CN109266384B - Two-stage C of pyrolysis gasoline 5 -C 9 Fraction hydrofining method - Google Patents
Two-stage C of pyrolysis gasoline 5 -C 9 Fraction hydrofining method Download PDFInfo
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- CN109266384B CN109266384B CN201811182994.8A CN201811182994A CN109266384B CN 109266384 B CN109266384 B CN 109266384B CN 201811182994 A CN201811182994 A CN 201811182994A CN 109266384 B CN109266384 B CN 109266384B
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- catalyst
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- oxide
- oil
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 239000003921 oil Substances 0.000 claims abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 11
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 38
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 38
- 229910000859 α-Fe Inorganic materials 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 36
- 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
- 238000002360 preparation method Methods 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229920000620 organic polymer Polymers 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 239000000843 powder Substances 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 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
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 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 13
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- 229910052785 arsenic Inorganic materials 0.000 abstract description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 24
- 229910052794 bromium Inorganic materials 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 150000001993 dienes Chemical class 0.000 description 18
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 12
- 239000011630 iodine Substances 0.000 description 12
- 229910052740 iodine Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910017318 Mo—Ni Inorganic materials 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910017313 Mo—Co Inorganic materials 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
- 239000004480 active ingredient Substances 0.000 description 2
- -1 alkylalkenyl arene Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 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
- 230000003213 activating effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- B01J23/84—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
-
- 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
-
- 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
Landscapes
- 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
The present invention relates toTwo-stage C of pyrolysis gasoline 5 ‑C 9 The distillate hydrofining method adopts an adiabatic bed reactor, the reaction pressure is more than 2.8MPa, the inlet temperature is 220-350 ℃, and the volume space velocity of fresh raw oil is 1.5-3.5 h ‑1 The volume ratio of hydrogen to oil (170:1) - (350:1) based on fresh oil. The catalyst takes molybdenum, cobalt, nickel and strontium as active components, silicon oxide-aluminum oxide as a carrier, and the catalyst comprises 9 to 19 weight percent of molybdenum oxide, 3.0 to 8.5 weight percent of cobalt oxide, 0.2 to 3.5 weight percent of nickel oxide and 0.1 to 2.0 weight percent of strontium oxide, wherein the content of the silicon oxide-aluminum oxide carrier is 75 to 85 weight percent. The catalyst has good colloid resistance, strong arsenic resistance, sulfur resistance and water resistance, and strong adaptability to oil products with different sulfur content, arsenic content and other impurities.
Description
Technical Field
The invention relates to the field of oil refining and chemical industry, in particular to a two-stage C of pyrolysis gasoline 5 -C 9 A distillate hydrofining method.
Background
With the increase of ethylene production capacity, ethylene byproduct pyrolysis gasoline, including C5-C10 fractions, is also increased. In the prior art, a two-stage hydrogenation technology is generally adopted for treating pyrolysis gasoline fractions, wherein the first stage of pyrolysis gasoline is selective hydrogenation, so that active components (such as alkyne, diolefin and alkylalkenyl arene) in the pyrolysis gasoline are enabled to generate corresponding mono-olefin and alkylaromatic hydrocarbon, a noble metal hydrogenation catalyst or a non-noble metal Ni catalyst is adopted to saturate the active unsaturated components in oil products at a lower temperature, so that coking in a second stage catalyst bed layer is reduced, the operation period of the device is ensured, and the second stage adopts a conventional non-noble metal catalyst such as Mo-Co catalyst to remove sulfur, nitrogen and other impurities in the oil products and saturate the rest mono-olefin. At present, the current time of the process, the active components are Ni-Mo, co-Mo, ni-W, co-W, co-Mo-Ni hydrofining catalysts of W-Mo-Ni and methods of preparation are reported in many. US4409131 discloses a method for preparing a CoMo/NiMo catalyst by one-step impregnation of a carrier with a solution containing an active ingredient and aqueous ammonia, which details the preparation of the impregnation solution, in which the dissolution of the active ingredient is promoted by heating the mixture.
