WO2011040224A1 - 炭化水素油の水素化脱硫触媒、その製造方法および水素化精製方法 - Google Patents
炭化水素油の水素化脱硫触媒、その製造方法および水素化精製方法 Download PDFInfo
- Publication number
- WO2011040224A1 WO2011040224A1 PCT/JP2010/065785 JP2010065785W WO2011040224A1 WO 2011040224 A1 WO2011040224 A1 WO 2011040224A1 JP 2010065785 W JP2010065785 W JP 2010065785W WO 2011040224 A1 WO2011040224 A1 WO 2011040224A1
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- Prior art keywords
- mass
- catalyst
- titania
- hydrocarbon oil
- carrier
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 180
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 40
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 40
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 183
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011148 porous material Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 230000000737 periodic effect Effects 0.000 claims abstract description 22
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims description 68
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- -1 silicate ions Chemical class 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 229910001773 titanium mineral Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 30
- 230000023556 desulfurization Effects 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000002002 slurry Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 150000007524 organic acids Chemical class 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 11
- 238000007865 diluting Methods 0.000 description 11
- 229910001388 sodium aluminate Inorganic materials 0.000 description 11
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 10
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 5
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J21/12—Silica and alumina
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- 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
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- C10G2300/10—Feedstock materials
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- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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- 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
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- 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
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- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
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- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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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
- C10G2300/70—Catalyst aspects
Definitions
- the present invention relates to a hydrodesulfurization catalyst for hydrocarbon oils, a method for producing the same, and a hydrorefining method for hydrocarbon oils. More specifically, the present invention is used for hydrotreating hydrocarbon oils, particularly gas oil fractions, and is highly desulfurized.
- the present invention relates to a hydrodesulfurization catalyst in which an active component is supported on a silica-titania-alumina carrier exhibiting activity, a production method thereof, and a hydrorefining method of hydrocarbon oil using the hydrodesulfurization catalyst.
- catalysts that have been used for the purpose of hydrotreating hydrocarbon oils include carriers of porous inorganic oxides such as alumina, alumina-silica, titania, alumina-titania, and the like in groups VIA and V Catalysts carrying an active metal component selected from Group VIII are widely used.
- the titania support is known to exhibit high desulfurization performance as compared with the alumina support, but generally has a problem that the specific surface area is small and the thermal stability at high temperature is low.
- Known titania-containing catalysts include a production method for preparing a titania carrier using titania gel (see Patent Document 1), a production method for preparing an alumina-titania carrier by supporting a water-soluble titania compound on an alumina carrier (see Patent Document 2), and the like. It has been.
- the catalyst described in Patent Document 1 contains a lot of expensive titania, and the price is high and the bulk density is high as compared with a catalyst using a conventional alumina carrier.
- the catalyst described in Patent Document 2 can carry titania only for the water absorption rate of the carrier, it is necessary to repeat the carrying process to make titania highly loaded on the carrier, which is expensive for industrial production. It was.
- An object of the present invention is to provide an inexpensive and high-performance hydrodesulfurization catalyst using a high specific surface area carrier containing alumina as a main component and containing silica and titania, a method for producing the same, and a hydrocarbon using the hydrodesulfurization catalyst It is to provide a method for hydrorefining oil.
- the present inventors have greatly improved desulfurization performance for hydrocarbon oils by using a silica-titania-alumina support having a specific structure and a hydrodesulfurization catalyst having a predetermined property. As a result, the present invention has been completed.
- the total area of the diffraction peak area showing the crystal structure of the anatase titania (101) plane and the diffraction peak area showing the crystal structure of the rutile titania (110) plane measured by X-ray diffraction analysis is
- the silica-titania-alumina support having a diffraction peak area of 1 ⁇ 4-alumina (400) plane, which is assigned to the ⁇ -alumina (400) plane, is selected from Group VIA and Group VIII of the periodic table.
- a basic aluminum salt aqueous solution and a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt are mixed so that the pH is 6.5 to 9.5.
- a first step for obtaining a hydrate a second step for obtaining a carrier by washing, molding, drying and calcining the hydrate sequentially, and the carrier comprises at least one selected from Group VIA and Group VIII of the periodic table.
- a third step of supporting one type of metal component relates to a method for producing a hydrodesulfurization catalyst for hydrocarbon oils.
- the present invention also relates to a hydrorefining method for hydrocarbon oil, characterized in that hydrocarbon oil is hydrotreated in a hydrogen atmosphere using the hydrodesulfurization catalyst.
- the hydrodesulfurization catalyst of the present invention exhibits a high desulfurization activity in hydrotreating hydrocarbon oils, particularly gas oil fractions, and is extremely effective. Further, in the method for producing a hydrodesulfurization catalyst of the present invention, titanium can be highly dispersed in the support, and therefore, high performance can be achieved with a relatively small amount of expensive titanium compared to alumina or silica. This makes it possible to obtain an inexpensive and high-performance catalyst. In addition, the hydrorefining method of the present invention can highly remove sulfur and nitrogen from hydrocarbon oil.
- FIG. 4 is a diagram showing the result of X-ray diffraction analysis of a carrier a in Example 1.
- the hydrodesulfurization catalyst of the present invention is the sum of the diffraction peak area showing the crystal structure of the anatase-type titania (101) plane and the diffraction peak area showing the crystal structure of the rutile-type titania (110) plane measured by X-ray diffraction analysis.
- the silica-titania-alumina support having an area of 1 ⁇ 4 or less of the diffraction peak area showing the aluminum crystal structure attributed to the ⁇ -alumina (400) plane is applied to a group VIA (IUPAC No. 6) of the periodic table.
- SA specific surface area
- PVo total pore volume
- PD average pore diameter
- PVP average pore diameter
- the silica-titania-alumina carrier in the hydrodesulfurization catalyst of the present invention preferably contains 1 to 10% by mass of silica as SiO 2 on a carrier basis, more preferably 2 to 7% by mass. More preferably, it is contained by mass%.
- silica content is less than 1% by mass, the specific surface area becomes low, and the titania particles tend to aggregate when the carrier is baked, and the crystal structures of anatase titania and rutile titania measured by X-ray diffraction analysis are obtained. The diffraction peak area shown increases.
- the content of silica exceeds 10% by mass, the sharpness of the pore distribution of the obtained carrier is deteriorated and the desired desulfurization activity may not be obtained.
- the silica-titania-alumina carrier in the present invention preferably contains 3 to 40% by mass of titania as TiO 2 based on the carrier, more preferably 15 to 35% by mass, and further preferably 15 to 25% by mass. It is desirable to contain.
- the titania content is less than 3% by mass, the addition effect of the titania component is small, and the obtained catalyst may not obtain the desired desulfurization activity.
- the titania content is more than 40% by mass, the mechanical strength of the catalyst may be lowered, and the crystallization of titania particles is facilitated when the support is fired, so that the specific surface area is lowered.
- the desulfurization performance corresponding to the economical efficiency of the increased titania amount is not exhibited, and it is not preferable because it is not an inexpensive and high-performance catalyst that is the object of the present invention.
- the silica-titania-alumina carrier in the present invention preferably contains 50 to 96% by mass of alumina as Al 2 O 3 based on the carrier, more preferably 58 to 83% by mass, and still more preferably 70 to 83%. It is desirable to contain by mass.
- alumina when the content of alumina is less than 50% by mass, catalyst deterioration tends to increase, such being undesirable.
- there is more content of alumina than 96 mass% since there exists a tendency for catalyst performance to fall, it is unpreferable.
- the hydrodesulfurization catalyst of the present invention contains at least one selected from Group VIA (IUPAC Group 6) and Group VIII (IUPAC Group 8 to Group 10) of the periodic table on the silica-titania-alumina support.
- the metal component is supported.
- Examples of the metal component of Group VIA of the periodic table include molybdenum (Mo) and tungsten (W).
- Examples of the metal component of Group VIII of the periodic table include cobalt (Co) and nickel (Ni). It can be illustrated. These metal components may be used alone or in combination of two or more.
- the metal component is preferably a combination of nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten, cobalt-tungsten, nickel-tungsten-cobalt, etc.
