CN112337488A - 硫化镍系加氢催化剂及裂解汽油加氢处理方法 - Google Patents
硫化镍系加氢催化剂及裂解汽油加氢处理方法 Download PDFInfo
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- CN112337488A CN112337488A CN202011171931.XA CN202011171931A CN112337488A CN 112337488 A CN112337488 A CN 112337488A CN 202011171931 A CN202011171931 A CN 202011171931A CN 112337488 A CN112337488 A CN 112337488A
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- Prior art keywords
- catalyst
- nickel sulfide
- hydrogenation catalyst
- hydrogenation
- stage
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 132
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 239000002612 dispersion medium Substances 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 150000001993 dienes Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 14
- 229910000510 noble metal Inorganic materials 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000002352 steam pyrolysis Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910001950 potassium oxide Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical class [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- -1 alkali metal lithium oxide Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- B01J35/635—0.5-1.0 ml/g
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/20—Sulfiding
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- 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
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Abstract
本发明公开了一种硫化镍系加氢催化剂及裂解汽油加氢处理方法。本发明硫化镍系加氢催化剂以镍为主活性金属，铜和/或钼为助活性金属，镁铝复合氧化物为分散介质，包括一段硫化镍系加氢催化剂和二段硫化镍系加氢催化剂。本发明方法包括：首先将一段、二段硫化镍系加氢催化剂分别装入两个串联的内置微孔分散内构件的固定床加氢反应器中，通入氮气置换反应器及管线中的空气，然后将预热后的加氢石脑油与氢气混合，通入固定床加氢反应器，同时升温至反应条件后，切换裂解汽油进行加氢处理反应。采用本发明催化剂和方法，可以直接通入高硫高烯烃的劣质催化裂解汽油进行处理，开工简单，反应条件缓和，活性和稳定性好，工艺过程绿色安全环保。
Description
技术领域
