CN106914251A - 渣油加氢脱硫催化剂及其制备方法 - Google Patents
渣油加氢脱硫催化剂及其制备方法 Download PDFInfo
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- CN106914251A CN106914251A CN201511001449.0A CN201511001449A CN106914251A CN 106914251 A CN106914251 A CN 106914251A CN 201511001449 A CN201511001449 A CN 201511001449A CN 106914251 A CN106914251 A CN 106914251A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000009938 salting Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 238000007598 dipping method Methods 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 150000003658 tungsten compounds Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 44
- 239000002184 metal Substances 0.000 description 43
- 239000000243 solution Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 26
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- 238000005507 spraying Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000001802 infusion Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002872 contrast media Substances 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JINUODOULZQQEG-UHFFFAOYSA-N N.[B].[Mo] Chemical compound N.[B].[Mo] JINUODOULZQQEG-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/882—Molybdenum and cobalt
-
- 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
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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
- B01J35/615—100-500 m2/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
- 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
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- 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
- B01J35/635—0.5-1.0 ml/g
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- B01J35/638—Pore volume more than 1.0 ml/g
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/70—Catalyst aspects
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明提供一种渣油加氢脱硫催化剂及其制备方法,该催化剂以氧化铝为载体,以Mo或W和Co或Ni为活性组分;催化剂中活性组分的氧化物占催化剂总重量的3.5~14%;其中,MoO3或WO3占催化剂总重量的3~10%,CoO或NiO占催化剂总重量的0.5~4%,所述催化剂的孔容为0.4~1.8ml/g,比表面积为100~280m2/g。本发明的制备方法,包括如下步骤:以氧化铝为载体,以Mo或W和Ni或Co为活性组分,采用分步浸渍法,将Mo或W的盐溶液与氧化铝载体接触,经过干燥,焙烧后,再引入Ni或Co,经过干燥,焙烧,最后得到含Mo或W和Co或Ni的渣油加氢脱硫催化剂。
Description
技术领域
本发明涉及一种渣油加氢脱硫催化剂及其制备方法。特别是重、渣油加氢深度脱硫、脱氮和脱残炭催化剂及其制备方法。
背景技术
全球性石油资源的紧缺和劣质化,导致原油市场上重质原油和高硫原油的比例不断提高;同时随着我国经济的高速发展和环保法规的日益严格,市场对清洁油品需求也在急速增加。因此,重质油轻质化和优质化是当前急需解决的重要任务。渣油加氢处理技术是解决上述问题的一种有效手段。在已有的渣油加氢技术中,固定床渣油加氢技术最为成熟、应用最广泛。通常固定床渣油加氢反应中,当油品经过保护剂床层、脱金属剂床层、脱硫剂床层后,大部分金属和硫有效脱除,但余下的杂质稳定性较高,具体表现在目前工业应用的固定床渣油加氢装置末反应器末段转化效率低,脱氮和脱残炭性不够理想,这对催化剂级配中末端装填催化剂的活性和活性稳定性提出了高要求。装置末反应器末段床层中发生的主要是一些存在于稠环芳烃中的较难反应的含硫、含氮化合物的脱除反应,硫化物主要以苯并噻吩等高分子化合物形式存在于稠环芳烃中。这些复杂化合物的存在使渣油加氢脱反应比平均相对分子质量较小的馏分油脱硫反应困难得多,有较多的积炭前躯物,反应过程中易在催化剂表面形成积炭,使催化剂活性下降。因此,深度加氢脱硫、脱残炭、和脱氮催化剂的开发重点是增加有利于多环重芳烃加氢的有效活性中心密度,使多环芳烃进一步加氢饱和、残炭值降低,增加加氢后渣油的氢含量,同时伴随着杂质Ni、V、S和N的进一步脱除。
众所周知,典型的加氢处理催化剂最常用的活性组元的组合是CoMo、NiMo和NiW等。通常认为钨、钼为主活性组元,镍、钴为助活性组元。钨、钼、镍、钴等活性组元引入催化剂的方式一般有共浸渍、分步浸渍两种。其中,共浸渍是将混合金属溶液与载体接触,但往往配制的混合溶液粘度大、流动性差,并且形成的混合金属盐稳定溶液中有分子较大的络合物或配合物,在浸渍过程中难以避免局部聚集,催化剂孔道不畅通的情况,造成催化剂有效活性表面下降,浪费金属原料,催化剂活性降低等弊端。
CN 94193604提供了一种含有载附于多孔耐火料载体上的催化促进剂外层的催化剂,所述载体含有内部的含Ⅷ族金属成分,该催化剂如下制备:首先向多孔耐火氧化物载体中掺混入Ⅷ族金属,随后掺混其它催化促进剂成分(通常为ⅥB族金属)。催化剂中NiO含量大于4wt%,ⅥB族金属氧化物含量大于17wt%。
CN95107484提供了一种加氢催化剂的制备方法,是先用浸渍法或混捏法制成MoO3含量为6~13wt%的含钼载体,然后用Ni-Mo混合物的氨水溶液浸渍,再经焙烧、还原。该发明提供的方法制得的催化剂具有较高的催化加氢活性。本专利在得到含钼载体后,用Ni-Mo混合物的氨水溶液浸渍,不是单一金属溶液,金属在催化剂上的分布效果不好。
CN99120515描述了一种加氢精制催化剂及其制备方法,催化剂以含硅氧化铝为载体,以Ⅷ族(Fe、Co、Ni)和ⅥB族(Mo、W)金属元素为活性组分,添加硼作为助剂,特别是含有钨、钼、镍三种活性组分。催化剂的制备方法是先分别配制钼硼氨水溶液和钨镍水溶液,然后对成型载体分两段浸渍,经过干燥和分段焙烧而制得。本专利采用两次浸渍,最后一次焙烧,并且后次浸渍为钨镍水溶液,不是单一金属溶液。
