CN109364966A - A kind of catalyst and preparation method of demercaptaning for gasoline - Google Patents
A kind of catalyst and preparation method of demercaptaning for gasoline Download PDFInfo
- Publication number
- CN109364966A CN109364966A CN201811193164.5A CN201811193164A CN109364966A CN 109364966 A CN109364966 A CN 109364966A CN 201811193164 A CN201811193164 A CN 201811193164A CN 109364966 A CN109364966 A CN 109364966A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- content
- nickel
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000003502 gasoline Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 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
- 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 46
- 229910000859 α-Fe Inorganic materials 0.000 claims description 32
- 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
- 229910052746 lanthanum Inorganic materials 0.000 claims description 30
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 22
- 229920000620 organic polymer Polymers 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon 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
- 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 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 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
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- -1 polyethylene Polymers 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
- 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
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- 239000002253 acid 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
- 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
- 230000001404 mediated effect Effects 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 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
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 13
- 150000001993 dienes Chemical class 0.000 abstract description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 16
- 239000011593 sulfur Substances 0.000 description 16
- 150000001336 alkenes Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 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
- 239000003921 oil Substances 0.000 description 7
- 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 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
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 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
- 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 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
- 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
- 230000008569 process Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- 239000011787 zinc oxide Substances 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
- 239000004372 Polyvinyl alcohol Substances 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 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
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical class [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 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
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
-
- 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
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The present invention relates to a kind of catalyst of demercaptaning for gasoline, catalyst includes silicaalumina carrier and metal active constituent nickel, molybdenum and the iron and auxiliary agent phosphorus that are carried on carrier, on the basis of the weight of catalyst, the content of nickel oxide is 2%~15wt%, the content of molybdenum oxide is 2~18wt%, the content of iron oxide is 0.1~5.5wt%, 0.01%~2.2wt% of content of auxiliary agent phosphorous oxide；Silicaalumina carrier content is 65-85wt%.Catalyst has removal of mercaptans activity height, and diolefin hydrogenation selectivity is high, the low feature of loss of octane number.
Description
Technical field
The present invention relates to a kind of gasoline sweetening catalysts and preparation method thereof.
Background technique
Increasingly strict with environmental regulation, countries in the world, which propose the quality of refinery products, to be increasingly stringenter
It is required that being especially increasingly stringenter to the limitation of refinery products sulfur content.Vulcanize owner contained in oils
It to be mercaptan (RSH), thioether (RSR) etc., wherein influence of the mercaptan to product quality is maximum, not only has foul smell, very strong
Corrosivity also will affect the stability of product.
US6692635B2 discloses a kind of method for producing the low gasoline of sulfur content, uses new removal of mercaptans in this method
Technology.Full distillation gasoline raw material is passed through a selective hydrogenation reactor by the technology, make alkene in mercaptan and gasoline or
Alkadienes occurs etherification reaction and generates high boiling sulfur-containing compound, then in a fractionating column to selective hydrogenation product into
Row fractionation is obtained without mercaptan and the lower light gasoline fraction of total sulfur content and the higher heavy naphtha of sulfur content.The technology
The characteristics of be to realize that mercaptan is removed from effective in light gasoline fraction and to heavy petrol by the addition reaction of mercaptan and alkadienes
The transfer of fraction, while the removing of mercaptan and the reduction of light petrol total sulfur content are realized, overcoming traditional Merox technique cannot
Deep desulfuration and there are problems that alkaline residue discharge.
