CN109321270B - 一种裂解汽油中间馏分不饱和烃选择性加氢方法 - Google Patents
一种裂解汽油中间馏分不饱和烃选择性加氢方法 Download PDFInfo
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- CN109321270B CN109321270B CN201811182780.0A CN201811182780A CN109321270B CN 109321270 B CN109321270 B CN 109321270B CN 201811182780 A CN201811182780 A CN 201811182780A CN 109321270 B CN109321270 B CN 109321270B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003921 oil Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 44
- 229910052746 lanthanum Inorganic materials 0.000 claims description 39
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 39
- 229910000859 α-Fe Inorganic materials 0.000 claims description 38
- 239000011148 porous material Substances 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 229920000620 organic polymer Polymers 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 19
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 229920002959 polymer blend Polymers 0.000 claims 1
- 239000000084 colloidal system Substances 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052785 arsenic Inorganic materials 0.000 abstract description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 30
- 229910052740 iodine Inorganic materials 0.000 description 30
- 239000011630 iodine Substances 0.000 description 30
- 150000001993 dienes Chemical class 0.000 description 28
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- -1 alkyl aromatic hydrocarbon Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 241000219793 Trifolium Species 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 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
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种裂解汽油中间馏分不饱和烃选择性加氢方法,包括如下过程:镍系催化剂在氢气存在下,400~500℃条件下还原,经降温钝化后调整到反应工艺条件:反应入口温度45~110℃,反应压力2.0‑4.5MPa,氢油体积比60~200:1;液体体积空速2.0‑5.5h‑1;催化剂包括氧化硅‑氧化铝载体和负载于载体上的金属活性组分镍、钼和镁。催化剂抗胶质能力好,抗砷、抗硫、抗水能力强,适用于装置的长周期稳定运转。
Description
技术领域
本发明涉及一种裂解汽油中间馏分不饱和烃选择性加氢方法,尤其是适用于裂解汽油一段选择性加氢。
背景技术
裂解汽油是蒸汽裂解工业生产乙烯、丙烯的重要副产,包括C5-C10馏份。裂解汽油组成很复杂,主要有苯、甲苯、二甲苯、单烯烃、双烯烃、直链烷烃、环烷烃以及氮、硫、氧、氯和重金属的有机化合物等,共200多个组份,其中苯、甲苯、二甲苯(统称BTX)约50-90%,不饱和烃25-30%。根据裂解汽油中含有大量芳烃的特点,其用途广泛,既可以作为汽油的调和组分,生产高辛烷值的汽油,也可以通过分离生产芳烃等。
由于裂解汽油组成复杂、热稳定性差,通常,先经一段选择性加氢除去二烯烃和苯乙烯,二段加氢脱硫后,主要用于芳烃抽提。目前工业上裂解汽油选择加氢用催化剂主要是Pd系或Ni系催化剂,中间馏分(C6~C8烃化合物馏分)加氢或全馏分(C5烃~干点为204℃的烃化合物馏分)加氢工艺。由于各乙烯装置裂解原料和裂解条件的差异,各装置裂解汽油原料组成相差较大,特别是裂解汽油的双烯、胶质(二烯烃及苯乙烯等不饱和组份发生聚合反应生成的高分子聚合物)以及As、重金属含量存在较大差异;有的装置粗裂解汽油双烯、胶质高,而有的装置粗裂解汽油原料中胶质及As、重金属等毒物含量较高,个别装置粗裂解汽油双烯、胶质及As、重金属等毒物含量均高。
裂解汽油中的二烯烃和炔烃在高温下容易聚合成胶质,沉积在催化剂表面,易造成催化剂失活,必须频繁活化和再生。裂解汽油一段加氢催化剂主要有Pd/Al2O3和Ni/Al2O3两种催化剂。
CN200610029962.5涉及一种用于全馏分裂解汽油选择性加氢的方法,主要解决现有技术中存在难以对胶质和游离水含量高的全馏分裂解汽油进行选择性加氢的技术问题。本发明通过采用以C5烃~干点为204℃的烃化合物馏分的裂解汽油和氢气为原料,在反应温度为30~80℃,反应压力为2.0~3.0MPa,新鲜油空速为2.5~5.0小时-1,氢/油体积比为60~120∶1的条件下,原料与催化剂接触,发生反应,使原料中的双烯烃和烯烃基芳烃组分转化成单烯烃和烷基芳烃,其中催化剂包括氧化铝载体、活性组分金属钯或其氧化物、至少一种选自元素周期表中IA或IIA的元素或其氧化物、至少一种选自元素周期表中IVA或VA的元素或其氧化物,载体比表面积为40~160米2/克,总孔容为0.3~1.2毫升/克,且载体具有复合孔分布的技术方案,较好地解决了该问题,可用于全馏分裂解汽油选择性加氢的工业生产中。CN200610118522.7涉及一种用于选择性加氢的具有复合孔结构的镍催化剂,主要解决现有技术中存在催化剂的低温活性低、抗干扰能力弱、容胶能力低、稳定性差、耐游离水性能差的技术问题。本发明通过采用以重量百分比计包括以下组分:(a)5.0~40.0%的金属镍或其氧化物;(b)0.01~20.0%的选自钼或钨中的至少一种元素或其氧化物;(c)0.01~10.0%的选自稀土中的至少一种元素或其氧化物;(d)0.01~2.0%的选自元素周期表中IA或IIA中的至少一种元素或其氧化物;(e)0~15.0%的选自硅、磷、硼或氟中的至少一种元素或其氧化物;(f)0~10.0%的选自元素周期表中IVB中的至少一种元素或其氧化物;(g)余量的载体氧化铝,其中载体的总孔容为0.5~1.2毫升/克,孔直径<30纳米的孔容占总孔容的5~65%,孔直径30~60纳米的孔容占总孔容的20~80%,孔直径>60纳米的孔容占总孔容的20~50%的技术方案较好地解决了该问题,可用于裂解汽油选择性加氢的工业生产中。