- a combination of cobalt-molybdenum and nickel-molybdenum-cobalt is more preferable.
- the supported amount of the metal component is preferably in the range of 1 to 35% by mass and more preferably in the range of 15 to 30% by mass as an oxide based on the catalyst.
- the metal component of Group VIA of the periodic table is preferably in the range of 10 to 30% by weight, more preferably in the range of 13 to 24% by weight, and the metal component of Group VIII of the periodic table is as oxide.
- it is in the range of 1 to 10% by mass, more preferably in the range of 2 to 6% by mass.
- the hydrodesulfurization catalyst of the present invention contains a metal component of Group VIA of the periodic table, it is preferable to dissolve the metal component using an acid.
- an inorganic acid and / or an organic acid as the acid.
- the inorganic acid include phosphoric acid and nitric acid, and phosphoric acid is more preferable.
- the organic acid a carboxylic acid compound is preferable, and specific examples include citric acid, malic acid, tartaric acid, and gluconic acid.
- phosphorus preferably contains 3 to 25% by mass of phosphoric acid, more preferably 10 to 15% by mass based on 100% by mass of the metal component of Group VIA of the periodic table.
- the organic acid is preferably contained in the range of 35 to 75% by mass, more preferably 55 to 65% by mass with respect to the metal component of Group VIA of the periodic table.
- the organic acid exceeds 75% by mass relative to the metal component of Group VIA of the periodic table, the viscosity of the solution containing the metal component (hereinafter also referred to as “supported metal-containing solution”) increases, and the impregnation step in the production is performed. It is not preferable because it becomes difficult, and if it is less than 35% by mass, the stability of the supported metal-containing solution is deteriorated and the catalyst performance tends to be deteriorated.
- the method for allowing the carrier to contain the metal component or further an inorganic acid (phosphoric acid or the like) and / or an organic acid is not particularly limited, and the compound containing the metal component or further an inorganic acid (phosphoric acid or the like).
- a known method such as an impregnation method using an organic acid (equilibrium adsorption method, pore filling method, initial wetting method), ion exchange method, or the like can be used.
- the impregnation method is a method of impregnating a support containing a solution containing an active metal, followed by drying and firing.
- the impregnation method it is preferable to simultaneously carry a metal component of Group VIA of the periodic table and a metal component of Group VIII of the periodic table. If the metals are supported separately, the desulfurization activity or denitrification activity may be insufficient.
- the loading is carried out by the impregnation method, the dispersibility of the metal component of Group VIA of the periodic table on the support becomes high, and the desulfurization activity and denitrogenation activity of the resulting catalyst become higher.
- the reaction is preferably carried out in the presence of an inorganic acid and / or an organic acid, more preferably in the presence of phosphoric acid and / or an organic acid.
- the organic acid is preferably a carboxylic acid compound, and specific examples thereof include citric acid, malic acid, tartaric acid, and gluconic acid.
- the hydrodesulfurization catalyst of the present invention needs to have a specific surface area (SA) measured by the BET method of 150 m 2 / g or more, preferably 170 m 2 / g or more. If the specific surface area (SA) is less than 150 m 2 / g, the active point of the desulfurization reaction is decreased, and there is a possibility that the desulfurization performance may be deteriorated.
- the upper limit is not particularly limited, but when the specific surface area (SA) exceeds 250 m 2 / g, the catalyst strength tends to decrease. Therefore, the upper limit is preferably 250 m 2 / g or less, and 230 m 2 / g or less. Is more preferable.
- the hydrodesulfurization catalyst of the present invention has a total pore volume (PVo) measured by a mercury intrusion method (mercury contact angle: 135 degrees, surface tension: 480 dyn / cm) of 0.30 ml / g or more. Is preferably 0.35 ml / g or more.
- the upper limit is not particularly limited. However, when the total pore volume (PVo) exceeds 0.60 ml / g, the catalyst strength tends to decrease. Therefore, the upper limit is preferably 0.60 ml / g or less. More preferably, it is 50 ml / g or less.
- the hydrodesulfurization catalyst of the present invention needs to have an average pore diameter (PD) in the range of 6 to 15 nm (60 to 150 mm), preferably in the range of 6.5 to 11 nm.
- PD average pore diameter
- the total pore volume (PVo) represents pores having a pore diameter of 4.1 nm (41 cm) or more, which is the quantification limit in measurement, and the average pore diameter (PD) is the total pore volume (PVo).
- the hydrodesulfurization catalyst of the present invention has a ratio (PVp / PVo) of the pore volume (PVp) having an average pore diameter (PD) ⁇ 30% to the total pore volume (PVo). ) Must be 70% or more, preferably 80% or more, and its pore distribution is sharp. When PVp / PVo is less than 70%, the pore distribution of the catalyst becomes broad and the desired desulfurization performance may not be obtained.
- the carrier of the hydrodesulfurization catalyst of the present invention has a diffraction peak area showing the crystal structure of the anatase titania (101) plane and a diffraction structure showing the crystal structure of the rutile titania (110) plane measured by X-ray diffraction analysis.
- the total peak area (hereinafter also referred to as “titania diffraction peak area”) is a diffraction peak area (hereinafter referred to as “alumina diffraction peak area”) indicating an aluminum crystal structure attributed to the ⁇ -alumina (400) plane. ), It is necessary to be 1/4 or less, preferably 1/5 or less, and more preferably 1/6 or less.
- titania diffraction peak area with respect to the alumina diffraction peak area is larger than 1/4, crystallization of titania proceeds and pores effective for the reaction decrease. Therefore, even if the amount of titania is increased, the desulfurization performance corresponding to the economic efficiency is not exhibited, and the inexpensive and high-performance catalyst which is the object of the present invention is not obtained.
- Each diffraction peak area is calculated by fitting a graph obtained by X-ray diffraction analysis with an X-ray diffractometer using the least square method and correcting the baseline to obtain the height from the maximum peak value to the baseline ( Peak intensity W)
- the peak width (half width) at the half value (W / 2) of the obtained peak intensity was determined, and the product of this half width and peak intensity was defined as the diffraction peak area. From the obtained diffraction peak areas, “titania diffraction peak area / alumina diffraction peak area” was calculated.
- the method for producing a hydrodesulfurization catalyst of the present invention comprises a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt (hereinafter also simply referred to as “mixed aqueous solution”), a basic aluminum salt aqueous solution, in the presence of silicate ions.
- mixed aqueous solution a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt
- a basic aluminum salt aqueous solution in the presence of silicate ions.
- a mixed aqueous solution may be added to the basic aluminum salt aqueous solution containing silicate ions
- a basic aluminum salt aqueous solution may be added to the mixed aqueous solution containing silicate ions.
- the silicate ion contained in the basic aluminum salt aqueous solution can be basic or neutral.
- the basic silicate ion source a silicate compound that generates silicate ions in water such as sodium silicate can be used.
- the silicate ions contained in the mixed aqueous solution of the titanium mineral acid salt and the acidic aluminum salt aqueous solution can be acidic or neutral.
- the acidic silicate ion source a silicate compound that generates silicate ions in water such as silicic acid can be used.
- the basic aluminum salt sodium aluminate, potassium aluminate or the like is preferably used.
- the acidic aluminum salt aluminum sulfate, aluminum chloride, aluminum nitrate and the like are preferably used, and as the titanium mineral acid salt, titanium tetrachloride, titanium trichloride, titanium sulfate, titanium nitrate and the like are exemplified. Titanium is preferably used because it is inexpensive.
- a basic aluminum salt aqueous solution containing a predetermined amount of basic silicate ions is put into a tank equipped with a stirrer, and is usually kept at 40 to 90 ° C., preferably 50 to 70 ° C., and the temperature of this solution ⁇
- a mixed aqueous solution of a predetermined amount of a titanium mineral acid salt and an acidic aluminum salt aqueous solution heated to 5 ° C., preferably ⁇ 2 ° C., more preferably ⁇ 1 ° C. has a pH of 6.5 to 9.5, preferably 6.5.
- the addition of the mixed aqueous solution to the basic aluminum salt aqueous solution is desirably 15 minutes or less because undesirable crystals such as bayerite and gibbsite may be generated in addition to pseudoboehmite as time goes on. More preferably less than a minute. Bayerite and gibbsite are not preferred because their specific surface area decreases when fired.
