JP4319812B2 - Hydroprocessing catalyst and hydrocarbon oil hydroprocessing method - Google Patents
Hydroprocessing catalyst and hydrocarbon oil hydroprocessing method Download PDFInfo
- Publication number
- JP4319812B2 JP4319812B2 JP2002234218A JP2002234218A JP4319812B2 JP 4319812 B2 JP4319812 B2 JP 4319812B2 JP 2002234218 A JP2002234218 A JP 2002234218A JP 2002234218 A JP2002234218 A JP 2002234218A JP 4319812 B2 JP4319812 B2 JP 4319812B2
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- JP
- Japan
- Prior art keywords
- catalyst
- pore volume
- silica
- pore
- alumina
- 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.)
- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims description 154
- 238000000034 method Methods 0.000 title claims description 53
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 29
- 229930195733 hydrocarbon Natural products 0.000 title claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 29
- 239000011148 porous material Substances 0.000 claims description 225
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 98
- 229910052751 metal Inorganic materials 0.000 claims description 71
- 239000002184 metal Substances 0.000 claims description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 59
- 238000005984 hydrogenation reaction Methods 0.000 claims description 53
- 238000009826 distribution Methods 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 238000002459 porosimetry Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 description 96
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 230000000694 effects Effects 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000007789 gas Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 28
- 238000004517 catalytic hydrocracking Methods 0.000 description 27
- 239000000017 hydrogel Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000499 gel Substances 0.000 description 20
- 239000000295 fuel oil Substances 0.000 description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 18
- 238000006477 desulfuration reaction Methods 0.000 description 16
