WO2006071963A1 - Hydrocracking catalysts for vacuum gas oil & de-metalized blend - Google Patents
Hydrocracking catalysts for vacuum gas oil & de-metalized blendInfo
- Publication number
- WO2006071963A1 WO2006071963A1 PCT/US2005/047341 US2005047341W WO2006071963A1 WO 2006071963 A1 WO2006071963 A1 WO 2006071963A1 US 2005047341 W US2005047341 W US 2005047341W WO 2006071963 A1 WO2006071963 A1 WO 2006071963A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalytic
- catalyst
- support material
- dmo
- metal
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000004517 catalytic hydrocracking Methods 0.000 title description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 47
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 35
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000013335 mesoporous material Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- -1 DMO hydrocarbon Chemical class 0.000 claims description 6
- 239000011959 amorphous silica alumina Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 230000000063 preceeding effect Effects 0.000 claims 7
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims 3
- 239000003921 oil Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000101 thioether group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101100224937 Paramecium tetraurelia DHC-8 gene Proteins 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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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
- 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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- 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
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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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
- 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
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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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
- 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
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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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
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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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
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- 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
Definitions
- This invention relates generally to the field of catalytic treatment of heavy hydrocarbons to produce desirable hydrocarbon products, in particular, a novel catalyst operable to catalytically treat de-metallized oil (DMO).
- DMO de-metallized oil
- the current invention includes a catalyst and a process for treating heavy hydrocarbons using the catalyst.
- the catalyst is particularly useful for treating de- metallize oil (DMO) and is particularly useful in VGO/DMO hydrocarbon blend.
- the catalyst acts to catalytically convert the VGO/DMO blend to shorter-chain valuable hydrocarbon products.
- the catalyst includes a catalytic support material, a catalytic metal impregnated upon the catalytic support material, and a promoter metal on the catalytic support material to enhance catalytic conversion.
- the combination of the catalytic support material with catalytic metal, also called active metal, and promoter metal is operable to catalytically convert VGO/DMO into hydrocarbon products having shorter carbon chains.
- the catalytic metal component includes molybdenum and the promoter metal includes nickel.
- one preferred embodiment includes ultra stable Y (USY) zeolite as the catalytic support material, ⁇ -alumina was used as binder for all catalyst prepared in this research. The amount of ⁇ -alumina used was around 70% of the total catalyst support for the test runs. In a particularly preferred embodiment, the USY zeolite is in an absence of ⁇ -zeolite.
- USY ultra stable Y
- a particularly preferred catalytic support material includes MCM-41 mesoporous material.
- the catalytic support material is jS-zeolite.
- the catalytic support material is amorphous silica alumina, also called ASA.
- ASA has a non-uniform structure with low acidity and high surface area. The non-uniform structure tends to create acidic sites that are not available to large molecules, which leads to inferior performance of ASA alone as compared to MCM-41 or a combination of MCM-41 with ASA.
- the USY and jS-zeolite supports suffer from drawbacks related to the microporous nature of the supports which makes the catalyst less efficient for large molecules since it is diffusion limited. These supports used alone tend to plug rapidly, thereby deactivating the catalyst.
- the MCM-41 alone or in combination with USY or ⁇ - zeolite supports, overcomes these flaws.
- the catalytic support material is solely ultra stable Y zeolite, MCM-41 mesoporous material, ⁇ - zeolite, amorphous silica alumina or combinations thereof.
- a particularly preferred embodiment includes a single catalytic support material that is substantially all MCM- 41.
- This material is mesoporous, that is, it is well-structured and has uniform morphology with high surface area. It also has low acidity as compared to beta and USY support materials.
- the invention includes the use of proper support material and a balance between acidic and metallic function with the proper distribution of metals throughout the support material. This is accomplished through the very well- structured morphology features of MCM-42 support material, which contains both acidic and metallic site that are accessibile to the large hydrocarbon molecules found in VGO and DMO. For this reason, high conversion is achieved.
- the lower acidity of MCM-41 as compared to other support materials drives conversion toward selectivity towards mid distillates and limits the production of undesirable light gases.
- the catalytic metal is in a sulfide form.
- molybdenum in the form of molybdenum sulfide is preferred.
- tungsten sulfide is a preferred embodiment.
- promoter metals include solely nickel, cobalt or combinations thereof.
- the catalyst of the invention is particularly useful for VGO/DMO hydrocarbon blend contains at least 10% DMO by volume. Test runs have been made for VGO/DMO hydrocarbon blend contains at least 15% DMO by volume.
