CN109370637A - 一种fcc汽油加氢脱硫醇的方法 - Google Patents
一种fcc汽油加氢脱硫醇的方法 Download PDFInfo
- Publication number
- CN109370637A CN109370637A CN201811193181.9A CN201811193181A CN109370637A CN 109370637 A CN109370637 A CN 109370637A CN 201811193181 A CN201811193181 A CN 201811193181A CN 109370637 A CN109370637 A CN 109370637A
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- China
- Prior art keywords
- catalyst
- carrier
- content
- nickel
- oxide
- Prior art date
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- 239000003502 gasoline Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 49
- 229910000859 α-Fe Inorganic materials 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 30
- 229910052746 lanthanum Inorganic materials 0.000 claims description 29
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 229920000620 organic polymer Polymers 0.000 claims description 22
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 239000000203 mixture Substances 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 19
- 238000003756 stirring Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003921 oil Substances 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
- 239000000843 powder Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 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 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 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 4
- 238000000465 moulding Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000002803 maceration Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 13
- 150000001993 dienes Chemical class 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 5
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 abstract 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 150000001336 alkenes Chemical class 0.000 description 13
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- -1 zeolite imidazole class Chemical class 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 239000000446 fuel 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
- 239000007788 liquid Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-RNFDNDRNSA-N Sulfur-36 Chemical compound [36S] NINIDFKCEFEMDL-RNFDNDRNSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- OMTKQJNJACHQNY-UHFFFAOYSA-N [Ni].[Zn].[Mo] Chemical compound [Ni].[Zn].[Mo] OMTKQJNJACHQNY-UHFFFAOYSA-N 0.000 description 1
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- AWOORJZBKBDNCP-UHFFFAOYSA-N molybdenum;oxotungsten Chemical compound [Mo].[W]=O AWOORJZBKBDNCP-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 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