Due to pyrolysis gasoline groupsComplex formation and poor thermal stability, and usually, the diene and the styrene are removed by first-stage selective hydrogenation, and after second-stage hydrodesulfurization, the catalyst is mainly used for aromatic hydrocarbon extraction. The current industrial catalyst for selective hydrogenation of pyrolysis gasoline is mainly Pd-series or Ni-series catalyst, middle distillate (C 6 ～C 8 Hydrogenation of hydrocarbon compounds fraction or whole fraction (C) 5 Hydrocarbon compound fraction having a hydrocarbon to dry point of 204 ℃). Because of the difference of cracking raw materials and cracking conditions of all ethylene devices, the composition of the cracking gasoline raw materials of all the devices has larger difference, especially the diene and colloid (high molecular polymer generated by polymerization reaction of unsaturated components such As diene, styrene and the like) of the cracking gasoline and the As and heavy metal content have larger difference; some devices have high content of diene and colloid in the raw material of the crude pyrolysis gasoline, while other devices have higher content of colloid, as, heavy metal and other toxic substances, and the individual devices have high content of diene, colloid, as, heavy metal and other toxic substances in the crude pyrolysis gasoline. The French IFP two-stage hydrogenation adopts two types of catalysts, namely LD and HR, wherein LD-145 is a Mo-Ni type catalyst, and HR-304B is a Mo-Co type catalyst. G-35B developed by Girdler catalyst Co., ltd. And S-12 catalyst developed by UOP Co., ltd. Are Co-Mo/Al 2 O 3 A catalyst. CN1353168A discloses a two-stage hydrofining catalyst suitable for pyrolysis gasoline and its preparation method, which uses alumina precursor, when it is formed, high polymer and IV subgroup metal are added, and after drying and roasting, the formed carrier is obtained, and after impregnating with ammonia Co-impregnating solution containing Mo, co and Ni active components, drying at 100-120 deg.c and activating at 400-700 deg.c to obtain the catalyst, the acid-base property of the carrier can be regulated, the coking and deactivation speed of the catalyst can be inhibited, and the hydrogenation activity of the catalyst is not high due to the lower specific surface area of the carrier.
Disclosure of Invention
The invention provides a two-stage C of pyrolysis gasoline 5 -C 9 The catalyst has higher activity, better selectivity, better colloid resistance, water resistance, arsenic resistance and sulfur resistance in the reaction, the carrier of the catalyst is a silica-alumina carrier, the carrier contains nickel doped lanthanum ferrite, active components comprise molybdenum, cobalt, nickel, strontium and the like, and the catalyst is particularly suitable forAnd (3) two-stage hydrofining of pyrolysis gasoline.
Two-stage C of pyrolysis gasoline 5 -C 9 The distillate hydrofining method adopts an adiabatic bed reactor, the reaction pressure is more than 2.8MPa, the inlet temperature is 220-350 ℃, and the volume space velocity of fresh raw oil is 1.5-3.5 h -1 The volume ratio of hydrogen to oil (170:1) - (350:1) based on fresh oil; the catalyst takes molybdenum, cobalt, nickel and strontium as active components, silicon oxide-aluminum oxide as a carrier, the catalyst comprises 9 to 19 weight percent of molybdenum oxide, 3.0 to 8.5 weight percent of cobalt oxide, 0.2 to 3.5 weight percent of nickel oxide, 0.1 to 2.0 weight percent of strontium oxide, 75 to 85 weight percent of silicon oxide-aluminum oxide carrier, 0.1 to 10 weight percent of silicon oxide, 0.1 to 12 weight percent of nickel doped lanthanum ferrite, 0.1 to 7.8 weight percent of magnesium oxide, 3 to 70 percent of carrier mesopores accounting for total pores, 1.5 to 55 percent of macropores accounting for total pores, and micropores, mesopores and macropores in the carrier are unevenly distributed.
Preferably, the molybdenum oxide content in the catalyst is 10-18wt% and the cobalt oxide content is 3.5-8.0wt%; the carrier mesoporous accounts for 2-60% of the total pores, and the macropores account for 3-50% of the total pores.
Preferably, the inlet temperature is 220-320 ℃, and the volume space velocity of the fresh raw oil is 1.5-3.0 h -1 The volume ratio of hydrogen to oil (190:1) - (300:1) based on fresh oil.