- Impregnation of the catalytic metal and the promoter metal onto the catalytic support is accomplished through methods known in the art, such as through co- impregnation or successive impregnation.
- the process of catalytically converting a heavy hydrocarbon containing de- metallized oil includes the steps of introducing the heavy hydrocarbon containing de- metallized oil into a reactor stage and introducing the catalyst into the reactor stage.
- the catalyst introduced into the reactor stage includes the catalytic support material, the catalytic metal impregnated upon the catalytic support material, and the promoter metal on the catalytic support material, to enhance catalytic conversion.
- the catalytic support material with catalytic metal and promoter metal operate to catalytically convert at least a portion of the de-metallized oil into hydrocarbon products having shorter carbon chains.
- the process reaches and maintains a pre-defined temperature in the reactor operable to achieve conversion, hi a preferred embodiment, the pre-defined temperature is at least 390 degrees C. hi a more particularly preferred embodiment, the pre-defined temperature is at least 400 degrees C.
- a majority of the pores of the catalyst support are located within 20 to 50 Angstrom ( 0 A) and the catalyst support has a large surface area as measured through pore size distribution.
- Table 1 shows examples of preferred embodiments.
- NiMo-MCM-41 showed higher hydrodesulfurization (HDS) and hydrogenation activities, rn addition, it had higher conversion and higher diesel yield than commercial catalyst.
- Most of the hydrocracking catalysts of commercial interest are dual functional in nature, consisting of both a hydrogenation-dehydrogenation component and an acidic support. The reactions catalyzed by the individual components are quite different. In specific catalysts, the relative strengths of the two components can be varied. The reactions occurring and the products formed are influenced by the balance between these two components. [0022] TABLE 2 Acidity for all prepared catalysts
- Table 4-2 shows the TPD of ammonia for all of the prepared hydrocracking catalysts.
- the acidity of the prepared catalysts ranges from 0.33 mmol/g (NiMo- MCM-41) to 0.59 mmol/g (NiMo-USY).
- the lower acidity of NiMo-MCM-41 catalyst is expected since MCM-41 is a sililca based material and has low amount of alumina. Therefore, NiMo-MCM-41 catalyst has lower amount of ⁇ -alumina than the other prepared catalysts.
- the catalytic metal, such as molybdenum, and the promoter metal provide the hydro genation-dehydrogenation functions. As noted, this is preferably in the sulfide form.
- group VIA and group VIIIA metals are useful as promoter metal and catalytic metal. These metals catalyze the hydrogenation of the feedstock, making it more reactive for cracking and heteroatom removal, as well as reducing the coking rate. They also initiate the cracking by forming a reactive olefin intermediate via dehydrogenation.
- hydrocracking of industrial feedstocks is to be carried in presence of hydrogen sulfide and organic sulfur compounds, it is preferred that the metal site be in a metal sulfide form of the VIA group promoted by a nickel or cobalt sulfide.
- the reactions that occur during the hydrocracking process take three major routes. First, non-catalytic thermal cleavage of C-C bonds via hydrocarbon radicals, with hydrogen addition (hydropyrolysis). Second, monofunctional C-C bond cleavage with hydrogen addition over hydrogenation components consisting of metals, oxides or sulfides (hydro genolysis).
- bifunctional C-C bond cleavage with hydrogen addition over bifunctional catalysts consisting of a hydrogenation component dispersed on a porous, acidic support.
- bifunctional catalysts consisting of a hydrogenation component dispersed on a porous, acidic support.
- hydrodesulfurization hydrodesulfurization, hydrodeintrofication, hydrodeoxigenation, olefin hydrogenation and partial aromatic hydrogenation.
- the commercial catalyst that was used for comparison is DHC-8 from Universal Oil
- ⁇ -alumina was used as binder for all catalyst prepared in this test shown above.
- the amount of ⁇ -alumina used was 70% of the total catalyst support.
- NiMo-MCM-41 catalyst had the lowest acidity and the highest surface area. This is attributed to the fact that MCM-41 is a silica-based material and has low amounts of alumina. This is one of the advantages of MCM-41 being mesoporous and having low acidity. The mesoporous feature along with the lower acidity of NiMo-MCM-41 catalyst promotes the highest conversion and the lowest gas make.