CN201210349977.5本发明是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,金属氧化物为助剂,该裂解汽油镍系选择性加氢催化剂的重量百分组成如下:氧化镍15~19,氧化钼6.5~20.0,助剂,2.2~4.5,氧化铝余量;所述助剂是氧化钾、氧化镁、氧化镧中的一种或其任意两种以上组合。
现有技术主要是改变载体化学组成和类型,以及添加活性助剂来提升催化剂性能。由于裂解汽油中As、S、O、N等杂质和胶质含量较高,使催化剂容易失活,因此需要裂解汽油催化剂具有抗胶质、抗水能力好,抗砷、抗硫能力强的特性。
发明内容
本发明提供一种不饱和烃选择性加氢方法,尤其适用于裂解汽油一段中间馏分(C6-C8馏分)选择性加氢,该工艺方法采用镍系选择性加氢催化剂,催化剂在反应中的活性更高,选择性更好,抗胶质、抗砷、抗硫、抗水能力强,对不同砷含量、不同硫含量的裂解汽油原料适应性强。催化剂的载体是一种氧化硅-氧化铝载体,载体中包含镍掺杂铁酸镧,活性组分包括镍、钼、镁等,
一种裂解汽油中间馏分不饱和烃选择性加氢方法,包括如下过程:镍系催化剂在氢气存在下,400~500℃条件下还原,经降温钝化后调整到反应工艺条件:反应入口温度45~110℃,反应压力2.0-4.5MPa,氢油体积比60~200:1;液体体积空速2.0-5.5h-1;催化剂包括氧化硅-氧化铝载体和负载于载体上的金属活性组分镍、钼和镁,以催化剂的总重量为基准包含以下组分:氧化镍含量为7-18wt%,氧化钼的含量为3.5-12wt%,氧化镁含量为2.5~7.8%;氧化硅-氧化铝载体含量为65-87wt%,氧化硅-氧化铝载体中包含0.1~10wt%的氧化硅,0.1~12wt%的镍掺杂铁酸镧,0.1~7.8wt%的氧化镁,载体介孔占总孔的3~70%,大孔占总孔的1.5~55%,载体中微孔、介孔、大孔不均匀分布。
优选地,所述裂解汽油一段中间馏分(C6-C8馏分)选择性加氢工艺条件为:反应入口温度50~85℃,反应压力2.0-3.5MPa,氢油体积比60~180:1;液体体积空速3.0-4.5h-1。
优选地,催化剂中氧化镍含量为7-15wt%,氧化钼的含量为4.5-10wt%。氧化镁含量为2.5~4.5%;载体介孔占总孔的2~60%,大孔占总孔的3~50%。
在本发明催化剂的制备方法中,所用的镍和钼的化合物可以是已有技术公开的任何一种适于制催化剂的化合物,如硝酸镍、硫酸镍、醋酸镍、钼酸铵、氧化钼等。
所述氧化硅-氧化铝载体的制备方法如下:将拟薄水铝石和田菁粉加入到捏合机中混合均匀,加入无机酸溶液和有机聚合物,捏合均匀,然后再加入镍掺杂铁酸镧,混合均匀得到氧化铝前驱体,备用;在有机聚合物的酸液中加入硅源和拟薄水铝石混合均匀,得到硅源-拟薄水铝石-有机聚合物混合物,氧化铝前驱体中单位含量的有机聚合物比硅源-拟薄水铝石-有机聚合物混合物(简记硅-铝-有机物混合物)中有机聚合物的含量高2倍以上,然后将硅源--拟薄水铝石-有机聚合物混合物与氧化铝前驱体混合,再加入镁源,经挤条、成型、干燥、焙烧,得到氧化硅-氧化铝载体。所述硅源是硅胶、硅酸钠或硅微粉。硅-铝-有机物混合物中氧化铝占载体中氧化铝的1~35wt%。
上述氧化硅-氧化铝载体的制备过程,所述有机聚合物为聚乙烯醇、聚丙烯酸、聚丙烯酸钠、聚乙二醇、聚丙烯酸酯中的一种或几种。
优选地,上述氧化硅-氧化铝载体中镍掺杂铁酸镧为0.1~12wt%,更优选0.2~8wt%,镍掺杂铁酸镧中镍占铁酸镧的0.1~8wt%。
所述镍掺杂铁酸镧的制备方法:将柠檬酸溶于去离子水中搅拌溶解,然后将硝酸镧与硝酸铁加入柠檬酸中,搅拌溶解,加入聚丙烯酸钠、聚丙烯酸酯或聚丙烯酸,聚丙烯酸钠、聚丙烯酸酯或聚丙烯酸的加入量为镍掺杂铁酸镧的0.1~10wt%,优选0.1~8.0wt%。再加入含镍化合物,搅拌,经干燥、焙烧、研磨得到成品。所述含镍化合物包括硝酸镍、醋酸镍等。裂解汽油催化剂中含有高含量Al2O3时,在高温还原镍离子的过程中,容易导致铝酸镍或偏铝酸镍生成,进而降低催化剂活性,催化剂稳定性差。本发明载体中同时含有添加有机聚合物的氧化硅和镍掺杂铁酸镧,有效抑制铝酸镍或偏铝酸镍的生成,提高镍催化剂的活性稳定性。