- the hydrate slurry obtained in the first step is aged as desired, and then washed to remove by-product salts to obtain a hydrate slurry containing silica, titania and alumina.
- the obtained hydrate slurry is further heat-aged if desired, and then, by conventional means, for example, heat-kneaded to form a kneaded product, which is then molded into a desired shape by extrusion molding or the like.
- it is further calcined at 400 to 800 ° C., preferably 450 to 600 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours to obtain silica.
- a silica-titania-alumina support containing titania and alumina is obtained.
- the hydrodesulfurization catalyst of the present invention is produced usually by calcining at 400 to 800 ° C., preferably 450 to 600 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours.
- a raw material for the metal component for example, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, and ammonium paratungstate are preferably used.
- the hydrodesulfurization catalyst described above is used to charge the hydrocarbon oil under high-temperature and high-pressure conditions in a hydrogen atmosphere by filling the fixed-bed reactor with the catalyst. Do.
- a light oil fraction is particularly preferably used.
- Gas oil fractions include straight-run light oil obtained from a crude oil atmospheric distillation apparatus, straight-run heavy oil obtained from an atmospheric distillation apparatus and residual oil obtained by treating the crude oil with a vacuum distillation apparatus, Catalytic cracked diesel oil obtained by catalytic cracking of light diesel oil or desulfurized heavy oil, hydrocracked diesel oil obtained by hydrocracking depressurized heavy diesel oil or desulfurized heavy oil, pyrolysis diesel oil obtained from thermal cracking equipment such as coker, etc. And a fraction containing 70% by volume or more of a fraction having a boiling point of 260 to 360 ° C.
- the oil to be treated in the atmospheric distillation apparatus is not particularly limited, and examples thereof include petroleum crude oil, synthetic crude oil derived from oil sand, coal liquefied oil, bitumen reformed oil, and the like.
- the value of distillation property (boiling point) here is a value measured according to the method described in JIS K2254 “Petroleum product-distillation test method”.
- the hydrorefining method of hydrocarbon oil according to the present invention is preferably performed under the following reaction conditions.
- the reaction temperature is not particularly limited, but is preferably 300 to 420 ° C, more preferably 320 to 380 ° C. If the reaction temperature is less than 300 ° C., the desulfurization and denitrification activities tend to be remarkably lowered, which is not practical. Further, when the reaction temperature exceeds 420 ° C., catalyst deterioration becomes remarkable, and it approaches the heat resistant temperature of the reaction apparatus (usually about 425 ° C.), which is not preferable.
- the reaction pressure is not particularly limited, but is preferably 3.0 to 15.0 MPa.
- the reaction pressure is less than 3.0 MPa, desulfurization and denitrogenation activities tend to be remarkably lowered, and therefore, 3.0 MPa or more is preferable and 4.0 MPa or more is more preferable.
- the reaction pressure exceeds 15.0 MPa, hydrogen consumption increases and the operating cost increases, which is not preferable. Therefore, it is preferably 15.0 MPa or less, more preferably 10.0 MPa or less, and even more preferably 7.0 MPa or less.
- Liquid hourly space velocity is not particularly limited, preferably from 0.5 ⁇ 4.0 h -1, more preferably 0.5 ⁇ 2.0 h -1. If the liquid space velocity is less than 0.5 h ⁇ 1 , the throughput is low and the productivity is low, which is not practical. On the other hand, if the liquid space velocity exceeds 4.0 h ⁇ 1 , the reaction temperature becomes high and the catalyst is rapidly deteriorated.
- the hydrogen / oil ratio is not particularly limited, but is preferably 120 to 420 NL / L, and more preferably 170 to 340 NL / L.
- a hydrogen / oil ratio of less than 120 NL / L is not preferable because the desulfurization rate decreases. Moreover, even if it exceeds 420 NL / L, since there is no big change in desulfurization activity and only an operating cost increases, it is not preferable.
- the sulfur content of the product oil obtained by hydrotreating the hydrocarbon oil according to the present invention is preferably 10 ppm by mass or less, more preferably 8 ppm by mass or less, and 7 ppm by mass or less. Further preferred. Moreover, it is preferable that the nitrogen content of produced
- the value of sulfur content (sulfur content concentration) here is a value measured according to the method described in JIS K2541 “Crude oil and petroleum products—Sulfur content test method”.
- the value of nitrogen content (nitrogen content concentration) is a value measured according to the method described in JIS K2609 “Crude oil and petroleum products—Test method for nitrogen content”.
- Example 1 Preparation of hydrodesulfurization catalyst a
- a tank with a steam jacket with a capacity of 100 L is charged with 8.16 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 41 kg of ion-exchanged water, and then 5 mass% silicic acid in terms of SiO 2 concentration. 1.80 kg of sodium solution was added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution.
- an acidic aluminum salt aqueous solution obtained by diluting 7.38 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 13 kg of ion-exchanged water, and 1.82 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration.
- the aqueous solution of titanium mineral salt dissolved in the ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution.
- Water containing silica, titania, and alumina is added to the tank containing the basic aqueous aluminum salt solution at a constant rate using a roller pump until the pH is 7.2 (addition time: 10 minutes).
- a Japanese slurry a was prepared.
- the obtained hydrate slurry a was aged at 60 ° C. for 1 hour with stirring, dehydrated using a flat plate filter, and further washed with 150 L of a 0.3 mass% aqueous ammonia solution.
- the cake-like slurry after washing was diluted with ion-exchanged water so as to be 10% by mass in terms of Al 2 O 3 concentration, and then the pH was adjusted to 10.5 with 15% by mass ammonia water. This was transferred to an aging tank equipped with a reflux machine and aged at 95 ° C. for 10 hours with stirring.
- the slurry after completion of aging was dehydrated and concentrated and kneaded to a predetermined moisture content while kneading with a double-arm kneader equipped with a steam jacket.
- the obtained kneaded product was molded into a cylindrical shape having a diameter of 1.8 mm by an extrusion molding machine and dried at 110 ° C.
- the dried molded product was baked in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain a carrier a.
- the carrier a silica is 3% by mass in terms of SiO 2 (support standard), titania is 20% by mass in terms of TiO 2 (support standard), and aluminum is 77% by mass in terms of Al 2 O 3 concentration (support standard). Contained.
- the carrier a was subjected to X-ray diffraction analysis using the Rigaku X-ray diffraction apparatus RINT2100 (the same applies to the following examples). The result is shown in FIG.
- the peak intensity from the baseline was defined as the anatase titania diffraction peak area.
- the total area of the anatase-type titania diffraction peak area and the rutile-type titania diffraction peak area was defined as the titania diffraction peak area. In carrier a, no rutile-type titania peak was detected.
- Example 2 Preparation of hydrodesulfurization catalyst b] (1) Add 8.49 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 37 kg of ion-exchanged water, and then stir 1.80 kg of 5 mass% sodium silicate solution in terms of SiO 2 concentration. And the basic aluminum salt aqueous solution prepared by heating to 60 ° C., and (2) an acid obtained by diluting 10.62 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 19 kg of ion-exchanged water.
- a mixed aqueous solution prepared by mixing an aqueous solution of aluminum salt and an aqueous solution of titanium mineral acid obtained by dissolving 0.91 kg of 33 wt% titanium sulfate in terms of TiO 2 concentration in 5 kg of ion-exchanged water has a constant pH.
- the difference from Example 1 is that the hydrate slurry b was prepared by adding until 7.2.
- carrier b was prepared from hydrate slurry b.
- the SiO 2 concentration was 3% by mass (carrier standard)
- the TiO 2 concentration was 10% by mass (carrier standard)
- the aluminum was 87% by mass in terms of Al 2 O 3 (carrier standard).
- a diffraction peak showing the crystal structure of anatase titania and rutile titania was not detected, and titania diffraction peak area / alumina diffraction peak area was less than 1 ⁇ 4.
- catalyst b was produced from carrier b.
- the catalyst b contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst b.
