CA2357024A1 - Multistage hydroprocessing using bulk multimetallic catalyst - Google Patents
Multistage hydroprocessing using bulk multimetallic catalyst Download PDFInfo
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- CA2357024A1 CA2357024A1 CA002357024A CA2357024A CA2357024A1 CA 2357024 A1 CA2357024 A1 CA 2357024A1 CA 002357024 A CA002357024 A CA 002357024A CA 2357024 A CA2357024 A CA 2357024A CA 2357024 A1 CA2357024 A1 CA 2357024A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8878—Chromium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
- C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
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- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1062—Lubricating oils
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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- C10G2300/301—Boiling range
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- C10G2300/302—Viscosity
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
Abstract
A two stage hydrodesulfurizing process for producing low sulfur distillates. A
distillate boiling range feedstock containing in excess of about 3,000 wppm sulfur is hydrodesulfurized in a first hydrdesulfurzing stage containing one or more reaction ones in the presence of hydrogen and a hydrodesulfurizing catalyst. The liquid product stream thereof is passed to a first separation stage wherein a vapor phase product stream and a liquid product stream are produced. The liquid product stream, which has a substantially lower sulfur and nitrogen content than the original feedstream is passed to a second hydrodesulfurizing stage also containing one or more reaction zones where it is reacted in the presence of hydrogen and a second hydrodesulfurizing catalyst at hydrodesulfurizing conditions. The catalyst in any one or more reaction zones is a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB
metals.
distillate boiling range feedstock containing in excess of about 3,000 wppm sulfur is hydrodesulfurized in a first hydrdesulfurzing stage containing one or more reaction ones in the presence of hydrogen and a hydrodesulfurizing catalyst. The liquid product stream thereof is passed to a first separation stage wherein a vapor phase product stream and a liquid product stream are produced. The liquid product stream, which has a substantially lower sulfur and nitrogen content than the original feedstream is passed to a second hydrodesulfurizing stage also containing one or more reaction zones where it is reacted in the presence of hydrogen and a second hydrodesulfurizing catalyst at hydrodesulfurizing conditions. The catalyst in any one or more reaction zones is a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB
metals.
Claims (26)
1. A multistage hydroprocessing process comprising:
a) reacting a feedstream in a first hydroprocessing stage in the presence of a hydrogen-containing treat gas, the first stage containing one or more reaction zones, each reaction zone operated at first stage hydroprocessing conditions and in the presence of a first hydroprocessing catalyst, thereby resulting in a first liquid product stream;
b) passing the first liquid product stream to a first separation zone where a first vapor phase product stream and a first liquid phase product stream are produced;
c) reacting the first liquid phase product stream of b) above in a second hydrodesprocessing stage in the presence of a hydrogen-containing treat gas, the second hydroprocessing stage containing one or more second stage reaction zones operated at second stage hydroprocessing conditions wherein each reaction zone contains a second hydroprocessing catalyst, thereby resulting in a second liquid product stream having less than about 1,000 wppm sulfur;
d) passing the second liquid product stream of step c) to a second separation zone wherein a second vapor phase stream and a second liquid phase stream are produced;
e) reacting the second liquid phase stream from d) in a third reaction stage in the presence of a hydrogen-containing treat gas, the third hydroprocessing stage containing one or more reaction zones operated at third stage hydroprocessing conditions in the presence of a third hydrotreating catalyst, in order to form a third liquid product stream;
f) passing the third liquid product stream to a third separation zone wherein a third vapor phase stream and a third liquid phase stream are produced;
and g) collecting both the third vapor phase stream and the third liquid phase stream;
wherein at least one of the reaction zones of at least one of the hydroprocessing stages contains a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10:1 to about 1:10.