催化剂的制备方法可以采用浸渍、喷涂等方法,将含活性组分镍、镁、钼的溶液浸渍、喷涂到氧化硅-载体上,然后对催化剂进行干燥、焙烧得到所述的催化剂。例如可以按以下步骤制备催化剂:配制硝酸镍、硝酸镁、钼酸铵溶液浸渍氧化硅-氧化铝载体,经110~160℃烘干3~9小时,400~650℃焙烧4~9小时,最终得到催化剂产品。
相比铁酸镧,氧化硅-氧化铝载体中加入镍掺杂铁酸镧,有效提高抗砷、抗硫、抗水性能,制备的镍钼系催化剂,有效提高炔烃或双烯加氢选择性。氧化硅-氧化铝载体的制备过程中,氧化铝前驱体中单位含量的有机聚合物比硅-铝-有机物混合物中有机聚合物的含量高2倍以上,并不是简单地扩孔,而是载体微孔、介孔、大孔不均匀分布,不同于简单扩孔,不但可以改善载体的孔结构,使载体微孔、介孔、大孔不均匀分布,提高催化剂抗胶质能力,提高催化剂的稳定性和使用寿命,有利于装置长周期运转;而且促进载体表面产生出更多的活性位负载中心,提高镍催化剂加氢活性。
具体实施方式
以下通过实施例进一步详细描述本发明,但这些实施例不应认为是对本发明的限制。
制备催化剂所用主要原料来源:本发明所用的原料试剂均为市售产品。
实施例1
1、制备镍掺杂铁酸镧
搅拌条件下,将2.51mol硝酸镧溶于120mL水中,加入柠檬酸搅拌溶解;再加入4.79mol硝酸铁,然后再加入190g聚丙烯酸钠,再加入含42g硝酸镍的水溶液,继续搅拌30min,经烘干、焙烧、研磨得到镍掺杂铁酸镧。
2、制备氧化硅-氧化铝载体
4.5g镍掺杂铁酸镧中加入柠檬酸备用。将300g拟薄水铝石粉子和25.0g田菁粉加入到捏合机中,加入硝酸,再加入40.2g聚丙烯酸钠硝酸溶液,并混合均匀,然后加入镍掺杂铁酸镧,混合均匀,得到氧化铝前驱体。5g聚丙烯酸钠溶于硝酸中,再加入38g硅微粉和50g拟薄水铝石粉子,搅拌均匀,得到硅微粉-拟薄水铝石-聚丙烯酸钠混合物(简记硅-铝-有机物混合物)。取1/8的硅-铝-有机物混合物,再加入上述氧化铝前驱体和4.2g硝酸镁,捏合均匀,经过捏合-挤条成型为三叶草形状。在130℃干燥7小时,620℃焙烧7小时,得到含镍掺杂铁酸镧的氧化硅-氧化铝的载体1。载体的介孔占总孔的55.2%,大孔占总孔的28.3%。
3、制备催化剂
配置硝酸镍、硝酸镁、钼酸铵溶液浸渍载体1,在140℃下干燥6小时,560℃焙烧5小时,得到催化剂1。催化剂1氧化镍含量为17.1wt%,氧化钼的含量为3.4wt%,氧化镁的含量为2.8wt%。
实施例2
镍掺杂铁酸镧的制备同实施例1,只是加入260g聚丙烯酸钠,氧化硅-氧化铝载体的制备同实施例1,氧化硅-氧化铝载体中包含4.4wt%的氧化硅,5.7wt%的镍掺杂铁酸镧,1.2wt%的镁,载体介孔占总孔的63.8%,大孔占总孔的25.9%。氧化铝前驱体中单位含量的聚丙烯酸钠比硅源-有机聚合物混合物中聚丙烯酸钠的含量高3倍。催化剂2的制备方法同实施例1,催化剂2氧化镍含量为11.4wt%,氧化钼的含量为4.75wt%,氧化镁的含量为3.8wt%。
实施例3
镍掺杂铁酸镧的制备同实施例1,只是加入220g聚丙烯酸,氧化硅-氧化铝载体的制备同实施例1,氧化硅-氧化铝载体中包含8.4wt%的氧化硅,2.6wt%的镍掺杂铁酸镧,2.1wt%的镁,载体介孔占总孔的54.9%,大孔占总孔的33.1%。氧化铝前驱体中单位含量的聚丙烯酸比硅源-有机聚合物混合物中聚丙烯酸的含量高3.3倍。催化剂3的制备方法同实施例1,催化剂3氧化镍含量为22.3wt%,氧化钼的含量为4.1wt%,氧化镁的含量为2.6wt%。
实施例4
镍掺杂铁酸镧的制备同实施例1,只是加入280g聚丙烯酸钠,氧化硅-氧化铝载体的制备同实施例1,氧化硅-氧化铝载体中包含8.4wt%的氧化硅,2.6wt%的镍掺杂铁酸镧,2.8wt%的镁,载体介孔占总孔的50.1%,大孔占总孔的39.7%。氧化铝前驱体中单位含量的聚丙烯酸酯比硅源-有机聚合物混合物中聚丙烯酸酯的含量高3.3倍。催化剂的制备方法同实施例1,催化剂4氧化镍含量为15.2wt%,氧化钼的含量为2.4wt%,氧化镁的含量为3.0%wt。
