JPH10180109A - Hydrodesulfurization catalyst, method for producing the catalyst, and method for hydrodesulfurization of heavy oil using the catalyst - Google Patents
Hydrodesulfurization catalyst, method for producing the catalyst, and method for hydrodesulfurization of heavy oil using the catalystInfo
- Publication number
- JPH10180109A JPH10180109A JP8341973A JP34197396A JPH10180109A JP H10180109 A JPH10180109 A JP H10180109A JP 8341973 A JP8341973 A JP 8341973A JP 34197396 A JP34197396 A JP 34197396A JP H10180109 A JPH10180109 A JP H10180109A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- mass
- hydrodesulfurization
- platinum
- platinum group
- 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 307
- 239000000295 fuel oil Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 claims abstract description 65
- 239000002184 metal Substances 0.000 claims abstract description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 17
- 230000000737 periodic effect Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 119
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 92
- 230000023556 desulfurization Effects 0.000 abstract description 92
- 239000003921 oil Substances 0.000 abstract description 50
- 230000003197 catalytic effect Effects 0.000 abstract description 44
- 239000000571 coke Substances 0.000 abstract description 15
- 230000006866 deterioration Effects 0.000 abstract description 15
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 59
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 53
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 41
- 238000002360 preparation method Methods 0.000 description 34
- 239000000377 silicon dioxide Substances 0.000 description 31
- 238000010521 absorption reaction Methods 0.000 description 28
- 229920006395 saturated elastomer Polymers 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 22
- 239000008188 pellet Substances 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- -1 Usually Chemical compound 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 150000004687 hexahydrates Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 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 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000004035 Cryptotaenia japonica Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 102000007641 Trefoil Factors Human genes 0.000 description 1
- 235000015724 Trifolium pratense Nutrition 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 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
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GBDZMMXUOBAJMN-UHFFFAOYSA-K azane;ruthenium(3+);trichloride Chemical compound N.N.N.N.N.N.[Cl-].[Cl-].[Cl-].[Ru+3] GBDZMMXUOBAJMN-UHFFFAOYSA-K 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 1
- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
(57)【要約】
【課題】間接脱硫装置による減圧軽油留分や直接脱硫装
置による常圧残油留分の接触水素化脱硫において、コー
ク劣化による触媒活性の低下が極めて少なく、上記重質
油留分中の硫黄化合物を長期間、高率にて除去すること
ができ、更に、上記重質油留分を軽質化することができ
る水素化脱硫触媒を提供することにある。
【解決手段】本発明による重質油の水素化脱硫触媒は、
(a) 周期律表鉄族から選ばれる少なくとも１種の金属が
酸化物換算にて３〜７ｍａｓｓ％と周期律表第VIＡ族か
ら選ばれる少なくとも１種の金属が酸化物換算にて１０
〜３０ｍａｓｓ％と残部が無機酸化物担体とからなる基
体触媒と、(b) 周期律表白金族から選ばれる少なくとも
１種の金属が金属換算にて0.２〜１０ｍａｓｓ％と残部
が無機酸化物担体とからなる白金族触媒とからなり、上
記基体触媒の表面に上記白金族触媒が基体触媒１００ｍ
ａｓｓ部当りに１〜２０ｍａｓｓ部の範囲にてコーティ
ングされてなることを特徴とする。(57) [Summary] [PROBLEMS] In the catalytic hydrodesulfurization of a reduced pressure gas oil fraction by an indirect desulfurization unit and a normal pressure residual oil fraction by a direct desulfurization unit, the reduction in catalytic activity due to coke deterioration is extremely small. An object of the present invention is to provide a hydrodesulfurization catalyst capable of removing sulfur compounds in a fraction at a high rate for a long period of time and further reducing the weight of the heavy oil fraction. The heavy oil hydrodesulfurization catalyst according to the present invention comprises:
(a) At least one metal selected from the iron group of the periodic table is 3 to 7 mass% in terms of oxide, and at least one metal selected from group VIA in the periodic table is 10 in terms of oxide.
(B) at least one metal selected from the platinum group of the periodic table in the range of 0.2 to 10 mass% in terms of metal, and the balance being inorganic oxide; A platinum-group catalyst comprising a support, and the platinum-group catalyst having a surface area of 100 m
It is characterized by being coated in the range of 1 to 20 mass parts per ass part.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、間接脱硫装置によ
る減圧軽油（以下、ＶＧＯという。）留分又は直接脱硫
装置による常圧残油（以下、ＡＲという。）留分の接触
水素化脱硫において、コーク劣化がよく抑えられて、上
記重質油留分中の硫黄化合物を長期間、高率にて除去す
ることができ、更に、上記重質油留分を軽質化すること
もできる重質油の水素化脱硫触媒、そのような水素化脱
硫触媒の製造方法及びそのような水素化脱硫触媒を用い
る重質油の水素化脱硫方法に関する。The present invention relates to the catalytic hydrodesulfurization of a vacuum gas oil (hereinafter referred to as VGO) fraction by an indirect desulfurization unit or an atmospheric residue (hereinafter referred to as AR) fraction by a direct desulfurization unit. , The coke deterioration is well suppressed, the sulfur compounds in the heavy oil fraction can be removed for a long time at a high rate, and the heavy oil fraction can also be lightened. The present invention relates to an oil hydrodesulfurization catalyst, a method for producing such a hydrodesulfurization catalyst, and a method for hydrodesulfurizing heavy oil using such a hydrodesulfurization catalyst.
【０００２】[0002]
【従来の技術】減圧蒸留装置から得られる留出油である
ＶＧＯや、原油を常圧蒸留装置で処理したときの塔底油
であるＡＲ等の重質油留分中には、硫黄化合物が高濃度
に存在するので、これらの重質油留分をそのまま燃料と
して用いた場合には、硫黄酸化物（ＳＯｘ）が大気中に
大量に排出される。硫黄酸化物は、人体に直接、有害な
影響を及ぼし、また、酸性雨の原因物質の一つでもあ
る。2. Description of the Related Art Sulfur compounds are contained in heavy oil fractions such as VGO, which is a distillate obtained from a vacuum distillation unit, and AR, which is a bottom oil when crude oil is processed by an atmospheric distillation unit. Since these heavy oil fractions are used as fuels as they are at high concentrations, large amounts of sulfur oxides (SOx) are emitted into the atmosphere. Sulfur oxides have a direct and harmful effect on the human body and are one of the causative agents of acid rain.
【０００３】そこで、従来、原油から種々の石油製品を
製造する工程の一つとして、間接脱硫装置や直接脱硫装
置による重質油留分の接触水素化脱硫処理が取り入れら
れ、これら重質油留分中の硫黄化合物を除去すること、
即ち、脱硫処理がなされているが、この脱硫に際して、
重質油留分の水素化分解も同時に進行するので、ナフ
サ、灯油、軽油等のような付加価値のより高い軽質留分
も生成する。Therefore, conventionally, as one of the processes for producing various petroleum products from crude oil, catalytic hydrodesulfurization treatment of heavy oil fractions by an indirect desulfurization unit or a direct desulfurization unit has been adopted. Removing sulfur compounds in the minute,
That is, although desulfurization treatment is performed, in this desulfurization,
Since the hydrocracking of the heavy oil fraction proceeds at the same time, higher value-added light fractions such as naphtha, kerosene, and gas oil are also produced.
【０００４】従来、ＶＧＯやＡＲ中の硫黄化合物を除去
すると同時に軽質化することを目的とする水素化脱硫処
理のための触媒は、周期律表第VIＡ族の金属と鉄族の金
属を活性成分とし、これらをアルミナ、マグネシア、シ
リカ等の無機酸化物担体に担持させてなる触媒であり、
通常、第VIＡ族金属としては、モリブデンが用いられ、
また、鉄族金属としては、コバルトやニッケルが用いら
れている。ここに、上記第VIＡ族金属は、脱硫触媒にお
ける必須の活性成分であって、これを硫化処理して硫化
物とすることによって、水素化脱硫活性が発現すると考
えられている。[0004] Conventionally, a catalyst for hydrodesulfurization treatment for the purpose of removing sulfur compounds in VGO and AR and at the same time reducing the weight of the compounds is composed of a group VIA metal of the periodic table and an iron group metal as active components. And these are alumina, magnesia, a catalyst which is supported on an inorganic oxide carrier such as silica,
Usually, molybdenum is used as the Group VIA metal,
Further, cobalt or nickel is used as the iron group metal. Here, the Group VIA metal is an essential active component in the desulfurization catalyst, and it is considered that hydrodesulfurization activity is exhibited by subjecting the group VIA to sulfuration treatment.
【０００５】更に、上述したような脱硫触媒の活性を向
上させるために、従来、触媒にリン、ホウ素等を添加す
ることが有効であることが知られている（特開昭５２−
１３５０３号公報）。また、上記担体中にゼオライトを
含有させることによって、活性を向上させ得ることも知
られている（特開昭５６−２００８７号公報）。Further, it has been conventionally known that it is effective to add phosphorus, boron or the like to the catalyst in order to improve the activity of the above-mentioned desulfurization catalyst (Japanese Patent Laid-Open No. 52-1982).
No. 13503). It is also known that the activity can be improved by adding zeolite to the carrier (Japanese Patent Application Laid-Open No. 56-20087).
【０００６】重質油留分の接触水素化脱硫処理は、間接
脱硫装置や直接脱硫装置の反応器中において、上述した
ような脱硫触媒の存在下に行なわれるが、実装置での商
業運転においては、従来、触媒の劣化が重要な問題とさ
れている。そこで、実運転においては、水素化脱硫反応
が高温ほど促進されるという特性を利用して、触媒の劣
化を反応温度の上昇によって補うという対処がなされて
いる。しかしながら、反応温度の上昇には、自ずから上
限があるので、反応温度がそのような上限温度に到達す
れば、上述したような対処によっては、最早、触媒の劣
化を補うことができなくなり、かくして、脱硫触媒は寿
命を迎えることとなる。上記接触水素化脱硫反応の上限
温度は、脱硫を目的とする原料油や用いる装置の種類に
よって、必ずしも一定しないが、通常、４１０℃程度で
あり、商業運転においては、このような上限温度の観点
から、通常、一年ごとに触媒が交換されている。従っ
て、従来、初期の脱硫活性が高く、且つ、劣化が小さい
水素化脱硫触媒が要望されている。 水素化脱硫処理に
おける触媒の劣化の要因としては、第一には、重質油留
分中のニッケル、バナジウム等の含有金属分によるもの
（メタル劣化）と、第二には、コーク析出によるもの
（コーク劣化）が主たるものとして挙げられる。このう
ち、メタル劣化は、触媒上へのメタル蓄積量の増加に伴
って進行し、不可逆的なものである。これに対して、コ
ーク劣化は、コーク生成と生成コークの水素化との間に
平衡が存在するので、可逆的である（化学工学会編「化
学工学の進歩」第２９集触媒工学）。[0006] The catalytic hydrodesulfurization treatment of a heavy oil fraction is carried out in the reactor of an indirect desulfurization unit or a direct desulfurization unit in the presence of a desulfurization catalyst as described above. Conventionally, deterioration of the catalyst has been regarded as an important problem. Therefore, in actual operation, measures have been taken to compensate for the deterioration of the catalyst by increasing the reaction temperature, utilizing the property that the hydrodesulfurization reaction is accelerated as the temperature increases. However, since the reaction temperature rise naturally has an upper limit, if the reaction temperature reaches such an upper limit temperature, by the above-described measures, it is no longer possible to compensate for the deterioration of the catalyst, and thus, The desulfurization catalyst will end its life. The upper limit temperature of the catalytic hydrodesulfurization reaction is not necessarily constant depending on the type of feedstock and the equipment used for the purpose of desulfurization, but is usually about 410 ° C. Therefore, the catalyst is usually replaced every year. Therefore, conventionally, a hydrodesulfurization catalyst having a high initial desulfurization activity and small deterioration has been demanded. The causes of catalyst degradation in hydrodesulfurization treatment are, firstly, due to metals contained in heavy oil fractions such as nickel and vanadium (metal degradation), and secondly, due to coke precipitation. (Coke degradation) is a major example. Of these, metal degradation proceeds with an increase in the amount of metal accumulated on the catalyst, and is irreversible. On the other hand, coke degradation is reversible because there is an equilibrium between coke formation and hydrogenation of the produced coke (Chemical Engineering Society, "Progress of Chemical Engineering" Vol. 29, Catalytic Engineering).