The preparation method of the silica-alumina carrier comprises the following steps: adding pseudo-boehmite and sesbania powder into a kneader, uniformly mixing, adding an inorganic acid solution and an organic polymer, uniformly kneading, then adding nickel-doped lanthanum ferrite, uniformly mixing to obtain an alumina precursor for later use; adding a silicon source and pseudo-boehmite into an acid solution of an organic polymer, uniformly mixing to obtain a silicon source-pseudo-boehmite-organic polymer mixture, wherein the organic polymer content per unit content in an alumina precursor is more than 2 times higher than the organic polymer content in the silicon source-pseudo-boehmite-organic polymer mixture (abbreviated as a silicon-aluminum-organic polymer mixture), then mixing the silicon source-pseudo-boehmite-organic polymer mixture with the alumina precursor, adding a magnesium source, extruding, forming, drying and roasting to obtain the silicon oxide-alumina carrier. The silicon source is silica gel, sodium silicate or silicon micropowder. The alumina in the silicon-aluminum-organic mixture accounts for 1-35 wt% of the alumina in the carrier. The addition of a magnesium source is beneficial for regulating acidity.
The preparation process of the silica-alumina carrier comprises the step of preparing the organic polymer from one or more of polyvinyl alcohol, polyacrylic acid, sodium polyacrylate, polyethylene glycol and polyacrylate.
Preferably, the nickel doped lanthanum ferrite in the silica-alumina carrier is 0.1 to 12wt%, more preferably 0.2 to 8wt%, and the nickel in the nickel doped lanthanum ferrite is 0.1 to 8wt% of the lanthanum ferrite.
The preparation method of the nickel-doped lanthanum ferrite comprises the following steps: dissolving citric acid in deionized water, stirring to dissolve, adding lanthanum nitrate and ferric nitrate into citric acid, stirring to dissolve, and adding sodium polyacrylate, polyacrylate or polyacrylic acid, wherein the addition amount of the sodium polyacrylate, the polyacrylate or the polyacrylic acid is 0.1-10wt%, preferably 0.1-8.0wt% of nickel doped lanthanum ferrite. Then adding a nickel-containing compound, stirring, drying, roasting and grinding to obtain a finished product. The nickel-containing compound includes nickel nitrate, nickel acetate, and the like.
The preparation method of the catalyst can adopt methods such as dipping, spraying and the like, dipping and spraying the solution containing the active components on a silicon oxide-carrier, and then drying and roasting the catalyst to obtain the catalyst. For example, the catalyst may be prepared as follows: preparing nickel nitrate, cobalt nitrate, strontium nitrate and ammonium molybdate solution to impregnate a silica-alumina carrier, and drying the carrier for 3 to 9 hours at 110 to 160 ℃ and roasting the carrier for 4 to 9 hours at 400 to 650 ℃ to finally obtain a catalyst product. In the preparation method of the catalyst of the present invention, the compound of nickel and molybdenum used may be any compound disclosed in the prior art as being suitable for preparing the catalyst, such as nickel nitrate, nickel sulfate, nickel acetate, ammonium molybdate, molybdenum oxide, etc.
Compared with lanthanum ferrite, the nickel doped lanthanum ferrite is added into the silicon oxide-aluminum oxide carrier, so that the arsenic resistance, sulfur resistance and water resistance are effectively improved. In the preparation process of the silica-alumina carrier, the organic polymer in unit content in the alumina precursor is higher than the organic polymer in the silica-alumina-organic matter mixtureThe pore structure of the carrier can be improved, so that the micropores, the mesopores and the macropores of the carrier are unevenly distributed, the colloid resistance of the catalyst is improved, the stability and the service life of the catalyst are improved, and the long-period running of the device is facilitated; and promote the carrier surface to generate more active site loading centers, and improve the hydrogenation activity of the nickel catalyst. The invention discloses pyrolysis gasoline C 5 ～C 9 The two-stage hydrofining method of distillate oil can hydrogenate saturated mono-olefin to the maximum extent, and can adapt to oil products with changeable colloid content, arsenic content, sulfur content and water content.
Detailed Description
The present invention is described in further detail by the following examples, which should not be construed as limiting the invention.
The main raw material sources for preparing the catalyst are as follows: the raw material reagents used in the invention are all commercial products.