- 230000023556 desulfurization Effects 0.000 description 16
- 230000000737 periodic effect Effects 0.000 description 14
- -1 boria Chemical compound 0.000 description 13
- 239000004115 Sodium Silicate Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000013049 sediment Substances 0.000 description 12
- 229910052911 sodium silicate Inorganic materials 0.000 description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 230000002902 bimodal effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000003350 kerosene Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000007848 Bronsted acid Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 6
- 235000012438 extruded product Nutrition 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
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- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000588731 Hafnia Species 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- NICUQYHIOMMFGV-UHFFFAOYSA-N 4-Methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C(C)=CC=C2 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- RAFNAMHEPCFDRC-UHFFFAOYSA-N [W].[Mo].[Co].[Ni] Chemical compound [W].[Mo].[Co].[Ni] RAFNAMHEPCFDRC-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
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- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
【０００１】
【発明が属する技術分野】
本発明は、炭化水素油の水素化処理用触媒およびそれを用いる炭化水素油の水素化処理方法に関するものであり、さらに詳しくは、シリカ−アルミナ系水素化処理用触媒およびそれを用いる炭化水素油、特に、ナフサ、ケロシン、軽油、減圧軽油（ＶＧＯ）、減圧残渣油（ＶＲ）等の燃料油留分の水素化処理方法に関するものである。
なお、本明細書において、本発明に関し「水素化処理」とは、炭化水素油と水素との接触による反応を総称したものであり、炭化水素油の水素化脱硫、水素化脱窒素、水素化脱芳香族、水添異性化、水素化精製および水素化分解等を包含するものである。
【０００２】
【従来の技術】
従来、石油等炭化水素油の水素化処理に用いられる触媒として、アルミナ、シリカ−アルミナ、ボリア、マグネシア、ジルコニア等およびこれらの混合組成からなる耐火性無機酸化物を担体とし、元素周期表第６Ａ族金属、同表第８族金属等を含有する活性成分を担持させた水素化処理用触媒が種々提案されている。例えば、特開昭６１−２８７４４６号公報には、アルミナ水和物とコロイド状シリカとの混合溶液に塩基性化合物を添加し増粘ゲル化後、触媒担体を調製する方法が開示され、また、特開昭６１−２４２６３９号公報によれば、燒結セラミックス構造体層と一体化した多孔性酸化物の高表面担体層を有するモノリシックであって、アルミナ５０〜９３重量％およびシリカ７〜５０重量％からなる触媒担体が開示されている。さらに、担体としてのボリア−シリカ−アルミナに元素周期表第６Ａ族金属および／または同表第８族金属を担持し、平均細孔直径が６０〜９０Åで平均細孔直径±１０Åの範囲の細孔容積が全細孔容積の６０％以上の水素化精製用触媒（特開平８−８９８０６号公報。）のほか、特開平９−２７６７１２号公報ではアルミナ、シリカおよびマグネシアを含有させた担体に元素周期表第６Ａ族金属および／または同表第８族金属を担持させてなり、平均細孔直径１９０〜３５０Åの水素化精製用触媒が提案されている。
