CA2579616A1 - Bulk ni-mo-w catalysts made from precursors containing an organic agent - Google Patents
Bulk ni-mo-w catalysts made from precursors containing an organic agent Download PDFInfo
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- CA2579616A1 CA2579616A1 CA002579616A CA2579616A CA2579616A1 CA 2579616 A1 CA2579616 A1 CA 2579616A1 CA 002579616 A CA002579616 A CA 002579616A CA 2579616 A CA2579616 A CA 2579616A CA 2579616 A1 CA2579616 A1 CA 2579616A1
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- 239000003054 catalyst Substances 0.000 title claims abstract 10
- 239000003795 chemical substances by application Substances 0.000 title claims abstract 4
- 239000002243 precursor Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 3
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 3
- 239000003863 metallic catalyst Substances 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims 12
- 229910000510 noble metal Inorganic materials 0.000 claims 6
- 239000007864 aqueous solution Substances 0.000 claims 5
- 150000003839 salts Chemical class 0.000 claims 5
- 239000003921 oil Substances 0.000 claims 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- -1 cyclic aliphatic amines Chemical class 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 238000005486 sulfidation Methods 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- 239000001993 wax Substances 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 241000282326 Felis catus Species 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000003863 ammonium salts Chemical group 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims 1
- 238000004517 catalytic hydrocracking Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 229920001021 polysulfide Polymers 0.000 claims 1
- 239000005077 polysulfide Substances 0.000 claims 1
- 150000008117 polysulfides Polymers 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
Novel bulk tri-metallic catalysts for use in the hydroprocessing of hydrocarbon feeds, as well as a method for preparing such catalysts. The catalysts are prepared from a catalyst precursor containing an organic agent.
Claims (15)
1. A bulk multi-metallic catalyst composition represented by the formula:
(X)a (Mo1-xW x)b[(CH3CH2)d N(CH3)3]e O z wherein X is one or more Group VIII non-noble metals, d is an integer from 10 to 40, x is between 0 and 1, the molar ratio of e:a is <= 2.0/1 and z =
((2a+6b)+ e)/2 and the molar ratio of a: (b) is 0.5/1 to 3/1; and wherein said catalyst composition after sulfidation is comprised of stacked layers of (Mo1-x W x)S2 stoichiometry, such that the average stack height is 10.ANG. to 20.ANG..
(X)a (Mo1-xW x)b[(CH3CH2)d N(CH3)3]e O z wherein X is one or more Group VIII non-noble metals, d is an integer from 10 to 40, x is between 0 and 1, the molar ratio of e:a is <= 2.0/1 and z =
((2a+6b)+ e)/2 and the molar ratio of a: (b) is 0.5/1 to 3/1; and wherein said catalyst composition after sulfidation is comprised of stacked layers of (Mo1-x W x)S2 stoichiometry, such that the average stack height is 10.ANG. to 20.ANG..
2. The catalyst composition of claim 1 wherein the molar ratio of a:b is from 0.75/1 to 1.5/1.
3. The catalyst composition of claim 1 wherein d is from 16 to 20 and e is from 0.5 to 1.5.
4. The catalyst composition of claim 1 wherein X is selected from Ni and Co.
5. A method for preparing a catalyst precursor composition represented by the formula:
(X)a(Mo1-x W x)b[(CH3CH2)d N(CH3)3]e O z wherein X is one or more Group VIII non-noble metals, d is an integer from 10 to 40, x is between 0 and 1, the molar ratio of e:a is <= 2.0/1 and z =
((2a+6b)+ e)/2 and the molar ratio of a: (b) is 0.5/1 to 3/1; which method comprises:
(a) preparing a first aqueous solution of a Group VIII non-noble metal water soluble salt;
(b) preparing a second aqueous solution containing Mo and W water soluble salts;
(c) heating both said first and second solutions to a temperature from 60°C
to 150°C;
(d) adding an effective amount of an organic agent into said second aqueous solution;
(e) introducing at least a portion of said second aqueous solution of step (d) into said first aqueous solution; and (f) heating the resulting solution of step (e) to an effective temperature to cause the precipitation of said catalyst precursor composition.
(X)a(Mo1-x W x)b[(CH3CH2)d N(CH3)3]e O z wherein X is one or more Group VIII non-noble metals, d is an integer from 10 to 40, x is between 0 and 1, the molar ratio of e:a is <= 2.0/1 and z =
((2a+6b)+ e)/2 and the molar ratio of a: (b) is 0.5/1 to 3/1; which method comprises:
(a) preparing a first aqueous solution of a Group VIII non-noble metal water soluble salt;
(b) preparing a second aqueous solution containing Mo and W water soluble salts;
(c) heating both said first and second solutions to a temperature from 60°C
to 150°C;
(d) adding an effective amount of an organic agent into said second aqueous solution;
(e) introducing at least a portion of said second aqueous solution of step (d) into said first aqueous solution; and (f) heating the resulting solution of step (e) to an effective temperature to cause the precipitation of said catalyst precursor composition.