本发明涉及加氢催化剂及加氢处理方法。具体地说，涉及硫化镍系加氢催化剂及用于裂解汽油深度加氢处理的方法。
背景技术
催化裂解工艺是近年来发展起来的多产低碳烯烃的炼化技术。催化裂解汽油是催化裂解工艺的副产品，它具有较高的辛烷值，是一种很好的高辛烷值汽油调和组分，同时可以作为生产BTX轻质芳烃的原料。但是，由于含有一些不稳定的化合物，主要是双烯烃和硫氮化合物，氧化安定性很差，不能满足汽油调和组分或芳烃抽提原料的要求。因此，裂解汽油出装置后，必须经过加氢处理，除去双烯烃以改善其安定性，脱硫同时还要避免芳烃饱和以保持较高辛烷值和轻质芳烃组分，才能进一步利用。
催化裂解工艺出现较晚，催化裂解汽油加氢催化剂和加氢处理工艺方面的专利文献很少。以蒸汽裂解汽油加氢催化剂为核心的加氢技术是加氢领域中一个重要分支，可以为催化裂解汽油加氢处理技术的开发提供借鉴。目前，采用的蒸汽裂解汽油加氢催化剂大致分为两类，一类是非贵金属镍催化剂；另一类是贵金属钯催化剂。US4,113,603报导用两段的加氢精制方法处理蒸气热裂解汽油，其第一段用含Ni-W的催化剂除去硫醇，第二段用贵金属Pd/Al2O3催化剂除去双烯烃。该发明采用贵金属催化剂，成本很高。非贵金属催化剂因结构差异和金属含量高等因素具有一定抗杂质和耐水能力，其价格优势也比较显著。因此，非贵金属催化剂工业化产品正在逐步取代贵金属催化剂应用于裂解产物加氢。CN1218822A报道了一种Ni/Al2O3适用于裂解汽油馏分的选择性加氢催化剂，该催化剂是将镍负载于含锂或碱土金属的氧化铝载体上制得的，NiO含量为5～25重％，锂或碱土金属含量为0.1～2.0重％。CN103657668B公开了一种选择性镍基加氢催化剂及其制备方法，以氧化铝为载体，以催化剂重量为100％计，含氧化镍14～19％，氧化锡2～5％，碱金属氧化锂和/或氧化钾0.1～8％，氧化铜和/或氧化锌0.5～8％，氧化钼和/或氧化钨0.3～8％，氧化硅和/或氧化磷0～8％。该发明采用络合浸渍法制备，加入助剂组分Sn等提高催化剂的双烯加氢选择性和抗硫、砷等性能。上述发明采用氧化铝负载法制备催化剂，活性金属镍为还原态，用于蒸汽裂解汽油二烯烃选择性加氢，但抗硫性能和芳烃加氢选择性没有公开。另外，负载型催化剂的金属分散性有待进一步提高。CN103657670B公开了一种裂解汽油镍系选择性加氢催化剂及其制备方法，属于包含金属或金属氧化物或氢氧化物的催化剂，其特征在于具有介孔-大孔或双介孔复合孔道，以氧化铝作载体，以镍为主活性组份，钼为助活性组分，氧化镧为助剂，重量百分组成如下：氧化镍15～19，氧化钼6.5～20.0，助剂2.2～4.5，氧化铝余量。该发明的催化剂用于全馏分裂解汽油选择性加氢时，双烯加氢率平均为99％。该发明采用还原态镍作为主活性组分，用于蒸汽裂解汽油加氢脱除二烯烃。没有提及催化剂处理高硫裂解汽油时的抗硫性能。另外，上述发明均采用普通固定床加氢工艺，且没有提及如何解决二烯烃结焦问题。
CN101037614公开了一种加氢精制催化剂、制备方法及应用，催化剂以钼、钴、镍为活性组分，添加助剂，以氧化铝为载体，以催化剂总重量为100％计，催化剂含有氧化钼14～20％，氧化钴1～6％，氧化镍1～4％，助剂碱金属的氧化物含量为1～3％，助剂P或/和Sb的氧化物含量为1～5％，Si或/和锡的氧化物含量为2～6％；催化剂的孔容为0.45～0.65cm3/g，比表面为150～280m2/g。该催化剂可用于中低馏分油C5～C8，特别是C6～C8馏分油的二段加氢精制，在加氢脱硫的同时，最大限度地加氢饱和单烯烃，能适应硫含量多变的油品及高空速的要求。CN101148616B公开了一种由裂解汽油生产清洁汽油的方法，裂解汽油进入常压分馏塔进行馏分分离，得到轻质裂解汽油和重质裂解汽油，切割点为78～85℃，重质裂解汽油与氢气混合后进入加氢反应区，在加氢精制催化剂的作用下进行反应，其反应生成物经冷却、气液分离后得到汽油产品。该发明采用轻重馏分切割后分别加氢的工艺，有利于防止全馏分裂解汽油结焦的问题，但切割能耗较大，加工流程复杂，经济性有待验证。CN101619239B公开了一种裂解汽油重馏分的加氢处理方法，采用一段串联工艺流程，裂解汽油重馏分原料与氢气在加氢精制条件下首先与第一反应器加氢催化剂接触，第一反应器中使用高活性金属含量的W-Mo-Ni系加氢催化剂；第一反应器流出物直接进入第二反应器，与第二反应器的两种加氢催化剂接触，反应物料先与W-Mo-Ni系加氢催化剂接触，然后与Mo-Co系加氢催化剂接触，反应产物进行分离处理。该发明针对蒸汽裂解汽油C9～C10重馏分进行加氢处理，通过催化剂级配的方法实现深度脱硫脱氮脱烯烃。但是采用普通的固定床加氢工艺，催化剂为氧化型，开工步骤繁琐，环保较差，没有提及如何防止二烯烃结焦问题；另外，该发明方法需要进一步提高芳烃加氢选择性，避免大量饱和。