CN200810113640提供了一种钼镍加氢催化剂及其制备方法,所述催化剂以重量计,包括MoO3为20~40%,NiO为2.5~12%,TiO2为1~6%,P2O5为1.5~4.5%,余量为γ-Al2O3。将MoO3、含钛化合物、含磷化合物加入到氧化铝和/或氧化铝前身物中,再加入硝酸溶液,混捏、挤条成型,经干燥、焙烧后得到含Ti、Mo、P的Al2O3成型物;再用含Ni的活性金属稳定溶液浸渍所述Al2O3成型物,经干燥、焙烧后得到钼镍加氢催化剂。本专利MoO3是混捏方式引入,金属在催化剂孔道中分布效果不好。
CN200910177170一种加氢催化剂及其制备方法,包括步骤:(1)用含钼和/或钨配原子的杂多配合物的水溶液浸渍载体;(2)干燥步骤(1)的浸渍产物;(3)用含镍和/或钴、有机酸根和铵离子的混合溶液浸渍步骤(2)的产物;(4)干燥步骤(3)的浸渍产物。本专利只有干燥,没有焙烧,金属分布效果不好。
CN201010240035涉及一种活性金属组分呈分层分布的加氢催化剂及其制备方法,催化剂颗粒中活性金属组分呈分层分布,核层为钼镍或钨镍活性金属组分,壳层为钼钴活性金属组分;核层至少有一种活性金属与壳层不同。本专利分为两次浸渍后再干燥和焙烧,金属分布效果不好。
CN201010519424提供了一种加氢催化剂及其制备方法和应用以及加氢精制方法,本发明的制备方法包括先后在载体上负载第一化合物和第二化合物,第一化合物为以第ⅥB族金属为配原子的杂多酸和/或杂多酸盐,第二化合物为以第Ⅷ族金属为阳离子的非金属含氧酸盐和/或以第Ⅷ族金属为阳离子的无氧酸盐。本专利分为两次浸渍和干燥,最后焙烧,金属分布效果不好。
CN201110043325涉及一种活性金属和碱性金属浓度呈梯度增加分布的加氢催化剂的制备方法,本专利采用钨、钼、镍、钴等混合金属溶液浸渍,不是单一金属溶液,金属分布效果不好。
CN201110401726提供了一种加氢催化剂及其制备方法。该制备方法采用ⅥB族和Ⅷ族金属活性组分进行分步负载,ⅥB族金属为钼,Ⅷ族金属为钴或镍,载体为多孔氧化物。本发明用悬浊液与载体在高压釜中接触,时间为10小时以上,不仅周期长,而且金属分布效果不好。
本发明采用分步浸渍法,将ⅥB族金属为钼或钨的盐溶液与氧化铝载体接触,经过干燥,焙烧后,再引入Ⅷ族金属为钴或镍,引入方式为钴或镍的盐溶液与氧化铝载体接触,经过干燥,焙烧,最后得到含钼或钨和镍或钴的催化剂。本发明的创新在于,首先将主活性组元以单一金属盐溶液浸渍到氧化铝载体上,由于单一的盐溶液中分子较小,也无其他金属竞争,根据毛细管吸附原理,故能够顺畅的优先浸渍分布到孔道深处,利于主活性组元高度分散;助活性组元以同样的道理引入,最终效果是本发明能够有效避免金属组元的聚集,保证催化剂孔道畅通,极大的提高了催化剂有效活性表面,并且能够使得催化剂孔道中活性由孔口向里逐渐增强,使得反应物快捷的进入到孔道深处,减少在孔道口的聚集结焦堵孔,从而保证了催化剂的高活性及活性稳定性。本发明还具有制备工艺简单,金属利用率极高,催化剂成本低的优势。
发明内容
本发明的目的是提供一种催化剂,催化剂孔道畅通,催化剂有效活性表面极高,具有深度脱除硫、氮、残炭等杂质能力。
本发明提供一种渣油加氢脱硫催化剂,其中,以氧化铝为载体,以Mo或W和Co或Ni为活性组分;
催化剂中活性组分的氧化物占催化剂总重量的3.5~14%;
其中,MoO3或WO3占催化剂总重量的3~10%,CoO或NiO占催化剂总重量的0.5~4%;
所述催化剂的孔容为0.4~1.8ml/g,比表面积为100~280m2/g。
本发明所述的渣油加氢脱硫催化剂,其中,CoO或NiO优选占催化剂总重量的0.8~3.5%。
本发明所述的渣油加氢脱硫催化剂,其中,所述催化剂的孔容优选为0.45~1.4ml/g;比表面积优选为130~260m2/g。
本发明还提供一种渣油加氢脱硫催化剂的制备方法,其是上述催化剂的制备方法,包括如下步骤:
以氧化铝为载体,以Mo或W和Ni或Co为活性组分,采用分步浸渍法,将Mo或W的盐溶液与氧化铝载体接触,经过干燥,焙烧后,再引入Ni或Co,经过干燥,焙烧,最后得到含Mo或W和Co或Ni的渣油加氢脱硫催化剂。
本发明所述的渣油加氢脱硫催化剂的制备方法,优选包括如下步骤:
(1)将钼或钨化合物与去离子水或氨水混合制成单金属浸渍溶液,采用饱和浸渍的方法与Al2O3载体接触,然后在70~160℃下干燥1~9h,再在280~650℃空气中焙烧1~7h,得到负载了氧化钼或氧化钨的前驱体;
(2)再将镍或钴化合物制成单金属浸渍溶液,采用饱和浸渍的方法,与步骤(1)中负载了氧化钼或氧化钨的前驱体接触,在70~160℃下干燥1~9h,再在280~650℃的空气中焙烧1~7h,得到渣油加氢脱硫催化剂。
本发明所述的渣油加氢脱硫催化剂的制备方法,其中,优选的是,所得渣油加氢脱硫催化剂中,MoO3或WO3占催化剂总重量的3~10%,CoO或NiO占催化剂总重量的0.5~4%。
本发明所述的渣油加氢脱硫催化剂的制备方法,其中,优选的是,所得渣油加氢脱硫催化剂中,CoO或NiO占催化剂总重量的0.8~3.5%。
本发明所述的渣油加氢脱硫催化剂的制备方法,其中,步骤(1)中所述焙烧,焙烧温度优选为400~560℃。
本发明所述的渣油加氢脱硫催化剂的制备方法,其中,步骤(2)中所述焙烧,焙烧温度优选为400~560℃。
本发明还可以详述如下:
本发明提供一种渣油加氢脱硫催化剂及其制备方法,以氧化铝为载体,来自ⅥB和Ⅷ族的氧化物为活性组分,优选Mo或W和Ni或Co,采用分步浸渍法,将ⅥB族金属为钼或钨的盐溶液与氧化铝载体接触,经过干燥,焙烧后,再引入Ⅷ族金属为钴或镍,引入方式为钴或镍的盐溶液与氧化铝载体接触,经过干燥,焙烧,最后得到含钼或钨和镍或钴的催化剂。
催化剂的具体制备过程是:
将钼或钨化合物与去离子水或氨水混合制成单金属浸渍溶液,采用饱和浸渍的方法与Al2O3为载体接触,然后在70~160℃下干燥1~9h,再在280~650℃,最好400~560℃的空气中焙烧1~7h;再将镍或钴化合物制成单金属浸渍溶液,采用饱和浸渍的方法,与上述负载了氧化钼或氧化钨的前驱体接触,在70~160℃下干燥1~9h,再在280~650℃,最好400~560℃的空气中焙烧1~7h,最终得到主活性金属组分优先分布在催化剂孔道深处的催化剂。按本发明方法制备的一种加氢催化剂,具有如下特点:
1)以氧化铝为载体;
2)孔容为0.4~1.8ml/g,最好为0.45~1.4ml/g;
3)比表面为100~280m2/g,最好为130~260m2/g;
4)催化剂中活性金属组分占催化剂总重量的3.5~14%,最好为3~10%的MoO3或WO3和0.5~4%的CoO或NiO,最好为0.8~3.5%的CoO或NiO。
本发明的有益效果:
主活性组元以单一金属盐溶液浸渍到氧化铝载体上,由于单一的盐溶液中分子较小,无其他金属竞争,根据毛细管吸附原理,故能够顺畅的优先浸渍分布到孔道深处,利于主活性组元高度分散;助活性组元以同样的道理引入,最终效果是本发明能够有效避免金属组元的聚集,保证催化剂孔道畅通,极大的提高了催化剂有效活性表面,并且能够使得催化剂孔道中活性由孔口向里逐渐增强,使得反应物快捷的进入到孔道深处,减少在孔道口的聚集结焦堵孔,从而保证了催化剂的高活性及活性稳定性,进而提高了催化剂的脱硫、氮、残炭等杂质能力。此外,本发明制备工艺简单,金属利用率极高。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
实施例1
以氧化铝为载体,吸水率为1.0mL/g。采用饱和浸渍方法制备活性组分为Mo、Ni的催化剂。称取150g载体,喷浸150mL含15.13g钼酸铵(含MoO382m%)溶液,在喷浸设备中均化15分钟后,在160℃下干燥2h,560℃空气氛围中焙烧2h,制得前驱体1;再在前驱体1上采用饱和浸渍法喷浸含7.21g硝酸镍(含NiO 25.2m%)的溶液,在喷浸设备中均化10分钟后,在160℃下干燥1h,560℃空气氛围中焙烧1h,制得催化剂记为C1,催化剂中含7.56%的MoO3、0.5%的NiO。
实施例2
以氧化铝为载体,吸水率为1.0mL/g。采用饱和浸渍方法制备活性组分为Mo、Ni的催化剂。称取150g载体,喷浸150mL含21.02g钼酸铵(含MoO382m%)溶液,在喷浸设备中均化15分钟后,在100℃下干燥3h,450℃空气氛围中焙烧4h,制得前驱体2;再在前驱体2上采用饱和浸渍法喷浸含20.52g硝酸镍(含NiO 25.2m%)的溶液,在喷浸设备中均化10分钟后,在100℃下干燥2h,450℃空气氛围中焙烧2h,制得催化剂记为C2,催化剂中含10%的MoO3、3%的NiO。