a) reacting a feedstream in a first hydroprocessing stage in the presence of a hydrogen-containing treat gas, the first stage containing one or more reaction zones, each reaction zone operated at first stage hydroprocessing conditions and in the presence of a first hydroprocessing catalyst, thereby resulting in a first liquid product stream;
b) passing the first liquid product stream to a first separation zone where a first vapor phase product stream and a first liquid phase product stream are produced;
c) reacting the first liquid phase product stream of b) above in a second hydrodesprocessing stage in the presence of a hydrogen-containing treat gas, the second hydroprocessing stage containing one or more second stage reaction zones operated at second stage hydroprocessing conditions wherein each reaction zone contains a second hydroprocessing catalyst, thereby resulting in a second liquid product stream having less than about 1,000 wppm sulfur;
d) passing the second liquid product stream of step c) to a second separation zone wherein a second vapor phase stream and a second liquid phase stream are produced;
e) reacting the second liquid phase stream from d) in a third reaction stage in the presence of a hydrogen-containing treat gas, the third hydroprocessing stage containing one or more reaction zones operated at third stage hydroprocessing conditions in the presence of a third hydrotreating catalyst, in order to form a third liquid product stream;
f) passing the third liquid product stream to a third separation zone wherein a third vapor phase stream and a third liquid phase stream are produced;
and g) collecting both the third vapor phase stream and the third liquid phase stream;
wherein at least one of the reaction zones of at least one of the hydroprocessing stages contains a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metal to Group VIII non-noble metal is from about 10:1 to about 1:10.
2. The process of claim 1 wherein bulk multimetallic catalyst is present in only the first reaction stage.
3. The process of claim 1 wherein the bulk multimetallic catalyst is present in only the second reaction stage.
4. The process of claim 1 wherein the bulk multimetallic catalyst is present in at least one of:
(i) the first and second reaction stages;
(ii) the first and third reaction stages; and (iii) the second and third reaction stages.
(i) the first and second reaction stages;
(ii) the first and third reaction stages; and (iii) the second and third reaction stages.
5. The process of claim 1 wherein the bulk multimetallic catalyst is present only in the third reaction stage.
6. The process of claim 1 wherein the bulk multimetallic catalyst is present in all three reaction stages.
7. The process of claim 1 wherein the Group VIII non-noble metal is selected from Ni and Co and the Group VIB metals are selected from Mo and W.
8. The process of claim 1 wherein the bulk multimetallic is represented by the formula:
(X)b(Mo)c(W)d O x wherein X is one or more a Group VIII non-noble metal, and the molar ratio of b: (c+d) is 0.5/1 to 3/1.
(X)b(Mo)c(W)d O x wherein X is one or more a Group VIII non-noble metal, and the molar ratio of b: (c+d) is 0.5/1 to 3/1.
9. The process of claim 8 wherein the molar ratio of b:(c+d) is 0.75/1 to 1.5/1.
10. The process of claim 8 wherein the molar ratio of c:d is preferably >
0.01/1.
0.01/1.
11. The process of claim 1 wherein the bulk multimetallic catalyst is essentially an amorphous material having a unique X-ray diffraction pattern showing crystalline peaks at d = 2.53 Angstroms and d = 1.70 Angstroms.
12. The process of claim 1 wherein the feedstock is a hydrocarbon with a boiling point in the range of 25°C to 575°C, and wherein the first and second stage hydroprocessing conditions include a reaction temperature in the range of about 40°C to 450°C, a pressure of 5 Bar to 1100 Bar, a space velocity of about 0.3 V/V/Hr to 10 V/V/Hr, and a hydrogen gas treat rate of 100 SCF/B to 1,000 SCF/B.
13. The process of claim 1 wherein the feedstock comprises at least one of naphtha, diesel, heavy gas oil, lube oil, and residuum.
14. The process of claim 13 wherein the feedstock is naphtha boiling in the range of 25°C to 210°C, and at least one of the first, second, and third stage hydroprocessing conditions include a reaction temperature of 100°C to 370°C, a pressure of 10 Bar to 60 Bar, a space velocity of 0.5 to 10 V/Hr, and a hydrogen gas treat rate of 100 SCF/B to 2,000 SCF/B.