6. The method of claim 5 wherein the salt of the Group VIII non-noble metal is selected from the group consisting of sulfate, nitrate, bromide, chloride, and acetate.
7. The method of claim 5 wherein the Mo salt is an ammonium salt selected from the group consisting of ammonium dimolybdate, ammonium tri-, tetra- hepta-, octa-, and tetradeca- molybdate and the W salt is an ammonium para-, meta-, hexa-, and polytungstate.
8. The method of claim 5 wherein the organic agent is selected from the group consisting of aromatic amines, cyclic aliphatic amines and polycyclic aliphatic amines.
9. The method of claim 5 wherein the catalyst precursor composition is formed in a suitable catalyst shape, dried, and calcined at a temperature from 100°C to 600°C in the presence of oxygen.
10. The method of claim 9 wherein the shaped, dried, and calcined catalyst shape is sulfided in the presence of a sulfur-containing compound, selected from the group consisting of elementary sulfur, hydrogen sulfide, and polysulfides, at sulfiding conditions.
11. A process wherein a hydrocarbon feedstock is hydroprocessed at hydroprocessing conditions, which process comprises:
reacting said feedstock at hydroprocessing conditions in the presence of a bulk multi-metallic catalyst composition derived from a catalyst precursor composition represented by the formula:
(X)a(Y)b[(CH3CH2)c N(CH3)3¦d O z wherein X is a Group VIII non-noble metal, Y is selected from Mo and W, c is an integer from 10 to 40, and the molar ratio of a:b is 0.5/1 to 3/1; wherein said catalyst composition, after sulfidation, is comprised of stacked layers of (Y)S2, such that the average stack height is 10.ANG. to 20.ANG..
reacting said feedstock at hydroprocessing conditions in the presence of a bulk multi-metallic catalyst composition derived from a catalyst precursor composition represented by the formula:
(X)a(Y)b[(CH3CH2)c N(CH3)3¦d O z wherein X is a Group VIII non-noble metal, Y is selected from Mo and W, c is an integer from 10 to 40, and the molar ratio of a:b is 0.5/1 to 3/1; wherein said catalyst composition, after sulfidation, is comprised of stacked layers of (Y)S2, such that the average stack height is 10.ANG. to 20.ANG..
12. The process of claim 11 wherein hydroprocessing is selected from the group consisting of hydrodemetallation, hydrodewaxing, hydrotreating, hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, hydroisomerization, and hydrocracking.
13. The process of claim 11 wherein the hydrocarbon feedstock is selected from the group consisting of whole and reduced petroleum crudes, atmospheric and vacuum residua, propane deasphalted residua, cycle oils, fluid cat cracked tower bottoms, gas oils, light to heavy distillates, hydrocrackates, hydrotreated oils, dewaxed oils, slack waxes, Fischer-Tropsch waxes, raffinates, naphthas, and mixtures thereof.
14. The process of claim 11 wherein the hydroprocessing is preformed at temperatures from 200°C to 450°C, hydrogen pressures from 5 to 300 bar (500 to 30,000 kPa), liquid hourly space velocities from 0.05 to 10 h -1, and hydrogen treat gas rates from 200 to 10,000 standard cubic feet per barrel and is conducted in two or more stages, which two or more stages can be the same or different hydroprossesing processes.