Example 1
1. Preparation of Nickel doped lanthanum ferrite
2.51mol of lanthanum nitrate is dissolved in 120mL of water under the stirring condition, and citric acid is added for stirring and dissolution; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, then adding an aqueous solution containing 42g of nickel nitrate, continuously stirring for 30min, and drying, roasting and grinding to obtain the nickel-doped lanthanum ferrite.
2. Preparation of silica-alumina support
4.5g of nickel-doped lanthanum ferrite is added with citric acid for standby. Adding 300g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.2g of sodium polyacrylate nitric acid solution, uniformly mixing, adding nickel doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor. 5g of sodium polyacrylate is dissolved in nitric acid, 38g of silicon micropowder and 50g of pseudo-boehmite powder are added, and the mixture is stirred uniformly to obtain a silicon micropowder-pseudo-boehmite-sodium polyacrylate mixture (abbreviated as silicon-aluminum-organic matter mixture). Taking 1/8 of the silicon-aluminum-organic mixture, adding the aluminum oxide precursor and 4.2g of magnesium nitrate, kneading uniformly, and forming into clover shape through kneading and extruding.
Drying at 130 ℃ for 7 hours and roasting at 620 ℃ for 7 hours to obtain the nickel-doped lanthanum ferrite-containing silica-alumina carrier 1. The mesopores of the support account for 55.2% of the total pores, and the macropores account for 28.3% of the total pores.
3. Preparation of the catalyst
Preparing nickel nitrate, cobalt nitrate, strontium nitrate and ammonium molybdate solution, adding ammonia water, then impregnating the carrier 1, drying at 120 ℃ for 6 hours, and roasting at 540 ℃ for 6 hours to obtain the catalyst 1. The catalyst 1 has molybdenum oxide content of 16.2%, cobalt oxide content of 3.2%, nickel oxide content of 0.7% and strontium oxide content of 0.7%.
Example 2
The preparation of the nickel-doped lanthanum ferrite was the same as in example 1 except that 260g of sodium polyacrylate was added, and the preparation of the silica-alumina carrier was the same as in example 1, the silica-alumina carrier comprising 4.4wt% silica, 5.7wt% nickel-doped lanthanum ferrite, 1.2wt% magnesium, the carrier mesopores accounting for 63.8% of the total pores and macropores accounting for 25.9% of the total pores. The sodium polyacrylate per unit content in the alumina precursor is 3 times higher than the sodium polyacrylate content in the silicon source-organic polymer mixture. The catalyst 2 was prepared in the same manner as in example 1, wherein the molybdenum oxide content of the catalyst 2 was 12.5%, the cobalt oxide content was 3.8%, the nickel oxide content was 2.7%, and the strontium oxide content was 1.9%.
Example 3
The preparation of the nickel-doped lanthanum ferrite was the same as in example 1 except that 220g of polyacrylic acid was added, and the preparation of the silica-alumina carrier was the same as in example 1, the silica-alumina carrier comprising 8.4wt% silica, 2.6wt% nickel-doped lanthanum ferrite, 2.1wt% magnesium, the carrier mesopores accounting for 54.9% of the total pores and macropores accounting for 33.1% of the total pores. The unit content of polyacrylic acid in the alumina precursor was 3.3 times higher than that in the silicon source-organic polymer mixture. The catalyst 3 was prepared in the same manner as in example 1, wherein the molybdenum oxide content of the catalyst 3 was 13.7%, the cobalt oxide content was 4.1%, the nickel oxide content was 1.5%, and the strontium oxide content was 1.3%.
Example 4
The preparation of the nickel-doped lanthanum ferrite was the same as in example 1 except that 280g of sodium polyacrylate was added, and the preparation of the silica-alumina carrier was the same as in example 1, and the silica-alumina carrier contained 8.4wt% of silica, 2.6wt% of nickel-doped lanthanum ferrite, 2.8wt% of magnesium, and the carrier mesoporous accounted for 50.1% of the total pores and the macropores accounted for 39.7% of the total pores. The polyacrylate per unit content in the alumina precursor was 3.3 times higher than the polyacrylate content in the silicon source-organic polymer mixture. The catalyst was prepared in the same manner as in example 1, except that the molybdenum oxide content of catalyst 4 was 11.8%, the cobalt oxide content was 5.6%, the nickel oxide content was 2.1% and the strontium oxide content was 0.4%.