实施例3
以氧化铝为载体,吸水率为1.0mL/g。采用饱和浸渍方法制备活性组分为Mo、Co的催化剂。称取150g载体,喷浸150mL含21.02g钼酸铵(含MoO382m%)溶液,在喷浸设备中均化15分钟后,在100℃下干燥3h,400℃空气氛围中焙烧1h,制得前驱体3;再在前驱体3上采用饱和浸渍法喷浸含20.34g硝酸钴(含CoO 25.2m%)的溶液,在喷浸设备中均化10分钟后,在110℃下干燥2h,560℃空气氛围中焙烧1h,制得催化剂记为C3,催化剂中含10%的MoO3、3%的CoO。
实施例4
以氧化铝为载体,吸水率为1.0mL/g。采用饱和浸渍方法制备活性组分为W、Co的催化剂。称取150g载体,喷浸150mL含5.90g偏钨酸铵(含WO382m%)溶液,在喷浸设备中均化15分钟后,在100℃下干燥3h,400℃空气氛围中焙烧3h,制得前驱体4;再在前驱体4上采用饱和浸渍法喷浸含25.59g(含CoO25.2m%)的溶液,在喷浸设备中均化10分钟后,在110℃下干燥2h,280℃空气氛围中焙烧2h,制得催化剂记为C4,催化剂中含3%的WO3、4%的CoO。
实施例5
以氧化铝为载体,吸水率为1.0mL/g。采用饱和浸渍方法制备活性组分为Mo、Ni的催化剂。称取150g载体,喷浸150mL含15.13g钼酸铵(含MoO382m%)溶液,在喷浸设备中均化15分钟后,在70℃下干燥9h,280℃空气氛围中焙烧7h,制得前驱体5;再在前驱体5上采用饱和浸渍法喷浸含7.21g硝酸镍(含NiO 25.2m%)的溶液,在喷浸设备中均化10分钟后,在110℃下干燥2h,400℃空气氛围中焙烧1h,制得催化剂记为C5,催化剂中含7.56%的MoO3、0.5%的NiO。
实施例6
以氧化铝为载体,吸水率为1.0mL/g。采用饱和浸渍方法制备活性组分为Mo、Ni的催化剂。称取150g载体,喷浸150mL含15.13g钼酸铵(含MoO382m%)溶液,在喷浸设备中均化15分钟后,在160℃下干燥1h,650℃空气氛围中焙烧1h,制得前驱体6;再在前驱体6上采用饱和浸渍法喷浸含7.21g硝酸镍(含NiO 25.2m%)的溶液,在喷浸设备中均化10分钟后,在110℃下干燥2h,650℃空气氛围中焙烧4h,制得催化剂记为C6,催化剂中含7.56%的MoO3、0.5%的NiO
对比例1
以氧化铝为载体,吸水率为1.0mL/g。采用饱和浸渍方法制备活性组分为Mo、Ni的催化剂。称取150g载体,喷浸150mL含20.52g硝酸镍(含NiO25.2m%)的溶液,在喷浸设备中均化15分钟后,在100℃下干燥3h,450℃空气氛围中焙烧4h,制得前驱体d1;再在前驱体d1上采用饱和浸渍法喷浸含21.02g钼酸铵(含MoO382m%)的溶液,在喷浸设备中均化10分钟后,在100℃下干燥2h,450℃空气氛围中焙烧2h,,制得催化剂,记为D1,催化剂中含10%的MoO3、3%的NiO。
对比例2
参照CN95107484实施例提供的方法制备出的催化剂,记为D2,催化剂中含10%的MoO3、3%的NiO。
对比例3
CN99120515实施例提供的方法制备出的催化剂,记为D3,催化剂中含7%的MoO3、3%的WO3、3%的NiO。
对比例4
CN200810113640实施例提供的方法制备出的催化剂,记为D4,催化剂中含10%的MoO3、3%的NiO、1%的TiO2,2%的P2O5。
对比例5
CN200910177170实施例提供的方法制备出的催化剂,记为D5,催化剂中含10%的MoO3、3%的NiO、0.3%的P2O5。
对比例6
CN201010240035实施例提供的方法制备出的催化剂,记为D6,催化剂中含10%的MoO3、3%的NiO。
对比例7
CN201010519424实施例提供的方法制备出的催化剂,记为D7,催化剂中含10%的MoO3、3%的NiO。2%的F,0.3%的P2O5。
对比例8