【０００７】[0007]
【発明が解決しようとする課題】本発明者らは、従来の
重質油の水素化脱硫触媒における上述したような問題を
解決するために、コーク劣化をよく抑制すれば、触媒寿
命を長くすることができ、かくして、ＶＧＯやＡＲ等の
重質油留分中の硫黄化合物を長期間にわたって高率で除
去することができ、それに伴って、ナフサ、灯油、軽油
等の軽質留分の増産も可能となる点に着目して、鋭意研
究を行なった。その結果、本発明者らは、周期律表鉄族
金属と第VIＡ族金属を無機酸化物担体に担持させてなる
基体触媒の表面に、白金族金属から選ばれる少なくとも
１種の金属を無機酸化物担体に担持させてなる白金族触
媒をコーティングして、複層構造を有する水素化脱硫触
媒とすることによって、ＶＧＯやＡＲのような重質油の
水素化脱硫において、コーク劣化がよく抑制されて、触
媒活性の低下が極めて少ないことを見出して、本発明を
完成するに至ったものである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems in the conventional heavy oil hydrodesulfurization catalyst, the present inventors have proposed to prolong the life of the catalyst if coke deterioration is well suppressed. As a result, sulfur compounds in heavy oil fractions such as VGO and AR can be removed at a high rate over a long period of time, and accordingly, the production of light fractions such as naphtha, kerosene and gas oil can be increased. Focusing on the possible points, we conducted intensive research. As a result, the present inventors have found that at least one metal selected from the platinum group metals is subjected to inorganic oxidation on the surface of a base catalyst comprising an iron group metal and a group VIA metal supported on an inorganic oxide carrier. By coating a platinum group catalyst supported on a material carrier to form a hydrodesulfurization catalyst having a multilayer structure, coke deterioration is well suppressed in hydrodesulfurization of heavy oils such as VGO and AR. As a result, the inventors have found that the reduction in the catalytic activity is extremely small, and have completed the present invention.
【０００８】即ち、本発明は、間接脱硫装置によるＶＧ
Ｏや直接脱硫装置によるＡＲの接触水素化脱硫におい
て、コーク劣化による触媒活性の低下が極めて少なく、
上記重質油留分中の硫黄化合物を長期間、高率にて除去
することができ、更に、上記重質油留分を軽質化するこ
とができる水素化脱硫触媒を提供することを目的とす
る。更に、本発明は、そのような水素化脱硫触媒の製造
方法とそのような水素化脱硫触媒を用いる重質油の水素
化脱硫方法を提供することを目的とする。[0008] That is, the present invention relates to a VG using an indirect desulfurization apparatus.
In catalytic hydrodesulfurization of AR with O and direct desulfurization equipment, the decrease in catalytic activity due to coke deterioration is extremely small,
It is an object of the present invention to provide a hydrodesulfurization catalyst capable of removing sulfur compounds in the heavy oil fraction for a long period of time at a high rate and further reducing the weight of the heavy oil fraction. I do. Further, another object of the present invention is to provide a method for producing such a hydrodesulfurization catalyst and a method for hydrodesulfurizing heavy oil using such a hydrodesulfurization catalyst.
【０００９】[0009]
【課題を解決するための手段】本発明による水素化脱硫
触媒は、(a) 周期律表鉄族から選ばれる少なくとも１種
の金属が酸化物換算にて３〜７ｍａｓｓ％と周期律表第
VIＡ族から選ばれる少なくとも１種の金属が酸化物換算
にて１０〜３０ｍａｓｓ％と残部が無機酸化物担体とか
らなる基体触媒と、(b) 周期律表白金族から選ばれる少
なくとも１種の金属が金属換算にて0.２〜１０ｍａｓｓ
％と残部が無機酸化物担体とからなる白金族触媒とから
なり、上記基体触媒の表面に上記白金族触媒が基体触媒
１００ｍａｓｓ部当りに１〜２０ｍａｓｓ部の範囲にて
コーティングされてなることを特徴とする。The hydrodesulfurization catalyst according to the present invention is characterized in that (a) at least one metal selected from the iron group of the periodic table is 3 to 7 mass% in terms of oxides,
A base catalyst comprising at least one metal selected from the group VIA in an amount of 10 to 30 mass% in terms of oxide and the balance being an inorganic oxide carrier; and (b) at least one metal selected from the platinum group of the periodic table Is 0.2 to 10 mass in metal conversion
% And the balance being a platinum group catalyst comprising an inorganic oxide carrier, wherein the surface of the base catalyst is coated with the platinum group catalyst in a range of 1 to 20 mass parts per 100 mass parts of the base catalyst. And
【００１０】本発明によるこのような水素化脱硫触媒
は、粒子径が１０〜１００μｍの範囲にある白金族触媒
の粒子を水に懸濁させて、スラリーとし、このスラリー
を基体触媒にコーティングし、乾燥させ、焼成して、上
記基体触媒の表面に上記白金族触媒がコーティングされ
てなる上記脱硫触媒の製造方法において、好ましくは、
上記基体触媒の飽和吸水量に対して、質量比にて、1.５
〜５倍であり、且つ、上記白金族触媒の粒子に対して、
質量比にて、２０〜２００倍の範囲の量の水に上記白金
族触媒の粒子を懸濁させて、スラリーとすることによっ
て、製造することができる。Such a hydrodesulfurization catalyst according to the present invention is obtained by suspending particles of a platinum group catalyst having a particle diameter in the range of 10 to 100 μm in water to form a slurry, coating the slurry on a base catalyst, Drying and calcining, in the method for producing a desulfurization catalyst in which the surface of the base catalyst is coated with the platinum group catalyst, preferably,
1.5% by mass with respect to the saturated water absorption of the base catalyst.
~ 5 times, and for the platinum group catalyst particles,
It can be produced by suspending the particles of the platinum group catalyst in water in an amount of 20 to 200 times by mass ratio to form a slurry.
【００１１】更に、本発明による重質油の水素化脱硫方
法は、水素分圧４〜１８ＭＰａ、温度３２０〜４１０℃
及び液空間速度0.１〜4.０ｈｒ-1の反応条件下に、重質
油を上記触媒と接触させることを特徴とする。Further, the method for hydrodesulfurization of heavy oil according to the present invention comprises a hydrogen partial pressure of 4 to 18 MPa and a temperature of 320 to 410 ° C.
And contacting the heavy oil with the catalyst under the reaction conditions of a liquid hourly space velocity of 0.1 to 4.0 hr -1 .
【００１２】[0012]
【発明の実施の形態】本発明による重質油の水素化脱硫
触媒は、(a) 周期律表鉄族から選ばれる少なくとも１種
の金属が酸化物換算にて３〜７ｍａｓｓ％と周期律表第
VIＡ族から選ばれる少なくとも１種の金属が酸化物換算
にて１０〜３０ｍａｓｓ％と残部が無機酸化物担体とか
らなる基体触媒と、(b) 周期律表白金族から選ばれる少
なくとも１種の金属が金属換算にて0.２〜１０ｍａｓｓ
％と残部が無機酸化物担体とからなる白金族触媒とから
なり、上記基体触媒の表面に上記白金族触媒が基体触媒
１００ｍａｓｓ部当りに１〜２０ｍａｓｓ部の範囲にて
コーティングされてなることを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The catalyst for hydrodesulfurization of heavy oil according to the present invention comprises: (a) at least one metal selected from the iron group of the periodic table is 3 to 7 mass% in terms of oxide; No.
A base catalyst comprising at least one metal selected from the group VIA in an amount of 10 to 30 mass% in terms of oxide and the balance being an inorganic oxide carrier; and (b) at least one metal selected from the platinum group of the periodic table Is 0.2 to 10 mass in metal conversion
% And the balance being a platinum group catalyst comprising an inorganic oxide carrier, wherein the surface of the base catalyst is coated with the platinum group catalyst in a range of 1 to 20 mass parts per 100 mass parts of the base catalyst. And
【００１３】本発明による水素化脱硫触媒は、成形固体
触媒である基体触媒と、その表面にコーティングされて
なる白金族触媒とからなる複層構造を有する。このよう
な複層構造を有する触媒において、上記基体触媒と白金
族触媒における無機酸化物担体は、同じであってもよ
く、異なっていてもよく、従来、水素化脱硫触媒の担体
として用いられているものであれば、適宜のものを用い
ることができる。従って、このような無機酸化物担体と
して、例えば、シリカ、アルミナ、ボリア、マグネシ
ア、チタニア、シリカ−アルミナ、シリカ−マグネシ
ア、シリカ−ジルコニア、シリカ−トリア、シリカ−ベ
リリア、シリカ−チタニア、シリカ−ボリア、アルミナ
−ジルコニア、アルミナ−チタニア、アルミナ−ボリ
ア、アルミナ−クロミア、チタニア−ジルコニア、シリ
カ−アルミナ−トリア、シリカ−アルミナ−ジルコニ
ア、シリカ−アルミナ−マグネシア、シリカ−マグネシ
ア−ジルコニア等を挙げることができ、これらは単独
で、又は２種以上を組み合わせて用いることができる。The hydrodesulfurization catalyst according to the present invention has a multilayer structure comprising a base catalyst which is a molded solid catalyst, and a platinum group catalyst coated on the surface thereof. In the catalyst having such a multilayer structure, the inorganic oxide carrier in the base catalyst and the platinum group catalyst may be the same or different, and is conventionally used as a carrier for a hydrodesulfurization catalyst. Any suitable one can be used. Accordingly, as such inorganic oxide carriers, for example, silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, silica-boria , Alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia and the like. These can be used alone or in combination of two or more.
【００１４】しかし、本発明によれば、これらのなかで
も、鉄族金属及び第VIＡ族金属の脱硫活性を最大限に発
揮させる好ましい担体として、アルミナ、シリカ−アル
ミナ、アルミナ−チタニア、アルミナ−ボリア又はアル
ミナ−ジルコニアを挙げることができ、特に、本発明に
よれば、アルミナが好ましく用いられる。However, according to the present invention, among these, alumina, silica-alumina, alumina-titania, alumina-boria, and the like are preferred as the preferable carrier for maximizing the desulfurization activity of the iron group metal and the group VIA metal. Or alumina-zirconia can be mentioned, and in particular, according to the present invention, alumina is preferably used.
【００１５】また、本発明によれば、必要に応じて、Ａ
型ゼオライト、Ｙ型ゼオライト、安定化Ｙ型ゼオライ
ト、超安定化Ｙ型ゼオライト、Ｌ型ゼオライト、ＺＳＭ
−５型ゼオライト等の結晶性アルミノケイ酸塩や、モン
モリロナイト、カオリン、ハロサイト、ベントナイト、
アダバルガイト、ボーキサイト、カオリナイト、ナクラ
イト、アノーキサイト等の粘土鉱物を単独で、又は２種
以上を組み合わせて、上記無機酸化物担体に配合し、こ
れを担体として用いてもよい。According to the present invention, if necessary, A
Zeolite, Y zeolite, stabilized Y zeolite, ultra-stabilized Y zeolite, L zeolite, ZSM
Crystalline aluminosilicates such as -5 type zeolite, montmorillonite, kaolin, hallosite, bentonite,
Clay minerals such as adavalgite, bauxite, kaolinite, nacrite, anoxite and the like may be used alone or in combination of two or more kinds in the inorganic oxide carrier and used as the carrier.