- Example 3 Preparation of hydrodesulfurization catalyst c] (1) 7.82 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was added, diluted with 44 kg of ion-exchanged water, and then 1.80 kg of 5 mass% sodium silicate solution in terms of SiO 2 concentration was stirred. And the basic aluminum salt aqueous solution prepared by heating to 60 ° C. and (2) an acid obtained by diluting 4.14 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 7 kg of ion-exchanged water.
- a mixed aqueous solution prepared by mixing an aqueous aluminum salt solution and an aqueous titanium mineral salt solution obtained by dissolving 2.73 kg of 33 wt% titanium sulfate in terms of TiO 2 concentration in 15 kg of ion-exchanged water has a pH at a constant rate.
- the point which added until it became 7.2 and the hydrate slurry c was prepared differs from Example 1.
- FIG. In the same manner as in Example 1, carrier c was prepared from hydrate slurry c. In the carrier c, the SiO 2 concentration was 3% by mass (carrier standard), the TiO 2 concentration was 30% by mass (carrier standard), and the aluminum was 67% by mass (carrier standard) in terms of Al 2 O 3 concentration.
- catalyst c was produced from support c.
- the catalyst c contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst c.
- Example 1 The point that the aqueous solution of aluminum salt was added at a constant rate until the pH reached 7.2 to prepare the hydrate slurry d was different from Example 1.
- carrier d was prepared from hydrate slurry d.
- the SiO 2 concentration was 3% by mass (carrier standard)
- the TiO 2 concentration was 0% by mass (carrier standard)
- the aluminum was 97% by mass in terms of Al 2 O 3 concentration (carrier standard).
- Example 2 As a result of X-ray diffraction analysis (not shown) as in Example 1, a diffraction peak showing the crystal structure of anatase titania and rutile titania was not detected, and titania diffraction peak area / alumina diffraction peak area was less than 1 ⁇ 4. Further, in the same manner as in Example 1, a catalyst d was produced from the carrier d.
- the catalyst d contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst d.
- the SiO 2 concentration was 3% by mass (carrier standard)
- the TiO 2 concentration was 45% by mass (carrier standard)
- the aluminum was 52% by mass (carrier standard) in terms of Al 2 O 3 concentration.
- the titania diffraction peak area / alumina diffraction peak area was 1/3.
- a catalyst e was produced from the carrier e.
- the catalyst e contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst e.
- Example 4 Preparation of hydrodesulfurization catalyst f] (1) Add 7.79 kg of 22% by mass sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 40 kg of ion-exchanged water, and then stir 4.20 kg of 5% by mass sodium silicate solution in terms of SiO 2 concentration.
- the basic aluminum salt aqueous solution prepared by heating and heating to 60 ° C., and (2) an acid obtained by diluting 6.81 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 12 kg of ion-exchanged water
- a mixed aqueous solution prepared by mixing an aqueous aluminum salt solution and an aqueous titanium mineral salt solution in which 1.82 kg of 33 mass% titanium sulfate in terms of TiO 2 concentration is dissolved in 10 kg of ion-exchanged water, has a pH at a constant rate.
- the difference from Example 1 is that hydrate slurry f was prepared by adding until 7.2.
- the carrier f was prepared from the hydrate slurry f.
- the SiO 2 concentration was 7% by mass (carrier standard)
- the TiO 2 concentration was 20% by mass (carrier standard)
- the aluminum was 73% by mass (carrier standard) in terms of Al 2 O 3 concentration.
- the titania diffraction peak area / alumina diffraction peak area was 1/8.
- a catalyst f was produced from the carrier f in the same manner as in Example 1.
- the catalyst f contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of the catalyst f.
- Example 5 Preparation of hydrodesulfurization catalyst g] (1) Add 7.52 kg of 22% by mass sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 40 kg of ion-exchanged water, and then stir 6.00 kg of 5% by mass sodium silicate solution in terms of SiO 2 concentration.
- the basic aluminum salt aqueous solution prepared by heating and heating to 60 ° C., and (2) an acid obtained by diluting 6.38 kg of a 7% by mass aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 11 kg of ion-exchanged water
- a mixed aqueous solution prepared by mixing an aqueous aluminum salt solution and an aqueous titanium mineral salt solution in which 1.82 kg of 33 mass% titanium sulfate in terms of TiO 2 concentration is dissolved in 10 kg of ion-exchanged water, has a pH at a constant rate.
- the difference from Example 1 is that hydrate slurry g was prepared by adding until 7.2.
- carrier g was prepared from hydrate slurry g.
- the carrier g had a SiO 2 concentration of 10% by mass (carrier standard), a TiO 2 concentration of 20% by mass (carrier standard), and aluminum in terms of Al 2 O 3 concentration of 70% by mass (carrier standard). Moreover, as a result of performing X-ray diffraction analysis in the same manner as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/8. Further, in the same manner as in Example 1, catalyst g was produced from carrier g. Catalyst g contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of catalyst g.
- the carrier h was prepared from the hydrate slurry h in the same manner as in Example 1.
- the SiO 2 concentration was 0% by mass (carrier standard)
- the TiO 2 concentration was 20% by mass (carrier standard)
- the aluminum was 80% by mass (carrier standard) in terms of Al 2 O 3 concentration.
- the titania diffraction peak area / alumina diffraction peak area was 1/4.
- a catalyst h was produced from the carrier h in the same manner as in Example 1.
- the catalyst h contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of catalyst h.
- the basic aluminum salt aqueous solution prepared by heating and heating to 60 ° C., and (2) an acid obtained by diluting 5.67 kg of 7 mass% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 10 kg of ion-exchanged water
- An aqueous solution of aluminum salt and a mixed aqueous solution prepared by mixing 1.82 kg of 33 wt% titanium sulfate in terms of TiO 2 concentration with 10 kg of ion-exchanged water and mixed with an aqueous solution of titanium mineral salt at a constant speed Is different from Example 1 in that the hydrate slurry i was prepared by adding the hydrate slurry to 7.2.
- carrier i was prepared from hydrate slurry i.
- the carrier i had a SiO 2 concentration of 15% by mass (carrier standard), a TiO 2 concentration of 20% by mass (carrier standard), and an aluminum content of 65% by mass in terms of Al 2 O 3 (carrier standard).
- the titania diffraction peak area / alumina diffraction peak area was 1/8.
- catalyst i was produced from carrier i.
- the catalyst i contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of catalyst i.
- Example 6 Preparation of hydrodesulfurization catalyst j
- the carrier a of Example 1 was used as the carrier. After suspending 278 g of molybdenum trioxide and 114 g of cobalt carbonate in 500 ml of ion-exchanged water and heating this suspension at 95 ° C. for 5 hours so that the liquid volume does not decrease, the suspension is heated, and then phosphoric acid. 68 g and 76 g of nitric acid were added and dissolved to prepare an impregnating solution. This impregnating solution was spray impregnated on 1000 g of carrier a, dried at 250 ° C., and further calcined at 550 ° C.
- hydrodesulfurization catalyst j The metal components of the catalyst j were 20% by mass of MoO 3 (catalyst reference), 5% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 3 shows the properties of the catalyst j.
- Example 7 Preparation of hydrodesulfurization catalyst k
- the carrier a of Example 1 was used as the carrier. After suspending 278 g of molybdenum trioxide and 114 g of cobalt carbonate in 500 ml of ion-exchanged water and heating this suspension at 95 ° C. for 5 hours so that the liquid volume does not decrease, the suspension is heated, and then phosphoric acid. 68 g and 174 g of malic acid were added and dissolved to prepare an impregnation solution. This impregnating solution was spray impregnated on 1000 g of support a, dried at 250 ° C., and further calcined at 550 ° C.
- the metal component of the catalyst k was 20% by mass of MoO 3 (catalyst reference), 5% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Properties of catalyst k are shown in Table 3.
- Example 8 Preparation of hydrodesulfurization catalyst 1
- the carrier a of Example 1 was used as the carrier. After 267 g of molybdenum trioxide and 109 g of cobalt carbonate were suspended in 500 ml of ion-exchanged water, this suspension was heated at 95 ° C. for 5 hours so that the liquid volume did not decrease, and then heated, followed by malic acid. 167 g was added and dissolved to prepare an impregnating solution. This impregnating solution was spray impregnated on 1000 g of carrier a, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst l.