综上所述，目前公开的专利报道多是蒸汽裂解汽油加氢催化剂和加氢处理工艺。由于水蒸气热裂解工艺所用的原料油馏分较轻，一般多用石脑油或轻柴油。轻馏分油的硫含量较低，因而蒸汽裂解汽油中的硫含量也不会太高，据有关文献报导一般＜100PPm。催化裂解工艺所用的原料是比水蒸气热裂解原料油重得多的减压瓦斯油(VGO)，甚至是渣油。而随着馏分越重，硫含量也越高。所以催化裂解汽油具有比水蒸气热裂解汽油高得多的硫含量。根据所用的原料油中硫含量的不同，催化裂解汽油的硫含量通常高达1000PPm甚至更高。另外，催化裂解汽油中的氮含量、双烯烃杂质含量明显高，在较高的反应温度下，在酸性较强的催化剂表面容易发生聚合而结焦，导致装置被迫停工。
发明内容
针对现有技术的不足，发明人研究认为：首先催化裂解汽油的加氢处理就不能采用耐硫性能较差的贵金属钯催化剂和传统的还原态镍催化剂；其次非贵金属镍系催化剂的制备工艺也需进行调整，还原态镍抗硫能力差，不适合该体系；再次，需要调整催化剂制备工艺，如加入助剂和特殊形状设计，并且采用专用加氢工艺，抑制二烯烃聚合，以满足长周期运转和产品质量的要求，本发明提供了一种可直接进料、成本低且具有更高的加氢活性、选择性和稳定性的硫化镍系加氢催化剂，以及一种开工简单，反应条件缓和，工艺过程绿色安全环保的裂解汽油加氢处理方法。
为解决上述技术问题，本发明采用如下技术方案予以实现：
本发明提供了一种硫化镍系加氢催化剂，该催化剂包括一段硫化镍系加氢催化剂和二段硫化镍系加氢催化剂，所述的一段硫化镍系加氢催化剂或二段硫化镍系加氢催化剂是以镍为主活性金属，铜和/或钼为助活性金属，镁铝复合氧化物为分散介质；其中，一段硫化镍系加氢催化剂采用齿球型外形，以催化剂总重量为100％计，硫化镍含量5～35wt％，硫化铜含量1～4wt％，硫化钼含量0.5～5wt％，氧化镁含量6～18wt％，氧化铝为余量；催化剂比表面积80～180m2/g，孔容0.4～0.65ml/g；二段硫化镍系加氢催化剂采用齿球型外形，以催化剂总重量为100％计，硫化镍含量1.5～12wt％，硫化钼含量3～18wt％，氧化镁含量2～8wt％，氧化铝为余量；催化剂比表面积120～260m2/g，孔容0.25～0.5ml/g。
本发明所述的硫化镍系加氢催化剂，其中所述的催化剂优选由如下方法制得：按比例将水溶性镍盐、铜盐和/或钼盐、镁盐、铝盐和氨基三乙酸溶解后配制成金属盐溶液Ⅰ，碳酸钠和硫化剂溶解后配制成溶液Ⅱ；在反应釜中加入一定量的去离子水，启动搅拌和加热系统至釜内水温度为60-90℃，将溶液Ⅰ、溶液Ⅱ并流加入反应釜中，反应0.5-2.0小时，然后密闭进行水热原位硫化1.0-6.0小时；反应物料洗涤过滤干燥后，滤饼直接成型即得一段或二段硫化镍系加氢催化剂。
本发明还提供了一种上述硫化镍系加氢催化剂加氢处理裂解汽油的方法，包括，首先将一段硫化镍系加氢催化剂和二段硫化镍系加氢催化剂分别装入两个串联的固定床加氢反应器中，通入氮气置换反应器及管线中的空气，然后将加氢石脑油预热后和氢气通入固定床加氢反应器，同时升温至反应条件后，切换裂解汽油进行加氢处理反应；
所述的固定床加氢反应器采用微孔分散内构件，氢气通过微孔分散内构件后进入裂解汽油物流中，充分混合呈乳化态后与硫化镍系加氢催化剂接触，进行加氢反应；
所述的反应条件为：一段硫化镍系加氢催化剂的反应温度50～220℃，氢分压0.5～3.5MPa，体积空速4～10h-1，体积氢油比5～50；二段硫化镍系加氢催化剂的反应温度180～320℃，氢分压2～10MPa，体积空速0.5～4.0h-1，体积氢油比40～250。