CN20111004332实施例提供的方法制备出的催化剂,记为D8,催化剂中含10%的MoO3、3%的NiO。
对比例9
CN201110401726实施例提供的方法制备出的催化剂,记为D9,催化剂中含10%的MoO3、3%的NiO。
实施例7
本实施例用以说明本发明所提供的催化剂及其对比剂的物化性质,见表1。
表1本发明实施例和对比例所得催化剂孔容和表面
实施例8
本实施例用以说明本发明所提供的催化剂的加氢性能,并与对比剂对比。在100mL小型固定床加氢装置上进行评价。评价原料油性质见表2。
表2试验原料油主要性质
968.1 | |
(Ni+V),μg/g | 100 |
硫,% | 4.10 |
氮,μg/g | 2000 |
残炭,% | 15.8 |
评价条件如表3所示。
表3评价工艺条件
压力,MPa | 15 |
氢油比(体积) | 1000 |
反应温度,℃ | 385 |
0.4 |
相对脱硫率、脱氮率、脱残炭率是以C1催化剂运转500h时的脱杂质率为1.0作基准比较而得。催化剂活性和稳定性对比结果见表4。由表4可以看出,随着运转时间延长,C2催化剂、C3催化剂的相对脱硫率、脱氮率、脱残炭率均明显高于对比催化剂,这是由于C2催化剂、C3催化剂中主活性组元助活性组元在孔道内分布合理,反应过程中,催化剂孔道内能充分接纳多环芳烃,使之进一步加氢饱和、残炭值降低,而对比催化剂则由于孔道口不畅通或是近孔道口位置活性组元分布多,都易导致多环芳烃等反应物在孔口即快速发生聚集,使得催化剂孔道内大部分活性无法发挥作用,从而影响了催化剂整体的活性和活性稳定性;并且C2催化剂、C3催化剂活性组分的分散度高于对比催化剂,活性利用率高。采用本发明制备的催化剂显示极高的脱硫、氮和残炭活性,以及很好的活性稳定性。
表4催化剂活性和稳定性对比
Claims (9)
1.一种渣油加氢脱硫催化剂,其特征在于,以氧化铝为载体,以Mo或W和Co或Ni为活性组分;
催化剂中活性组分的氧化物占催化剂总重量的3.5~14%;
其中,MoO3或WO3占催化剂总重量的3~10%,CoO或NiO占催化剂总重量的0.5~4%;
所述催化剂的孔容为0.4~1.8ml/g,比表面积为100~280m2/g。
2.根据权利要求1所述的渣油加氢脱硫催化剂,其特征在于,CoO或NiO占催化剂总重量的0.8~3.5%。
3.根据权利要求1所述的渣油加氢脱硫催化剂,其特征在于,所述催化剂的孔容为0.45~1.4ml/g;比表面积为130~260m2/g。
4.一种渣油加氢脱硫催化剂的制备方法,其是权利要求1~3任一项所述催化剂的制备方法,包括如下步骤:
以氧化铝为载体,以Mo或W和Ni或Co为活性组分,采用分步浸渍法,将Mo或W的盐溶液与氧化铝载体接触,经过干燥,焙烧后,再引入Ni或Co,经过干燥,焙烧,最后得到含Mo或W和Co或Ni的渣油加氢脱硫催化剂。
5.根据权利要求4所述的渣油加氢脱硫催化剂的制备方法,包括如下步骤:
(1)将钼或钨化合物与去离子水或氨水混合制成单金属浸渍溶液,采用饱和浸渍的方法与Al2O3载体接触,然后在70~160℃下干燥1~9h,再在280~650℃空气中焙烧1~7h,得到负载了氧化钼或氧化钨的前驱体;
(2)再将镍或钴化合物制成单金属浸渍溶液,采用饱和浸渍的方法,与步骤(1)中负载了氧化钼或氧化钨的前驱体接触,在70~160℃下干燥1~9h,再在280~650℃的空气中焙烧1~7h,得到渣油加氢脱硫催化剂。
6.根据权利要求5所述的渣油加氢脱硫催化剂的制备方法,其特征在于,所得渣油加氢脱硫催化剂中,MoO3或WO3占催化剂总重量的3~10%,CoO或NiO占催化剂总重量的0.5~4%。
7.根据权利要求6所述的渣油加氢脱硫催化剂的制备方法,其特征在于,所得渣油加氢脱硫催化剂中,CoO或NiO占催化剂总重量的0.8~3.5%。
8.根据权利要求5所述的渣油加氢脱硫催化剂的制备方法,其特征在于,步骤(1)中所述焙烧,焙烧温度为400~560℃。
9.根据权利要求5所述的渣油加氢脱硫催化剂的制备方法,其特征在于,步骤(2)中所述焙烧,焙烧温度为400~560℃。
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