- the metal component of the catalyst 1 was 20% by mass (catalyst reference) of MoO 3 , 5% by mass (catalyst reference) of CoO, and 0% by mass (catalyst reference) of P 2 O 5 .
- the properties of catalyst 1 are shown in Table 3.
- Example 9 Preparation of hydrodesulfurization catalyst m
- the carrier a of Example 1 was used as the carrier. After suspending 306 g of molybdenum trioxide and 76 g of nickel carbonate in 500 ml of ion-exchanged water and heating this suspension at 95 ° C. for 5 hours so that the liquid volume does not decrease, phosphoric acid is added. 68 g was added and dissolved to prepare an impregnating solution. The impregnating solution was impregnated with 1000 g of carrier a by spraying, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst m.
- the metal components of the catalyst m were 22% by mass of MoO 3 (catalyst reference), 3% by mass of NiO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference).
- Table 3 shows the properties of the catalyst m.
- Example 10 Preparation of hydrodesulfurization catalyst n]
- An acidic aluminum salt aqueous solution obtained by diluting 7.17 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 13 kg of ion-exchanged water, and 1.82 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration was mixed with an aqueous solution of titanium mineral salt dissolved in 10 kg of ion-exchanged water, and further mixed with 1.88 kg of a 4.8% by mass silicic acid solution in terms of SiO 2 concentration.
- Example 2 A basic aluminum salt aqueous solution prepared by adding 8.22 kg of 22 mass% sodium aluminate aqueous solution in terms of 3 concentrations, diluted with 41 kg of ion-exchanged water, and heated to 60 ° C. has a pH of 7.2 at a constant rate.
- the difference from Example 1 is that the hydrate slurry n was added until In the same manner as in Example 1, carrier n was prepared from hydrate slurry n.
- the carrier n had a SiO 2 concentration of 3% by mass (carrier standard), a TiO 2 concentration of 20% by mass (carrier standard), and aluminum 77% by mass (based on the carrier) in terms of Al 2 O 3 concentration.
- catalyst n was produced from carrier n.
- the catalyst n contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference).
- Table 3 shows the properties of catalyst n.
- Table 1 shows the results of confirming the influence of the amount of titania in the carrier.
- the amount of titania in the support increases, the desulfurization performance improves, but when it exceeds 40%, the sharpness of the pore distribution deteriorates and the performance deteriorates.
- Table 2 shows the results of confirming the influence of the amount of silica in the support.
- the amount of silica in the carrier also exceeds 10%, the sharpness of the pore distribution deteriorates and the performance deteriorates.
- Table 3 shows the results of confirming the influence of the supported metal component. Both nickel-molybdenum and cobalt-molybdenum have high desulfurization performance.
- the catalyst of the present invention has a low temperature at which the sulfur content of the product oil becomes 7 mass ppm and is excellent in desulfurization activity.
- the carrier of the present invention is an inexpensive and high-performance catalyst whose main component is inexpensive alumina and does not significantly increase the production cost as compared with conventional alumina and alumina-silica catalysts.
- Example 11 A reaction tube (inner diameter 20 mm) filled with catalyst a (100 ml) was attached to a fixed bed flow type hydrodesulfurization apparatus. Thereafter, using straight-run gas oil added with dimethyl sulfide so that the sulfur content concentration becomes 1.5 mass%, the catalyst layer average temperature 350 ° C., hydrogen partial pressure 5.0 MPa, liquid space velocity 1.0 h ⁇ 1 , hydrogen The catalyst was presulfided for 48 hours under the condition of an oil ratio of 200 NL / L.
- Example 12 The middle east straight-run gas oil (characterized in Table 4) was hydrotreated in the same manner as in Example 11 except that the reaction temperature was 335 ° C. Table 5 shows the hydrotreating conditions and the properties of the resulting product oil.
- Example 13 A middle east straight gas oil (characterized in Table 4) was hydrogenated in the same manner as in Example 11 except that the hydrogen partial pressure was 4.0 MPa.
- Table 5 shows the hydrotreating conditions and the properties of the resulting product oil.
- Example 14 The middle east straight gas oil (characterized in Table 4) was hydrotreated in the same manner as in Example 11 except that the catalyst c was used instead of the catalyst a.
- Table 5 shows the hydrotreating conditions and the properties of the resulting product oil.
- Example 15 Hydrogenation of the catalytic cracked gas oil was performed in the same manner as in Example 11 except that the catalytic cracked gas oil (characteristics are shown in Table 4) was used instead of the Middle East straight-run gas oil. Table 5 shows the hydrotreating conditions and the properties of the resulting product oil.
- a Middle East straight gas oil (characterized in Table 4) under a hydrogen atmosphere was reacted at 350 ° C., hydrogen partial pressure 5.0 MPa, liquid space velocity 1.0 h ⁇ 1 , hydrogen / oil ratio 200 NL / The oil was passed through under the condition of L to carry out the hydrogenation treatment.