CN1229838A discloses a kind of method for transformation of hydrocarbon ils, and this method is to be catalyzed feedstock oil and a kind of hydrofinishing
Agent removal of mercaptans under the process conditions of hydro-sweetening, the Hydrobon catalyst contain the oxygen of load on the alumina support
Change tungsten (molybdenum), nickel oxide and cobalt oxide, wherein the content of tungsten oxide (molybdenum) is 4~10wt%, the content of nickel oxide is 1~
5wt%, the content of cobalt oxide are 0.01~0.1wt%, the total atom number and nickel of nickel and cobalt, cobalt, tungsten (molybdenum) total atom number it
Than being 0.3~0.9.CN102451694A discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalysis
Agent is using aluminium oxide or silicon-containing alumina as carrier, using phosphorus as adjuvant component, using copper and zinc as active component, is with catalyst quality
Benchmark, the content of auxiliary agent phosphorus are 0.5~3.0wt%, and the content of zinc oxide is 3~15wt%, the content of copper oxide is 5~
30wt%.Because the catalyst has very strong hydrogenation activity, for when handling full fraction FCC gasoline, mercaptans content to be by 38 μ g/
G is reduced to 3 μ g/g, while olefin(e) centent is also reduced to 20v% by 25v%, and RON loss is up to 1.3 units.
CN00136870.2 provides a kind of for removing the selectively mercaptan-eliminating catalyst of mercaptan sulfur and its preparation side in aviation fuel
Method.Catalyst includes following component: 1. molybdenum oxide 7-20 according to parts by weight；2. cobalt oxide 0.1-5；3. nickel oxide 0-5 is 4.
Silica 0-10；5. phosphorus or boron or fluorine 0-4；6. aluminium oxide 0-40；7. titanium dioxide 60-100.The preparation side of catalyst
Method is to impregnate catalyst carrier maceration extract 1-2 hours, then dry at 100-130 DEG C；Finally at 400-550 DEG C
Obtain catalyst within roasting 2-6 hours.This catalyst has good removal effect and preferable to the mercaptan sulfur in jet fuel
Low temperature active.CN201210393263.4 is related to a kind of preparation method and application of new type gasoline removal of mercaptans adsorbent.The gasoline
The preparation method of removal of mercaptans adsorbent is old the following steps are included: solvent, metal ion presoma, mesoporous material are uniformly mixed
Change, organic ligand is added, carries out hydrothermal crystallizing processing；Then, the product of hydrothermal crystallizing processing filtered, washed, dried,
Obtain zeolite imidazole class framework material/mesoporous material compound；To the zeolite imidazole class framework material/mesoporous material compound
Compression molding, crushing and screening are carried out, demercaptaning for gasoline adsorbent is obtained.Zeolite imidazole class framework material/Jie provided by the invention
In Porous materials compound, the specific surface area of zeolite imidazole class framework material is high, while being in high dispersion state on mesoporous material, has
It solves to effect and spreads limitation caused by reunion.The solvent is in deionized water, methanol, ethyl alcohol and n,N-Dimethylformamide
One or more of combinations；The metal ion is Zn2+、Cu2+And Co2+One or more of combination.
CN200910082945.1 is related to a kind of selective hydrogenation catalyst for catalytic cracking gasoline and preparation method thereof.Catalyst of the present invention
By Al2O3-TiO2Composite oxide carrier and reactive metal oxides composition, based on the weight percent to catalyst, activity
NiO content in metal oxide is 10~20w%, MoO3Content is 5~12w%；Wherein carrier Al2O3-TiO2Oxide
TiO2∶Al2O3Weight ratio be 0.01~1: 1.Catalyst of the present invention low temperature (100~200 DEG C), low pressure (1~3.0MPa),
Under conditions of low hydrogen/gasoline ratio (hydrogen to oil volume ratio 5: 1~100: 1), catalytically cracked gasoline is handled, very high de- diolefin is shown
And removal of mercaptans activity, selectivity and stability.CN200910187903.4 discloses a kind of hydrodesulfurization alcohol catalyst and its system
Preparation Method and application.The catalyst with HZSM-5 molecular sieve be main carrier component, using copper and zinc as active component.Active component
In terms of oxide weight, the content of copper oxide is 5%~27%, and the content of zinc oxide is 3%~15%, using saturation total immersion skill
Art preparation.Catalyst of the invention is suitable for carrying out the reaction of selective hydrodesulfurization alcohol to light-end products, has removal of mercaptans activity
The features such as height, low hydrogenation of olefins activity, and liquid yield height, loss of octane number are seldom after reaction.CN201610187374.8 is mentioned
For the light hydrocarbons mercaptan-eliminating catalyst and its preparation method regulated and controled based on aluminium oxide crystal face, which is with hydro-thermal of the present invention
Gama-alumina after processing regulation is carrier, using nickel and molybdenum as active metal.Light hydrocarbons mercaptan-eliminating catalyst of the present invention
For high activity and high-selectivity catalyst, it can be used for being catalyzed mercaptan and alkadienes effect in light hydrocarbons and generate macromolecular vulcanization
Object, and it can be also catalyzed the selective hydrogenation saturation of diolefin, compared with existing catalyst, catalyst provided by the present invention is de-
Thiol active is high, diolefin hydrogenation selectivity is high, and active component is not lost, not easy in inactivation, thus the catalyst runs period is long.
