JP2006516222A - 水素化処理触媒及びその製造方法、ならびにその炭化水素精製における使用 - Google Patents
水素化処理触媒及びその製造方法、ならびにその炭化水素精製における使用 Download PDFInfo
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- JP2006516222A JP2006516222A JP2006502101A JP2006502101A JP2006516222A JP 2006516222 A JP2006516222 A JP 2006516222A JP 2006502101 A JP2006502101 A JP 2006502101A JP 2006502101 A JP2006502101 A JP 2006502101A JP 2006516222 A JP2006516222 A JP 2006516222A
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- Prior art keywords
- catalyst
- compound
- hydrotreating
- hydrocarbon
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 25
- 238000000746 purification Methods 0.000 title description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- -1 sulfoxide compound Chemical class 0.000 claims abstract description 23
- 150000003457 sulfones Chemical class 0.000 claims abstract description 16
- 238000006477 desulfuration reaction Methods 0.000 claims description 29
- 230000023556 desulfurization Effects 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 230000001590 oxidative effect Effects 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- FCEHBMOGCRZNNI-UHFFFAOYSA-N thianaphthalene Natural products C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 13
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000005987 sulfurization reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 150000003462 sulfoxides Chemical class 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000002432 hydroperoxides Chemical class 0.000 claims description 5
- 150000004966 inorganic peroxy acids Chemical class 0.000 claims description 5
- 150000003464 sulfur compounds Chemical class 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 4
- 150000004967 organic peroxy acids Chemical class 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract 1
- 229930192474 thiophene Natural products 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JTNXQVCPQMQLHK-UHFFFAOYSA-N thioacetone Chemical class CC(C)=S JTNXQVCPQMQLHK-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including oxidation as the refining step in the absence of hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
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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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- 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
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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
-
- 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
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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
-
- 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
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- 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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- 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
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing 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
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- B01J37/06—Washing
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
本例では、5種類の硫黄化された触媒の製造を説明するが、これらの触媒は、続いて脱硫、脱窒素および脱芳香族成分処理に使用する。これらの触媒はすべて、市販の触媒Aから製造するものであり、この触媒は、アルミナ担体上にコバルト3%およびモリブデン10%の組合せを含んでなり、市販されており、一般的に製油業者により水素化脱硫装置で使用されているものである。
本例は、本発明の触媒が、未変性の市販触媒Aよりも、水素化脱硫および脱窒素において、はるかに高い活性を有することを示す。
本発明の新たに変成した水素化処理触媒、これと同様の触媒を水素化処理サイクル後に再生した触媒、次いで本発明により変成した触媒、の性を本例で比較する。
Claims (21)
- 耐火性酸化物から形成された担体、いずれも酸化された形態にある、少なくとも一種のVIII族金属、および少なくとも一種のVI族金属、を含んでなる変成された水素化処理触媒であって、少なくとも一種のベンゾチオフェン化合物から誘導された少なくとも一種のスルホン化合物および/またはスルホキシド化合物を含んでなる、触媒。
- 前記化合物が、ベンゾチオフェン、ジベンゾチオフェン、および、より一般的には、所望により脂肪族および/または芳香族環を含んでなるアルキルまたはアリル炭化水素鎖により置換されていても、いなくてもよいポリアリールチオフェン、のスルホンおよびスルホキシドから選択されるものであり、前記化合物が、単独で、または同じ群の他の化合物との混合物として使用される、請求項1に記載の触媒。