- Table 5 shows the hydrotreating conditions and the properties of the resulting product oil.
- Examples 11 to 15 satisfying the conditions of the hydrorefining method for hydrocarbon oil of the present invention can reduce sulfur content and nitrogen content to a higher degree than Comparative Example 5, and are excellent in desulfurization activity.
- the hydrodesulfurization catalyst of the present invention has a high desulfurization activity particularly in the hydrotreatment of a light oil fraction, and is extremely useful industrially.
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Abstract
Description
一般にディーゼルの主基材は、常圧蒸留塔や分解装置等から留出する軽油留分である。従って、硫黄分の低いクリーンなディーゼルを製造するためには、水素化精製装置により硫黄分を除去する必要がある。
通常、軽油の水素化精製は固定床反応塔に脱硫触媒を充填し、水素気流中、高温高圧の反応条件下で行なわれる。
チタニア担体は、アルミナ担体と比べ高脱硫性能を示すことが知られているが、一般的に比表面積が小さく、また高温での熱安定性が低いといった問題があった。チタニア含有触媒としては、チタニアゲルを用いてチタニア担体を調製する製法(特許文献1参照)、水溶性チタニア化合物をアルミナ担体に担持させアルミナ-チタニア担体を調製する製法(特許文献2参照)などが知られている。特許文献1に記載の触媒は、高価なチタニアが多く含有されており、従来のアルミナ担体を用いた触媒と比較して、価格が高くなると共に、嵩密度が高くなっていた。また、特許文献2に記載の触媒は、担体の吸水率分しかチタニアを担持できないため、チタニアを担体に高担持させるには担持工程を繰り返す必要があり、工業的に製造するには高価となっていた。また、アルミナ調製時にチタニアを混合させアルミナ中にチタニアを高分散させる製法(特許文献3参照)などもある。本製法は、チタニアをアルミナ中に高分散させることができるが、チタニアの含有量が増えるにつれチタニアの結晶化が進み易くなり比表面積が低下し、細孔分布のシャープネスが悪くなるという欠点があるうえ、これまで10質量ppm規制に対応できる十分な性能を有する触媒ではなかった。
このようにクリーンな燃料を製造する為に脱硫触媒の改良が精力的に行われてきたが、長年の研究開発にも拘らず、高い脱硫活性を満足する触媒技術はいまだに未完成である。その理由として、複数ある脱硫反応経路とそれらに有効な活性点構造が不明確であること、更に担体組成の違いが脱硫活性に異なる影響を与えることが原因と考えられる。
また、本発明は、前記の水素化脱硫触媒を用いて、水素雰囲気下で炭化水素油を水素化処理することを特徴とする炭化水素油の水素化精製方法に関する。
本発明の水素化脱硫触媒は、X線回折分析により測定されるアナターゼ型チタニア(101)面の結晶構造を示す回折ピーク面積及びルチル型チタニア(110)面の結晶構造を示す回折ピーク面積の合計の面積が、γ-アルミナ(400)面に帰属されるアルミニウム結晶構造を示す回折ピーク面積に対して、1/4以下であるシリカ-チタニア-アルミナ担体に、周期表第VIA族(IUPAC 第6族)及び第VIII族(IUPAC 第8族~第10族)から選ばれる少なくとも1種の金属成分が担持されたものであり、かつ、(a)比表面積(SA)が150m2/g以上、(b)全細孔容積(PVo)が0.30ml/g以上、(c)平均細孔直径(PD)が6~15nm(60~150Å)の範囲、および(d)平均細孔径(PD)±30%の細孔直径の細孔容積(PVp)の占める割合が全細孔容積(PVo)の70%以上のものである。
周期表第VIA族の金属成分としては、モリブデン(Mo)、タングステン(W)等を例示することができ、周期表第VIII族の金属成分としては、コバルト(Co)、ニッケル(Ni)等を例示することができる。これらの金属成分は1種を単独で又は2種以上を組合せて用いても良い。触媒性能の点から、金属成分としては、ニッケル-モリブデン、コバルト-モリブデン、ニッケル-モリブデン-コバルト、ニッケル-タングステン、コバルト-タングステン、ニッケル-タングステン-コバルト等の組合せが好ましく、特に、ニッケル-モリブデン、コバルト-モリブデン、ニッケル-モリブデン-コバルトの組合せがより好ましい。
リン酸を用いる場合、周期表第VIA族の金属成分100質量%に対してリンは酸化物換算で3~25質量%のリン酸を含有させることが好ましく、より好ましくは10~15質量%の範囲で含有されることが好ましい。含有量が25質量%を超えると触媒性能が低下する傾向にあるので好ましくなく、3質量%未満だと担持金属溶液の安定性が悪くなり好ましくない。
また、有機酸を用いる場合、有機酸は好ましくは周期表第VIA族の金属成分に対し35~75質量%、より好ましくは55~65質量%の範囲で含有されることが好ましい。有機酸が周期表第VIA族の金属成分に対し75質量%を超えると該金属成分を含有した溶液(以下、「担持金属含有溶液」ともいう。)の粘度が上がり、製造での含浸工程が困難になるため好ましくなく、35質量%未満だと担持金属含有溶液の安定性が悪くなる上、触媒性能が低下する傾向にあり好ましくない。
それぞれの回折ピーク面積の算出方法は、X線回折装置でX線回折分析によって得られたグラフを最小二乗法によりフィッティングしベースライン補正を行い、最大ピーク値からベースラインまでの高さを求め(ピーク強度W)得られたピーク強度の半分の値(W/2)のときのピーク幅(半値幅)を求め、この半値幅とピーク強度との積を回折ピーク面積とした。求めた各回折ピーク面積から、「チタニア回折ピーク面積/アルミナ回折ピーク面積」を算出した。
本発明の水素化脱硫触媒の製造方法は、珪酸イオンの存在下で、チタニウム鉱酸塩及び酸性アルミニウム塩の混合水溶液(以下、単に「混合水溶液」ともいう。)と、塩基性アルミニウム塩水溶液とを、pHが6.5~9.5になるように混合して水和物を得る第1工程と、前記水和物を順次洗浄、成型、乾燥、及び焼成して担体を得る第2工程と、前記担体に、周期表第VIA族(IUPAC 第6族)及び第VIII族(IUPAC 第8族~第10族)から選ばれる少なくとも1種の金属成分を担持する第3工程とを有する。以下、それぞれの工程について説明する。
まず、珪酸イオンの存在下で、チタニウム鉱酸塩及び酸性アルミニウム塩の混合水溶液(これは酸性の水溶液である。)と、塩基性アルミニウム塩水溶液(これはアルカリ性の水溶液である。)とを、pHが6.5~9.5、好ましくは6.5~8.5、より好ましくは6.5~7.5になるように混合して、シリカ、チタニア及びアルミナを含む水和物を得る。
ここで、(1)の場合、塩基性アルミニウム塩水溶液に含有される珪酸イオンは、塩基性または中性のものが使用できる。塩基性の珪酸イオン源としては、珪酸ナトリウムなどの水中で珪酸イオンを生じる珪酸化合物が使用可能である。また、(2)の場合、チタニウム鉱酸塩及び酸性アルミニウム塩水溶液の混合水溶液に含有される珪酸イオンは、酸性または中性のものが使用できる。酸性の珪酸イオン源としては、珪酸などの水中で珪酸イオンを生じる珪酸化合物が使用可能である。
第1工程で得られた水和物のスラリーを、所望により熟成した後、洗浄して副生塩を除き、シリカ、チタニア及びアルミナを含む水和物のスラリーを得る。得られた水和物のスラリーを、所望によりさらに加熱熟成した後、慣用の手段により、例えば、加熱捏和して成型可能な捏和物とした後、押出成型などにより所望の形状に成型し、通常70~150℃、好ましくは90~130℃で乾燥した後、更に400~800℃、好ましくは450~600℃で、0.5~10時間、好ましくは2~5時間焼成して、シリカ、チタニア及びアルミナを含むシリカ-チタニア-アルミナ担体を得る。
得られたシリカ-チタニア-アルミナ担体に、周期表第VIA族及び第VIII族から選ばれた少なくとも1種の金属成分を上述したとおり、慣用の手段(含浸法、浸漬法など)で担持した後、通常400~800℃、好ましくは450~600℃で、0.5~10時間、好ましくは2~5時間焼成し、本発明の水素化脱硫触媒を製造する。
金属成分の原料としては、例えば、硝酸ニッケル、炭酸ニッケル、硝酸コバルト、炭酸コバルト、三酸化モリブデン、モリブデン酸アンモン、パラタングステン酸アンモンなどが好ましく使用される。
本発明における炭化水素油の水素化精製方法は、上述の水素化脱硫触媒を用いて、固定床反応装置に当該触媒を充填して水素雰囲気下、高温高圧条件で炭化水素油の水素化処理を行なう。
なお、ここでいう蒸留性状(沸点)の値は、JIS K2254「石油製品‐蒸留試験方法」に記載の方法に準拠して測定される値である。
なお、ここでいう硫黄分(硫黄分濃度)の値は、JIS K2541「原油及び石油製品-硫黄分試験方法」に記載の方法に準拠して測定される値である。また窒素分(窒素分濃度)の値は、JIS K2609「原油及び石油製品-窒素分試験方法」に記載の方法に準拠して測定される値である。
容量が100Lのスチームジャケット付のタンクに、Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液8.16kgを入れ、イオン交換水41kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液1.80kgを攪拌しながら添加し、60℃に加温して、塩基性アルミニウム塩水溶液を作成した。また、Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液7.38kgを13kgのイオン交換水で希釈した酸性アルミニウム塩水溶液と、TiO2濃度換算で33質量%の硫酸チタン1.82kgを10kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合し、60℃に加温して、混合水溶液を作成した。塩基性アルミニウム塩水溶液が入ったタンクに、ローラーポンプを用いて混合水溶液をpHが7.2となるまで一定速度で添加(添加時間:10分)し、シリカ、チタニア、及びアルミナを含有する水和物スラリーaを調製した。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液8.49kgを入れ、イオン交換水37kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液1.80kgを攪拌しながら添加し、60℃に加温して作製した塩基性アルミニウム塩水溶液と、(2)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液10.62kgを19kgのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、TiO2濃度換算で33質量%の硫酸チタン0.91kgを5kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーbを調製した点が、実施例1と異なる。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、アナターゼ型チタニア及びルチル型チタニアの結晶構造を示す回折ピークが検出されず、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/4未満であった。