The present invention relates to the catalyst of mercaptan sulfur in a kind of low temperature removing catalytically cracked gasoline and its preparation sides by CN201310251750.1
Method belongs to field of gasoline desulfurization.A kind of low temperature removes the catalyst of mercaptan sulfur in catalytically cracked gasoline, with aluminium oxide or nanometer
HZSM-5 molecular sieve and alumina composite solid acid are carrier, based on the mass percent for accounting for catalyst gross mass, comprising: oxidation
Zinc 5%~20%, iron oxide 5%~15%, lanthana 0.5%~5%, phosphorous oxide 0.5%~5%.Catalyst of the invention
Suitable for carrying out the reaction of low temperature hydrodesulfurisation alcohol to catalytically cracked gasoline, have removal of mercaptans activity high, olefins hydrogenation activity
Low, liquid receives the features such as high and octane number does not lose substantially.
The composition and comparision contents of above-mentioned catalyst are more, and preparation process is complicated, and produce catalyst prod matter in enormous quantities
Amount is difficult to control.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance
Energy.For the defect for overcoming the above prior art, a kind of completely new hydrodesulfurization alcohol catalyst is found, removal of mercaptans activity is high, diene
The problem of hydrocarbon hydrogenation selectivity is high, and stability is good, and the low characteristic of loss of octane number is those skilled in the art's urgent need to resolve it
One.
Summary of the invention
The present invention provides a kind of gasoline sweetening catalyst and preparation method, and while removing mercaptan, side reaction is few, activity
Height, loss of octane number are low.
The present invention provides a kind of gasoline sweetening catalyst, and catalyst includes silicaalumina carrier and is carried on load
Metal active constituent nickel, molybdenum and iron and auxiliary agent phosphorus on body, on the basis of the weight of catalyst, the content of nickel oxide is 2%
~15wt%, the content of molybdenum oxide are 2~18wt%, and the content of iron oxide is 0.1~5.5wt%, the content of auxiliary agent phosphorous oxide
0.01%~2.2wt%；Silicaalumina carrier content is 65-85wt%, in silicaalumina carrier comprising 0.1~
The silica of 12wt%, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium of 0.1~2.5wt%, carrier is mesoporous account for total hole 3~
75%, macropore accounts for the 1.5~60% of total hole.Micropore, mesoporous, macropore uneven distribution in carrier.
It preferably, include following components: nickel oxide content 4-15wt%, molybdenum oxide on the basis of the total weight of catalyst
Content be 4.5-18wt%.Carrier is mesoporous to account for the 3~65% of total hole, and macropore accounts for the 1.5~50% of total hole.
In the preparation method of catalyst of the present invention, the compound of nickel used and molybdenum can be prior art disclosed
A kind of what compound suitable for catalyst processed, such as nickel nitrate, nickel sulfate, nickel acetate, ammonium molybdate, molybdenum oxide.