Comparative example 1
1. Preparation of lanthanum ferrite
2.51mol of lanthanum nitrate is dissolved in 120mL of water under the stirring condition, and citric acid is added for stirring and dissolution; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, stirring for 30min, and drying, roasting and grinding to obtain the nickel-doped lanthanum ferrite.
2. Preparation of silica-alumina support
5g of sodium polyacrylate is dissolved in nitric acid, 38g of silicon micropowder and 50g of pseudo-boehmite powder are added, and uniformly stirred, so as to obtain a silicon micropowder-pseudo-boehmite-sodium polyacrylate mixture (abbreviated as silicon-aluminum-organic matter mixture), 1/8 of the mixture is taken for standby, and 4.5g of lanthanum ferrite is added with citric acid for standby. Adding 300g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.2g of sodium polyacrylate nitric acid solution, uniformly mixing, adding the silicon micropowder-sodium polyacrylate mixture, uniformly kneading, adding lanthanum ferrite and 4.2g of magnesium nitrate, uniformly mixing, and forming into clover shape through kneading and extruding. Drying at 130 deg.c for 7 hr and roasting at 620 deg.c for 7 hr to obtain the carrier 1-1 of silica-alumina containing lanthanum ferrite.
3. Preparation of comparative catalyst 1
Preparing nickel nitrate, cobalt nitrate, strontium nitrate and ammonium molybdate solution, adding ammonia water, then impregnating the carrier 1-1, drying at 120 ℃ for 6 hours, and roasting at 540 ℃ for 6 hours to obtain the catalyst comparative catalyst 1. The comparative catalyst 1 had a molybdenum oxide content of 16.2%, a cobalt oxide content of 3.2%, a nickel oxide content of 0.7% and a strontium oxide content of 0.7%.
Comparative example 2
1. Preparation of Nickel doped lanthanum ferrite
2.51mol of lanthanum nitrate is dissolved in 120mL of water under the stirring condition, and citric acid is added for stirring and dissolution; then adding 4.79mol of ferric nitrate, then adding 190g of sodium polyacrylate, then adding an aqueous solution containing 42g of nickel nitrate, continuously stirring for 30min, and drying, roasting and grinding to obtain the nickel-doped lanthanum ferrite.
2. Preparation of silica-alumina support
Adding citric acid into 4.5g of nickel-doped lanthanum ferrite for standby, adding 350g of pseudo-boehmite powder and 25.0g of sesbania powder into a kneader, adding nitric acid, adding 40.7g of sodium polyacrylate nitric acid solution, uniformly mixing, adding 4.8g of silicon micropowder, uniformly kneading, adding nickel-doped lanthanum ferrite and 4.2g of magnesium nitrate, uniformly mixing, and forming into clover shape through kneading and extruding. Drying at 130 deg.c for 7 hr and roasting at 620 deg.c for 7 hr to obtain carrier 1-2 of silica-alumina containing lanthanum ferrite.
3. Preparation of comparative catalyst 2
Preparing nickel nitrate, cobalt nitrate, strontium nitrate and ammonium molybdate solution, adding ammonia water, then impregnating the carrier 1-2, drying at 120 ℃ for 6 hours, and roasting at 540 ℃ for 6 hours to obtain the comparative catalyst 2. The comparative catalyst 2 had a molybdenum oxide content of 16.2%, a cobalt oxide content of 3.2%, a nickel oxide content of 0.7% and a strontium oxide content of 0.7%.