15. The method or process of any of claims 5 to 14 wherein the Group VIII non-noble metal is selected from Ni and Co.
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US61204404P | 2004-09-22 | 2004-09-22 | |
US60/612,044 | 2004-09-22 | ||
PCT/US2005/033284 WO2006036610A1 (en) | 2004-09-22 | 2005-09-16 | BULK Ni-Mo-W CATALYSTS MADE FROM PRECURSORS CONTAINING AN ORGANIC AGENT |
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JP (1) | JP5033631B2 (en) |
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US8697598B2 (en) | 2005-04-21 | 2014-04-15 | China Petroleum & Chemical Corporation | Hydrogenation catalyst and use thereof |
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US7544632B2 (en) * | 2004-09-22 | 2009-06-09 | Exxonmobil Research And Engineering Company | Bulk Ni-Mo-W catalysts made from precursors containing an organic agent |
SG10201610092XA (en) * | 2006-10-11 | 2017-01-27 | Exxonmobil Res & Eng Co | Hydroprocessing methods for bulk group viii/group vib metal catalysts |
US7951746B2 (en) * | 2006-10-11 | 2011-05-31 | Exxonmobil Research And Engineering Company | Bulk group VIII/group VIB metal catalysts and method of preparing same |
US20090107880A1 (en) * | 2007-10-31 | 2009-04-30 | Chevron U.S.A. Inc. | Method of upgrading heavy hydrocarbon streams to jet products |
EP2424659A4 (en) * | 2009-04-29 | 2014-08-27 | Chevron Usa Inc | Hydroconversion multi-metallic catalyst and method for making thereof |
EP2424658B1 (en) * | 2009-04-29 | 2019-05-22 | Chevron U.S.A., Inc. | Method for making a hydroconversion multi-metallic catalyst |
US9187702B2 (en) * | 2009-07-01 | 2015-11-17 | Chevron U.S.A. Inc. | Hydroprocessing catalyst and method of making the same |
IT1398288B1 (en) | 2009-09-30 | 2013-02-22 | Eni Spa | TRANSITIONAL METAL-MIXED OXIDES, TREATMENT CATALYSTS OBTAINED BY THEM, AND PREPARATION PROCESS INCLUDING SOL-GEL PROCEDURES |
CA2781893C (en) | 2009-12-08 | 2016-10-04 | Exxonmobil Research And Engineering Company | Hydroprocessing of high nitrogen feed using bulk catalyst |
WO2011075463A2 (en) * | 2009-12-18 | 2011-06-23 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
CN103025429A (en) * | 2010-06-01 | 2013-04-03 | 埃克森美孚研究工程公司 | Hydroprocessing catalysts and their production |
US10022712B2 (en) | 2010-06-01 | 2018-07-17 | Exxonmobil Research And Engineering Company | Hydroprocessing catalysts and their production |
ITMI20110510A1 (en) * | 2011-03-30 | 2012-10-01 | Eni Spa | TRANSITIONAL METAL MIXED OXIDES, TREATMENT CATALYSTS OBTAINED BY THEM, AND PREPARATION PROCESS |
CA2883517C (en) * | 2012-09-05 | 2021-03-09 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalysts and method for making thereof |
WO2014126566A1 (en) * | 2013-02-14 | 2014-08-21 | Sachem, Inc. | Sol-gel method for preparation of ceramic material |
US9919987B1 (en) * | 2016-11-22 | 2018-03-20 | Chevron U.S.A. Inc. | Naphthene ring opening over self-supported multi-metallic catalysts |
CN106925288A (en) * | 2017-02-08 | 2017-07-07 | 辽宁石油化工大学 | A kind of auxiliary agent PEG and SB powder that adds is modified the preparation method of Ni-based ternary unsupported catalyst |
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US4540482A (en) * | 1982-07-20 | 1985-09-10 | Exxon Research And Engineering Co. | Supported carbon-containing molybdenum and tungsten sulfide catalysts, their preparation and use |
US4666878A (en) * | 1984-12-28 | 1987-05-19 | Exxon Research And Engineering Company | Amorphous, iron promoted Mo and W sulfide hydroprocessing catalysts and uses thereof |
FR2629368B1 (en) * | 1988-03-29 | 1991-01-04 | Europ Retraitement Catalyse | METHOD FOR PRESULFURIZING AND CONTROLLING THE ACTIVITY OF A HYDROCARBON PROCESSING CATALYST |
US4902404A (en) * | 1988-07-05 | 1990-02-20 | Exxon Research And Engineering Company | Hydrotreating process with catalyst staging |
US5319119A (en) * | 1991-03-15 | 1994-06-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Oleophilic molybdenum compound for use in hydroconversion of a hydrocarbon and a method for producing the same |
JP3201823B2 (en) * | 1991-03-15 | 2001-08-27 | 旭化成株式会社 | Lipophilic molybdenum compound and method for producing the same |
US6758963B1 (en) * | 1997-07-15 | 2004-07-06 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk group VIII/group vib catalysts |
US6162350A (en) * | 1997-07-15 | 2000-12-19 | Exxon Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901) |
AU2001289625A1 (en) * | 2000-07-12 | 2002-01-21 | Akzo Nobel N.V. | Process for preparing an additive-based mixed metal catalyst |
EP1227064A1 (en) * | 2001-01-25 | 2002-07-31 | Eidgenössische Technische Hochschule Zürich | Process for the production of molybdenum oxide, molybdenum oxide produced from this process and use thereof |
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- 2005-09-16 WO PCT/US2005/033284 patent/WO2006036610A1/en active Application Filing
- 2005-09-16 EP EP05801123A patent/EP1791639A1/en not_active Withdrawn
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US8697598B2 (en) | 2005-04-21 | 2014-04-15 | China Petroleum & Chemical Corporation | Hydrogenation catalyst and use thereof |
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WO2006036610A1 (en) | 2006-04-06 |
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