- 239000013110 organic ligand Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 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
- 239000011973 solid acid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 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
- 229910001845 yogo sapphire Inorganic materials 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
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Abstract
本发明涉及一种FCC汽油加氢脱硫醇的方法,采用固定床反应器,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、锌和锶,以催化剂的重量为基准,氧化镍的含量为2%~15wt%,氧化钼的含量为2~18wt%,氧化锌的含量为0.1~5wt%,氧化锶的含量为0.1~2.0wt%;氧化硅‑氧化铝载体含量为65‑85wt%,反应工艺条件为:反应温度110‑240℃,反应压力1.1‑5.5MPa,体积空速1.2‑5.5h‑1,氢油体积比7‑25:1。催化剂具脱硫醇活性高,双烯烃加氢选择性高,对不同原料适应性强的特点。
Description
技术领域
本发明涉及一种FCC汽油加氢脱硫醇的方法。
背景技术
随着环保法规的日益严格,世界各国对石油加工产品的质量提出了越来越严格的要求,特别是对石油加工产品硫含量的限制越来越严格。轻质石油产品中所含的硫化物主要为硫醇(RSH)、硫醚(RSR)等,其中硫醇对产品质量的影响最大,不仅具有恶臭味,很强的腐蚀性,还会影响产品的安定性。
US6692635B2公开了一种生产含硫量低的汽油的方法,该方法中采用新的脱硫醇技术。该技术将全馏分汽油原料通入一个选择性加氢反应器,使硫醇与汽油中的烯烃或者二烯烃发生醚化反应生成高沸点的含硫化合物,然后在一个分馏塔中对选择性加氢产物进行分馏,得到不含硫醇且总硫含量较低的轻汽油馏分和硫含量较高的重汽油馏分。该技术的特点是通过硫醇与二烯烃的加成反应实现硫醇从轻汽油馏分中的有效脱除和向重汽油馏分的转移,同时实现了硫醇的脱除和轻汽油总硫含量的降低,克服了传统Merox工艺不能深度脱硫和存在碱渣排放的问题。
CN1229838A公开了一种烃油的转化方法,该方法是将原料油与一种加氢精制催化剂在加氢脱硫醇的工艺条件下脱硫醇,所述加氢精制催化剂含有负载在氧化铝载体上的氧化钨(钼)、氧化镍和氧化钴,其中氧化钨(钼)的含量为4~10wt%,氧化镍的含量为1~5wt%,氧化钴的含量为0.01~0.1wt%,镍和钴的总原子数与镍、钴、钨(钼)的总原子数之比为0.3~0.9。CN102451694A公开了一种加氢脱硫醇催化剂及其制备方法和应用。该催化剂以氧化铝或含硅氧化铝为载体,以磷为助剂组分,以铜和锌为活性组分,以催化剂质量为基准,助剂磷的含量为0.5~3.0wt%,氧化锌的含量为3~15wt%,氧化铜的含量为5~30wt%。因该催化剂具有很强的加氢活性,在用于处理全馏分FCC汽油时,硫醇含量由38μg/g降低到3μg/g,同时烯烃含量也由25v%降低到20v%,RON损失高达1.3个单位。CN00136870.2提供了一种用于脱除航空燃料中硫醇硫的选择性脱硫醇催化剂及其制备方法。催化剂按重量份数计包括如下组分:①氧化钼7-20;②氧化钴0.1-5;③氧化镍0-5④二氧化硅0-10;⑤磷或硼或氟0-4;⑥氧化铝0-40;⑦二氧化钛60-100。催化剂的制备方法是将催化剂载体用浸渍液浸渍1-2小时,然后在100-130℃下干燥;最后在400-550℃焙烧2-6小时即得到催化剂。本催化剂对喷气燃料中的硫醇硫具有良好脱除效果和较好的低温活性。CN201210393263.4涉及一种新型汽油脱硫醇吸附剂的制备方法及应用。该汽油脱硫醇吸附剂的制备方法包括以下步骤:将溶剂、金属离子前驱体、介孔材料混合均匀,陈化,加入有机配体,进行水热晶化处理;然后,对水热晶化处理的产物进行抽滤、洗涤、干燥,得到沸石咪唑类骨架材料/介孔材料复合物;对所述沸石咪唑类骨架材料/介孔材料复合物进行压片成型、破碎筛分,得到汽油脱硫醇吸附剂。本发明提供的沸石咪唑类骨架材料/介孔材料复合物中,沸石咪唑类骨架材料的比表面积高,同时在介孔材料上呈高分散状态,有效地解决了团聚造成的扩散限制。所述溶剂为去离子水、甲醇、乙醇和N,N-二甲基甲酰胺中的一种或几种的组合;所述金属离子为Zn2+、Cu2+和Co2+中的一种或几种的组合。CN200910082945.1涉及一种催化裂化汽油选择性加氢催化剂及其制备方法。本发明催化剂由Al2O3-TiO2复合氧化物载体和活性金属氧化物组成,按对催化剂的重量百分比计,其活性金属氧化物中的NiO含量为10~20w%,MoO3含量为5~12w%;其中载体Al2O3-TiO2氧化物TiO2∶Al2O3的重量比为0.01~1∶1。本发明催化剂在低温(100~200℃)、低压(1~3.0MPa)、低氢油比(氢油体积比5∶1~100∶1)的条件下,处理催化裂化汽油,表现出很高的脱双烯烃及脱硫醇活性、选择性和稳定性。CN200910187903.4公开了一种加氢脱硫醇催化剂及其制备方法和应用。该催化剂以HZSM-5分子筛为主要载体组分,以铜和锌为活性组分。活性组分以氧化物重量计,氧化铜的含量为5%~27%,氧化锌的含量为3%~15%,采用饱和共浸技术制备。本发明的催化剂适用于对轻质油品进行选择性加氢脱硫醇反应,具有脱硫醇活性高、烯烃加氢活性低等特点,且反应后液体收率高、辛烷值损失很少。CN201610187374.8提供基于氧化铝晶面调控的轻质烃类脱硫醇催化剂及其制法,该催化剂是以本发明所述水热处理调控后的γ-氧化铝为载体,以镍及钼为活性金属。本发明所述轻质烃类脱硫醇催化剂为高活性和高选择性催化剂,其可用于催化轻质烃类中硫醇与二烯烃作用生成大分子硫化物,并且还可催化双烯烃的选择性加氢饱和,与现有催化剂相比,本发明所提供的催化剂脱硫醇活性高、双烯烃加氢选择性高,且活性组分不流失、不易失活,因而催化剂运转周期长。CN201310251750.1本发明涉及一种低温脱除催化裂化汽油中硫醇硫的催化剂及其制备方法,属于汽油脱硫领域。一种低温脱除催化裂化汽油中硫醇硫的催化剂,以氧化铝或纳米HZSM-5分子筛与氧化铝复合固体酸为载体,按占催化剂总质量的质量百分比计,包括:氧化锌5%~20%、氧化铁5%~15%、氧化镧0.5%~5%、氧化磷0.5%~5%。本发明的催化剂适用于对催化裂化汽油进行低温加氢脱硫醇反应,具有脱硫醇活性高,烯烃加氢饱和活性低,液收高和辛烷值基本不损失等特点。