Using pyrolysis gasoline C 5 -C 9 The first-stage hydrogenation product of the fraction is used as a raw material, diene is 1.43 g of iodine per 100 g of oil, bromine value is 19.45 g of bromine per 100 g of oil, colloid content is 28mg per 100ml of oil, free water content is 753ppm, sulfur content is 35ppm and arsenic content is 22ppb. Putting catalysts 1-4 and comparative catalysts 1 and 2 into 100ml adiabatic bed reactor, adding carbon disulfide into cyclohexane to make sulfur content of vulcanized oil 1350ppm, introducing hydrogen under 2.8Mp pressure, heating catalyst bed to 200deg.C, and feeding vulcanized oil with volume space velocity of vulcanized oil 2.5 hr -1 Continuously raising the temperature of the catalyst bed to 320 ℃ at the speed of 10 ℃/hour, and after maintaining for 20 hours, starting to cool to 26And (5) at 0 ℃, and finishing vulcanization. Changing raw oil, and evaluating conditions: the reaction pressure is 2.8MPa, the inlet temperature is 250 ℃, and the volume space velocity of fresh raw oil is 3.0h -1 The volume ratio of hydrogen to oil is 290:1. After 180 hours of reaction, the diene of the hydrogenation product of the catalyst 1 is 0.06 g iodine per 100 g oil, and the bromine valence is 0.53 g bromine per 100 g oil; the diene of the hydrogenation product of the catalyst 2 is 0.08 g iodine per 100 g oil, and the bromine value is 0.87 g bromine per 100 g oil; catalyst 3 hydrogenation product diene 0.04 g iodine/100 g oil, bromine valence 0.66 g bromine/100 g oil; catalyst 4 the hydrogenation product had a diene of 0.07 g iodine per 100 g oil and a bromine number of 0.76 g bromine per 100 g oil. The catalyst has high activity, good selectivity, strong colloid resistance, water resistance, arsenic resistance and sulfur resistance. The diene of the hydrogenation product of comparative catalyst 1 was 0.56 g iodine per 100 g oil, the bromine number was 2.24 g bromine per 100 g oil; the comparative catalyst 2 hydrogenation product had a diene of 0.75 g iodine per 100 g oil and a bromine number of 1.71 g bromine per 100 g oil.
After 1000 hours of operation of catalysts 1 and 3, the diene of the hydrogenated product of catalyst 1 was 0.08 g iodine per 100 g oil, and the bromine number was 0.60 g bromine per 100 g oil; catalyst 3 the diene of the hydrogenated product was 0.06 g iodine per 100 g oil and the bromine number was 0.71 g bromine per 100 g oil. The carrier contains silicon oxide added with organic polymer and nickel doped lanthanum ferrite, which effectively inhibits the generation of nickel aluminate and improves the activity stability of nickel catalyst. The catalyst is insensitive to impurities such as water, colloid and the like, has good colloid and water resistance, strong arsenic and sulfur resistance, and the micropores, mesopores and macropores of the catalyst carrier are unevenly distributed, so that the catalyst has good activity, good stability and long service life, and is beneficial to long-period operation of the device.
Using pyrolysis gasoline C 5 -C 9 Fraction one-stage hydrogenation product is used as raw material, diene is 1.76 g iodine/100 g oil, bromine value is 20.76 g bromine/100 g oil, colloid content is 69mg/100ml oil, free water content is 1325ppm, sulfur content is 58ppm and arsenic content is 41ppb. Catalysts 1 and 3 were placed in a 100ml adiabatic bed reactor, cyclohexane was used to make the sulfur content of the sulfided oil 1350ppm, hydrogen was introduced under a pressure of 2.8Mp, the catalyst bed temperature was raised to 200℃and started to feed the sulfided oil, the volume space velocity of the sulfided oil was 2.5h -1 The catalyst bed temperature was continuously raised at a rate of 10 c/hrAfter the temperature reaches 320 ℃ and is maintained for 20 hours, the temperature begins to be reduced to 260 ℃ and the vulcanization is finished. Changing raw oil, and evaluating conditions: the reaction pressure is 3.5MPa, the inlet temperature is 320 ℃, and the volume space velocity of fresh raw oil is 4.2 -1 The volume ratio of hydrogen to oil is 300:1. After 180 hours of reaction, the diene of the hydrogenation product of the catalyst 1 is 0.05 g iodine per 100 g oil, and the bromine value is 0.38 g bromine per 100 g oil; catalyst 3 the diene of the hydrogenated product was 0.04 g iodine per 100 g oil and the bromine number was 0.40 g bromine per 100 g oil. The catalyst has strong adaptability to oil products with different free water content, sulfur content, arsenic content and colloid content, and has good activity and selectivity.