The silicaalumina carrier the preparation method is as follows: boehmite and sesbania powder are added to kneader
In be uniformly mixed, inorganic acid solution and organic polymer is added, mediates uniformly, then adds nickel doped lanthanum ferrite, mixing is equal
It is even to obtain alumina precursor, it is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtains
Silicon source-boehmite-organic polymer mixture, the organic polymer of unit content is more quasi- than silicon source-in alumina precursor
The high 2 times or more of content of organic polymer in boehmite-organic polymer mixture (brief note silicon-aluminium-organic admixture),
Then by silicon source -- boehmite-organic polymer mixture is mixed with alumina precursor, adds potassium resource, through extrusion,
Molding, dry, roasting, obtain silicaalumina carrier.The silicon source is silica gel, sodium metasilicate or silicon powder.Silicon-aluminium-is organic
Aluminium oxide accounts for 1~35wt% of aluminium oxide in carrier in object mixture.
The preparation process of above-mentioned silicaalumina carrier, the organic polymer are polyvinyl alcohol, polyacrylic acid, gather
One or more of sodium acrylate, polyethylene glycol, polyacrylate.
Preferably, in above-mentioned silicaalumina carrier nickel doped lanthanum ferrite be 0.1~12wt%, more preferable 0.2~
8wt%, nickel accounts for 0.1~8wt% of cadmium ferrite in nickel doped lanthanum ferrite.
The preparation method of the nickel doped lanthanum ferrite: citric acid is dissolved in stirring and dissolving in deionized water, then by nitric acid
Lanthanum and ferric nitrate are added in citric acid, and Sodium Polyacrylate, polyacrylate or polyacrylic acid, polyacrylic acid is added in stirring and dissolving
The additional amount of sodium, polyacrylate or polyacrylic acid is the 0.1~10wt%, preferably 0.1~8.0wt% of nickel doped lanthanum ferrite.
Nickel compound containing is added, stirs, obtains finished product through drying, roasting, grinding.The nickel compound containing includes nickel nitrate, acetic acid
Nickel etc..
Solution containing active component can be impregnated, be sprayed to using the methods of dipping, spraying by the preparation method of catalyst
On silica-carrier, then catalyst is dried, roasts and obtains the catalyst.Such as it can make according to the following steps
Standby catalyst: preparing solution oxide impregnation silicon-alumina support containing active component and adjuvant component, dries through 110~160 DEG C
3~9 hours, 400~650 DEG C roasted 4~9 hours, finally obtained catalyst prod.
Compared to cadmium ferrite, nickel doped lanthanum ferrite is added in silicaalumina carrier, effectively improves anti-arsenic, sulfur resistance,
The nickel molybdenum series catalyst of preparation effectively improves diolefin hydrogenation selectivity and removal of mercaptans activity, the preparation of silicaalumina carrier
In the process, the organic polymer of unit content contains than organic polymer in silicon-aluminium-organic admixture in alumina precursor
High 2 times or more is measured, the pore structure of carrier can be not only improved, makes carrier micropore, mesoporous, macropore uneven distribution, is effectively inhibited
Active olefin polymerization and monoolefine saturation (hydrogen is not added to the alkene in raw material), improve catalyst anticol mass-energy power, and raising is urged
The stability and service life of agent, are conducive to device long-term operation；And carrier surface is promoted to produce more activity
Position load centre improves catalyst HDS alcohol activity.
Mercaptan-eliminating catalyst of the present invention be suitable for removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or
Mercaptan and/or alkadienes in coker gasoline；Catalyst choice is good.The octane number RON of gasoline loses 0.3~0.4 point or so.