【００１６】本発明において、担体は、その比表面積、
細孔容積、平均細孔径等において、特に、限定されるも
のではないが、ＶＧＯやＡＲの水素化脱硫反応を促進さ
せるためには、通常、比表面積は２００〜４００ｍ2 ｇ
-1、細孔容積は0.４〜1.２ｃｍ3 ｇ-1、平均細孔径は５
０〜１３０Å（オングストローム）が好ましい。In the present invention, the carrier has a specific surface area,
Although there is no particular limitation on the pore volume, average pore diameter, etc., in order to promote the hydrodesulfurization reaction of VGO or AR, the specific surface area is usually 200 to 400 m 2 g.
-1 , pore volume is 0.4 to 1.2 cm 3 g -1 , average pore diameter is 5
0-130 ° (angstrom) is preferred.
【００１７】担体に鉄族金属と第VIＡ族金属とを担持さ
せてなる基体触媒を調製する方法は、特に、限定される
ものではなく、従来、知られている適宜の方法によるこ
とができ、例えば、鉄族金属と第VIＡ族金属を従来より
知られている含浸法、共沈法、混練法、沈着法等によっ
て、担体に担持させればよい。The method for preparing a base catalyst comprising a support carrying an iron group metal and a group VIA metal is not particularly limited, and may be a conventionally known suitable method. For example, the iron group metal and the group VIA metal may be supported on a carrier by a conventionally known impregnation method, coprecipitation method, kneading method, deposition method, or the like.
【００１８】例えば、含浸法によれば、鉄族金属の化合
物と第VIＡ族金属の化合物との適当の濃度の溶液を担体
に含浸させ、乾燥させた後、空気中、３５０〜７００
℃、好ましくは、４００〜６００℃の範囲の温度で、限
定されるものではないが、通常、１〜１０時間程度、焼
成することによって、基体触媒を調製することができ
る。空気中での焼成温度は約３５０〜７００℃、好まし
くは約４００〜６００℃であり、時間は約１〜１０時間
である。しかし、必要ならば、担体を先ず、鉄族金属の
化合物の適当の濃度の溶液を含浸させ、乾燥させた後、
空気中で焼成し、次いで、このように処理した担体を第
VIＡ族金属の化合物の適当の濃度の溶液に含浸させ、乾
燥させた後、空気中で焼成してもよい。担体に第VIＡ族
金属を担持させた後、鉄族金属を担持させてもよい。For example, according to the impregnation method, a carrier is impregnated with a solution of a compound of an iron group metal and a compound of a group VIA metal having an appropriate concentration, dried, and then dried in air at 350-700.
The base catalyst can be prepared by baking at a temperature of preferably from 400 to 600 ° C. for about 1 to 10 hours. The firing temperature in air is about 350-700 ° C, preferably about 400-600 ° C, and the time is about 1-10 hours. However, if necessary, the support is first impregnated with a solution of the compound of the iron group metal at a suitable concentration and dried,
The carrier calcined in air and then treated in this way is
It may be impregnated with a solution of an appropriate concentration of a compound of a VIA metal, dried, and then calcined in air. After the group VIA metal is supported on the carrier, the iron group metal may be supported.
【００１９】本発明によれば、鉄族の金属としては、
鉄、コバルト又はニッケルが用いられるが、好ましく
は、コバルト又はニッケルが用いられる。これらの鉄族
金属の化合物としては、種々のものを用いることができ
るが、例えば、硝酸塩、硫酸塩、炭酸塩、酢酸塩、シュ
ウ酸塩、塩化物等が好ましく用いられる。従って、鉄化
合物としては、硝酸第二鉄、塩化第二鉄、シュウ酸第一
鉄等を挙げることができ、コバルト化合物としては、例
えば、硝酸コバルト、硫酸コバルト、炭酸コバルト、酢
酸コバルト、シュウ酸コバルト、塩化コバルト等を挙げ
ることができ、また、ニッケル化合物としては、例え
ば、硝酸ニッケル、硫酸ニッケル、炭酸ニッケル、酢酸
ニッケル、シュウ酸ニッケル、塩化ニッケル等を挙げる
ことができる。According to the present invention, the iron group metal includes
Iron, cobalt or nickel is used, but preferably cobalt or nickel is used. Various compounds can be used as these iron group metal compounds. For example, nitrates, sulfates, carbonates, acetates, oxalates, chlorides and the like are preferably used. Therefore, examples of the iron compound include ferric nitrate, ferric chloride, and ferrous oxalate. Examples of the cobalt compound include cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt acetate, and oxalic acid. Examples of the nickel compound include cobalt nitrate, nickel sulfate, nickel carbonate, nickel acetate, nickel oxalate, and nickel chloride.
【００２０】また、第VIＡ族金属としては、クロム、モ
リブデン又はタングステンが用いられるが、特に、モリ
ブデン又はタングステンが好ましく用いられる。これら
第VIＡ族金属の化合物も、種々のものを用いることがで
きるが、モリブデン化合物の具体例として、例えば、モ
リブデン酸アンモニウム、酸化モリブデン、モリブデン
縮合酸塩等が挙げることができる。また、タングステン
合物の具体例として、例えば、タングステン酸アンモニ
ウム、酸化タングステン、タングステン縮合酸塩等を挙
げることができる。As the Group VIA metal, chromium, molybdenum or tungsten is used. In particular, molybdenum or tungsten is preferably used. Various compounds of the group VIA metal can be used. Specific examples of the molybdenum compound include, for example, ammonium molybdate, molybdenum oxide, and molybdenum condensate. Specific examples of the tungsten compound include, for example, ammonium tungstate, tungsten oxide, and tungsten condensate.
【００２１】上述した鉄族及び第VIＡ族の金属化合物の
溶液としては、通常、水溶液が好ましく用いられる、そ
こで、これら化合物の水溶液における水溶性を高めるた
めに、水溶液にリン酸を加えてもよい。ここに、リン酸
としては、オルトリン酸、メタリン酸、三リン酸、四リ
ン酸等の種々のものを用いることができる。また、上記
化合物の溶液のための溶媒として、水以外にも、アルコ
ール類、エーテル類、ケトン類、これらの水溶液、芳香
族炭化水素類等、種々の溶媒を単独で、又は２種以上の
混合物として用いることもできる。As the solution of the above-mentioned metal compound of the iron group and the group VIA, an aqueous solution is usually preferably used. Therefore, phosphoric acid may be added to the aqueous solution in order to increase the water solubility of these compounds in the aqueous solution. . Here, various phosphoric acids such as orthophosphoric acid, metaphosphoric acid, triphosphoric acid, and tetraphosphoric acid can be used. In addition, as a solvent for the solution of the compound, in addition to water, various solvents such as alcohols, ethers, ketones, aqueous solutions thereof, aromatic hydrocarbons, and the like, or a mixture of two or more kinds thereof Can also be used.
【００２２】上記鉄族及び第VIＡ族の金属化合物の溶液
におけるそれぞれの金属化合物の量は、得られる基体触
媒において、鉄族金属が酸化物換算で３〜７ｍａｓｓ
％、好ましくは、４〜６ｍａｓｓ％、第VIＡ族金属が酸
化物換算で１０〜３０ｍａｓｓ％、好ましくは、１３〜
２３ｍａｓｓ％、無機酸化物担体が残部となるように用
いられる。The amount of each metal compound in the solution of the metal compound of the iron group and the group VIA may be 3 to 7 mass in terms of oxide in the obtained base catalyst.
%, Preferably 4 to 6 mass%, and the amount of the Group VIA metal is 10 to 30 mass%, preferably 13 to
23 mass%, the inorganic oxide carrier is used so as to be the balance.
【００２３】上述したように、金属化合物の水溶液にリ
ン酸を配合する場合には、リン酸は、基体触媒中、Ｐ2
Ｏ5 換算にて、0.１〜４ｍａｓｓ％、好ましくは、１〜
３ｍａｓｓ％となるように用いられる。このリン酸の量
は、無機酸化物担体の量に含まれるものとるする。As described above, when phosphoric acid is added to an aqueous solution of a metal compound, phosphoric acid is added to the base catalyst in the presence of P 2.
At O 5 converted, 0.1～4Mass%, preferably, 1 to
It is used so as to be 3 mass%. The amount of the phosphoric acid is included in the amount of the inorganic oxide carrier.
【００２４】本発明において、基体触媒中の鉄族金属成
分が３ｍａｓｓ％未満であるときは、得られる触媒が所
要の脱硫触媒活性において十分でなく、他方、７ｍａｓ
ｓ％を越えるときは、その金属成分の使用条件下におけ
る化合物（硫化物）の状態では、高い分散状態を維持し
難いためとみられるが、著しいシンタリング（焼結）が
発生し、触媒活性が低下しやすい傾向がある。同様に、
第VIＡ族金属成分が１０ｍａｓｓ％未満であるときは、
得られる触媒が所要の脱硫触媒活性において十分でな
く、他方、第VIＡ族金属成分は、金属成分の使用条件下
における化合物（硫化物）の状態では、前記鉄族金属に
比べて、高い分散状態を維持することができるとみられ
るが、しかし、３０ｍａｓｓ％を越えるときは、同様
に、シンタリング（焼結）が生じ、触媒の比表面積が小
さくなって、高い触媒活性を得ることができない。In the present invention, when the iron group metal component in the base catalyst is less than 3 mass%, the obtained catalyst is not sufficient in the required desulfurization catalytic activity, while the
When the content exceeds s%, it is considered that it is difficult to maintain a high dispersion state in the state of the compound (sulfide) under the use condition of the metal component, but remarkable sintering (sintering) occurs and the catalytic activity is reduced. It tends to decrease. Similarly,
When the Group VIA metal component is less than 10 mass%,
The resulting catalyst is not sufficient in the required desulfurization catalytic activity, whereas the Group VIA metal component has a higher dispersion state in the compound (sulfide) state under the conditions of use of the metal component than the iron group metal. However, when it exceeds 30 mass%, sintering (sintering) similarly occurs, the specific surface area of the catalyst becomes small, and high catalyst activity cannot be obtained.
【００２５】本発明において、基体触媒は、成形固体触
媒であって、その形状は、ＶＧＯやＡＲ等の重質油留分
の触媒層の流通を考慮し、円柱状、三葉柱状、四葉柱状
のペレット形状であることが望ましいが、しかし、反応
条件下で触媒層の前後で圧力差が発生しないものであれ
ば、その形状は、特に限定されない。同様に、このペレ
ットも、反応条件下で触媒層の前後で圧力差が発生しな
いように、ペレット径は、１／１０〜１／３６インチの
範囲にあることが好ましい。ここに、ペレット径は、ペ
レットの形状が円柱であるもの以外は、その最も太い部
分の長さとする。In the present invention, the base catalyst is a shaped solid catalyst, and its shape is cylindrical, trilobular, or tetralobular in consideration of the distribution of the catalyst layer of a heavy oil fraction such as VGO or AR. The shape of the pellet is preferably, but the shape is not particularly limited as long as no pressure difference occurs before and after the catalyst layer under the reaction conditions. Similarly, the pellet diameter is preferably in the range of 1/10 to 1/36 inches so that no pressure difference occurs before and after the catalyst layer under the reaction conditions. Here, the diameter of the pellet is the length of the thickest portion of the pellet except for the pellet having a cylindrical shape.
【００２６】本発明による水素化脱硫触媒は、以上のよ
うな基体触媒の表面に白金族から選ばれる少なくとも１
種の金属を無機酸化物担体に担持させてなる白金族触媒
をコーティングすることによって得ることができる。The hydrodesulfurization catalyst according to the present invention comprises at least one member selected from the platinum group on the surface of the base catalyst as described above.
It can be obtained by coating a platinum group catalyst in which a seed metal is supported on an inorganic oxide carrier.
【００２７】この白金族触媒も、その調製方法について
は、特に、制限はなく、従来より知られている適宜の方
法、例えば、含浸法、共沈法、混練法、沈着法、イオン
交換法等、種々の方法にて、調製することができる。無
機酸化物担体も、前述したように、種々の無機酸化物を
用いることができるが、通常、シリカ、アルミナ、マグ
ネシア等が好ましく用いられる。The method for preparing this platinum group catalyst is not particularly limited, either, and any conventionally known suitable method, for example, an impregnation method, a coprecipitation method, a kneading method, a deposition method, an ion exchange method, etc. Can be prepared by various methods. As described above, various inorganic oxides can be used as the inorganic oxide carrier, but usually, silica, alumina, magnesia and the like are preferably used.