実施例1と同様にして、担体bから触媒bを製造した。触媒bは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表1に触媒bの性状を示す。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液7.82kgを入れ、イオン交換水44kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液1.80kgを攪拌しながら添加し、60℃に加温して作製した塩基性アルミニウム塩水溶液と、(2)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液4.14kgを7kgのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、TiO2濃度換算で33質量%の硫酸チタン2.73kgを15kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーcを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーcから担体cを調製した。担体cは、SiO2濃度が3質量%(担体基準)、TiO2濃度が30質量%(担体基準)、アルミニウムがAl2O3濃度換算で67質量%(担体基準)であった。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/5であった。
実施例1と同様にして、担体cから触媒cを製造した。触媒cは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表1に触媒cの性状を示す。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液8.82kgを入れ、イオン交換水34kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液1.80kgを攪拌しながら添加し、60℃に加温して作製した塩基性アルミニウム塩水溶液に、(2)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液13.86kgを25kgのイオン交換水で希釈した酸性アルミニウム塩水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーdを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーdから担体dを調製した。担体dは、SiO2濃度が3質量%(担体基準)、TiO2濃度が0質量%(担体基準)、アルミニウムがAl2O3濃度換算で97質量%(担体基準)であった。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、アナターゼ型チタニア及びルチル型チタニアの結晶構造を示す回折ピークが検出されず、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/4未満であった。
更に、実施例1と同様にして、担体dから触媒dを製造した。触媒dは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表1に触媒dの性状を示す。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液7.09kgを入れ、イオン交換水47kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液1.80kgを攪拌しながら添加し、60℃に加温して作製した塩基性アルミニウム塩水溶液に、(2)TiO2濃度換算で33質量%の硫酸チタン4.09kgを23kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーeを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーeから担体eを調製した。担体eは、SiO2濃度が3質量%(担体基準)、TiO2濃度が45質量%(担体基準)、アルミニウムがAl2O3濃度換算で52質量%(担体基準)であった。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/3であった。
更に、実施例1と同様にして、担体eから触媒eを製造した。触媒eは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表1に触媒eの性状を示す。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液7.79kgを入れ、イオン交換水40kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液4.20kgを攪拌しながら添加し、60℃に加温して作製した塩基性アルミニウム塩水溶液と、(2)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液6.81kgを12kgのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、TiO2濃度換算で33質量%の硫酸チタン1.82kgを10kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーfを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーfから担体fを調製した。担体fは、SiO2濃度が7質量%(担体基準)、TiO2濃度が20質量%(担体基準)、アルミニウムがAl2O3濃度換算で73質量%(担体基準)であった。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/8であった。
更に、実施例1と同様にして、担体fから触媒fを製造した。触媒fは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表2に触媒fの性状を示す。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液7.52kgを入れ、イオン交換水40kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液6.00kgを攪拌しながら添加し、60℃に加温して作製した塩基性アルミニウム塩水溶液と、(2)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液6.38kgを11kgのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、TiO2濃度換算で33質量%の硫酸チタン1.82kgを10kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーgを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーgから担体gを調製した。担体gは、SiO2濃度が10質量%(担体基準)、TiO2濃度が20質量%(担体基準)、アルミニウムがAl2O3濃度換算で70質量%(担体基準)であった。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/8であった。
更に、実施例1と同様にして、担体gから触媒gを製造した。触媒gは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表2に触媒gの性状を示す。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液8.43kgを入れ、イオン交換水41kgで希釈後、60℃に加温して作製した塩基性アルミニウム塩水溶液と、(2)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液7.81kgを14kgのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、TiO2濃度換算で33質量%の硫酸チタン1.82kgを10kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーhを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーhから担体hを調製した。担体hは、SiO2濃度が0質量%(担体基準)、TiO2濃度が20質量%(担体基準)、アルミニウムがAl2O3濃度換算で80質量%(担体基準)であった。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/4であった。
更に、実施例1と同様にして、担体hから触媒hを製造した。触媒hは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表2に触媒hの性状を示す。
(1)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液7.07kgを入れ、イオン交換水40kgで希釈後、SiO2濃度換算で5質量%の珪酸ナトリウム溶液9.00kgを攪拌しながら添加し、60℃に加温して作製した塩基性アルミニウム塩水溶液と、(2)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液5.67kgを10kgのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、TiO2濃度換算で33質量%の硫酸チタン1.82kgを10kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液とを、一定速度でpHが7.2となるまで添加して、水和物スラリーiを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーiから担体iを調製した。担体iは、SiO2濃度が15質量%(担体基準)、TiO2濃度が20質量%(担体基準)、アルミニウムがAl2O3濃度換算で65質量%(担体基準)であった。
また、実施例1と同様にX線回折分析を行った結果(図示せず)、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/8であった。
更に、実施例1と同様にして、担体iから触媒iを製造した。触媒iは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表2に触媒iの性状を示す。
担体は実施例1の担体aを用いた。
三酸化モリブデン278gと炭酸コバルト114gとを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間液容量が減少しないように適当な還流措置を施して加熱した後、リン酸68gと硝酸76gとを加えて溶解させ、含浸液を作製した。この含浸液を、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒jを得た。触媒jの金属成分は、MoO3が20質量%(触媒基準)で、CoOが5質量%(触媒基準)で、P2O5が3質量%(触媒基準)であった。触媒jの性状を表3に示す。
担体は実施例1の担体aを用いた。
三酸化モリブデン278gと炭酸コバルト114gとを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間液容量が減少しないように適当な還流措置を施して加熱した後、リン酸68gとリンゴ酸174gとを加えて溶解させ、含浸液を作製した。この含浸液を、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒kを得た。触媒kの金属成分は、MoO3が20質量%(触媒基準)で、CoOが5質量%(触媒基準)で、P2O5が3質量%(触媒基準)であった。触媒kの性状を表3に示す。