15. The process of claim 13 wherein the feedstock is diesel boiling in the range of 170°C to 350°C, and at least one of the first, second, and third hydroprocessing conditions include a reaction temperature of 200°C to 400°C, a pressure of 15 Bar to 110 Bar, a space velocity of 0.5 V/V/Hr to 4 V/V/Hr, and a hydrogen gas treat rate of 500 SCF/B to 6,000 SCF/B.
16. The process of claim 13 wherein the feedstock is heavy gas oil boiling in the range of 325°C to 475°C, and wherein at least one of the first, second, and third stage hydroprocessing conditions include a reaction temperature of 260°C to 430°C, a pressure of 15 Bar to 170 Bar, a space velocity of 0.3 V/V/Hr, and a hydrogen gas treat rate of 1,000 SCF/B to 6,000 SCF/B.
17. The process of claim 13 wherein the feedstock is a lubricating oil boiling in the range of 290°C to 550°C, and wherein at least one of the first, second, and third stage hydroprocessing conditions include a reaction temperature of 200°C
to 450°C, a pressure of 6 Bar to 210 Bar, a space velocity of 0.2 V/V/Hr to 5 V/V/Hr, and a hydrogen gas treat rate of 100 SCF/B to 10,000 SCF/B.
to 450°C, a pressure of 6 Bar to 210 Bar, a space velocity of 0.2 V/V/Hr to 5 V/V/Hr, and a hydrogen gas treat rate of 100 SCF/B to 10,000 SCF/B.
18. The process of claim 9 wherein the feedstock is a residuum having a 10% to 50% boiling range of 575°C, and wherein at least one of the first, second, and third stage hydroprocessing conditions include a reaction temperature of 340°C
to 450°C, a pressure of 65 Bar to 1100 Bar, a space velocity of 0.1 V/V/Hr to 1 V/V/Hr, and a hydrogen gas treat rate of 2,000 SCF/B to 10,000 SCF/B.
to 450°C, a pressure of 65 Bar to 1100 Bar, a space velocity of 0.1 V/V/Hr to 1 V/V/Hr, and a hydrogen gas treat rate of 2,000 SCF/B to 10,000 SCF/B.
19. The process of claim 1 wherein the bulk multimetallic catalyst is in the form of particles having a median diameter of at least 50 nm, a surface area of at least m2/gm, a pore volume ranging from 0.05 to 5 ml/g, and an absence of pores smaller than 1 nm.
20. The process of claim 19 wherein the bulk multimetallic catalyst particle has a core-shell structure.
21. The process of claim 20 wherein at least one of the first, second, and third stage hydroprocessing catalyst further comprises a catalytically effective amount of a second catalyst.
22. The process of claim 21 wherein the second catalyst provides at least one of a desulfurization functionality, a denitrogenation functionality, an aromatics saturation functionality, a cracking functionality, and an isomerization functionality.
23. The process of claim 21 wherein, for the stage(s) containing both the bulk multimetallic catalyst and the second catalyst, the second catalyst is located in at least one of:
(i) a region upstream of the bulk multimetallic catalyst;
(ii) a region containing the bulk multimetallic catalyst; and (iii) a region downstream of the bulk muitimetallic catalyst.
(i) a region upstream of the bulk multimetallic catalyst;
(ii) a region containing the bulk multimetallic catalyst; and (iii) a region downstream of the bulk muitimetallic catalyst.