【００２８】白金族金属としては、白金、パラジウム、
ロジウム、ルテニウム、イリジウム又はオスミウムを挙
げることができ、これらのなかでは、特に、白金、パラ
ジウム、ロジウム、ルテニウム又はイリジウムが好まし
い。白金化合物としては、例えば、塩化白金酸、ジニト
ロジアミン白金等を、パラジウム化合物としては、例え
ば、塩化パラジウム、テトラアンミンジクロロパラジウ
ム、テトラアンミンジニトロパラジウム、硝酸パラジウ
ム等を、ロジウム化合物としては、例えば、塩化ロジウ
ム、ヘキサアンミントリクロロロジウム、硝酸ロジウム
等を、ルテニウム化合物としては、例えば、塩化ルテニ
ウム、ヘキサアンミントリクロロルテニウム、ヘキサア
ンミントリニトロルテニウム等を、また、イリジウム化
合物としては、例えば、塩化イリジウム、硫酸イリジウ
ム、ヘキサクロロジアミンイリジウム等を挙げることが
できる。これらは単独で、又は２種以上を組み合わせて
用いることができる。Platinum group metals include platinum, palladium,
Rhodium, ruthenium, iridium or osmium can be mentioned, and among them, platinum, palladium, rhodium, ruthenium or iridium is particularly preferable. As the platinum compound, for example, chloroplatinic acid, dinitrodiamine platinum, etc., as the palladium compound, for example, palladium chloride, tetraamminedichloropalladium, tetraamminedinitropalladium, palladium nitrate, etc., as the rhodium compound, for example, rhodium chloride, Hexamminetrichlororhodium, rhodium nitrate, etc., as ruthenium compounds, for example, ruthenium chloride, hexaamminetrichlororuthenium, hexaamminetrinitroruthenium, etc., and as iridium compounds, for example, iridium chloride, iridium sulfate, hexachlorodiamine Iridium and the like can be mentioned. These can be used alone or in combination of two or more.
【００２９】例えば、含浸法によって、白金族触媒を調
製するには、白金族金属の化合物の水溶液や、又はアル
コール溶液、エーテル溶液、ケトン溶液等、適当な有機
溶媒を用いる溶液に担体を含浸させ、乾燥させた後、空
気中で焼成すればよい。For example, to prepare a platinum group catalyst by an impregnation method, the carrier is impregnated with an aqueous solution of a compound of a platinum group metal or a solution using an appropriate organic solvent such as an alcohol solution, an ether solution, a ketone solution or the like. After drying, firing may be performed in the air.
【００３０】白金族触媒において、白金族金属の量は、
金属換算で、0.２〜１０ｍａｓｓ％、好ましくは、0.８
〜７ｍａｓｓ％の範囲である。白金族触媒において、白
金族金属の量が金属換算で0.２ｍａｓｓ％よりも少ない
ときは、得られる脱硫触媒において、コーク劣化を抑え
て、触媒活性を長期間にわたって高く維持するという所
期の効果を殆ど得ることができず、他方、１０ｍａｓｓ
％より多くしても、金属の分散性が低く、多量の添加に
見合う効果を得ることができないのみならず、不必要に
触媒製造費用を上昇させる。In the platinum group catalyst, the amount of the platinum group metal is
0.2 to 10 mass% in metal conversion, preferably 0.8
７7 mass%. In the platinum group catalyst, when the amount of the platinum group metal is less than 0.2 mass% in terms of metal, the desired effect of suppressing the coke deterioration and maintaining the catalyst activity high over a long period of time in the obtained desulfurization catalyst. Can hardly be obtained, while 10 mass
%, The dispersibility of the metal is low, and not only the effect corresponding to the large amount of addition cannot be obtained, but also the catalyst production cost is unnecessarily increased.
【００３１】担体に白金族化合物の溶液を含浸させた
後、これを空気中で焼成する際の温度は、通常、４００
〜７００℃、好ましくは、４５０〜６００℃の範囲であ
り、焼成時間は、通常、１〜１０時間程度である。焼成
後の水素等での還元処理は、行なっても、行なわなくて
も、触媒性能に大きな差はない。After the support is impregnated with the solution of the platinum group compound, the temperature at which it is calcined in air is usually 400 ° C.
To 700 ° C., preferably 450 to 600 ° C., and the firing time is usually about 1 to 10 hours. Whether the reduction treatment with hydrogen or the like after calcination is performed or not, there is no significant difference in catalytic performance.
【００３２】白金族触媒は、これを前記基体触媒の表面
にコーティングするには、その粒子径を１０〜１００μ
ｍ、好ましくは、３０〜８０μｍの範囲に粉砕して用い
ることが必要である。白金族触媒を粒子径が１０μｍよ
り小さい微粒子に粉砕することは困難であり、他方、白
金族触媒が１００μｍより大きい粒子であるときは、コ
ーティング効果、即ち、コーティングされた白金族触媒
の粒子と基体触媒との協奏的又は協同的な脱硫活性の向
上とコーク劣化防止の効果が低いほか、コーティングさ
れた白金族触媒が基体触媒の表面から剥離しやすい。In order to coat the platinum group catalyst on the surface of the base catalyst, the particle diameter of the platinum group catalyst is 10 to 100 μm.
m, preferably in the range of 30 to 80 μm. It is difficult to pulverize the platinum group catalyst into fine particles having a particle diameter smaller than 10 μm, while when the platinum group catalyst is a particle larger than 100 μm, the coating effect, that is, the coated platinum group catalyst particles and the substrate The effect of improving the desulfurization activity cooperatively or cooperatively with the catalyst and the effect of preventing coke deterioration are low, and the coated platinum group catalyst is easily peeled off from the surface of the base catalyst.
【００３３】白金族触媒を基体触媒の表面にコーティン
グするには、上記白金族触媒の微粒子を水に懸濁させて
スラリーとし、このスラリーを基体触媒の表面に塗布、
乾燥し、必要に応じて、この操作を数回繰り返して、得
られる水素化脱硫触媒において、基体触媒と白金族触媒
とが所定の割合となるようにする。To coat the platinum group catalyst on the surface of the base catalyst, the platinum group catalyst fine particles are suspended in water to form a slurry, and this slurry is applied to the surface of the base catalyst.
After drying, if necessary, this operation is repeated several times so that the obtained hydrodesulfurization catalyst has a predetermined ratio of the base catalyst and the platinum group catalyst.
【００３４】本発明による水素化脱硫触媒において、白
金族触媒は、基体触媒１００ｍａｓｓ部当りに１〜２０
ｍａｓｓ部、好ましくは、１〜１０ｍａｓｓ部、特に、
好ましくは、２〜８ｍａｓｓ部である。基体触媒１００
ｍａｓｓ部当りに白金族触媒が１ｍａｓｓ部より少ない
ときは、触媒のコーク劣化を抑えて、触媒活性を長期間
にわたって高く維持するという所期の効果を殆ど得るこ
とができず、他方、基体触媒１００ｍａｓｓ部当りに白
金族触媒が１０ｍａｓｓ部よりも多いときは、白金族触
媒が基体触媒をが完全に被覆するので、得られる水素化
脱硫触媒は、脱硫活性が著しく低い。In the hydrodesulfurization catalyst according to the present invention, the platinum group catalyst is used in an amount of 1 to 20 per 100 parts by mass of the base catalyst.
mass part, preferably 1 to 10 mass part, in particular,
Preferably, it is 2 to 8 mass parts. Base catalyst 100
When the amount of the platinum group catalyst per mass part is less than 1 mass part, the expected effect of suppressing the coke deterioration of the catalyst and maintaining the catalyst activity high for a long period of time can hardly be obtained. When the amount of the platinum group catalyst is more than 10 mass parts per part, the resulting hydrodesulfurization catalyst has remarkably low desulfurization activity because the platinum group catalyst completely covers the base catalyst.
【００３５】本発明によれば、白金族触媒の微粒子を水
に懸濁させる際、その白金族触媒の微粒子を懸濁させる
ために用いる水の量は、前記基体触媒が吸水し得る水の
最大質量（以下、単に、飽和吸水量という。）に対し
て、1.５〜５倍の範囲であり、且つ、白金族触媒の微粒
子を懸濁させるために用いる水の質量／コーティングす
る白金族触媒の質量の比が２０〜２００の範囲である量
とするのが好ましい。According to the present invention, when suspending the fine particles of the platinum group catalyst in water, the amount of water used for suspending the fine particles of the platinum group catalyst is the maximum amount of water that can be absorbed by the base catalyst. The mass (hereinafter simply referred to as the saturated water absorption) is 1.5 to 5 times, and the mass of water used for suspending the fine particles of the platinum group catalyst / the platinum group catalyst to be coated. It is preferable that the mass ratio is in the range of 20 to 200.
【００３６】例えば、基体触媒５０ｇ（吸水量３０ｇ）
に対して、白金族触媒2.５ｇ（基体触媒１００ｍａｓｓ
部に対して５ｍａｓｓ部）をコーティングする場合に
は、上記の要件を満たす水の量（白金族触媒の微粒子を
懸濁させるために用いる水の量）は、５０〜１５０ｇの
範囲である。白金族触媒の微粒子を懸濁させるために用
いる水の量をこのように規定する理由は、スラリーの濃
度が余りに高いときは、スラリーを基体触媒に均一にコ
ーティングすることができず、反対に、スラリーの濃度
が余りに小さいときは、コーティング操作を不必要に多
数回、繰り返して行なう必要があるためである。For example, 50 g of base catalyst (30 g of water absorption)
2.5 g of platinum group catalyst (100 mass of base catalyst)
In the case of coating with 5 mass parts per part, the amount of water satisfying the above requirements (the amount of water used to suspend the fine particles of the platinum group catalyst) is in the range of 50 to 150 g. The reason for defining the amount of water used to suspend the platinum group catalyst fine particles in this way is that when the concentration of the slurry is too high, the slurry cannot be uniformly coated on the base catalyst, and conversely, If the concentration of the slurry is too low, it is necessary to repeat the coating operation unnecessarily many times.
【００３７】貴金属触媒の微粒子を懸濁させたスラリー
は、得られる脱硫触媒において、白金族触媒が基体触媒
から容易に剥離しないように、シリカゾル、アルミナゾ
ル、ジルコニアゾル等をバインダーとして含んでいるこ
とが好ましい。このようなバインダーの量は、スラリー
中の水１００ｍａｓｓ部に対して、通常、２〜２０ｍａ
ｓｓ部、好ましくは、５〜１５ｍａｓｓ部の範囲であ
る。スラリー中の水１００ｍａｓｓ部に対して、バイン
ダーの量が２ｍａｓｓ部よりも少ないときは、バインダ
ーとしての効果が十分でなく、他方、２０ｍａｓｓ部よ
りも多いときは、白金族触媒のみならず、基体触媒も、
バインダーを構成する上記酸化物によって被覆される結
果、脱硫活性が低下するのみならず、スラリーの粘度が
高く、コーティング操作が困難である。The slurry in which the fine particles of the noble metal catalyst are suspended may contain silica sol, alumina sol, zirconia sol or the like as a binder in the obtained desulfurization catalyst so that the platinum group catalyst is not easily separated from the base catalyst. preferable. The amount of such a binder is usually 2 to 20 ma per 100 mass parts of water in the slurry.
It is in the range of ss part, preferably 5 to 15 mass part. When the amount of the binder is less than 2 mass parts with respect to 100 mass parts of water in the slurry, the effect as a binder is not sufficient. On the other hand, when the amount is more than 20 mass parts, not only the platinum group catalyst but also the base catalyst is used. Also,
As a result of being coated with the above-mentioned oxide constituting the binder, not only the desulfurization activity is reduced, but also the viscosity of the slurry is high, and the coating operation is difficult.