Abstract
Description
Claims
Priority Applications (4)
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EP05855836A EP1835993A1 (en) | 2004-12-29 | 2005-12-29 | Hydrocracking catalysts for vacuum gas oil&de-metalized blend |
JP2007549608A JP5260059B2 (en) | 2004-12-29 | 2005-12-29 | Hydrocracking catalyst for vacuum gas oil and demetallized blends |
BRPI0519581-0A BRPI0519581A2 (en) | 2004-12-29 | 2005-12-29 | catalysts for vacuum gas demetalized mixture hydrocracking |
CN2005800455824A CN101094720B (en) | 2004-12-29 | 2005-12-29 | Hydrocracking catalysts for vacuum gas oil & de-metalized blend |
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US63990904P | 2004-12-29 | 2004-12-29 | |
US60/639,909 | 2004-12-29 |
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WO2006071963A1 true WO2006071963A1 (en) | 2006-07-06 |
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PCT/US2005/047341 WO2006071963A1 (en) | 2004-12-29 | 2005-12-29 | Hydrocracking catalysts for vacuum gas oil & de-metalized blend |
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US (1) | US20060157386A1 (en) |
EP (1) | EP1835993A1 (en) |
JP (1) | JP5260059B2 (en) |
CN (1) | CN101094720B (en) |
BR (1) | BRPI0519581A2 (en) |
RU (1) | RU2416462C2 (en) |
WO (1) | WO2006071963A1 (en) |
Cited By (1)
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US7455762B2 (en) * | 2004-08-31 | 2008-11-25 | Exxonmobil Research And Engineering Company | Selective hydrodesulfurization process |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8206575B2 (en) * | 2007-10-31 | 2012-06-26 | Chevron U.S.A. Inc. | Hydroconversion processes employing multi-metallic catalysts and method for making thereof |
US20090271306A1 (en) * | 2008-04-29 | 2009-10-29 | Iovation Inc. | System and Method to Facilitate Secure Payment of Digital Transactions |
US8173009B2 (en) * | 2009-02-06 | 2012-05-08 | Uop Llc | Process for improving a hydrotreated stream |
US8080492B2 (en) * | 2009-04-29 | 2011-12-20 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964525B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964524B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7931799B2 (en) * | 2009-04-29 | 2011-04-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8383543B2 (en) * | 2009-04-29 | 2013-02-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964526B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8058203B2 (en) * | 2009-04-29 | 2011-11-15 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
JP6254165B2 (en) | 2012-09-05 | 2017-12-27 | シェブロン ユー.エス.エー. インコーポレイテッド | HYDROGEN CONVERSION MULTIMETAL CATALYST AND METHOD FOR PREPARING THE SAME |
RU2672269C1 (en) * | 2017-08-08 | 2018-11-13 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Catalyst for hydrogenation of olefins at producing synthetic oil and method for synthesis thereof (options) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993001884A1 (en) | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Hydroprocessing catalyst |
WO1993002159A1 (en) | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Hydrocracking with ultra large pore size catalysts |
WO2004052537A1 (en) | 2002-12-06 | 2004-06-24 | Abb Lummus Global Inc. | Mesoporous material with active metals |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3853742A (en) * | 1971-10-20 | 1974-12-10 | Union Oil Co | Selective midbarrel hydrocracking |
US3928176A (en) * | 1974-04-01 | 1975-12-23 | Exxon Research Engineering Co | Heavy crude conversion |
US4179356A (en) * | 1977-09-30 | 1979-12-18 | Uop Inc. | Hydrocracking with catalyst modified by Group IIA |
US4141860A (en) * | 1977-09-30 | 1979-02-27 | Uop Inc. | Hydrocracking catalyst |
US4198286A (en) * | 1978-06-29 | 1980-04-15 | Uop Inc. | Hydrocracking catalyst selective to middle distillate |
US4210522A (en) * | 1978-10-25 | 1980-07-01 | Uop Inc. | Hydrocracking catalyst |
US4683050A (en) * | 1979-10-15 | 1987-07-28 | Union Oil Company Of California | Mild hydrocracking with a catalyst containing an intermediate pore molecular sieve |