上述催化剂的组成及含量比较多,制备工艺复杂,而且大批量生产催化剂产品质量很难控制。
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。为克服以上现有技术的缺陷,寻找一种全新的加氢脱硫醇催化剂,脱硫醇活性高,双烯烃加氢选择性高,稳定性好,辛烷值损失低的特性,是本领域技术人员亟需解决的问题之一。
发明内容
本发明提供一种FCC汽油加氢脱硫醇的方法,脱除硫醇的同时,副反应少,活性高,辛烷值损失低。
本发明提供一种FCC汽油加氢脱硫醇的方法,采用固定床反应器,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、锌和锶,以催化剂的重量为基准,氧化镍的含量为2%~15wt%,氧化钼的含量为2~18wt%,氧化锌的含量为0.1~5wt%,氧化锶的含量为0.1~2.0wt%;氧化硅-氧化铝载体含量为65-85wt%,氧化硅-氧化铝载体中包含0.1~12wt%的氧化硅,0.1~10wt%的镍掺杂铁酸镧,0.1~2.5wt%的钾,载体介孔占总孔的3~75%,大孔占总孔的1.5~60%。载体中微孔、介孔、大孔不均匀分布;反应工艺条件为:反应温度110-240℃,反应压力1.1-5.5MPa,体积空速1.2-5.5h-1,氢油体积比7-25:1。
优选地,反应工艺条件为:反应温度110-180℃,反应压力1.1-3.0MPa,体积空速1.5-3.5h-1,氢油体积比7-20:1。
优选地,以催化剂的总重量为基准包含以下组分:氧化镍的含量为4%~15wt%,氧化钼的含量为5~16wt%。载体介孔占总孔的3~65%,大孔占总孔的1.5~50%。
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,再加入钾源,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。
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:配制含活性组分及助剂组分的溶液浸渍氧化硅-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、抗硫性能,制备的镍钼锌系催化剂,有效提高双烯加氢选择性和脱硫醇活性,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,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,有效抑制活泼烯烃聚合和单烯烃饱和(即对原料中的烯烃不加氢),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,提高催化剂加氢脱硫醇活性。
本发明所述脱硫醇催化剂适用于脱除液化石油气、FCC汽油、催化裂解汽油和/或焦化汽油中的硫醇和/或二烯烃;催化剂选择性好。汽油的辛烷值RON损失0.3~0.4点左右。催化剂脱硫醇活性高,双烯烃加氢选择性高,烯烃饱和率低,辛烷值损失低。
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
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,再加入上述硅微粉-聚丙烯酸钠混合物,捏合均匀,然后加入镍掺杂铁酸镧和2.5g硝酸钾,混合均匀,经过捏合-挤条成型为三叶草形状。在120℃干燥8小时,650℃焙烧6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55.4%,大孔占总孔的28.6%。
3、制备催化剂
配置硝酸镍、硝酸锶、硝酸锌、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。催化剂的组成见表1。
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,1.6wt%的钾,载体介孔占总孔的64.2%,大孔占总孔的25.6%。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。
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,0.8wt%的钾,载体介孔占总孔的54.6%,大孔占总孔的33.5%。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。
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,2.5wt%的钾,载体介孔占总孔的49.3%,大孔占总孔的39.4%。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。
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2.5g硝酸钾,混合均匀,经过捏合-挤条成型为三叶草形状。在120℃干燥8小时,650℃焙烧6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、硝酸锶、硝酸锌、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2.5g硝酸钾,混合均匀,经过捏合-挤条成型为三叶草形状。在120℃干燥8小时,650℃焙烧6小时,得到含镍掺杂铁酸镧的氧化硅-氧化铝的载体1-2。