【００３８】本発明による水素化脱硫触媒を間接脱硫装
置や直接脱硫装置の反応器に充填して、重質油の接触水
素化脱硫に用いるには、従来と同じく、触媒を充填した
反応器に原料油としての重質油を導入して、従来より知
られている高温高圧及び相当の水素分圧の条件下で処理
すればよい。In order to charge the hydrodesulfurization catalyst according to the present invention into a reactor of an indirect desulfurization unit or a direct desulfurization unit and use it for catalytic hydrodesulfurization of heavy oil, as in the conventional case, a reactor filled with the catalyst is used. Heavy oil as a feedstock may be introduced and treated under conventionally known conditions of high temperature, high pressure and substantial hydrogen partial pressure.
【００３９】最も一般的には、本発明による脱硫触媒を
固定床として反応器中に維持し、原料油にこの固定床を
上方から下方に通過させる。触媒は、単独の反応器に充
填して用いてもよく、また、直列に連結した複数の反応
器のそれぞれに触媒を充填してもよい。特に、原料油が
ＡＲの場合には、ＡＲは、高濃度のニッケル、バナジウ
ム等の金属分を含んでいるので、脱硫触媒に脱メタル機
能を有した触媒系を組み合わせた多段反応器を用いるこ
とが好ましい。Most commonly, the desulfurization catalyst according to the invention is maintained in the reactor as a fixed bed and the feedstock is passed through the fixed bed from top to bottom. The catalyst may be used after being filled in a single reactor, or the catalyst may be filled in each of a plurality of reactors connected in series. In particular, when the raw material oil is AR, AR contains a high concentration of metals such as nickel and vanadium. Therefore, use a multi-stage reactor combining a desulfurization catalyst with a catalyst system having a demetallation function. Is preferred.
【００４０】反応条件は、特に、限定されるものではな
いが、例えば、５容量％留出温度が２４０℃以上、９５
容量％留出温度が４５０℃以上である減圧軽油（ＶＧ
Ｏ）留分や、４０容量％留出温度が４５０℃以上の常圧
残油（ＡＲ）等を本発明による脱硫触媒を用いて接触水
素化脱硫する場合、好ましくは、水素分圧４〜１８ＭＰ
ａ、原料油温度３２０〜４１０℃、液空間速度0.１〜4.
０ｈｒ-1の範囲の条件下で、本発明による触媒と接触さ
せればよい。The reaction conditions are not particularly limited, but, for example, the 5% by volume distillation temperature is 240 ° C. or more,
Vacuum gas oil with a volume% distillation temperature of 450 ° C or higher (VG
O) When catalytically hydrodesulfurizing a fraction or an atmospheric residue (AR) having a 40% by volume distillation temperature of 450 ° C. or more using the desulfurization catalyst according to the present invention, the hydrogen partial pressure is preferably 4 to 18 MPa.
a, feedstock temperature 320-410 ° C, liquid hourly space velocity 0.1-4.
It may be contacted with the catalyst according to the invention under conditions in the range of 0 hr -1 .
【００４１】このような反応条件下で上記重質油を水素
化脱硫するとき、本発明による脱硫触媒の劣化は、従来
の脱硫触媒の劣化に比べて著しく小さいので、実装置で
の商業運転における触媒寿命を、従来の１年程度から、
1.５〜２年とすることもできる。その理由は、必ずしも
明らかではないが、本発明に従って、基体触媒の表面に
水素化能の高い白金族触媒をコーティングすることによ
って、脱硫触媒中でのコーク析出の原因の一つであると
考えられている多環芳香族炭化水素類の核水素化（開
環）反応が促進されるためであるとみられる。When the above-mentioned heavy oil is hydrodesulfurized under the above reaction conditions, the deterioration of the desulfurization catalyst according to the present invention is significantly smaller than the deterioration of the conventional desulfurization catalyst. Catalyst life is reduced from about one year
It can be 1.5 to 2 years. Although the reason is not necessarily clear, it is thought that by coating the surface of the base catalyst with a platinum group catalyst having high hydrogenation ability according to the present invention, it is one of the causes of coke precipitation in the desulfurization catalyst. It is thought that this is because the nuclear hydrogenation (ring opening) reaction of the polycyclic aromatic hydrocarbons is accelerated.
【００４２】更に、本発明による脱硫触媒は、初期の脱
硫活性が従来の触媒よりも高いという効果をも有してい
るので、触媒劣化が著しくはない９０容量％留出温度が
２５０℃以下の灯油留分や、９０容量％留出温度が４０
０℃以下の軽油留分に対する水素化脱硫にも有効に用い
ることができる。Further, since the desulfurization catalyst according to the present invention has an effect that the initial desulfurization activity is higher than that of the conventional catalyst, the 90% by volume distillation temperature at which the catalyst is not significantly deteriorated is 250 ° C. or less. Kerosene fraction or 90% by volume distillation temperature is 40
It can also be used effectively for hydrodesulfurization of gas oil fractions at 0 ° C or lower.
【００４３】[0043]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.
【００４４】（基体触媒Ａの調製） 基体触媒Ａ１ （５ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持ア
ルミナ（円柱状ペレット）の調製）イオン交換水２５ｇ
中にモリブドリン酸３０水和物１０ｇとオルトリン酸1.
８５ｇと酢酸コバルト４水和物8.０ｇを溶解させた水溶
液を円柱状（１／１６インチ）アルミナペレット（日本
ケッチェン社製、表面積３８５ｍ2 ｇ-1）３６ｇに含浸
させ、室温にて乾燥させた後、５００℃で３時間焼成し
て、５ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持
アルミナを得た。(Preparation of base catalyst A) Base catalyst A1 (Preparation of alumina (columnar pellet) supporting 5 mass% CoO-15 mass% MoO 3 ) 25 g of ion-exchanged water
In it, 10 g of molybdophosphoric acid 30 hydrate and orthophosphoric acid 1.
An aqueous solution in which 85 g and 8.0 g of cobalt acetate tetrahydrate are dissolved is impregnated into 36 g of cylindrical (1/16 inch) alumina pellets (manufactured by Nippon Ketjen Co., Ltd., surface area: 385 m 2 g -1 ), and dried at room temperature. Then, it was calcined at 500 ° C. for 3 hours to obtain alumina supporting 5 mass% CoO-15 mass% MoO 3 .
【００４５】基体触媒Ａ２ （５ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持ア
ルミナ（四葉状ペレット）の調製）基体触媒Ａ１の調製
において、円柱状（１／１６インチ）アルミナペレット
の代わりに、四葉状（１／２０インチ）アルミナペレッ
ト（日本ケッチェン社製、表面積３７８ｍ2 ｇ-1）を用
いた以外は、基体触媒Ａ１と同様にして、５ｍａｓｓ％
ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持アルミナを得た。Preparation of Substrate Catalyst A2 (Preparation of 5 Mass% CoO-15 Mass% MoO 3 -Supported Alumina (Trefoil Pellets)) In the preparation of the base catalyst A1, instead of the columnar (1/16 inch) alumina pellets, a four-lobe (1 / 20 inch) 5 mass% in the same manner as the base catalyst A1 except that alumina pellets (378 m 2 g −1 surface area, manufactured by Nippon Ketjen Co., Ltd.) were used.
CoO-15 mass% MoO 3 -supported alumina was obtained.
【００４６】基体触媒Ａ３ （５ｍａｓｓ％ＮｉＯ−１５ｍａｓｓ質量％ＭｏＯ3 担
持アルミナの調製）基体触媒Ａ１の調製において、酢酸
コバルト４水和物8.０ｇの代わりに、酢酸ニッケル４水
和物8.０ｇを用いた以外は、基体触媒Ａ１と同様にし
て、５ｍａｓｓ％ＮｉＯ−１５ｍａｓｓ質量％ＭｏＯ3
担持アルミナを得た。Base Catalyst A3 (Preparation of alumina supporting 5 mass% NiO-15 mass% MoO 3 ) In the preparation of base catalyst A1, 8.0 g of nickel acetate tetrahydrate was used instead of 8.0 g of cobalt acetate tetrahydrate. 5 mass% NiO-15 mass% MoO 3 in the same manner as the base catalyst A1 except that
A supported alumina was obtained.
【００４７】基体触媒Ａ４ （2.５ｍａｓｓ％ＣｏＯ−2.５ｍａｓｓ％ＮｉＯ−１５
ｍａｓｓ％ＭｏＯ3 担持アルミナの調製）基体触媒Ａ１
の調製において、酢酸コバルト４水和物8.０ｇの代わり
に、酢酸コバルト４水和物4.０ｇと酢酸ニッケル４水和
物4.０ｇを用いた以外は、基体触媒Ａ１と同様にして、
2.５ｍａｓｓ％ＣｏＯ−2.５ｍａｓｓ％ＮｉＯ−１５ｍ
ａｓｓ％ＭｏＯ3 担持アルミナを得た。Base Catalyst A4 (2.5 mass% CoO-2.5 mass% NiO-15
Preparation of Mass% MoO 3 -Supported Alumina) Base Catalyst A1
Was prepared in the same manner as the base catalyst A1, except that 4.0 g of cobalt acetate tetrahydrate and 4.0 g of nickel acetate tetrahydrate were used instead of 8.0 g of cobalt acetate tetrahydrate.
2.5mass% CoO-2.5mass% NiO-15m
As% MoO 3 -supported alumina was obtained.
【００４８】基体触媒Ａ５ （５ｍａｓｓ％ＣｏＯ−１５ｍａｓｓＭｏＯ3 担持アル
ミナ−シリカの調製）基体触媒Ａ１の調製において、円
柱状（１／１６インチ）アルミナペレットの代わりに、
円柱状（１／１６インチ）アルミナ−シリカペレット
（日本ケッチェン社製、２０ｍａｓｓ％ＳｉＯ2 含有、
表面積３９１ｍ2 ｇ-1）を用いた以外は、基体触媒Ａ１
と同様にして、５ｍａｓｓ％ＣｏＯ−１５ｍａｓｓＭｏ
Ｏ3 担持アルミナ−シリカを得た。Base Catalyst A5 (Preparation of 5 mass% CoO-15 mass MoO 3 -Supported Alumina-Silica) In the preparation of the base catalyst A1, instead of the columnar (1/16 inch) alumina pellets,
Cylindrical (1/16 inch) alumina-silica pellets (manufactured by Nippon Ketjen Co., containing 20 mass% SiO 2 ,
Except that the surface area was 391 m 2 g −1 ), the base catalyst A1 was used.
5 mass% CoO-15massMo
O 3 supported alumina-silica was obtained.
【００４９】基体触媒Ａ６ （５ｍａｓｓ％ＣｏＯ−２０ｍａｓｓ％ＭｏＯ3 担持ア
ルミナの調製）基体触媒Ａ１の調製において、モリブド
リン酸３０水和物１3.３ｇと円柱状（１／１６インチ）
アルミナペレット３3.５ｇを用いた以外は、基体触媒Ａ
１と同様にして、５ｍａｓｓ％ＣｏＯ−２０ｍａｓｓ％
ＭｏＯ3 担持アルミナを得た。Base Catalyst A6 (Preparation of alumina supporting 5 mass% CoO-20 mass% MoO 3 ) In the preparation of base catalyst A1, 13.3 g of molybdophosphoric acid 30 hydrate and a columnar (1/16 inch)
Except that 33.5 g of alumina pellets were used, the base catalyst A was used.
5 mass% CoO-20 mass% in the same manner as 1.
MoO 3 -supported alumina was obtained.
【００５０】基体触媒Ａ７ （２ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持ア
ルミナの調製）基体触媒Ａ１の調製において、酢酸コバ
ルト４水和物3.２ｇと円柱状（１／１６インチ）アルミ
ナペレット３7.７ｇを用いた以外は、基体触媒Ａ１と同
様にして、２ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ
3 担持アルミナを得た。Base Catalyst A7 (Preparation of alumina supporting 2 mass% CoO-15 mass% MoO 3 ) In the preparation of the base catalyst A1, 3.2 g of cobalt acetate tetrahydrate and 37.7 g of columnar (1/16 inch) alumina pellets were used. 2 mass% CoO-15 mass% MoO in the same manner as in the base catalyst A1 except that
3 supported alumina was obtained.