对比例1
1、制备铁酸镧
搅拌条件下,将2.51mol硝酸镧溶于120mL水中,加入柠檬酸搅拌溶解;再加入4.79mol硝酸铁,然后再加入190g聚丙烯酸钠,搅拌30min,经烘干、焙烧、研磨得到镍掺杂铁酸镧。
2、制备氧化硅-氧化铝载体
5g聚丙烯酸钠溶于硝酸中,再加入38g硅微粉和50g拟薄水铝石粉子,搅拌均匀,得到硅微粉-拟薄水铝石-聚丙烯酸钠混合物(简记硅-铝-有机物混合物),取1/8的量备用,4.5g铁酸镧中加入柠檬酸备用。将300g拟薄水铝石粉子和25.0g田菁粉加入到捏合机中,加入硝酸,再加入40.2g聚丙烯酸钠硝酸溶液,并混合均匀,再加入上述硅微粉-聚丙烯酸钠混合物,捏合均匀,然后加入铁酸镧和4.2g硝酸镁,混合均匀,经过捏合-挤条成型为三叶草形状。在130℃干燥7小时,620℃焙烧7小时,得到含铁酸镧的氧化硅-氧化铝的载体1-1。
3、制备对比催化剂1
配置硝酸镍、硝酸镁、钼酸铵溶液浸渍载体1-1,在140℃下干燥6小时,560℃焙烧5小时,得到对比催化剂1。对比催化剂1氧化镍含量为17.1wt%,氧化钼的含量为3.4wt%,氧化镁的含量为2.8wt%。
对比例2
1、制备镍掺杂铁酸镧
搅拌条件下,将2.51mol硝酸镧溶于120mL水中,加入柠檬酸搅拌溶解;再加入4.79mol硝酸铁,然后再加入190g聚丙烯酸钠,再加入含42g硝酸镍的水溶液,继续搅拌30min,经烘干、焙烧、研磨得到镍掺杂铁酸镧。
2、制备氧化硅-氧化铝载体
4.5g镍掺杂铁酸镧中加入柠檬酸备用,将350g拟薄水铝石粉子和25.0g田菁粉加入到捏合机中,加入硝酸,再加入40.7g聚丙烯酸钠硝酸溶液,并混合均匀,再加入4.8g硅微粉,捏合均匀,然后加入镍掺杂铁酸镧和4.2g硝酸镁,混合均匀,经过捏合-挤条成型为三叶草形状。在130℃干燥7小时,620℃焙烧7小时,得到含铁酸镧的氧化硅-氧化铝的载体1-2。
3、制备对比催化剂2
配置硝酸镍、硝酸镁、钼酸铵溶液浸渍载体1-1,在140℃下干燥6小时,560℃焙烧5小时,得到对比催化剂2。对比催化剂2氧化镍含量为17.1wt%,氧化钼的含量为3.4wt%,氧化镁的含量为2.8wt%。
将催化剂1-4及对比催化剂1和2分别装入100ml绝热床反应装置中,在温度440℃氢气条件下还原8小时,降温到50℃后用环己烷钝化3小时后进原料油,裂解汽油C6-C8馏分,双烯含量为39.34g碘/100g油、碘价为90.1g碘/100g油、胶质含量为76mg/100ml油、游离水含量为923ppm、、硫含量为121ppm和砷含量为78ppb;反应工艺条件为:入口温度55℃,氢油体积比140∶1,反应压力3.0MPa,新鲜油空速3.3h-1;运转180h后,催化剂1加氢产品的双烯为0.81克碘/100克油,碘价为35.8g碘/100g油,双烯加氢率99.2%;催化剂2加氢产品的双烯为1.23克碘/100克油,碘价为37.5g碘/100g油,双烯加氢率98.8%;催化剂3加氢产品的双烯为0.86克碘/100克油,碘价为36.5g碘/100g油,双烯加氢率98.9%;催化剂4加氢产品的双烯为1.01克碘/100克油,碘价为37.0g碘/100g油,双烯加氢率98.6%。催化剂活性高,选择性好,抗胶质、抗水抗砷、抗硫能力强。相比对比催化剂1和2,本发明催化剂载体中同时含有添加有机聚合物的氧化硅和镍掺杂铁酸镧,有效抑制铝酸镍或偏铝酸镍的生成,提高镍催化剂的活性稳定性。
运转500h后,催化剂1加氢产品的双烯为0.84克碘/100克油,碘价为36.1g碘/100g油,双烯加氢率99.1%;催化剂3加氢产品的双烯为0.89克碘/100克油,碘价为37.0g碘/100g油,双烯加氢率98.9%。催化剂载体中含有镍掺杂铁酸镧,有利于抑制二烯烃及苯乙烯等不饱和组分发生聚合反应;催化剂对水、胶质等杂质不敏感,催化剂抗胶质、抗水能力好,抗砷、抗硫能力强,催化性能稳定。催化剂载体微孔、介孔、大孔不均匀分布,催化剂活性好,稳定性好,使用寿命长,有利于装置长周期运转。