本发明方法采用水热原位硫化法制备硫化镍系非贵金属加氢催化剂，催化剂本身已经是具有较高活性的硫化态。本发明方法采用内置微孔分散内构件的一段串联固定床加氢工艺，直接通入高硫高烯烃的劣质催化裂解汽油进行加氢深度加氢处理，开工简单，反应条件缓和，活性和稳定性好，工艺过程绿色安全环保。
本发明的硫化镍系加氢催化剂及裂解汽油加氢处理方法中，裂解汽油优选为催化裂解工艺副产的催化裂解汽油，硫含量100～1000μg/g，氮含量8～100μg/g，烯烃含量5～30v％，二烯值0.5～5.0gI/100g。
本发明与现有的技术相比具有如下优点：
(1)本发明方法的催化裂解汽油深度加氢处理工艺采用硫化镍系非贵金属加氢催化剂，催化剂本身已经是具有较高活性的硫化态，能够处理硫含量较高的催化裂解汽油，不存在贵金属催化剂的硫中毒问题；可以直接进料，无需还原或硫化物钝化，与传统的选择性加氢催化剂相比开工简单，安全环保。
(2)本发明方法的硫化镍系非贵金属加氢催化剂采用水热原位硫化法引入所需种类和数量的活性金属，同时实现活性金属的硫化，制备步骤简单，成本低，经济性好；催化剂的酸性可控，比表面积大，金属分散性好，能够有效抑制二烯烃聚合结焦和芳烃加氢饱和，具有更高的加氢活性、选择性和稳定性。
(3)本发明方法采用一段串联加氢工艺，固定床加氢反应器采用微孔分散内构件，氢气通过微孔分散内构件后进入裂解汽油物流中，充分混合呈乳化态与催化剂接触，进行加氢反应。另外，采用不同金属组成和活性的硫化镍系加氢催化剂，分别装填在串联的两个固定床加氢反应器中。裂解汽油物流首先通过一段催化剂，在较低的温度下进行二烯烃饱和反应，防止催化剂结焦；然后在二段催化剂进一步脱硫脱氮和烯烃饱和，满足后续汽油调和或芳烃抽提的要求。
(4)本发明方法采用高活性和选择性硫化镍系加氢催化剂，创造性的采用微孔分散内构件固定床一段串联加氢工艺，直接通入高硫催化裂解汽油进行加氢深度加氢处理，开工简单，反应条件缓和，工艺过程绿色安全环保。流程简单，反应温度和氢油比低，操作费用低，运行周期长。
具体实施方式
本发明的硫化镍系加氢催化剂及裂解汽油加氢处理方法是首先将一段硫化镍系加氢催化剂和二段硫化镍系加氢催化剂分别装入两个串联的固定床加氢反应器中，通入氮气置换反应器及管线中的空气，然后将加氢石脑油预热后和氢气通入固定床加氢反应器，同时升温至反应条件后，切换裂解汽油进行加氢处理反应。
下面通过实施例进一步描述本发明的技术特点，但这些实施例不能限制本发明。在下面的实施例中，涉及的百分含量为重量百分含量。
实施例1一段硫化镍系加氢催化剂的制备
将计量的硝酸镍、硝酸铜、钼酸钠、硝酸镁、硫酸铝和氨基三乙酸溶解后配制成金属盐溶液Ⅰ，碳酸钠和硫脲溶解后配制成溶液Ⅱ。在100L反应釜中加入10L去离子水，调节搅拌转速50转/min，加热至70℃，将溶液Ⅰ、溶液Ⅱ并流加入反应釜中，控制pH在6～8，加料时间控制在1小时，然后继续反应1小时后，将反应釜密闭进行水热原位硫化2.5小时。反应物料洗涤过滤后，将滤饼直接挤条切球成型，在氮气保护气氛下120℃干燥6h，380℃焙烧3h，得到一段硫化镍系加氢催化剂成品，标记为C-I-X。催化剂为粒径2.0～2.5mm的齿球形，组成和物性指标见表1。
实施例2二段硫化镍系加氢催化剂的制备
二段硫化镍系加氢催化剂的制备步骤与实施例1相同，标记为C-II-X。催化剂为粒径2.0～2.5mm的齿球形，组成和物性指标见表1。
对比例1氧化镍系加氢催化剂的制备
采用CN103657668B和CN101037614公开的专利方法制备对比催化剂R-I和R-II，分别为裂解汽油一段加氢催化剂和裂解汽油二段加氢催化剂，均为氧化镍系加氢催化剂。R-I催化剂组成如下：氧化镍19％，氧化锡4％，氧化钾0.6％，氧化铜3％，氧化钼0.8％，氧化硅4％。R-II催化剂组成如下：氧化钼16％，氧化钴4.2％，氧化镍2.7％，氧化钾1～3％，氧化磷3.5％，氧化硅2.4％。
实施例3催化剂的加氢活性评价
在100ml加氢反应装置上进行催化剂的裂解汽油加氢处理活性评价，加氢反应器采用微孔分散内构件，氢气通过微孔分散内构件后进入裂解汽油物流中，然后与催化剂接触。评价用原料油为工业装置生产的催化裂解汽油，其密度为0.822g/cm3，硫含量为528μg/g，氮含量为66μg/g，溴价26gBr/100g，二烯值4.3gI/100g，烯烃含量15.6V％，芳烃75.8w％，馏程为43～188℃。