【００５１】基体触媒Ａ８ （８ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持ア
ルミナの調製）基体触媒Ａ１の調製において、酢酸コバ
ルト４水和物１2.８ｇと円柱状（１／１６インチ）アル
ミナペレット３4.６ｇを用いた以外は、基体触媒Ａ１と
同様にして、８ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％Ｍｏ
Ｏ3 担持アルミナを得た。Base Catalyst A8 (Preparation of 8 mass% CoO-15 mass% MoO 3 -Supported Alumina) In the preparation of the base catalyst A1, 12.8 g of cobalt acetate tetrahydrate and 34.6 g of columnar (1/16 inch) alumina pellets were used. 8 mass% CoO-15 mass% Mo in the same manner as the base catalyst A1 except that
O 3 supported alumina was obtained.
【００５２】基体触媒Ａ９ （５ｍａｓｓ％ＣｏＯ−８ｍａｓｓ％ＭｏＯ3 担持アル
ミナの調製）基体触媒Ａ１の調製において、モリブドリ
ン酸３０水和物5.３ｇと円柱状（１／１６インチ）アル
ミナペレット３9.４ｇを用いた以外は、基体触媒Ａ１と
同様にして、５ｍａｓｓ％ＣｏＯ−８ｍａｓｓ％ＭｏＯ
3 担持アルミナを得た。Base Catalyst A9 (Preparation of alumina supporting 5 mass% CoO-8 mass% MoO 3 ) In the preparation of the base catalyst A1, 5.3 g of molybdophosphoric acid 30 hydrate and 39.4 g of cylindrical (1/16 inch) alumina pellets were used. 5 mass% CoO-8 mass% MoO in the same manner as the base catalyst A1 except that
3 supported alumina was obtained.
【００５３】基体触媒Ａ１０ （５ｍａｓｓ％ＣｏＯ−３５ｍａｓｓ％ＭｏＯ3 担持ア
ルミナの調製）基体触媒Ａ１の調製において、モリブド
リン酸３０水和物２3.３ｇと円柱状（１／１６インチ）
アルミナペレット２8.７ｇを用いた以外は、基体触媒Ａ
１と同様にして、５ｍａｓｓ％ＣｏＯ−３５ｍａｓｓ％
ＭｏＯ3 担持アルミナを得た。Base Catalyst A10 (Preparation of alumina supporting 5 mass% CoO-35 mass% MoO 3 ) In preparing the base catalyst A1, 23.3 g of molybdophosphoric acid 30 hydrate and a columnar (1/16 inch) were used.
Except that 28.7 g of alumina pellets were used, the base catalyst A was used.
5 mass% CoO-35 mass% in the same manner as 1.
MoO 3 -supported alumina was obtained.
【００５４】（白金族触媒Ｂの調製） 白金族触媒Ｂ１ （１ｍａｓｓ％白金担持シリカの調製）塩化白金酸６水
和物１ｇをイオン交換水２５ｇに溶解させた。この水溶
液6.６ｇにイオン交換水1.４ｇを加えて、８ｇとした。
この水溶液を１６〜２８メッシュ（１〜0.５９ｍｍ）に
粉砕したシリカ（ダヴィソン社製、表面積３３５ｍ2 ｇ
-1）１０ｇに含浸させ、８０℃にて減圧乾燥した後、５
００℃で３時間焼成して、１ｍａｓｓ％白金担持シリカ
を得た。(Preparation of Platinum Group Catalyst B) Platinum Group Catalyst B1 (Preparation of 1 mass% platinum-supported silica) Chloroplatinic acid 6 water
1 g of the hydrate was dissolved in 25 g of ion-exchanged water. This water soluble
1.4 g of ion-exchanged water was added to 6.6 g of the liquid to make 8 g.
This aqueous solution is reduced to 16-28 mesh (1-0.59 mm)
Crushed silica (Davison, surface area 335mTwog
-1) 10 g, impregnated at 80 ° C. under reduced pressure,
Firing at 00 ° C for 3 hours, 1 mass% platinum-supported silica
I got
【００５５】白金族触媒Ｂ２ （１ｍａｓｓ％パラジウム担持シリカの調製）テトラア
ンミンジクロロパラジウム１水和物１ｇをイオン交換水
２５ｇに溶解させた。この水溶液6.２ｇにイオン交換水
1.８ｇを加えて、８ｇとした。この水溶液を用いた以外
は、白金族触媒Ｂ１と同様にして、１ｍａｓｓ％パラジ
ウム担持シリカを得た。Platinum Group Catalyst B2 (Preparation of 1 mass% Palladium-Supported Silica) 1 g of tetraamminedichloropalladium monohydrate was dissolved in 25 g of ion-exchanged water. To 6.2 g of this aqueous solution, add ion-exchanged water.
1.8 g was added to make 8 g. Except that this aqueous solution was used, 1 mass% palladium-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００５６】白金族触媒Ｂ３ （１ｍａｓｓ％ロジウム担持シリカの調製）塩化ロジウ
ム３水和物１ｇをイオン交換水２５ｇに溶解させた。こ
の水溶液6.４ｇにイオン交換水1.６ｇを加えて、８ｇと
した。この水溶液を用いた以外は、白金族触媒Ｂ１と同
様にして、１ｍａｓｓ％ロジウム担持シリカを得た。Platinum Group Catalyst B3 (Preparation of 1 mass% rhodium-supported silica) 1 g of rhodium chloride trihydrate was dissolved in 25 g of ion-exchanged water. 1.6 g of ion-exchanged water was added to 6.4 g of this aqueous solution to make 8 g. Except that this aqueous solution was used, 1 mass% rhodium-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００５７】白金族触媒Ｂ４ （0.５ｍａｓｓ％ルテニウム担持シリカの調製）塩化ル
テニウム３水和物１ｇをイオン交換水５０ｇに溶解させ
た。この水溶液5.６ｇにイオン交換水を加えて、８ｇと
した。この水溶液を用いた以外は、白金族触媒Ｂ１と同
様にして、0.５ｍａｓｓ％ルテニウム担持シリカを得
た。Platinum Group Catalyst B4 (Preparation of 0.5 Mass% Ruthenium-Supported Silica) 1 g of ruthenium chloride trihydrate was dissolved in 50 g of ion-exchanged water. Deionized water was added to 5.6 g of this aqueous solution to make 8 g. Except that this aqueous solution was used, 0.5 mass% ruthenium-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００５８】白金族触媒Ｂ５ （0.５ｍａｓｓ％イリジウム担持シリカの調製）塩化イ
リジウム３水和物１ｇをイオン交換水５０ｇに溶解させ
た。この水溶液4.２ｇにイオン交換水を加えて、８ｇと
した。この水溶液を用いた以外は、白金族触媒Ｂ１と同
様にして、0.５ｍａｓｓ％イリジウム担持シリカを得
た。Platinum Group Catalyst B5 (Preparation of 0.5 mass% iridium-supported silica) 1 g of iridium chloride trihydrate was dissolved in 50 g of ion-exchanged water. Deionized water was added to 4.2 g of this aqueous solution to make 8 g. Except that this aqueous solution was used, 0.5 mass% iridium-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００５９】白金族触媒Ｂ６ （0.５ｍａｓｓ％白金担持シリカの調製）塩化白金酸６
水和物0.５ｇをイオン交換水２５ｇに溶解させた。この
水溶液6.６ｇを用いた以外は、白金族触媒Ｂ１と同様に
して、0.５ｍａｓｓ％白金担持シリカを得た。Platinum Group Catalyst B6 (Preparation of 0.5 mass% Platinum-Supported Silica) Chloroplatinic Acid 6
0.5 g of the hydrate was dissolved in 25 g of ion-exchanged water. Except that 6.6 g of this aqueous solution was used, 0.5 mass% platinum-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００６０】白金族触媒Ｂ７ （２ｍａｓｓ％白金担持シリカの調製）塩化白金酸６水
和物２ｇをイオン交換水２５ｇに溶解させた。この水溶
液6.６ｇを用いた以外は、白金族触媒Ｂ１と同様にし
て、２ｍａｓｓ％白金担持シリカを得た。Platinum Group Catalyst B7 (Preparation of 2 mass% platinum-supported silica) 2 g of chloroplatinic acid hexahydrate was dissolved in 25 g of ion-exchanged water. Except for using 6.6 g of this aqueous solution, a 2 mass% platinum-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００６１】白金族触媒Ｂ８ （５ｍａｓｓ％白金担持シリカの調製）塩化白金酸６水
和物５ｇをイオン交換水２５ｇに溶解させた。この水溶
液6.６ｇを用いた以外は、白金族触媒Ｂ１と同様にし
て、５ｍａｓｓ％白金担持シリカを得た。Platinum Group Catalyst B8 (Preparation of 5 Mass% Platinum-Supported Silica) 5 g of chloroplatinic acid hexahydrate was dissolved in 25 g of ion-exchanged water. Except for using 6.6 g of this aqueous solution, 5 mass% platinum-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００６２】白金族触媒Ｂ９ （１ｍａｓｓ％白金担持シリカの調製）担体として、ア
ルミナ（水沢化学社製、表面積１９０ｍ2 ｇ-1）１０ｇ
を用いた以外は、白金族触媒Ｂ１と同様にして、１ｍａ
ｓｓ％白金担持シリカを得た。Platinum Group Catalyst B9 (Preparation of 1 mass% Platinum-Supported Silica) 10 g of alumina (manufactured by Mizusawa Chemical Co., surface area 190 m 2 g -1 ) as a carrier
Was used in the same manner as in the platinum group catalyst B1 except that
ss% platinum supported silica was obtained.
【００６３】白金族触媒Ｂ１０ （１ｍａｓｓ％白金担持ジルコニアの調製）担体とし
て、ジルコニア（第一希元素社製、表面積２７ｍ
2 ｇ-1）を用いた以外は、白金族触媒Ｂ１と同様にし
て、１ｍａｓｓ％白金担持ジルコニアを得た。Platinum Group Catalyst B10 (Preparation of 1 mass% Platinum-Supported Zirconia) As a carrier, zirconia (manufactured by Daiichi Rare Element Co., surface area 27 m
Except for using 2 g -1 ), 1 mass% platinum-supported zirconia was obtained in the same manner as in the platinum group catalyst B1.
【００６４】白金族触媒Ｂ１１ （0.１ｍａｓｓ％白金担持シリカの調製）塩化白金酸６
水和物0.１ｇをイオン交換水２５ｇに溶解させた。この
水溶液6.６ｇを用いた以外は、白金族触媒Ｂ１と同様に
して、0.１ｍａｓｓ％白金担持シリカを得た。Platinum Group Catalyst B11 (Preparation of 0.1 mass% Platinum-Supported Silica) Chloroplatinic Acid 6
0.1 g of the hydrate was dissolved in 25 g of ion-exchanged water. Except that 6.6 g of this aqueous solution was used, 0.1 mass% platinum-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００６５】白金族触媒Ｂ１２ （１２ｍａｓｓ％白金担持シリカの調製）塩化白金酸６
水和物１２ｇをイオン交換水２５ｇに溶解させた。この
水溶液6.６ｇを用いた以外は、白金族触媒Ｂ１と同様に
して、１２ｍａｓｓ％白金担持シリカを得た。Platinum group catalyst B12 (Preparation of 12 mass% platinum-supported silica) Chloroplatinic acid 6
12 g of the hydrate was dissolved in 25 g of ion-exchanged water. Except for using 6.6 g of this aqueous solution, a 12 mass% platinum-supported silica was obtained in the same manner as in the platinum group catalyst B1.