24. A two stage hydroprocessing process comprising:
a) reacting a feedstream in a first hydroprocessing stage in the presence of a hydrogen-containing treat gas, said first hydrotreating stage containing one or more reaction zones, each first stage reaction zone operated at first stage hydroprocessing conditions and in the presence of at least one first stage hydroprocessing catalyst, thereby resulting in a liquid product stream having a sulfur content less than about 3,000 wppm;
b) passing the liquid product stream of the first hydroprocessing stage to a first separation zone where a first vapor phase product stream and a first liquid phase product stream are produced;
c) reacting the first liquid phase product stream of b) in a second hydroprocessing stage in the presence of a hydrogen-containing treat gas, the second hydroprocessing stage containing one or more second stage reaction zones operated at second stage hydroprocessing conditions wherein each second stage reaction zone contains at least one second stage hydroprocessing catalyst;
d) passing the second liquid product stream of step c) to a second separation zone wherein a second vapor phase stream and a second liquid phase stream are produced;
e) collecting both the second vapor phase stream and the second liquid phase stream;
(i) wherein at least one of the first stage and second stage hydroprocessing catalyst comprises a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metals to Group VIII non-noble metal is from about 10:1 to about 1:10;
(ii) wherein the second stage hydroprocessing catalyst in at least one second stage reaction zone is an aromatics saturation catalyst; and (iii) wherein the second stage hydroprocessing conditions in the second stage reaction zone containing the aromatics saturation catalyst hydrodearomatization conditions include a temperature ranging from about 40°C
to about 400°C, a pressure ranging from about 100 psig to about 3,000 psig, and a liquid hourly space velocity ranging from about 0.3 V/V/Hr to about 2.0 V/V/Hr.
a) reacting a feedstream in a first hydroprocessing stage in the presence of a hydrogen-containing treat gas, said first hydrotreating stage containing one or more reaction zones, each first stage reaction zone operated at first stage hydroprocessing conditions and in the presence of at least one first stage hydroprocessing catalyst, thereby resulting in a liquid product stream having a sulfur content less than about 3,000 wppm;
b) passing the liquid product stream of the first hydroprocessing stage to a first separation zone where a first vapor phase product stream and a first liquid phase product stream are produced;
c) reacting the first liquid phase product stream of b) in a second hydroprocessing stage in the presence of a hydrogen-containing treat gas, the second hydroprocessing stage containing one or more second stage reaction zones operated at second stage hydroprocessing conditions wherein each second stage reaction zone contains at least one second stage hydroprocessing catalyst;
d) passing the second liquid product stream of step c) to a second separation zone wherein a second vapor phase stream and a second liquid phase stream are produced;
e) collecting both the second vapor phase stream and the second liquid phase stream;
(i) wherein at least one of the first stage and second stage hydroprocessing catalyst comprises a bulk multimetallic catalyst comprised of at least one Group VIII non-noble metal and at least two Group VIB metals and wherein the ratio of Group VIB metals to Group VIII non-noble metal is from about 10:1 to about 1:10;
(ii) wherein the second stage hydroprocessing catalyst in at least one second stage reaction zone is an aromatics saturation catalyst; and (iii) wherein the second stage hydroprocessing conditions in the second stage reaction zone containing the aromatics saturation catalyst hydrodearomatization conditions include a temperature ranging from about 40°C
to about 400°C, a pressure ranging from about 100 psig to about 3,000 psig, and a liquid hourly space velocity ranging from about 0.3 V/V/Hr to about 2.0 V/V/Hr.
25. The process of claim 24 wherein the aromatics saturation catalyst is the bulk multimetallic catalyst.
26. The process of claim 1 wherein at least one of the first, second, and third stage hydroprocessing catalyst is sulfided.