将一段硫化镍系加氢催化剂A和二段硫化镍系加氢催化剂B分别装填入两个串联的加氢反应器，催化剂装填量分别为50ml和100ml，氮气试压后，接通氢气置换，保持压力为3.0MPa，氢气流量10L/h，通入加氢石脑油，进料量100ml/h，以10℃/h的升温速度将反应器温度升至300℃，保持2小时。然后切换进裂解石脑油，调整操作条件，稳定24小时后取样分析。
反应条件为：进料量300ml/h，一段硫化镍系加氢催化剂A的反应温度180℃，氢分压3.0MPa，氢气量为9L/h；二段硫化镍系加氢催化剂B的反应温度290℃，氢分压3.0MPa，氢气量为36L/h。
对比例4催化剂加氢活性评价
在100ml加氢反应装置上进行催化剂的裂解汽油加氢处理活性评价，加氢反应器不采用微孔分散内构件，氢气和裂解汽油原料在管线中混合后直接与催化剂接触。评价用原料油、催化剂装填、开工、操作条件及取样分析与实施例3相同。
实施例和对比例的催化剂的活性和稳定性评价结果见表2，3和4。由表中数据可见，采用本发明方法制备的硫化镍系加氢催化剂，脱硫、脱氮和二烯烃饱和活性明显高于对比例氧化镍系加氢催化剂，且芳烃饱和率更低，表明加氢选择性良好。同时，采用本发明方法的微孔分散内构件，加氢活性、稳定性和选择性均具有一定程度的提高，3000h小时评价结果稳定性，表明本专利发明方法能够显著提高催化裂解汽油深度加氢处理效果。
表1催化剂的组成和物性指标
表2催化剂的加氢活性评价数据(采用微孔分散内构件)
表3催化剂的加氢活性评价数据(不采用微孔分散内构件)
表4催化剂的加氢稳定性评价数据
Claims (4)
1.一种硫化镍系加氢催化剂，其特征在于：所述的催化剂以镍为主活性金属，铜和/或钼为助活性金属，镁铝复合氧化物为分散介质，包括一段硫化镍系加氢催化剂和二段硫化镍系加氢催化剂；其中，一段硫化镍系加氢催化剂采用齿球型外形，以催化剂总重量为100％计，硫化镍含量5～35wt％，硫化铜含量1～4wt％，硫化钼含量0.5～5wt％，氧化镁含量6～18wt％，氧化铝为余量；催化剂比表面积80～180m2/g，孔容0.4～0.65ml/g；二段硫化镍系加氢催化剂采用齿球型外形，以催化剂总重量为100％计，硫化镍含量1.5～12wt％，硫化钼含量3～18wt％，氧化镁含量2～8wt％，氧化铝为余量；催化剂比表面积120～260m2/g，孔容0.25～0.5ml/g。
2.根据权利要求1所述的硫化镍系加氢催化剂，其特征在于，所述的催化剂由如下方法制得：按比例将水溶性镍盐、铜盐和/或钼盐、镁盐、铝盐和氨基三乙酸溶解后配制成金属盐溶液Ⅰ，碳酸钠和硫化剂溶解后配制成溶液Ⅱ；在反应釜中加入去离子水，启动搅拌和加热系统至釜内水温度为60-90℃，将溶液Ⅰ、溶液Ⅱ并流加入反应釜中，反应0.5-2.0小时，然后密闭进行水热原位硫化1.0-6.0小时；反应物料洗涤过滤干燥后，滤饼直接成型即得一段或二段硫化镍系加氢催化剂。
3.一种权利要求1所述的硫化镍系加氢催化剂加氢处理裂解汽油的方法，其特征在于，首先将一段硫化镍系加氢催化剂和二段硫化镍系加氢催化剂分别装入两个串联的固定床加氢反应器中，通入氮气置换反应器及管线中的空气，然后将加氢石脑油预热后和氢气通入固定床加氢反应器，同时升温至反应条件后，切换裂解汽油进行加氢处理反应；
所述的固定床加氢反应器采用微孔分散内构件，氢气通过微孔分散内构件后进入裂解汽油物流中，充分混合呈乳化态后与硫化镍系加氢催化剂接触，进行加氢反应；所述的反应条件为：一段硫化镍系加氢催化剂的反应温度50～220℃，氢分压0.5～3.5MPa，体积空速4～10h-1，体积氢油比5～50；二段硫化镍系加氢催化剂的反应温度180～320℃，氢分压2～10MPa，体积空速0.5～4.0h-1，体积氢油比40～250。
4.按照权利要求1所述的硫化镍系加氢催化剂加氢处理裂解汽油的方法，其特征在于，所述的裂解汽油为催化裂解工艺副产的催化裂解汽油，硫含量100～1000μg/g，氮含量8～100μg/g，烯烃含量5～30v％，二烯值0.5～5.0gI/100g。
