or metals are chelated by at least one neutral, nitrogen-containing polydentate ligand, L, said contacting occurring for a time sufficient to remove at least a portion of nitrogen from said feed.
Claim 23
Dependent Claim 90 words
The process of claim 19 wherein said tetrathiometallate salt has the formula (ML) (Mo y W 1-y S 4 ) wherein M comprises at least one metal selected from the group consisting of (a) divalent iron and (b) mixtures of divalent iron with one or more metals selected from the group consisting of divalent Ni, Co, Mn, Cu, and Zn, wherein y is any value ranging from 0 to 1 and wherein L is one or more neutral, nitrogen-containing ligands, at least one of which is a chelating polydentate ligand.
Claim 24
Dependent Claim 22 words
The process of claim 20 wherein said precursor salt is formed in the presence of a slurry of particles of support material.
Claim 25
Dependent Claim 29 words
The process of any of claims 19, 20 or 21 wherein ligand L is selected from the group consisting of alkyl amines, aryl amines, nitrogen heterocycles and mixtures thereof.
Claim 26
Dependent Claim 32 words
The process of claim 22 wherein said precursor salt contains iron and at least one additional promoter metal selected from the group consisting of Ni, Co, Zn, Cu, Mn and mixture thereof.
Claim 27
Dependent Claim 12 words
The process of claim 23 wherein said ligand comprises an alkyl amine.
Claim 28
Dependent Claim 16 words
The process of claim 24 wherein said catalyst is formed in the presence of excess sulfur.
Claim 29
Dependent Claim 13 words
The process of claim 25 wherein said feed is a lube oil fraction.
Claim 30
Dependent Claim 13 words
The process of claim 19 wherein said feed is a lube oil fraction.
Claim 31
Dependent Claim 13 words
The process of claim 23 wherein said feed is a lube oil fraction.

References Cited (Backward Citations)

US4357229A Cited
US4435277A Cited
US4381993A Cited
US4457836A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1989-12-29 1990-06-30 1990-12-30 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1993-12-29 1994-06-30 1994-12-30 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1997-12-29 1998-06-30 1998-12-30 $7700.00 Window Closed / Lapsed

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