【０００３】
かかる水素化処理用触媒は、例えば常圧蒸留および減圧蒸留の留出油または残渣油の水素化脱硫、水素化脱窒素および水素化分解、潤滑油留分の水素化精製、ワックス留分の水添異性化等に用いられるが、各種炭化水素油の水素化処理において水素化処理用触媒の細孔構造および細孔分布、ならびに触媒表面の酸性質およびその量が触媒活性および活性維持能にとって重要なキイファクターであることが認識されてきた。従って、例えば、本出願人によっても、主として留出油の水素化脱硫、脱窒素、芳香族水添等において高活性を発揮する触媒として、直径３００Å以上の特定領域の細孔容積を低く制御し、均一な細孔分布を有するシリカ−アルミナ担体に水素化活性成分を担持させた水素化処理用触媒（特公平３−３１４９６号公報）および該水素化処理用触媒に係る発明を発展させ、細孔直径３００〜１５０，０００Åの領域に０．０１〜０．２５ｍｌ／ｇの細孔容積を有し、かつ細孔直径３００〜６００Åの領域の細孔容積が、直径３００〜１５０，０００Å領域の細孔容積の４０％以上である水素化処理用触媒を提案した（特開平８−８９８１６号公報）。さらに、特開平６−１２７９３１号公報により、細孔直径３０〜３００Åの範囲および３００〜１５００Åの範囲にそれぞれ細孔容積分布のピークを有するバイモダル構造のシリカ−アルミナ系触媒についても提案した。
【０００４】
しかしながら、近年、環境保全の観点からサルファー含有量を著しく低減したクリーン燃料（ガソリンおよび軽油についてはＳ分として５０ｐｐｍ以下。）の製造が義務づけられ、さらに将来、サルファーを殆ど含有しないサルファーフリー燃料の製造のための高度脱硫処理技術が強く求められることが必至である。また、芳香族成分を大巾に低減した燃料性状についても自動車エミッションに対する影響の調査研究が積極的に進められており、将来にはこれを低減するための議論がなされている。かかる状況に対処するために前記の如き従来提案されてきた水素化処理用触媒では、脱硫性能、脱窒素性能、芳香族水添性能および水素化分解性能、さらにはその活性維持能の観点では必ずしも十分でなく、より高性能な水素化処理用触媒の開発が不可欠の状況となっている。特に、重質油の水素化分解処理において、高分解率運転を行なうと水素化分解反応および熱分解反応が生じる一方、脱水素および重縮合反応も激しく起こり、プロダクト中にアスファルテンおよびセディメント固形物が生成・増大するため、これらによりリアクター内および下流の蒸留装置および配管類へのセディメント蓄積によるファウリングが発生し、装置運転上深刻な問題を招く。従って、重質油の水素化分解プロセスにおいては、クリーン燃料への要求から触媒の水素化能を強化することにより分解率、水素化脱硫、脱窒素、脱芳香族の各活性を向上させる必要があるが、一方で水素化能向上によりプロダクトの芳香族性が低下し溶存しているアスファルテン等の巨大縮合芳香族化合物の析出によるセディメントの増加をもたらすという弊害が生ずる。
【０００５】
このように、従来の重質油の水素化分解プロセスにおいては、水素化能の強化とセディメント低減効果との間にはトレードオフの関係があり、前記の如き従来提案された水素化処理用触媒では高度水素化分解とセディメント生成の抑制の両者を同時に達成することができず、かかる両性能を備えた水素化処理用触媒の開発が切望されている。
【０００６】
【発明が解決しようとする課題】
従って、本発明の課題は、前記の如き水素化処理用触媒の開発状況に鑑み、各種炭化水素油に対し、脱硫活性、脱窒素活性、芳香族水添活性および水素化分解活性に優れた水素化処理用触媒であり、特に、軽油および減圧軽油（ＶＧＯ）の水素化および水素化脱硫・脱窒素活性に優れた水素化処理用触媒ならびに重質油の水素化分解において高度水素化活性とセディメント生成抑制能を併有する水素化処理用触媒を提供することにある。
【０００７】
【課題を解決するための手段】
そこで、本発明者らは、前記課題を解決するべく、鋭意検討を重ねた結果、シリカ−アルミナ系担体に少なくとも一種の水素化活性金属成分を担持させてなる水素化処理用触媒であって、細孔容積分布において、特定のバイモダル細孔構造を有する水素化処理用触媒が、軽質油はもちろん重質油の水素化処理において脱硫活性、脱窒素活性、芳香族水添活性および水素化分解活性において顕著な作用効果を奏することを見い出し、さらに該水素化処理用触媒を用いる水素化処理方法により重質油から高品質のクリーン燃料を提供できることに着目し、これらの知見に基づいて本発明の完成に到達した。