将催化剂1和3分别装入100ml绝热床反应装置中,在温度410℃氢气条件下还原8小时,降温到50℃后用环己烷钝化4小时后进原料油,裂解汽油C6-C8馏分,双烯含量为37.56g碘/100g油、碘价为84.5g碘/100g油、胶质含量为54mg/100ml油、硫含量为94ppm和砷含量为72ppb;反应工艺条件为:入口温度60℃,氢油体积比150∶1,反应压力2.86MPa,新鲜油空速3.02h-1;运转180h后,催化剂1加氢产品的双烯为0.78克碘/100克油,碘价为33.1g碘/100g油,双烯加氢率99.4%;催化剂3加氢产品的双烯为0.81克碘/100克油,碘价为33.4g碘/100g油,双烯加氢率99.2%。催化剂对不同原料油适应性强,性能稳定。
Claims (4)
1.一种裂解汽油中间馏分不饱和烃选择性加氢方法,其特征在于,包括如下过程:镍系催化剂在氢气存在下,400~500℃条件下还原,经降温钝化后调整到反应工艺条件:反应入口温度45~110℃,反应压力2.0-4.5MPa,氢油体积比60~200:1;液时体积空速2.0-5.5h-1;催化剂包括氧化硅-氧化铝载体和负载于载体上的金属活性组分镍、钼和镁,以催化剂的总重量为基准包含以下组分:氧化镍含量为7-18wt%,氧化钼的含量为3.5-12wt%,氧化镁含量为2.5~7.8%;氧化硅-氧化铝载体含量为65-87wt%,氧化硅-氧化铝载体中包含0.1~10wt%的氧化硅,0.1~12wt%的镍掺杂铁酸镧,0.1~7.8wt%的氧化镁,载体介孔占总孔的50.1~70%,大孔占总孔的25.9~55%,载体中微孔、介孔、大孔不均匀分布;所述氧化硅-氧化铝载体的制备方法如下:将拟薄水铝石和田菁粉加入到捏合机中混合均匀,加入无机酸溶液和有机聚合物,捏合均匀,然后再加入镍掺杂铁酸镧,混合均匀得到氧化铝前驱体,备用;在有机聚合物的酸液中加入硅源和拟薄水铝石混合均匀,得到硅源-拟薄水铝石-有机聚合物混合物,氧化铝前驱体中单位含量的有机聚合物比硅源-拟薄水铝石-有机聚合物混合物中有机聚合物的含量高2倍以上,然后将硅源-拟薄水铝石-有机聚合物混合物与氧化铝前驱体混合,再加入镁源,经挤条、成型、干燥、焙烧,得到氧化硅-氧化铝载体,所述硅源为硅微粉;所述有机聚合物为聚丙烯酸或聚丙烯酸钠;所述镍掺杂铁酸镧的制备方法:将柠檬酸溶于去离子水中搅拌溶解,然后将硝酸镧与硝酸铁加入柠檬酸中,搅拌溶解,加入聚丙烯酸钠或聚丙烯酸,聚丙烯酸钠或聚丙烯酸的加入量为镍掺杂铁酸镧的0.1~10wt%,再加入含镍化合物,搅拌,经干燥、焙烧、研磨得到成品;所述催化剂的制备方法包括如下步骤:将含活性组分镍、钼、镁的浸渍液浸渍、喷涂到载体上,然后对催化剂进行干燥、焙烧得到所述的催化剂;所述催化剂的制备过程如下:配制硝酸镍、硝酸镁、钼酸铵等溶液浸渍氧化硅-氧化铝载体,经110~160℃烘干3~9小时,400~650℃焙烧4~9小时,最终得到催化剂产品。
2.根据权利要求1所述的裂解汽油中间馏分不饱和烃选择性加氢方法,其特征在于,所述不饱和烃为裂解汽油C6-C8馏分油;所述选择性加氢工艺条件为:反应入口温度50~85℃,反应压力2.0-3.5MPa,氢油体积比60~180:1;液时体积空速3.0-4.5h-1。
3.根据权利要求1所述的裂解汽油中间馏分不饱和烃选择性加氢方法,其特征在于,所述载体介孔占总孔的50.1~60%,大孔占总孔的25.9~50%;所述催化剂的总重量为基准包含以下组分:氧化镍含量为7-15wt%,氧化钼的含量为4.5-10wt%,氧化镁含量为2.5~4.5wt%。
4.根据权利要求1所述的裂解汽油中间馏分不饱和烃选择性加氢方法,其特征在于,所述氧化硅-氧化铝载体中镍掺杂铁酸镧为0.2~8wt%。
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