Catalyst desulfurizing alcohol activity is high, and diolefin hydrogenation selectivity is high, and alkene saturation factor is low, and loss of octane number is low.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
5g Sodium Polyacrylate is dissolved in nitric acid, is added 38g silicon powder and 50g boehmite powder, is stirred evenly, obtain
To silicon powder-boehmite-Sodium Polyacrylate mixture (brief note silicon-aluminium-organic admixture), take 1/8 amount spare,
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite.300g boehmite powder and 25.0g sesbania powder are added to kneading
In machine, nitric acid is added, adds 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, adds above-mentioned silicon powder-poly- third
Olefin(e) acid sodium mixture is mediated uniformly, nickel doped lanthanum ferrite and 2.5g potassium nitrate is then added, is uniformly mixed, by kneading-extrusion
It is shaped to clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the silica-of nickeliferous doped lanthanum ferrite
The carrier 1 of aluminium oxide.The mesoporous of carrier accounts for the 55.4% of total hole, and macropore accounts for the 28.6% of total hole.
3, catalyst is prepared
Nickel nitrate, ferric nitrate, phosphomolybdic acid, ammonium molybdate solution impregnated carrier 1 are configured, it is 6 hours, 560 DEG C dry at 140 DEG C
Roasting 5 hours, obtains catalyst 1.The composition of catalyst is shown in Table 1.
Embodiment 2
260g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 4.4wt% silica, the nickel doped lanthanum ferrite of 5.7wt%,
The potassium of 1.6wt%, carrier is mesoporous to account for the 64.2% of total hole, and macropore accounts for the 25.6% of total hole.Unit content in alumina precursor
Sodium Polyacrylate it is 3 times higher than the content of Sodium Polyacrylate in silicon source-organic polymer mixture.The preparation method of catalyst 2
With embodiment 1.
Embodiment 3
220g polyacrylic acid is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite, silicaalumina carrier
Preparation includes the silica of 8.4wt% with embodiment 1, in silicaalumina carrier, the nickel doped lanthanum ferrite of 2.6wt%,
The potassium of 0.8wt%, carrier is mesoporous to account for the 54.6% of total hole, and macropore accounts for the 33.5% of total hole.Unit content in alumina precursor
Polyacrylic acid it is 3.3 times higher than the content of polyacrylic acid in silicon source-organic polymer mixture.The preparation method of catalyst 3 is same
Embodiment 1.
Embodiment 4
280g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 8.4wt% silica, the nickel doped lanthanum ferrite of 2.6wt%,
The potassium of 2.5wt%, carrier is mesoporous to account for the 49.3% of total hole, and macropore accounts for the 39.4% of total hole.Unit content in alumina precursor
Polyacrylate it is 3.3 times higher than the content of polyacrylate in silicon source-organic polymer mixture.The preparation side of catalyst 3
Method is the same as embodiment 1.
Comparative example 1
1, cadmium ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, stir 30min, drying, roasting, grinding obtain nickel doping iron
Sour lanthanum.
2, silicaalumina carrier is prepared
5g Sodium Polyacrylate is dissolved in nitric acid, is added 38g silicon powder and 50g boehmite powder, is stirred evenly, obtain
To silicon powder-boehmite-Sodium Polyacrylate mixture (brief note silicon-aluminium-organic admixture), take 1/8 amount spare,
It is spare that citric acid is added in 4.5g cadmium ferrite.300g boehmite powder and 25.0g sesbania powder are added in kneader, added
Enter nitric acid, add 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is mixed to add above-mentioned silicon powder-Sodium Polyacrylate
Object is closed, mediates uniformly, cadmium ferrite and 2.5g potassium nitrate is then added, be uniformly mixed, is cloverleaf pattern by kneading-extruded moulding
Shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the carrier 1-1 of the silica-alumina of Fe-laden acid lanthanum.
3, comparative catalyst 1 is prepared
Nickel nitrate, ferric nitrate, phosphomolybdic acid, ammonium molybdate solution impregnated carrier 1-1 are configured, it is 6 hours dry at 140 DEG C, 560
DEG C roasting 5 hours, obtain comparative catalyst 1.