【０００８】
かくして、本発明によれば、
アルミナ表面上にシリカ層を形成した構造を有し、シリカを担体全重量基準で２〜４０重量％含有するシリカ−アルミナ系担体に、少なくとも一種の水素化活性金属成分を担持してなる水素化処理用触媒であって、
水銀圧入法により測定される細孔容積分布において、
【０００９】
（１）細孔直径４０〜２００Åの範囲に細孔容積分布の第一のピークを有し、
（２）細孔直径２００〜２０００Åの範囲に細孔容積分布の第二のピークを有し、
（３）全細孔容積に対する細孔直径４０〜２００Åの領域の細孔容積が４０〜
９０％であり、
（４）全細孔容積に対する細孔直径２００〜１０００Åの領域の細孔容積が１０〜
６０％であり、
（５）全細孔容積に対する細孔直径１０００Å以上の領域の細孔容積が２０％以下
であり、
（６）前記細孔直径４０〜２００Åの範囲に存在する前記第一のピークの位置に
対応する細孔直径±２０Åの範囲の細孔容積が、前記細孔直径４０〜２００Åの
範囲の細孔容積の５０％以上であり、
（７）平均細孔直径が６０〜１５０Åであり、
窒素吸着法により測定される比表面積が１５０〜４００ｍ２／ｇ
であることを特徴とする水素化処理用触媒
が提供される。
【００１０】
また、本発明によれば、水素化処理用触媒に適した触媒担体として
アルミナ表面上にシリカ層を形成した構造を有し、シリカを担体全重量基準で２〜４０重量％含有するシリカ−アルミナ系担体であって、
水銀圧入法により測定される細孔容積分布において、
【００１１】
▲１▼ 細孔直径４０〜２００Åの範囲に細孔容積分布の第一のピークを有し、
▲２▼ 細孔直径２００〜２０００Åの範囲に細孔容積分布の第二のピークを有し、
▲３▼ 全細孔容積に対する細孔直径４０〜２００Å領域の細孔容積が４０〜９０％であり、
▲４▼ 全細孔容積に対する細孔直径２００〜１０００Å領域の細孔容積が１０〜６０％であり、
▲５▼ 全細孔容積に対する細孔直径１０００Å以上の領域の細孔容積が２０％以下であり、
▲６▼ 前記細孔直径４０〜２００Åの範囲に存在する前記第一のピークの位置に対応する細孔直径±２０Åの範囲の細孔容積が、前記細孔直径４０〜２００Åの範囲の細孔容積の５０％以上であり、
▲７▼ 平均細孔直径が６０〜１５０Å
であることを特徴とするシリカ−アルミナ系担体
が提供される。
【００１２】
さらに、本発明によれば、
アルミナ表面上にシリカ層を形成した構造を有し、シリカを担体全重量基準で２〜４０重量％含有するシリカ−アルミナ系担体に、少なくとも一種の水素化活性金属成分を担持してなる水素化処理用触媒であって、水銀圧入法により測定される細孔容積分布において、
【００１３】
（１）細孔直径４０〜２００Åの範囲に細孔容積分布の第一のピークを有し、
（２）細孔直径２００〜２０００Åの範囲に細孔容積分布の第二のピークを有し、
（３）全細孔容積に対する細孔直径４０〜２００Åの領域の細孔容積が４０〜
９０％であり、
（４）全細孔容積に対する細孔直径２００〜１０００Åの領域の細孔容積が１０
〜６０％であり、
（５）全細孔容積に対する細孔直径１０００Å以上の領域の細孔容積が２０％
以下であり、
（６）前記細孔直径４０〜２００Åの範囲に存在する前記第一のピークの位置に
対応する細孔直径±２０Åの範囲の細孔容積が、前記細孔直径４０〜２００Åの
範囲の細孔容積の５０％以上であり、
（７）平均細孔直径が６０〜１５０Åであり、
窒素吸着法により測定される比表面積が１５０〜４００ｍ２／ｇ
である水素化処理用触媒の存在下において、炭化水素油を水素化処理条件下で水素とを接触させることを特徴とする炭化水素油の水素化処理方法
が提供される。
【００１４】
本発明によれば、前記水素化処理用触媒および該水素化処理用触媒を用いる炭化水素油の水素化処理方法を提供するものであるが、さらに好ましい実施の態様として次の１）〜１４）に掲げるものを包含する。
【００１５】
１）前記シリカ−アルミナ系担体に配合させてもよい第三担体成分が、マグネシア、酸化カルシウム、ボリア、ジルコニア、チタニア、トリア、セリア、ハフニア、酸化リンからなる群より選択される少なくとも一種の酸化物である前記水素化処理用触媒。
２）前記水素化活性金属成分が、元素周期表第６Ａ族金属成分の少なくとも一種と同表第８族金属成分の少なくとも一種とからなる金属成分である前記水素化処理用触媒。