担体は実施例1の担体aを用いた。
三酸化モリブデン267gと炭酸コバルト109gとを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間液容量が減少しないように適当な還流措置を施して加熱した後、リンゴ酸167gを加えて溶解させ、含浸液を作製した。この含浸液を、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒lを得た。触媒lの金属成分は、MoO3が20質量%(触媒基準)で、CoOが5質量%(触媒基準)で、P2O5が0質量%(触媒基準)であった。触媒lの性状を表3に示す。
担体は実施例1の担体aを用いた。
三酸化モリブデン306gと炭酸ニッケル76gとを、イオン交換水500mlに懸濁させ、この懸濁液を95℃で5時間液容量が減少しないように適当な還流措置を施して加熱した後、リン酸68gを加えて溶解させ、含浸液を作製した。この含浸液を、担体a1000gに噴霧含浸させた後、250℃で乾燥し、更に電気炉にて550℃で1時間焼成して水素化脱硫触媒mを得た。触媒mの金属成分は、MoO3が22質量%(触媒基準)で、NiOが3質量%(触媒基準)で、P2O5が3質量%(触媒基準)であった。触媒mの性状を表3に示す。
(1)Al2O3濃度換算で7質量%の硫酸アルミニウム水溶液7.17kgを13kgのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、TiO2濃度換算で33質量%の硫酸チタン1.82kgを10kgのイオン交換水に溶解したチタニウム鉱酸塩水溶液を混合し、さらにSiO2濃度換算で4.8質量%珪酸液1.88kgを混合して作製した混合水溶液に、(2)Al2O3濃度換算で22質量%のアルミン酸ナトリウム水溶液8.22kgを入れ、イオン交換水41kgで希釈後、60℃に加温して作製した塩基性アルミニウム塩水溶液を、一定速度でpHが7.2となるまで添加して、水和物スラリーnを調製した点が、実施例1と異なる。
実施例1と同様にして、水和物スラリーnから担体nを調製した。担体nは、SiO2濃度が3質量%(担体基準)、TiO2濃度が20質量%(担体基準)、アルミニウムがAl2O3濃度換算で77質量%(担体基準)であった。また、実施例1と同様に担体nのX線回折分析を行った結果(図示せず)、チタニア回折ピーク面積/アルミナ回折ピーク面積は1/7であった。
実施例1と同様にして、担体nから触媒nを製造した。触媒nは、MoO3を22質量%(触媒基準)、CoOを3質量%(触媒基準)、P2O5を3質量%(触媒基準)含有していた。表3に触媒nの性状を示す。
触媒a~nを使用して、次の性状を有する原料油をザイテル社製の水素化脱硫装置により水素化処理した。ここで、生成油の硫黄分が7質量ppmとなる温度(以下、「反応温度」という)を求め、各触媒の脱硫性能を比較した。なお、水素化処理反応は以下の条件で行った。この結果を表1~3に示す。
《原料油の性状》
原料油 :直留軽油(沸点範囲208~390℃)
密度@15℃:0.8493g/cm3
硫黄分 :1.32質量%
窒素分 :105質量ppm
《反応条件》
液空間速度 :1.0hr-1
水素圧力 :4.9MPa
水素/油比 :250NL/L
以上の結果により、本発明の触媒は、生成油の硫黄分が7質量ppmとなる温度が低く、脱硫活性に優れていることが分かった。また、本発明の担体は、安価なアルミナが主成分であり従来のアルミナ及びアルミナシリカ系触媒と比較して大幅に生産コストが向上せず、安価で高性能な触媒であると言える。
触媒a(100ml)を充填した反応管(内径20mm)を固定床流通式水素化脱硫装置に取り付けた。その後、硫黄分濃度が1.5質量%となるようにジメチルサルファイドを加えた直留軽油を用いて触媒層平均温度350℃、水素分圧5.0MPa、液空間速度1.0h-1、水素/油比200NL/Lの条件下で、48時間触媒の予備硫化を行なった。
予備硫化後、水素雰囲気下、中東系直留軽油(表4に性状を示す。)を反応温度350℃、水素分圧5.0MPa、液空間速度1.0h-1、水素/油比200NL/Lの条件で通油して水素化処理を行なった。水素化処理条件及び得られた生成油の性状を表5に示す。
反応温度を335℃とした以外は実施例11と同様にして、中東系直留軽油(表4に性状を示す。)の水素化処理を行なった。水素化処理条件及び得られた生成油の性状を表5に示す。
水素分圧を4.0MPaとした以外は実施例11と同様にして、中東系直留軽油(表4に性状を示す。)の水素化処理を行なった。水素化処理条件及び得られた生成油の性状を表5に示す。
触媒aの代わりに触媒cを用いた以外は実施例11と同様にして、中東系直留軽油(表4に性状を示す。)の水素化処理を行なった。水素化処理条件及び得られた生成油の性状を表5に示す。
中東系直留軽油の代わりに接触分解軽油(表4に性状を示す。)を用いた以外は実施例11と同様にして、接触分解軽油の水素化処理を行なった。水素化処理条件及び得られた生成油の性状を表5に示す。
触媒e(100ml)を充填した反応管(内径20mm)を固定床流通式水素化脱硫装置に取り付けた。その後、硫黄分濃度が1.5質量%となるようにジメチルサルファイドを加えた直留軽油を用いて触媒層平均温度350℃、水素分圧5.0MPa、液空間速度1.0h-1、水素/油比200NL/Lの条件下で、48時間触媒の予備硫化を行なった。
予備硫化後、水素雰囲気下、中東系直留軽油(表4に性状を示す。)を反応温度350℃、水素分圧5.0MPa、液空間速度1.0h-1、水素/油比200NL/Lの条件で通油して水素化処理を行なった。水素化処理条件及び得られた生成油の性状を表5に示す。
Claims (10)
- X線回折分析により測定されるアナターゼ型チタニア(101)面の結晶構造を示す回折ピーク面積及びルチル型チタニア(110)面の結晶構造を示す回折ピーク面積の合計の面積が、γ-アルミナ(400)面に帰属されるアルミニウム結晶構造を示す回折ピーク面積に対して、1/4以下であるシリカ-チタニア-アルミナ担体に、周期表第VIA族及び第VIII族から選ばれる少なくとも1種の金属成分を担持してなる炭化水素油の水素化脱硫触媒であって、(a)比表面積(SA)が150m2/g以上、(b)全細孔容積(PVo)が0.30ml/g以上、(c)平均細孔直径(PD)が6~15nm(60~150Å)の範囲、および(d)平均細孔径(PD)±30%の細孔直径の細孔容積(PVp)の占める割合が全細孔容積(PVo)の70%以上であることを特徴とする炭化水素油の水素化脱硫触媒。
- 前記シリカ-チタニア-アルミナ担体が、担体基準で、シリカの含有量がSiO2として1~10質量%の範囲、チタニアの含有量がTiO2として3~40質量%の範囲、アルミナの含有量がAl2O3として50~96質量%の範囲であることを特徴とする請求項1記載の炭化水素油の水素化脱硫触媒。
- 前記周期表第VIA族及び第VIII族から選ばれる金属成分が、モリブデン、タングステン、コバルトおよびニッケルから選ばれることを特徴とする請求項1又は請求項2に記載の炭化水素油の水素化脱硫触媒。
- 前記周期表第VIA族及び第VIII族から選ばれる金属成分の担持量が、触媒基準で、酸化物として1~35質量%の範囲であることを特徴とする請求項1~3のいずれかに記載の炭化水素油の水素化脱硫触媒。
- 珪酸イオンの存在下で、塩基性アルミニウム塩水溶液と、チタニウム鉱酸塩及び酸性アルミニウム塩の混合水溶液とを、pHが6.5~9.5になるように混合して水和物を得る第1工程と、前記水和物を順次洗浄、成型、乾燥及び焼成して担体を得る第2工程と、前記担体に、周期表第VIA族及び第VIII族から選ばれる少なくとも1種の金属成分を担持する第3工程とを有することを特徴とする請求項1~4のいずれかに記載の炭化水素油の水素化脱硫触媒の製造方法。
- 請求項1~4に記載の水素化脱硫触媒を用いて、水素雰囲気下で炭化水素油を水素化処理することを特徴とする炭化水素油の水素化精製方法。
- 前記炭化水素油の水素化処理における反応温度が300~420℃、水素分圧が3.0~15.0MPa、液空間速度が0.5~4.0h-1、水素/油比が120~420NL/Lであることを特徴とする請求項6に記載の炭化水素油の水素化精製方法。
- 前記炭化水素油が、直留軽油、減圧軽油、接触分解軽油、水素化分解軽油および熱分解軽油から選ばれることを特徴とする請求項6又は7に記載の炭化水素油の水素化精製方法。
- 前記炭化水素油が沸点260~360℃の留分を70容量%以上含むことを特徴とする請求項6~8のいずれかに記載の炭化水素油の水素化精製方法。
- 前記炭化水素油の水素化処理によって得られる生成油の硫黄分が10質量ppm以下であり、かつ窒素分が3質量ppm以下であることを特徴とする請求項6~9のいずれかに記載の炭化水素油の水素化精製方法。
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JP2015508708A (ja) * | 2012-02-17 | 2015-03-23 | アドバンスド・リフアイニング・テクノロジーズ・エルエルシー | 残油脱金属用触媒の押出し加工品 |
US10279335B2 (en) | 2012-02-17 | 2019-05-07 | Advanced Refining Technologies Llc | Spheroidal resid hydrodemetallation catalyst |
US10584288B2 (en) | 2012-02-17 | 2020-03-10 | Advanced Refining Technologies Llc | Extruded resid demetallation catalyst |
US10589254B2 (en) | 2012-02-17 | 2020-03-17 | Advanced Refining Technologies Llc | Spheroidal resid hydrodemetallation catalyst |
WO2018180377A1 (ja) * | 2017-03-30 | 2018-10-04 | Jxtgエネルギー株式会社 | 炭化水素油の水素化脱硫触媒及び水素化脱硫触媒の製造方法 |
JP2018167196A (ja) * | 2017-03-30 | 2018-11-01 | Jxtgエネルギー株式会社 | 炭化水素油の水素化脱硫触媒及び水素化脱硫触媒の製造方法 |
US11167266B2 (en) | 2017-03-30 | 2021-11-09 | Eneos Corporation | Hydrodesulfurization catalyst for hydrocarbon oil and method for manufacturing hydrodesulfurization catalyst |
JP2020164370A (ja) * | 2019-03-29 | 2020-10-08 | Eneos株式会社 | 複合酸化物およびその製造方法 |
JP7166214B2 (ja) | 2019-03-29 | 2022-11-07 | Eneos株式会社 | 複合酸化物およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
DK2484745T3 (da) | 2021-01-25 |
EP2484745B1 (en) | 2020-11-18 |
CN102575175B (zh) | 2014-06-25 |
EP2484745A1 (en) | 2012-08-08 |
CN102575175A (zh) | 2012-07-11 |
US20120181219A1 (en) | 2012-07-19 |
SG10201406228YA (en) | 2014-11-27 |
US9067191B2 (en) | 2015-06-30 |
SG179173A1 (en) | 2012-05-30 |
EP2484745A4 (en) | 2016-01-13 |
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