US4672048A (en) * | 1979-10-15 | 1987-06-09 | Union Oil Company Of California | Hydrocracking catalyst |
US4513097A (en) * | 1982-08-16 | 1985-04-23 | Union Oil Company Of California | Hydrotreating catalyst and a method for preparing the catalyst |
US4576709A (en) * | 1982-09-02 | 1986-03-18 | Ashland Oil, Inc. | Catalytic upgrading of reduced crudes and residual oils with a coke selective catalyst |
US4440629A (en) * | 1982-09-13 | 1984-04-03 | Uop Inc. | Hydrocarbon hydrocracking process |
US4447315A (en) * | 1983-04-22 | 1984-05-08 | Uop Inc. | Hydrocracking process |
JPS62199687A (en) * | 1986-04-28 | 1987-09-03 | ユニオン・オイル・コンパニ−・オブ・カリフオルニア | Hydrogenation using catalyst having large pores |
US5009768A (en) * | 1989-12-19 | 1991-04-23 | Intevep, S.A. | Hydrocracking high residual contained in vacuum gas oil |
US5183561A (en) * | 1990-01-25 | 1993-02-02 | Mobil Oil Corp. | Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material |
SG43938A1 (en) * | 1991-07-24 | 1997-11-14 | Mobil Oil Corp | Production of hydrocracked lubricants |
US5288395A (en) * | 1991-07-24 | 1994-02-22 | Mobil Oil Corporation | Production of high viscosity index lubricants |
US5320743A (en) * | 1992-05-29 | 1994-06-14 | Texaco Inc. | Mild hydrocracking of heavy hydrocarbon feedstocks employing silica-alumina catalysts |
US5851378A (en) * | 1994-06-03 | 1998-12-22 | Akzo Nobel Nv | Hydrocracking catalyst comprising coated cracking component particles |
US5755955A (en) * | 1995-12-21 | 1998-05-26 | Petro-Canada | Hydrocracking of heavy hydrocarbon oils with conversion facilitated by control of polar aromatics |
JPH11561A (en) * | 1997-06-13 | 1999-01-06 | Tonen Corp | Additive catalyst for catalytic cracking of heavy oil |
US6635599B1 (en) * | 1997-07-15 | 2003-10-21 | Exxonmobil Research & Engineering Company | Mixed metal catalyst, its preparation by co-precipitation, and its use |
US6696258B1 (en) * | 1998-01-20 | 2004-02-24 | Drexel University | Mesoporous materials and methods of making the same |
ES2260892T3 (en) * | 1998-06-25 | 2006-11-01 | Institut Francais Du Petrole | HYDRO CRAQUEO CATALYST THAT INCLUDES A BETA ZEOLITE AND A VB GROUP ELEMENT. |
US6534437B2 (en) * | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
JP3824464B2 (en) * | 1999-04-28 | 2006-09-20 | 財団法人石油産業活性化センター | Method for hydrocracking heavy oils |
US6926882B2 (en) * | 2000-01-05 | 2005-08-09 | Exxonmobil Chemical Patents Inc. | Porous inorganic macrostructure materials and process for their preparation |
WO2003104148A1 (en) * | 2002-06-10 | 2003-12-18 | 科学技術振興事業団 | Method for synthesizing mesoporous zeolite |
-
2005
- 2005-12-29 JP JP2007549608A patent/JP5260059B2/en not_active Expired - Fee Related
- 2005-12-29 WO PCT/US2005/047341 patent/WO2006071963A1/en active Application Filing
- 2005-12-29 RU RU2007128968/04A patent/RU2416462C2/en not_active IP Right Cessation
- 2005-12-29 EP EP05855836A patent/EP1835993A1/en not_active Withdrawn
- 2005-12-29 US US11/320,928 patent/US20060157386A1/en not_active Abandoned
- 2005-12-29 BR BRPI0519581-0A patent/BRPI0519581A2/en not_active Application Discontinuation
- 2005-12-29 CN CN2005800455824A patent/CN101094720B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993001884A1 (en) | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Hydroprocessing catalyst |
WO1993002159A1 (en) | 1991-07-24 | 1993-02-04 | Mobil Oil Corporation | Hydrocracking with ultra large pore size catalysts |
WO2004052537A1 (en) | 2002-12-06 | 2004-06-24 | Abb Lummus Global Inc. | Mesoporous material with active metals |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7455762B2 (en) * | 2004-08-31 | 2008-11-25 | Exxonmobil Research And Engineering Company | Selective hydrodesulfurization process |
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JP2008525194A (en) | 2008-07-17 |
RU2007128968A (en) | 2009-02-10 |
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EP1835993A1 (en) | 2007-09-26 |
JP5260059B2 (en) | 2013-08-14 |
US20060157386A1 (en) | 2006-07-20 |
CN101094720B (en) | 2013-04-24 |
RU2416462C2 (en) | 2011-04-20 |
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