３）前記元素周期表第６Ａ族金属成分がモリブデンおよび／またはタングステンであり、前記元素周期表第８族金属成分が、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウムおよび白金からなる群より選択される少なくとも一種の金属成分である前記水素化処理用触媒。
４）前記第二のピークが細孔直径２００〜１５００Åの範囲にある前記水素化処理用触媒。
５）前記細孔直径４０〜２００Åの領域の細孔容積が全細孔容積に対して４５〜８０％である前記水素化処理用触媒。
６）前記細孔直径２００〜１０００Åの領域の細孔容積が全細孔容積に対して２０〜５０％である前記水素化処理用触媒。
７）前記細孔直径１０００Å以上の領域の細孔容積が全細孔容積に対して１５％以下である前記水素化処理用触媒。
８）前記細孔直径４０〜２００Åの範囲に存在する前記第一のピークの位置に対応する細孔直径±１０Åの範囲の細孔容積が、前記細孔直径４０〜２００Åの範囲の細孔容積の３０％以上である前記水素化処理用触媒。
９）前記比表面積が１６０〜３７０ｍ2/ｇである前記水素化処理用触媒。
１０）アルミナ表面上にシリカ層を形成した構造を有し、シリカを担体全重量基準で２〜４０重量％含有するシリカ−アルミナ系担体に少なくとも一種の水素化活性金属成分を担持してなる水素化処理用触媒であって、該触媒の細孔特性において、
▲１▼前記第一のピークが細孔直径４０〜２００Åの範囲にあり、
▲２▼前記第二のピークが細孔直径２００〜１５００Åの範囲にあり、
▲３▼前記細孔直径４０〜２００Åの範囲の細孔容積が全細孔容積に対して４５〜８０％であり、
▲４▼前記細孔直径２００〜１０００Åの範囲の細孔容積が全細孔容積に対して２０〜５０％であり、
▲５▼前記細孔直径１０００Å以上の範囲の細孔容積が全細孔容積に対して１５％以下であり、
▲６▼前記細孔直径４０〜２００Åの範囲に存在する前記第一のピークの位置に対応する細孔直径±１０Åの範囲の細孔容積が、前記細孔直径４０〜２００Åの範囲の細孔容積の３０％以上であり、
▲７▼前記平均細孔直径が６０〜１５０Åであり、
▲８▼全細孔容積が０．３〜１．２ｍｌ／ｇであり、
▲９▼前記比表面積が１６０〜３７０ｍ2／ｇ
である前記水素化処理用触媒。
１１）前記炭化水素油が、ナフサ、ケロシン、軽油および減圧軽油からなる群より選択される燃料油留分である前記水素化処理方法。
１２）前記炭化水素油が、常圧蒸留残渣油、減圧蒸留残渣油、減圧軽油および分解軽油からなる群より選択される重質油である前記水素化処理方法。
１３）前記燃料油留分の水素化処理条件が、
水素圧力(Psig)： 100〜3000
水素トリートガスレート(SCF/B)：300〜5000
液空間速度(V/H/V)： 0.1〜4
温度(℃)： 200〜470
の条件から選択された特定反応条件である前記水素化処理方法。
１４）前記重質油の水素化処理条件が、
水素圧力(Psig)： 600〜3000
水素トリートガスレート(SCF/B)：500〜5000
液空間速度(V/H/V)： 0.1〜3
温度(℃)： 350〜470
の各条件から選択された特定反応条件である前記水素化処理方法。
【００１６】
【発明の実施の形態】
以下、本発明についてさらに詳細に説明する。
本発明の水素化処理用触媒の特異性の一つは、アルミナ表面上に高度に分散したシリカ層を形成させてなり、シリカ含有量が担体全重量基準で２〜４０重量％であって、高比表面積を有し、かつブレンステッド酸を含有するシリカ−アルミナ系担体上に少なくとも一種の水素化活性金属成分を担持させてなる点にある。
【００１７】
また、第二の特異性は、水素化処理用触媒の細孔容積分布において特定のバイモダル細孔構造を有する点にあり、かかる細孔構造を有することにより後記する如く、軽油および減圧軽油（ＶＧＯ）の水素化脱硫、脱窒素、脱芳香族反応において、初期活性劣化の抑制および分子拡散性の向上による活性向上を実現し、かつ重質油を含めた各種炭化水素油と水素との接触において制御された水素化処理反応を行なうことができ、特に、重質油の水素化処理において高水素化性能およびセディメント抑制性能に優れた水素化処理用触媒を実現するものである。
【００１８】