【００６６】白金族触媒Ｂ１３ （0.５ｍａｓｓ％白金−0.５ｍａｓｓ％パラジウム担持
シリカの調製）塩化白金酸６水和物１ｇをイオン交換水
２５ｇに溶解させた水溶液3.３ｇとテトラアンミンジク
ロロパラジウム１水和物１ｇをイオン交換水２５ｇに溶
解させた水溶液3.１を用いた以外は、白金族触媒Ｂ１と
同様にして、0.５ｍａｓｓ％白金−0.５ｍａｓｓ％パラ
ジウム担持シリカを得た。Platinum Group Catalyst B13 (Preparation of 0.5 mass% Platinum-0.5 Mass% Palladium-Supported Silica) 3.3 g of an aqueous solution obtained by dissolving 1 g of chloroplatinic acid hexahydrate in 25 g of ion-exchanged water and tetraammine dichloropalladium 1 0.5 mass% platinum-0.5 mass% palladium-supported silica was obtained in the same manner as for the platinum group catalyst B1, except that an aqueous solution 3.1 in which 1 g of hydrate was dissolved in 25 g of ion-exchanged water was used.
【００６７】単層構造触媒Ｃ１ （１ｍａｓｓ％白金−５ｍａｓｓ％ＣｏＯ−１５ｍａｓ
ｓ％ＭｏＯ3 担持アルミナの調製）イオン交換水２５ｇ
中にモリブドリン酸３０水和物１０ｇとオルトリン酸1.
８５ｇと酢酸コバルト４水和物8.０ｇを溶解させた水溶
液を円柱状（１／１６インチ）アルミナペレット（日本
ケッチェン社製、表面積３８５ｍ2 ｇ-1）３６ｇに含浸
させ、室温にて乾燥させた後、５００℃で３時間焼成し
て、５ｍａｓｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持
アルミナを得た。Single-layer catalyst C1 (1 mass% platinum-5 mass% CoO-15 mass
Preparation of alumina supporting s% MoO 3 ) 25 g of ion-exchanged water
In it, 10 g of molybdophosphoric acid 30 hydrate and orthophosphoric acid 1.
An aqueous solution in which 85 g and 8.0 g of cobalt acetate tetrahydrate are dissolved is impregnated into 36 g of cylindrical (1/16 inch) alumina pellets (manufactured by Nippon Ketjen Co., Ltd., surface area: 385 m 2 g -1 ), and dried at room temperature. Then, it was calcined at 500 ° C. for 3 hours to obtain alumina supporting 5 mass% CoO-15 mass% MoO 3 .
【００６８】別に、塩化白金酸６水和物５ｇをイオン交
換水２５ｇに溶解させ、この水溶液6.６ｇにイオン交換
水を加えて、２５ｇとした。この水溶液を上記５ｍａｓ
ｓ％ＣｏＯ−１５ｍａｓｓ％ＭｏＯ3 担持アルミナに含
浸させ、８０℃にて減圧乾燥させた後、５００℃で３時
間焼成して、１ｍａｓｓ％白金−５ｍａｓｓ％ＣｏＯ−
１５ｍａｓｓ％ＭｏＯ3 担持アルミナを得た。Separately, 5 g of chloroplatinic acid hexahydrate was dissolved in 25 g of ion-exchanged water, and ion-exchanged water was added to 6.6 g of this aqueous solution to make 25 g. This aqueous solution is mixed with the above 5mas
s% CoO—15 mass% MoO 3 , impregnated with alumina, dried at 80 ° C. under reduced pressure, and calcined at 500 ° C. for 3 hours to obtain 1 mass% platinum-5 mass% CoO—
15 mass% MoO 3 supported alumina was obtained.
【００６９】（原料油）以下の実施例及び比較例におい
て用いた原料油は次のとおりである。(Raw material oil) The raw material oil used in the following Examples and Comparative Examples is as follows.
【００７０】原料油Ｒ１（減圧軽油（ＶＧＯ）） 原 油：アラビアンヘビー 密 度：0.８９９０ｇ・ｃｍ-3（１５℃） 硫黄分：3.０６ｍａｓｓ％ 金属分：Ｎｉ及びＶ＝1.３ｍａｓｓ ｐｐｍ 蒸留性状：留出温度 ５容量％＝３０６℃ ５０容量％＝４０４℃ ９５容量％＝５１０℃Raw material oil R1 (vacuum gas oil (VGO)) Crude oil: Arabian heavy Density: 0.8990 g · cm -3 (15 ° C.) Sulfur content: 3.06 mass% Metal content: Ni and V = 1.3 mass ppm Distillation properties: Distillation temperature 5% by volume = 306 ° C. 50% by volume = 404 ° C. 95% by volume = 510 ° C.
【００７１】原料油Ｒ２（常圧残油（ＡＲ）） 原 油：アラビアンライト 密 度：0.９７２４ｇ・ｃｍ-3（１５℃） 硫黄分：3.２５ｍａｓｓ％ 金属分：Ｎｉ及びＶ＝８８ｍａｓｓ ｐｐｍ 蒸留性状：留出温度 ５容量％＝４０４℃ ４０容量％＝４９３℃ ５４容量％＝５３８℃Raw oil R2 (normal pressure residual oil (AR)) Crude oil: Arabian light Density: 0.9724 g · cm −3 (15 ° C.) Sulfur content: 3.25 mass% Metal content: Ni and V = 88 mass ppm Distillation properties: Distillation temperature 5% by volume = 404 ° C. 40% by volume = 493 ° C. 54% by volume = 538 ° C.
【００７２】（反応条件）以下の実施例及び比較例にお
いて用いた反応条件は次のとおりである。(Reaction conditions) The reaction conditions used in the following Examples and Comparative Examples are as follows.
【００７３】反応条件Ｐ１ 水素分圧 ：4.９ＭＰａ 反応温度 ：４００℃ 液空間速度：0.６６ｈｒ-1 水素／油比：４２２Ｎｍ3 ｋＬ-1 （注）本反応条件はＶＧＯ留分の水素化脱硫処理に対す
るものである。Reaction conditions P1 Hydrogen partial pressure: 4.9 MPa Reaction temperature: 400 ° C. Liquid hourly space velocity: 0.66 hr −1 Hydrogen / oil ratio: 422 Nm 3 kL −1 (Note) This reaction condition is for hydrogenation of VGO fraction. This is for desulfurization.
【００７４】反応条件Ｐ２ 水素分圧 ：１0.３ＭＰａ 反応温度 ：３９０℃ 液空間速度：0.４ｈｒ-1 水素／油比：９９７Ｎｍ3 ｋＬ-1 （注）本反応条件はＡＲ留分の水素化脱硫処理に対する
ものである。Reaction condition P2 Hydrogen partial pressure: 0.3 MPa Reaction temperature: 390 ° C. Liquid hourly space velocity: 0.4 hr −1 Hydrogen / oil ratio: 997 Nm 3 kL −1 (Note) This reaction condition is for hydrogenation of AR fraction. This is for desulfurization.
【００７５】（触媒の水素化脱硫活性の評価）触媒の水
素化脱硫活性は、以下に示す算式より導かれた反応速度
定数ｋ値にて評価した。ここに、ｋ値が高いほど、触媒
活性がすぐれていることを示す。 ｋ＝〔（１／生成油のＳ濃度n ）−（１／原料油Ｓ濃度
n ）×液空間速度 ここに、原料油がＶＧＯのとき、ｎ＝０．５、ＡＲのと
き、ｎ＝１である。(Evaluation of Hydrodesulfurization Activity of Catalyst) The hydrodesulfurization activity of the catalyst was evaluated by a reaction rate constant k value derived from the following formula. Here, it is shown that the higher the k value, the better the catalytic activity. k = [(1 / S concentration of product oil n ) − (1 / S concentration of feed oil)
n ) × Liquid space velocity Here, when the feed oil is VGO, n = 0.5, and when AR, n = 1.
【００７６】以下に、前記基体触媒の表面に白金族触媒
をコーティングしてなる脱硫触媒Ｍを用いて、上記原料
油を上記反応条件にて水素化脱硫した実施例を比較例と
共に示す。Examples of hydrodesulfurization of the raw material oil under the above reaction conditions using a desulfurization catalyst M obtained by coating the surface of the base catalyst with a platinum group catalyst will be described below together with comparative examples.
【００７７】実施例１ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ１を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 1 A platinum group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M1. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００７８】実施例２ ５５〜７３μｍに整粒した白金族触媒Ｂ２（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３２ｇ）にコーティングし
て、脱硫触媒Ｍ２を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 2 A platinum-group catalyst B2 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , A saturated water absorption of 32 g) to prepare a desulfurization catalyst M2. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００７９】実施例３ ５５〜７３μｍに整粒した白金族触媒Ｂ３（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ３を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 3 A platinum-group catalyst B3 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００８０】実施例４ ５５〜７３μｍに整粒した白金族触媒Ｂ４（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ４を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 4 A platinum-group catalyst B4 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M4. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００８１】実施例５ ５５〜７３μｍに整粒した白金族触媒Ｂ５（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ５を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 5 A platinum group catalyst B5 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M5. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００８２】実施例６ ５５〜７３μｍに整粒した白金族触媒Ｂ６（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ６を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 6 A platinum-group catalyst B6 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M6. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００８３】実施例７ ５５〜７３μｍに整粒した白金族触媒Ｂ７（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ７を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 7 A platinum-group catalyst B7 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M7. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００８４】実施例８ ５５〜７３μｍに整粒した白金族触媒Ｂ８（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ８を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 8 A platinum-group catalyst B8 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M8. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００８５】実施例９ ５５〜７３μｍに整粒した白金族触媒Ｂ９（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ９を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Example 9 A platinum-group catalyst B9 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M9. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００８６】実施例１０ ５５〜７３μｍに整粒した白金族触媒Ｂ１０（1.０ｇ）
をイオン交換水９０ｇとシリカゾル１０ｇを含むシリカ
ゾル含有イオン交換水１００ｇに懸濁させ、これを基体
触媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティング
して、脱硫触媒Ｍ１０を調製した。この脱硫触媒１０ｇ
を用いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱
硫を行なった。結果を表１に示す。Example 10 A platinum group catalyst B10 (1.0 g) sized to 55 to 73 μm
Was suspended in 100 g of silica-sol-containing ion-exchange water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was coated on a base catalyst A1 (50 g, saturated water absorption 30 g) to prepare a desulfurization catalyst M10. 10 g of this desulfurization catalyst
Was used to perform catalytic hydrodesulfurization of the feedstock R1 under the reaction condition P1. Table 1 shows the results.
【００８７】実施例１１ ５５〜７３μｍに整粒した白金族触媒Ｂ１３（1.０ｇ）
をイオン交換水９０ｇとシリカゾル１０ｇを含むシリカ
ゾル含有イオン交換水１００ｇに懸濁させ、これを基体
触媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティング
して、脱硫触媒Ｍ１１を調製した。この脱硫触媒１０ｇ
を用いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱
硫を行なった。結果を表１に示す。Example 11 A platinum group catalyst B13 (1.0 g) sized to 55 to 73 μm
Was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was coated on a base catalyst A1 (50 g, saturated water absorption 30 g) to prepare a desulfurization catalyst M11. 10 g of this desulfurization catalyst
Was used to perform catalytic hydrodesulfurization of the feedstock R1 under the reaction condition P1. Table 1 shows the results.
【００８８】実施例１２ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｍ１１を調製した。この脱硫触媒１０ｇを
用いて、原料油Ｒ２を反応条件Ｐ２にて接触水素化脱硫
を行なった。結果を表１に示す。Example 12 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 30 g) to prepare a desulfurization catalyst M11. Using 10 g of this desulfurization catalyst, the feed oil R2 was subjected to catalytic hydrodesulfurization under the reaction condition P2. Table 1 shows the results.