Comparative example 2
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite, 350g boehmite powder and 25.0g sesbania powder are added
Enter into kneader, nitric acid is added, adds 40.7g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is micro- to add 4.8g silicon
Powder is mediated uniformly, nickel doped lanthanum ferrite and 2.5g potassium nitrate is then added, is uniformly mixed, and is three leaves by kneading-extruded moulding
Careless shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the load of the silica-alumina of nickeliferous doped lanthanum ferrite
Body 1-2.
3, comparative catalyst 2 is prepared
Nickel nitrate, ferric nitrate, phosphomolybdic acid, ammonium molybdate solution impregnated carrier 1-2 are configured, it is 6 hours dry at 140 DEG C, 560
DEG C roasting 5 hours, obtain comparative catalyst 2.
Catalyst 1-4 and comparative example Catalyst packing are subjected to evaluation catalyst reaction into fixed bed reactors respectively
Performance.Presulfurization, sulfide stress 3.2MPa, hydrogen to oil volume ratio 300, vulcanization oil volume sky are carried out to catalyst with sulfurized oil
Speed is 3.5h-1, vulcanization program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After to vulcanizing treatment, it is switched to full fraction
Then FCC gasoline replacement Treatment 6h is adjusted to reaction process condition, carry out sweetening reaction.612 μ of FCC feedstock content of sulfur in gasoline
G/g, mercaptan sulfur 41 μ g/g, arsenic content 33ppb, olefin(e) centent 35.78v%, RON 91.05.Reaction process condition are as follows: reaction
115 DEG C of device temperature, volume space velocity 4.0h-1, hydrogen to oil volume ratio 22:1, reaction pressure 3.2MPa.Sampling analysis after reaction about 60h,
Reaction result is shown in Table 2.
1 embodiment of table/comparative example catalyst wt% composition
| Embodiment/comparative example | Molybdenum oxide | Nickel oxide | Iron oxide | Phosphorous oxide |
| Embodiment 1 | 16.1 | 9.9 | 0.2 | 0.1 |
| Embodiment 2 | 13.7 | 8.9 | 0.3 | 0.1 |
| Embodiment 3 | 9.8 | 14.1 | 1.0 | 0.2 |
| Embodiment 4 | 11.5 | 10.9 | 0.1 | 0.3 |
| Comparative example 1 | 16.1 | 9.9 | 0.2 | 0.1 |
| Comparative example 2 | 16.1 | 9.9 | 0.2 | 0.1 |
2 embodiments of table/comparative example reaction 60h result
| Embodiment/comparative example | Mercaptan sulfur content/μ g/g | Olefin(e) centent v% | Loss of octane number | Yield of gasoline wt%； |
| Embodiment 1 | 0.4 | 35.13 | 0.2 | 98.4 |
| Embodiment 2 | 0.3 | 35.65 | 0.3 | 98.6 |
| Embodiment 3 | 0.6 | 34.36 | 0.5 | 98.5 |
| Embodiment 4 | 0.5 | 35.01 | 0.4 | 98.4 |
| Comparative example 1 | 17 | 24.24 | 3.9 | 87.7 |
| Comparative example 2 | 11 | 29.85 | 2.9 | 91.4 |
The result of 3 embodiment of table reaction 600h
| Embodiment | Mercaptan sulfur content/μ g/g | Olefin(e) centent v% | Loss of octane number | Yield of gasoline wt%； |
| Embodiment 1 | 0.4 | 34.97 | 0.3 | 98.5 |
| Embodiment 2 | 0.3 | 35.53 | 0.3 | 98.5 |
Reaction result shows that olefin(e) centent is basically unchanged, and reaction loss of octane number is 0.3~0.4, catalyst diolefin hydrogenation
Selectivity and removal of mercaptans activity are high, and anti-arsenic, sulfur resistance are good, and loss of octane number is low.Comparative example catalyst activity is low, and catalyst can
Can plastic even coking and activity decline.