本発明に係る水素化処理用触媒の構成成分としてのシリカ−アルミナ系担体は核としてのアルミナの表面にシリカ層が形成した構造を有するものであり、シリカ−アルミナ担体中のシリカ成分は触媒の固体酸性度の制御および向上に好適であり、水素化活性金属成分の分散性を著しく向上させると共に触媒に比較的強い酸点を付与し分解活性を増大させることができる。従って、シリカ含有量は水素化処理の反応の種類および反応条件により適宜選択することができるが、水素化脱硫反応、水素化脱窒素反応に対しては過度の分解反応に伴なう水素消費量の増加およびコークの生成等を抑制するために、また、水素化分解においては適度な分解反応を制御する観点から担体全重量基準で２〜４０重量％の範囲で採用することができる。特に、水素化脱硫反応等の水素化精製に対しては４〜２０重量％、水素化分解に対しては５〜２５重量％をより好ましい範囲として選択することができる。シリカ含有量が４０重量％を超えると原料油の分解を過度に進行させ、コークアップが激しくなるという難点が生ずる。シリカ−アルミナ系担体中のアルミナ成分としてはγ−アルミナ、χ−アルミナまたはη−アルミナのいずれかまたはそれらの混合体が好適である。アルミナ成分の形態としては本発明の水素化処理用触媒の構成成分として前記の特定の細孔構造および細孔容積分布ならびに特性値を与えるものであれば、いずれのものでも特に制限されることなく好ましく使用することができる。
【００１９】
また、シリカ−アルミナ系担体には、他の耐火性無機酸化物、例えば、マグネシア、酸化カルシウム、ボリア、ジルコニア、チタニア、トリア、セリア、ハフニア、酸化リンおよび結晶性ゼオライト等からなる群より選択される一種または二種以上を第三成分として含有させることができる。
【００２０】
従って、具体的には、シリカ−アルミナ−マグネシア、シリカ−アルミナ−酸化カルシウム、シリカ−アルミナ−ボリア、シリカ−アルミナ−ジルコニア、シリカ−アルミナ−チタニア、シリカ−アルミナ−トリア、シリカ−アルミナ−セリア、シリカ−アルミナ−ハフニア、シリカ−アルミナ−酸化リン、シリカ−アルミナ−結晶性ゼオライト、シリカ−アルミナ−酸化リン−ボリア等のシリカ−アルミナ系担体を例示することができる。かかる第三成分としての耐火性無機酸化物の含有量は、担体全重量基準で０．１〜１０重量％の範囲が適当である。これらの耐火性無機酸化物、例えば、マグネシアは、シリカ−アルミナ等が有する比較的強い酸点を減少させ同時に弱酸点を増加させて触媒の選択性を向上させることができる。
【００２１】
次に、本発明に係る水素化処理用触媒の細孔構造について説明すると、当該触媒は、比較的小細孔径領域および大細孔径領域の両領域の細孔容積分布においてそれぞれ一つ以上のピークが現われるバイモダル構造を有するものであり、具体的には水銀圧入法で測定される細孔構造または細孔容積分布において少なくとも下記の構成要素（１）〜（９）を有するものである。以下に各要素の特徴点について説明する。
【００２２】
要素（１）細孔直径４０〜２００Åの範囲に細孔容積分布の第一のピークを有する。この場合において細孔直径２００Å以上の領域に該第一のピークを有する触媒は、比表面積が低下し高活性が得られないという難点が生じる。一方、細孔直径４０Å以下の領域にピークを有する触媒の製造は困難であり、本発明が要求する効果を奏する触媒を得ることには現実性に乏しいものである。なお、細孔直径４０〜２００Åの範囲内に存在するピークは、二つ以上に分岐したものであってもよい。
要素（２）細孔直径２００〜２０００Åの範囲に細孔容積分布の第二のピークを有する。第二のピークの位置は、細孔直径２００〜１５００Åの範囲に存在することが特に好ましい。これにより重質油の水素化分解反応において特定サイズの分子種（アスファルテンおよびレジンに代表される巨大芳香族分子）に対する選択性が高く、分解率および水素化、水素化脱硫、脱窒素を適度に制御することができ、軽油および減圧軽油の脱硫、脱窒素反応およびその活性維持能を向上させ、また重質油の水素化分解において高度分解率で水素化性能とセディメント抑制能を発揮させる基本となるものと推定される。なお、第２のピークの位置が細孔直径２０００Å以上にあると触媒強度が著しく低下して使用に耐えられないおそれが生ずる。なお、細孔直径２００〜２０００Åにおけるピークは当該範囲内にあれば二つ以上に分岐していてもよい。
要素（３）前記第一のピークが存在する細孔直径４０〜２００Å領域の細孔孔容積は、全細孔容積の４０〜９０％、好ましくは４５〜８０％である。細孔直径４０〜２００Åの範囲の細孔容積が４０％に達しないと大細孔部位が増えすぎ、触媒強度の問題が生じ、一方、９０％を超えると所望の大細孔領域が少なすぎ、期待する活性が得られないおそれがある。
要素（４）細孔直径２００〜１０００Åの範囲の細孔容積が、全細孔容積の１０〜６０％、好ましくは２０〜５０％を占める。細孔直径２００〜１０００Åの領域の細孔容積が、１０％に達しないと大孔径細孔が少なくなりすぎ、一方、６０％を超えると拡散する細孔分布のバランスが悪くなり、十分な効果が得られない。また、触媒強度が著しく低下して使用に耐えられないおそれが生ずる。
要素（５）細孔直径１０００Å以上の細孔の容積が、全細孔容積の２０％以下、好ましくは１５％以下に制御されたものである。当該細孔容積が２０％を超えると触媒強度の維持に難点が生ずる。