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB962777A (en) * | 1961-09-21 | 1964-07-01 | California Research Corp | Hydrogenative conversion of hydrocarbon oil with activated nickel sulfide catalysts |
| CN101619239A (zh) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | 一种裂解汽油重馏分的加氢处理方法 |
| WO2010144512A2 (en) * | 2009-06-11 | 2010-12-16 | Shell Oil Company | A process for the selective hydrogenation and hydrodesulferization of a pyrolysis gasoline feedstock |
| CN102382259A (zh) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | 一种加氢石油树脂的工业制造方法 |
| CN104646010A (zh) * | 2015-01-29 | 2015-05-27 | 中国海洋石油总公司 | 一种硫化型加氢精制催化剂的工艺改进方法 |
| CN105478129A (zh) * | 2014-09-17 | 2016-04-13 | 中国石油化工股份有限公司 | 一种加氢处理催化剂及其应用 |
-
2020
- 2020-10-28 CN CN202011171931.XA patent/CN112337488B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB962777A (en) * | 1961-09-21 | 1964-07-01 | California Research Corp | Hydrogenative conversion of hydrocarbon oil with activated nickel sulfide catalysts |
| CN101619239A (zh) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | 一种裂解汽油重馏分的加氢处理方法 |
| WO2010144512A2 (en) * | 2009-06-11 | 2010-12-16 | Shell Oil Company | A process for the selective hydrogenation and hydrodesulferization of a pyrolysis gasoline feedstock |
| CN102382259A (zh) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | 一种加氢石油树脂的工业制造方法 |
| CN105478129A (zh) * | 2014-09-17 | 2016-04-13 | 中国石油化工股份有限公司 | 一种加氢处理催化剂及其应用 |
| CN104646010A (zh) * | 2015-01-29 | 2015-05-27 | 中国海洋石油总公司 | 一种硫化型加氢精制催化剂的工艺改进方法 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736713A (zh) * | 2022-04-10 | 2022-07-12 | 辽宁新瑞环保实业有限公司 | 劣质裂解碳九加氢生产溶剂油的装置和方法 |
| CN114736713B (zh) * | 2022-04-10 | 2023-09-01 | 辽宁新瑞环保实业有限公司 | 劣质裂解碳九加氢生产溶剂油的装置和方法 |
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