Applications Claiming Priority (3)
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US09/231,156 | 1999-01-15 | ||
US09/231,156 US6162350A (en) | 1997-07-15 | 1999-01-15 | Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901) |
PCT/US2000/000979 WO2000042124A1 (en) | 1999-01-15 | 2000-01-14 | Multistage process for hydrodesulfurizing-hydrogenating distillates using bulk multimetallic catalyst |
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CA2357024A1 true CA2357024A1 (en) | 2000-07-20 |
CA2357024C CA2357024C (en) | 2011-03-15 |
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CA2356920A Expired - Lifetime CA2356920C (en) | 1999-01-15 | 2000-01-14 | Hydroconversion process using bulk group viii/group vib catalysts |
CA2357528A Expired - Lifetime CA2357528C (en) | 1999-01-15 | 2000-01-14 | Hydrotreating using bulk group viii/group vib catalysts |
CA2358695A Expired - Lifetime CA2358695C (en) | 1999-01-15 | 2000-01-14 | Hydrofining process using bulk group viii/group vib catalysts |
CA2359192A Expired - Lifetime CA2359192C (en) | 1999-01-15 | 2000-01-14 | Hydrocracking process using bulk group viii/group vib catalysts |
CA2358905A Expired - Lifetime CA2358905C (en) | 1999-01-15 | 2000-01-14 | Production of low sulfur/low nitrogen hydrocrackates |
CA002360035A Abandoned CA2360035A1 (en) | 1999-01-15 | 2000-01-14 | Improved process for preparing alcohols by the oxo process |
CA2358910A Expired - Lifetime CA2358910C (en) | 1999-01-15 | 2000-01-14 | Slurry hydroprocessing using bulk multimetallic catalysts |
CA2357022A Expired - Lifetime CA2357022C (en) | 1999-01-15 | 2000-01-14 | Two stage process for hydroprocessing using bulk multimetallic catalyst |
CA2356909A Expired - Lifetime CA2356909C (en) | 1999-01-15 | 2000-01-14 | Hydroprocessing using bulk group viii/group vib catalysts |
CA2357024A Expired - Lifetime CA2357024C (en) | 1999-01-15 | 2000-01-14 | Multistage hydroprocessing using bulk multimetallic catalyst |
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CA2358901A Expired - Lifetime CA2358901C (en) | 1999-01-15 | 2000-01-14 | Hydroprocessing using bulk multimetallic catalysts |
CA2356920A Expired - Lifetime CA2356920C (en) | 1999-01-15 | 2000-01-14 | Hydroconversion process using bulk group viii/group vib catalysts |
CA2357528A Expired - Lifetime CA2357528C (en) | 1999-01-15 | 2000-01-14 | Hydrotreating using bulk group viii/group vib catalysts |
CA2358695A Expired - Lifetime CA2358695C (en) | 1999-01-15 | 2000-01-14 | Hydrofining process using bulk group viii/group vib catalysts |
CA2359192A Expired - Lifetime CA2359192C (en) | 1999-01-15 | 2000-01-14 | Hydrocracking process using bulk group viii/group vib catalysts |
CA2358905A Expired - Lifetime CA2358905C (en) | 1999-01-15 | 2000-01-14 | Production of low sulfur/low nitrogen hydrocrackates |
CA002360035A Abandoned CA2360035A1 (en) | 1999-01-15 | 2000-01-14 | Improved process for preparing alcohols by the oxo process |
CA2358910A Expired - Lifetime CA2358910C (en) | 1999-01-15 | 2000-01-14 | Slurry hydroprocessing using bulk multimetallic catalysts |
CA2357022A Expired - Lifetime CA2357022C (en) | 1999-01-15 | 2000-01-14 | Two stage process for hydroprocessing using bulk multimetallic catalyst |
CA2356909A Expired - Lifetime CA2356909C (en) | 1999-01-15 | 2000-01-14 | Hydroprocessing using bulk group viii/group vib catalysts |
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EP (12) | EP1153046B1 (en) |
JP (12) | JP2002534580A (en) |
KR (1) | KR20010101526A (en) |
CN (1) | CN1136236C (en) |
AT (7) | ATE465225T1 (en) |
AU (11) | AU755642B2 (en) |
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CA (11) | CA2358901C (en) |
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DK (5) | DK1157083T3 (en) |
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MX (1) | MXPA01007139A (en) |
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