Claims (4)
1. Two-stage C of pyrolysis gasoline 5 -C 9 The fraction hydrofining process features that adiabatic bed reactor with reaction pressure over 2.8MPa and inlet temperature of 250-350 deg.c and fresh material oil volume space velocity of 1.5-3.5 hr -1 The volume ratio of hydrogen to oil (170:1) - (350:1) based on fresh oil; the catalyst takes molybdenum, cobalt, nickel and strontium as active components, silicon oxide-aluminum oxide as a carrier, the catalyst comprises 9-19 wt% of molybdenum oxide, 3.0-5.6 wt% of cobalt oxide, 1.5-3.5 wt% of nickel oxide, 0.1-2.0 wt% of strontium oxide, the content of the silicon oxide-aluminum oxide carrier is 75-85wt%, the silicon oxide-aluminum oxide carrier comprises 4.4-10 wt% of silicon oxide, 2.6-12 wt% of nickel doped lanthanum ferrite, 0.1-7.8 wt% of magnesium oxide, carrier mesopores account for 3-70% of total pores, macropores account for 25.9-55% of total pores, and micropores, mesopores and macropores in the carrier are unevenly distributed; the preparation method of the nickel-doped lanthanum ferrite comprises the following steps: dissolving citric acid in deionized water, stirring and dissolving, adding lanthanum nitrate and ferric nitrate into citric acid, stirring and dissolving, adding sodium polyacrylate, polyacrylate or polyacrylic acid, wherein the addition amount of the sodium polyacrylate, the polyacrylate or the polyacrylic acid is 0.1-10wt% of nickel-doped lanthanum ferrite, adding a nickel-containing compound, stirring, drying, roasting and grinding to obtain a finished product, and nickel in the nickel-doped lanthanum ferrite accounts for 0.1-8wt% of lanthanum ferrite; the preparation method of the silica-alumina carrier comprises the following steps: adding pseudo-boehmite and sesbania powder into a kneader, mixing uniformly, adding inorganic acid solution and organic polymer, kneadingUniformly mixing, adding nickel doped lanthanum ferrite, and uniformly mixing to obtain an alumina precursor for later use; adding a silicon source and pseudo-boehmite into an acid solution of an organic polymer, and uniformly mixing to obtain a silicon source-pseudo-boehmite-organic polymer mixture, wherein the organic polymer is one or more of polyacrylic acid, sodium polyacrylate and polyacrylate; the method comprises the steps of mixing a silicon source-pseudo-boehmite-organic polymer mixture with an alumina precursor, adding a magnesium source, extruding, forming, drying and roasting to obtain a silicon oxide-alumina carrier, wherein the content of the organic polymer in the unit content in the alumina precursor is more than 2 times that in the silicon source-pseudo-boehmite-organic polymer mixture; the preparation method of the catalyst comprises the following steps: impregnating and spraying the impregnation liquid containing the active components on a carrier, and then drying and roasting the catalyst to obtain the catalyst.
2. Pyrolysis gasoline two-stage C according to claim 1 5 -C 9 The distillate hydrofining method is characterized in that the inlet temperature is 250-320 ℃, and the volume space velocity of fresh raw oil is 1.5-3.0 h -1 The volume ratio of hydrogen to oil (190:1) - (300:1) based on fresh oil.
3. Pyrolysis gasoline two-stage C according to claim 1 5 -C 9 The distillate hydrofining method is characterized in that the content of molybdenum oxide in the catalyst is 10-18wt% and the content of cobalt oxide is 3.5-5.6wt%; the mesoporous of the catalyst carrier accounts for 3-60% of the total pores, and the macroporous accounts for 25.9-50% of the total pores.
4. Pyrolysis gasoline two-stage C according to claim 1 5 -C 9 The distillate hydrofining method is characterized in that the catalyst is prepared by the following steps: preparing nickel nitrate, cobalt nitrate, strontium nitrate and ammonium molybdate solution to impregnate a silica-alumina carrier, and baking the carrier for 3 to 9 hours at a temperature of between 110 and 160 ℃ and roasting the carrier for 4 to 9 hours at a temperature of between 400 and 650 ℃ to obtain a catalyst product.
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| CN102335612A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and preparation method thereof |
| CN107754818A (en) * | 2017-11-24 | 2018-03-06 | 福州大学 | A kind of hydrocracking catalyst for suspension bed and preparation method |
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| CN102335612A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and preparation method thereof |
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