Stability test is carried out to catalyst, reaction operation 600h reaction result is shown in Table 3, and olefin(e) centent is basically unchanged, and is urged
It is good that agent is not easy plastic even coking and deactivation, stability.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (10)
1. a kind of gasoline sweetening catalyst, which is characterized in that catalyst includes silicaalumina carrier and is carried on carrier
On metal active constituent nickel, molybdenum and iron and auxiliary agent phosphorus, on the basis of the weight of catalyst, the content of nickel oxide is 2%~
15wt%, the content of molybdenum oxide are 2~18wt%, and the content of iron oxide is 0.1~5.5wt%, the content of auxiliary agent phosphorous oxide
0.01%~2.2wt%；Silicaalumina carrier content is 65-85wt%, in silicaalumina carrier comprising 0.1~
The silica of 12wt%, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium of 0.1~2.5wt%, carrier is mesoporous account for total hole 3~
75%, macropore accounts for the 1.5~60% of total hole, micropore, mesoporous, macropore uneven distribution in carrier.
2. gasoline sweetening catalyst according to claim 1, which is characterized in that the catalyst is on the basis of total weight
Include following components: nickel oxide content 4-15wt%, the content of molybdenum oxide are 4.5-18wt%.
3. gasoline sweetening catalyst according to claim 1, which is characterized in that the carrier is mesoporous account for total hole 3~
65%, macropore accounts for the 1.5~50% of total hole.
4. gasoline sweetening catalyst according to claim 1, which is characterized in that the silicaalumina carrier
It is uniformly mixed the preparation method is as follows: boehmite and sesbania powder are added in kneader, inorganic acid solution and organic is added
Polymer is mediated uniformly, then adds nickel doped lanthanum ferrite, is uniformly mixed and obtains alumina precursor, spare；Organic poly-
It closes addition silicon source and boehmite in the acid solution of object to be uniformly mixed, obtains silicon source-boehmite-organic polymer mixing
Object, the organic polymer of unit content is more organic than in silicon source-boehmite-organic polymer mixture in alumina precursor
The high 2 times or more of the content of polymer, then by silicon source -- boehmite-organic polymer mixture and alumina precursor are mixed
It closes, adds potassium resource, through extrusion, molding, drying, roasting, obtain silicaalumina carrier.
5. gasoline sweetening catalyst according to claim 4, which is characterized in that the silicon source be silica gel, sodium metasilicate or
Silicon powder, aluminium oxide accounts for 1~35wt% of aluminium oxide in carrier in silicon source-boehmite-organic polymer mixture.
6. gasoline sweetening catalyst according to claim 4, which is characterized in that the organic polymer is polyethylene
One or more of alcohol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
7. gasoline sweetening catalyst according to claim 4, which is characterized in that in the silicaalumina carrier
Nickel doped lanthanum ferrite is 0.1~12wt%.
8. described in any item gasoline sweetening catalysts according to claim 1~7, which is characterized in that the nickel ferrite-doping
The preparation method of lanthanum: being dissolved in stirring and dissolving in deionized water for citric acid, and then lanthanum nitrate and ferric nitrate are added in citric acid,
Sodium Polyacrylate, polyacrylate or polyacrylic acid, Sodium Polyacrylate, polyacrylate or polyacrylic acid is added in stirring and dissolving
Additional amount be nickel doped lanthanum ferrite 0.1~10wt%, add nickel compound containing, stir, through drying, roasting, grind
To finished product.
9. described in any item gasoline sweetening catalysts according to claim 1~7, which is characterized in that the system of the catalyst
Preparation Method includes the following steps: that the maceration extract dipping of active component will be contained, sprays on carrier, then does to catalyst
Dry, roasting obtains the catalyst.
10. gasoline sweetening catalyst according to claim 9, which is characterized in that the preparation process of the catalyst is such as
Under: nickel nitrate, ferric nitrate, ammonium phosphomolybdate, ammonium molybdate solution oxide impregnation silicon-alumina support are prepared, is dried through 110~160 DEG C
3~9 hours dry, 400~650 DEG C roast 4~9 hours, finally obtain catalyst prod.
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