- 前記化合物が、市販のスルホンおよび/またはスルホキシド化合物、または原油の精製により得られる炭化水素留分中に存在するベンゾチオフェン化合物を酸化して得られるスルホンおよび/またはスルホキシド化合物である、請求項1または2に記載の触媒。
- 前記スルホンおよび/またはスルホキシド化合物の少なくとも一種が、脱硫された、または脱硫されていない炭化水素留分を、有機および無機の過酸化物およびヒドロペルオキシド、ならびに有機または無機過酸から選択される酸化性化合物により、所望により触媒の存在下で、酸化することにより得られるものである、請求項1〜3のいずれか一項に記載の触媒。
- 少なくとも一種のスルホンおよび/またはスルホキシド化合物を少なくとも0.01重量%含んでなる、請求項1〜4のいずれか一項に記載の触媒。
- 請求項1〜5のいずれか一項に記載の触媒の製造方法であって、スルホンおよび/またはスルホキシド化合物を、耐火性酸化物から形成された担体、ならびに、VI族およびVIII族のそれぞれから選択された少なくとも一種の酸化された形態にある金属、を含んでなる金属触媒の表面で形成する工程、および/または前記表面に堆積させる工程を含んでなる、方法。
- 前記金属触媒を含んでなる反応器中に、少なくとも一種のベンゾチオフェン化合物と、有機または無機の過酸化物およびヒドロペルオキシド、ならびに有機または無機過酸からなる群から選択された酸化性化合物、とを含んでなる有機液体を導入し、常温および大気圧から出発して、次いで、形成されたスルホキシドおよび/またはスルホン化合物を担持している触媒を回収する、請求項6に記載の方法。
- 前記有機液体が、パラフィン、芳香族およびナフテン系炭化水素およびベンゾチオフェン化合物用の溶剤、ならびに原油精製から得られる炭化水素留分、から選択されるものである、請求項7に記載の方法。
- 前記有機液体が、最低および最高沸点が40〜560℃である炭化水素留分である、請求項7に記載の方法。
- 前記金属触媒の存在下で、最低および最高沸点が40〜560℃である炭化水素留分の酸化脱硫を行う、請求項6〜9のいずれか一項に記載の方法。
- 前記触媒が、シリカおよび/またはアルミナから製造された担体と、VI族およびVIII族の、ニッケル/モリブデン、コバルト/モリブデン、ニッケル/タングステン、ニッケル/コバルト/モリブデンおよびニッケル/タングステン/モリブデンの組合せからなる群から選択された、酸化された形態にある金属の組合せ、とを含んでなる、請求項6〜10のいずれか一項に記載の方法。
- 前記金属触媒が未使用であるか、または再生されている、請求項6〜11のいずれか一項に記載の方法。
- 前記水素化処理触媒の製造が、水素化処理反応器の中または外で行われる、請求項6〜12のいずれか一項に記載の方法。
- 請求項1〜5のいずれか一項に記載の触媒の、前記触媒を反応器の中または外で、硫化水素、メルカプタン、硫化物、および/または多硫化物、および他の硫黄化する化合物から選択された少なくとも一種の硫黄化合物により、または水素化処理すべき原料により硫黄化した後での、炭化水素の水素化処理への使用。
- 硫黄含有、窒素含有、および/または芳香族炭化水素、の原料を、硫黄分10ppm未満にまで精製するための方法であって、請求項1〜5のいずれか一項に記載の触媒の存在下で、前記触媒を硫黄化した後で、炭化水素原料を水素化処理する第一工程、および前記水素化処理された原料を酸化脱硫する第二工程を含んでなる、方法。
- 前記酸化脱硫が、VI族およびVIII族のそれぞれから選択された少なくとも一種の金属を担持する耐火性酸化物を基材とする金属触媒、および、有機または無機の過酸化物およびヒドロペルオキシド、ならびに有機または無機過酸、好ましくは過酸化水素およびtert−ブチルヒドロペルオキシド、から選択された酸化剤、の存在下で行われる、請求項15に記載の方法。
- 前記酸化脱硫サイクルの後で得られる変成された金属触媒が、水素化処理反応器外で硫黄化されるか、または水素化処理反応器中で硫黄化された後に、水素化処理触媒として使用される、請求項16に記載の方法。
- 同じ反応器中で、または少なくとも2基の個別の反応器中で行われる、請求項15〜17のいずれか一項に記載の方法。
- 前記2基の個別反応器が、水素化処理および酸化脱硫で交互に稼働し、それぞれ異なった処理を行う、請求項18に記載の方法。
- 前記反応器の一方が常に水素化処理で稼働し、他方の反応器が常に酸化脱硫で稼働する、請求項18に記載の方法。
- 前記炭化水素原料が、最低および最高沸点が40〜560℃である炭化水素原料である、請求項15〜20のいずれか一項に記載の方法。
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FR0300439A FR2850041B1 (fr) | 2003-01-16 | 2003-01-16 | Catalyseur d'hydrotraitement, son procede de preparation et son utilisation dans un procede de purification d'hydrocarbures. |
PCT/FR2004/000071 WO2004067683A1 (fr) | 2003-01-16 | 2004-01-15 | Catalyseur d'hydrotraitement, son procede de preparation et son utilisation dans un procede de purification d'hydrocarbures |
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KR20170078653A (ko) * | 2014-11-06 | 2017-07-07 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | 향상된 활성 및 자기-활성화 특징을 갖는 자기-활성화 수소화처리 촉매 및 잔유 공급원료를 처리하기 위한 이의 용도 |
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FR2910351B1 (fr) * | 2006-12-22 | 2009-02-27 | Total France Sa | Catalyseur d'hydrotraitement, son procede de preparation et son utilisation. |
US20090223868A1 (en) * | 2008-03-06 | 2009-09-10 | Opinder Kishan Bhan | Catalyst and process for the selective hydrodesulfurization of an olefin containing hydrocarbon feedstock |
JP2013521103A (ja) | 2009-03-06 | 2013-06-10 | アルベマール・ユーロプ・エスピーアールエル | 塊状硫化混合金属触媒ならびに合成ガスからアルコールへの変換におけるその製造および使用のための方法 |
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US7686947B2 (en) | 2010-03-30 |
FR2850041B1 (fr) | 2006-07-07 |
CN1738889A (zh) | 2006-02-22 |
WO2004067683A1 (fr) | 2004-08-12 |
CN100556993C (zh) | 2009-11-04 |
JP4541352B2 (ja) | 2010-09-08 |
US20060054537A1 (en) | 2006-03-16 |
EP1587897A1 (fr) | 2005-10-26 |
DK1587897T3 (da) | 2014-06-16 |
KR20050090007A (ko) | 2005-09-09 |
FR2850041A1 (fr) | 2004-07-23 |
KR101113294B1 (ko) | 2012-02-20 |
EP1587897B1 (fr) | 2014-03-12 |
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