【００８９】比較例１ ５５〜７３μｍに整粒した白金族触媒Ｂ１１（1.０ｇ）
をイオン交換水９０ｇとシリカゾル１０ｇを含むシリカ
ゾル含有イオン交換水１００ｇに懸濁させ、これを基体
触媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティング
して、脱硫触媒Ｋ１を調製した。この脱硫触媒１０ｇを
用いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫
を行なった。結果を表１に示す。Comparative Example 1 A platinum group catalyst B11 (1.0 g) sized to 55 to 73 μm
Was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was coated on a base catalyst A1 (50 g, saturated water absorption 30 g) to prepare a desulfurization catalyst K1. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００９０】比較例２ ５５〜７３μｍに整粒した白金族触媒Ｂ１２（1.０ｇ）
をイオン交換水９０ｇとシリカゾル１０ｇを含むシリカ
ゾル含有イオン交換水１００ｇに懸濁させ、これを基体
触媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティング
して、脱硫触媒Ｋ２を調製した。この脱硫触媒１０ｇを
用いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫
を行なった。結果を表１に示す。Comparative Example 2 A platinum group catalyst B12 (1.0 g) sized to 55 to 73 μm
Was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was coated on a base catalyst A1 (50 g, saturated water absorption 30 g) to prepare a desulfurization catalyst K2. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００９１】比較例３ ５５〜７３μｍに整粒した白金族触媒Ｂ１（0.２５ｇ）
をイオン交換水９０ｇとシリカゾル１０ｇを含むシリカ
ゾル含有イオン交換水１００ｇに懸濁させ、これを基体
触媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティング
して、脱硫触媒Ｋ３を調製した。この脱硫触媒１０ｇを
用いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫
を行なった。結果を表１に示す。Comparative Example 3 A platinum group catalyst B1 (0.25 g) sized to 55 to 73 μm
Was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was coated on a base catalyst A1 (50 g, saturated water absorption 30 g) to prepare a desulfurization catalyst K3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００９２】比較例４ ５５〜７３μｍに整粒した白金族触媒Ｂ１（１４ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１（５０ｇ、飽和吸水量３０ｇ）にコーティングし
て、脱硫触媒Ｋ４を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表１に示す。Comparative Example 4 A platinum-group catalyst B1 (14 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. The water-absorbing amount was 30 g) to prepare a desulfurization catalyst K4. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.
【００９３】実施例１３ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ２（５０ｇ、飽和吸水量３２ｇ）にコーティングし
て、脱硫触媒Ｎ１を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Example 13 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 32 g) to prepare a desulfurization catalyst N1. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【００９４】実施例１４ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ３（５０ｇ、飽和吸水量２９ｇ）にコーティングし
て、脱硫触媒Ｎ２を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Example 14 A platinum group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , A saturated water absorption of 29 g) to prepare a desulfurization catalyst N2. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【００９５】実施例１５ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ４（５０ｇ、飽和吸水量３３ｇ）にコーティングし
て、脱硫触媒Ｎ３を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Example 15 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 33 g) to prepare a desulfurization catalyst N3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【００９６】実施例１６ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ５（５０ｇ、飽和吸水量３６ｇ）にコーティングし
て、脱硫触媒Ｎ４を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Example 16 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 36 g) to prepare a desulfurization catalyst N4. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【００９７】実施例１７ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ６（５０ｇ、飽和吸水量２５ｇ）にコーティングし
て、脱硫触媒Ｎ５を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Example 17 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 25 g) to prepare a desulfurization catalyst N5. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【００９８】実施例１８ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ２（５０ｇ、飽和吸水量３２ｇ）にコーティングし
て、脱硫触媒Ｎ１を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ２を反応条件Ｐ２にて接触水素化脱硫を
行なった。結果を表２に示す。Example 18 A platinum group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchange water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 32 g) to prepare a desulfurization catalyst N1. Using 10 g of this desulfurization catalyst, the feed oil R2 was subjected to catalytic hydrodesulfurization under the reaction condition P2. Table 2 shows the results.
【００９９】比較例５ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ７（５０ｇ、飽和吸水量３４ｇ）にコーティングし
て、脱硫触媒Ｌ１を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Comparative Example 5 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 34 g) to prepare a desulfurization catalyst L1. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【０１００】比較例６ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ８（５０ｇ、飽和吸水量２８ｇ）にコーティングし
て、脱硫触媒Ｌ２を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Comparative Example 6 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , A saturated water absorption of 28 g) to prepare a desulfurization catalyst L2. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【０１０１】比較例７ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ９（５０ｇ、飽和吸水量２２ｇ）にコーティングし
て、脱硫触媒Ｌ３を調製した。この脱硫触媒１０ｇを用
いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫を
行なった。結果を表２に示す。Comparative Example 7 A platinum-group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 22 g) to prepare a desulfurization catalyst L3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【０１０２】比較例８ ５５〜７３μｍに整粒した白金族触媒Ｂ１（1.０ｇ）を
イオン交換水９０ｇとシリカゾル１０ｇを含むシリカゾ
ル含有イオン交換水１００ｇに懸濁させ、これを基体触
媒Ａ１０（５０ｇ、飽和吸水量１８ｇ）にコーティング
して、脱硫触媒Ｌ４を調製した。この脱硫触媒１０ｇを
用いて、原料油Ｒ１を反応条件Ｐ１にて接触水素化脱硫
を行なった。結果を表２に示す。Comparative Example 8 A platinum group catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. , Saturated water absorption 18 g) to prepare a desulfurization catalyst L4. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.
【０１０３】比較例９ 単層触媒Ｃ１を１０ｇ用いて、原料油Ｒ１を反応条件Ｐ
１にて接触水素化脱硫した。結果を表２に示す。Comparative Example 9 Using 10 g of the single-layer catalyst C1, the feed oil R1 was reacted under the reaction conditions P
In 1, catalytic hydrodesulfurization was performed. Table 2 shows the results.
【０１０４】比較例１０ 基体触媒Ａ１を１０ｇ用いて、原料油Ｒ１を反応条件Ｐ
１にて接触水素化脱硫した。結果を表２に示す。Comparative Example 10 Using 10 g of the base catalyst A1 and the starting oil R1 under the reaction conditions P
In 1, catalytic hydrodesulfurization was performed. Table 2 shows the results.
【０１０５】[0105]
【表１】 [Table 1]
【０１０６】[0106]
【表２】 [Table 2]
【０１０７】[0107]
【発明の効果】以上のように、本発明の水素化脱硫触媒
は、これを用いて、ＶＧＯやＡＲ等の重質油留分を脱硫
するとき、コーク劣化がよく抑えられて、触媒活性を高
く維持しながら、長期間にわたって、減圧軽油（ＶＧ
Ｏ）留分や常圧残油（ＡＲ）中の硫黄化合物を高率にて
除去することができる。As described above, when the hydrodesulfurization catalyst of the present invention is used to desulfurize heavy oil fractions such as VGO and AR, coke deterioration is well suppressed and catalyst activity is reduced. Vacuum gas oil (VG
O) It is possible to remove sulfur compounds in fractions and atmospheric residual oil (AR) at a high rate.
フロントページの続き (72)発明者 中嶋 伸昌 埼玉県幸手市権現堂1134−２ 株式会社コ スモ総合研究所研究開発センター内 (72)発明者 出井 一夫 埼玉県幸手市権現堂1134−２ 株式会社コ スモ総合研究所研究開発センター内 (72)発明者 山本 靖夫 埼玉県幸手市権現堂1134−２ 株式会社コ スモ総合研究所研究開発センター内Continued on the front page (72) Inventor Nobumasa Nakajima 1134-2 Gongendo, Satte-shi, Saitama Kosmo Research Institute R & D Center (72) Inventor Kazuo Dei 1134-2 Gongendo, Satte-shi, Saitama Within the Sumo Research Institute R & D Center (72) Inventor Yasuo Yamamoto 1134-2 Gongendo, Satte City, Saitama
Claims (4)
１種の金属が酸化物換算にて３〜７ｍａｓｓ％と周期律
表第VIＡ族から選ばれる少なくとも１種の金属が酸化物
換算にて１０〜３０ｍａｓｓ％と残部が無機酸化物担体
とからなる基体触媒と、 (b) 周期律表白金族から選ばれる少なくとも１種の金属
が金属換算にて0.２〜１０ｍａｓｓ％と残部が無機酸化
物担体とからなる白金族触媒とからなり、 上記基体触媒の表面に上記白金族触媒が基体触媒１００
ｍａｓｓ部当りに１〜２０ｍａｓｓ部の範囲にてコーテ
ィングされてなることを特徴とする水素化脱硫触媒。(A) at least one metal selected from the iron group of the periodic table is 3 to 7 mass% in terms of oxide; and at least one metal selected from group VIA of the periodic table is in terms of oxide. (B) at least one metal selected from the platinum group of the periodic table has a metal content of 0.2 to 10 mass% and a balance of 0.2 to 10 mass% with the balance being an inorganic oxide carrier; A platinum group catalyst comprising an inorganic oxide carrier;
A hydrodesulfurization catalyst, which is coated in a range of 1 to 20 mass parts per mass part.
コバルト又はニッケルであり、第VIＡ族から選ばれる少
なくとも１種の金属がモリブデンであり、白金族から選
ばれる少なくとも１種の金属が白金、パラジウム、ロジ
ウム、ルテニウム又はイリジウムである請求項１に記載
の水素化脱硫触媒。2. At least one metal selected from the iron group is cobalt or nickel, at least one metal selected from the group VIA is molybdenum, and at least one metal selected from the platinum group is platinum. 2. The hydrodesulfurization catalyst according to claim 1, which is selected from the group consisting of, palladium, rhodium, ruthenium and iridium.
金族触媒の粒子を水に懸濁させて、スラリーとし、この
スラリーを基体触媒にコーティングし、乾燥させ、焼成
して、上記基体触媒の表面に上記白金族触媒がコーティ
ングされてなる請求項１又は２に記載の水素化脱硫触媒
の製造方法において、上記基体触媒の飽和吸水量に対し
て、質量比にて、1.５〜５倍であり、且つ、上記白金族
触媒の粒子に対して、質量比にて、２０〜２００倍の範
囲の量の水に上記白金族触媒の粒子を懸濁させて、スラ
リーとすることを特徴とする水素化脱硫触媒の製造方
法。3. A slurry comprising suspending particles of a platinum group catalyst having a particle size in the range of 10 to 100 μm in water to form a slurry, coating the slurry on a base catalyst, drying and calcining the slurry. 3. The method for producing a hydrodesulfurization catalyst according to claim 1, wherein the platinum group catalyst is coated on the surface of the catalyst. 4. Times, and the particles of the platinum group catalyst are suspended in water in an amount of 20 to 200 times the mass of the particles of the platinum group catalyst with respect to the particles of the platinum group catalyst to form a slurry. A method for producing a hydrodesulfurization catalyst.
１０℃及び液空間速度0.１〜4.０ｈｒ-1の反応条件下
に、重質油を請求項１又は２に記載の触媒と接触させる
ことを特徴とする重質油の水素化脱硫処理方法。4. A partial pressure of hydrogen of 4 to 18 MPa and a temperature of 320 to 4.
3. A hydrodesulfurization treatment of a heavy oil, comprising contacting the heavy oil with the catalyst according to claim 1 under the reaction conditions of 10 ° C. and a liquid hourly space velocity of 0.1 to 4.0 hr −1. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34197396A JP3797731B2 (en) | 1996-12-20 | 1996-12-20 | Hydrodesulfurization catalyst, method for producing the catalyst, and method for hydrodesulfurization of heavy oil using the catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34197396A JP3797731B2 (en) | 1996-12-20 | 1996-12-20 | Hydrodesulfurization catalyst, method for producing the catalyst, and method for hydrodesulfurization of heavy oil using the catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10180109A true JPH10180109A (en) | 1998-07-07 |
| JP3797731B2 JP3797731B2 (en) | 2006-07-19 |
Family
ID=18350202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34197396A Expired - Fee Related JP3797731B2 (en) | 1996-12-20 | 1996-12-20 | Hydrodesulfurization catalyst, method for producing the catalyst, and method for hydrodesulfurization of heavy oil using the catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3797731B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019061A1 (en) * | 1997-10-14 | 1999-04-22 | Japan Energy Corporation | Hydrotreating catalyst for heavy oil, carrier for the catalyst, and process for the preparation of the catalyst |
-
1996
- 1996-12-20 JP JP34197396A patent/JP3797731B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019061A1 (en) * | 1997-10-14 | 1999-04-22 | Japan Energy Corporation | Hydrotreating catalyst for heavy oil, carrier for the catalyst, and process for the preparation of the catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3797731B2 (en) | 2006-07-19 |
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