3、制备对比催化剂2
配置硝酸镍、硝酸锶、硝酸锌、钼酸铵溶液浸渍载体1-2,在140℃下干燥6小时,560℃焙烧5小时,得到对比催化剂2。
分别将催化剂1-4及对比例催化剂装填到固定床反应器中,进行评价催化剂反应性能。用硫化油对催化剂进行预硫化,硫化压力为3.2MPa,氢油体积比为300,硫化油体积空速为3.5h-1,硫化程序为分别在240℃、280℃硫化处理6h。待硫化处理结束后,切换为全馏分FCC汽油置换处理6h,然后调整到反应工艺条件,进行脱硫醇及二烯烃反应。FCC原料汽油硫含量365μg/g,硫醇硫36μg/g,砷含量为37ppb,烯烃含量38.9v%,RON 91.3。反应工艺条件为:反应器温度120℃,体积空速3.0h-1,氢油体积比16:1,反应压力2.6MPa。反应约60h后取样分析,反应结果见表2。
表1实施例/对比例催化剂组成/wt%
实施例/对比例 | 氧化钼 | 氧化镍 | 氧化锌 | 氧化锶 |
实施例1 | 16.6 | 10.1 | 3.4 | 0.1 |
实施例2 | 11.8 | 9.4 | 1.9 | 0.2 |
实施例3 | 9.1 | 13.2 | 0.6 | 0.1 |
实施例4 | 13.2 | 8.5 | 0.8 | 0.3 |
对比例1 | 16.6 | 10.1 | 3.4 | 0.1 |
对比例2 | 16.6 | 10.1 | 3.4 | 0.1 |
表2实施例/对比例反应60h的结果
实施例/对比例 | 硫醇硫含量/μg/g | 烯烃含量v% | 辛烷值损失 | 汽油收率wt%; |
实施例1 | 0.4 | 38.3 | 0.2 | 98.8 |
实施例2 | 0.3 | 38.5 | 0.3 | 98.7 |
实施例3 | 0.6 | 38.4 | 0.3 | 98.5 |
实施例4 | 0.5 | 38.3 | 0.4 | 98.7 |
对比例1 | 17 | 25.2 | 3.7 | 86.4 |
对比例2 | 11 | 27.5 | 2.7 | 90.2 |
表3实施例反应600h的结果
实施例 | 硫醇硫含量/μg/g | 烯烃含量v% | 辛烷值损失 | 汽油收率wt%; |
实施例1 | 0.4 | 38.4 | 0.2 | 98.6 |
实施例2 | 0.3 | 38.3 | 0.3 | 98.7 |
反应结果表明,烯烃含量基本不变,反应辛烷值损失在0.3~0.4,催化剂双烯加氢选择性和脱硫醇活性高,抗砷、抗硫性能好,辛烷值损失低。对比例催化剂活性低,催化剂可能成胶甚至结焦而活性下降。
对催化剂进行稳定性试验,反应运行600h反应结果见表3,烯烃含量基本不变,催化剂不易成胶甚至结焦失活,稳定性好。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明的保护范围。
Claims (10)
1.一种FCC汽油加氢脱硫醇的方法,其特征在于,采用固定床反应器,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、锌和锶,以催化剂的重量为基准,氧化镍的含量为2%~15wt%,氧化钼的含量为2~18wt%,氧化锌的含量为0.1~5wt%,氧化锶的含量为0.1~2.0wt%;氧化硅-氧化铝载体含量为65-85wt%,氧化硅-氧化铝载体中包含0.1~12wt%的氧化硅,0.1~10wt%的镍掺杂铁酸镧,0.1~2.5wt%的钾,载体介孔占总孔的3~75%,大孔占总孔的1.5~60%,载体中微孔、介孔、大孔不均匀分布;反应工艺条件为:反应温度110-240℃,反应压力1.1-5.5MPa,体积空速1.2-5.5h-1,氢油体积比7-25:1。
2.根据权利要求1所述的FCC汽油加氢脱硫醇的方法,其特征在于,反应工艺条件为:反应温度110-180℃,反应压力1.1-3.0MPa,体积空速1.5-3.5h-1,氢油体积比7-20:1。
3.根据权利要求1所述的FCC汽油加氢脱硫醇催化剂,其特征在于,所述载体介孔占总孔的3~65%,大孔占总孔的1.5~50%,所述催化剂以总重量为基准包含以下组分:氧化镍的含量为4%~15wt%,氧化钼的含量为5~16wt%。
4.根据权利要求1所述的FCC汽油加氢脱硫醇的方法,其特征在于,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,再加入钾源,经挤条、成型、干燥、焙烧,得到氧化硅-氧化铝载体。
5.根据权利要求4所述的FCC汽油加氢脱硫醇的方法,其特征在于,所述硅源是硅胶、硅酸钠或硅微粉,硅源-拟薄水铝石-有机聚合物混合物中氧化铝占载体中氧化铝的1~35wt%。
6.根据权利要求4所述的FCC汽油加氢脱硫醇的方法,其特征在于,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。
7.根据权利要求4所述的FCC汽油加氢脱硫醇催化剂,其特征在于,所述氧化硅-氧化铝载体中镍掺杂铁酸镧为0.1~12wt%。
8.根据权利要求1~7任一项所述的FCC汽油加氢脱硫醇催化剂,其特征在于,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%,再加入含镍化合物,搅拌,经干燥、焙烧、研磨得到成品。
9.根据权利要求1~7任一项所述的FCC汽油加氢脱硫醇催化剂,其特征在于,所述催化剂的制备方法包括如下步骤:将含活性组分的浸渍液浸渍、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。
10.根据权利要求9所述的FCC汽油加氢脱硫醇催化剂,其特征在于,所述催化剂的制备过程如下:配制硝酸镍、硝酸锶、硝酸锌、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。
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