要素（６）前記細孔直径４０〜２００Åの範囲に存在する前記第一のピークの位置に対応する細孔直径±２０Åの範囲の細孔容積が、前記細孔直径４０〜２００Åの範囲の細孔容積の５０％以上であることが本発明に係る水素化処理用触媒の細孔特性として最も特異的な要素の一つである。特に好ましい細孔構造は、前記第一のピークの位置に対応する細孔直径±１０Åの範囲の細孔容積が、前記４０〜２００Åの範囲の細孔容積の３０％以上のものである。
かかる細孔特性は、細孔直径４０〜２００Åの範囲において第一のピークに係る細孔容積分布がシャープであり、ピーク位置に対応する直径を有する細孔を中心に均一の細孔が多く存在することを示すものである。この結果、第一のピークの半値巾は、７０Å以下、好ましくは５０Å以下のものとなる。
第一のピークの位置に対応する細孔直径±２０Åの範囲の細孔容積が５０％に満たないと不適切な直径の細孔が増加しすぎ、著しい強度低下を招き、触媒粉化による△Ｐおよびファウリングの発生により実生産上安定な装置運転に支障が生じる。また、全細孔容積が１．２ｍｌ／ｇ超える高容量触媒となり、触媒のＣＢＤ (Compacted Bulk Density)が著しく低下してリアクター体積活性が低下するという問題が生ずる。
なお、ピークが分岐した場合は、最大のピークを対象とし、そのピーク位置に対応する細孔直径を採用して細孔直径±２０Åの細孔容積を算出する。
要素（７）平均細孔直径が６０〜１５０Åの範囲にある。
要素（８）全細孔容積が０.３〜１.２ｍｌ／ｇ、好ましくは０.３５〜０.９５ｍｌ／ｇのものである。
要素（９）比表面積が１５０〜４００ｍ2／ｇであり、高比表面積を実現したものである。
【００２３】
本発明に係る水素化処理用触媒の水素化活性金属成分としては、周期表第６Ａ族金属および同表第８族金属からなる群より選択される少なくとも一種の金属を用いることができる。すなわち、第６Ａ族のクロム、モリブデン、およびタングステン、第８族のコバルト、ニッケル、パラジウム、白金、オスミウム、イリジウム、ルテニウムおよびロジウム等からなる群より一種または二種以上の金属を選択することができる。炭化水素油の水素化脱硫、水素化脱窒素、水素化分解、水素化脱芳香族等のためには周期表第６Ａ族金属の少なくとも一種と同表第８族金属の少なくとも一種との組合せが好適であり、例えば、モリブデン−コバルト、モリブデン−ニッケル、タングステン−ニッケル、モリブデン−コバルト−ニッケル、タングステン−コバルト−ニッケルまたはモリブデン−タングステン−コバルト−ニッケル等の組合せが好ましい。
さらに、これらの活性金属成分に周期表第７Ａ族金属、例えば、マンガンおよび同表第４Ｂ族金属、例えば、錫、ゲルマニウムまたは鉛等を添加して使用することもできる。
これらの水素化活性金属成分は、酸化物および／または硫化物として担持させたものが好適であり、硫化物は後記の如き触媒の予備硫化処理により触媒上に形成させることができる。
【００２４】
前記周期表第８族および第６Ａ族の水素化活性金属成分の含有量は、酸化物として触媒全重量基準で第８族金属については０．５〜３０重量％、好ましくは１〜１０重量％であり、第６Ａ族金属については５〜３０重量％、好ましくは８〜２５重量％である。第８族金属が０．５重量％に達しないと十分な脱硫・脱窒素活性が得られず、水素化脱芳香族、水素化能が十分発揮されない。一方、３０重量％を超えると担体と結合しない遊離の金属成分が増加し、第６Ａ族金属と不活性の複合酸化物を生成し、その結果、第６Ａ族金属の分散性を低下させるという難点が生ずる。また、第６Ａ族金属が５重量％未満では脱硫・脱窒素活性が得られず、一方、３０重量％を超えると金属成分の分散性が低下すると共に第８族金属の助触媒効果が発揮されないという弊害が生ずる。
【００２５】
本発明に係る水素化処理用触媒は、以上説明してきた如く、前記シリカ−アルミナ系担体と該担体に担持された水素化活性金属成分とからなり、比表面積１５０〜４００ｍｍ2／ｇおよび全細孔容積０．３〜１．２ｍｌ／ｇを有し、特定の細孔直径４０〜２００Åの範囲に細孔容積分布の第一のピークを有し、かつ細孔直径２００〜２０００Åの範囲に第二のピークを有すると共に、かかる二つの細孔直径の領域においてそれぞれ特異な細孔特性を示し、特に、第一のピークは、本発明者らにより始めて具現化したシャープな形態を有するものである。
【００２６】
かかる水素化活性金属成分および細孔構造から炭化水素油の水素化処理において予期せざる作用効果を奏するものであり、炭化水素油の触媒内への拡散をより容易にし、触媒活性劣化を大幅に低減することができるので、ナフサ、ケロシン、直留軽油、減圧軽油（ＶＧＯ）と水素とを接触させる水素化精製において脱硫活性、脱窒素活性、芳香族水添活性を大幅に向上させることができる。また、本発明に係る水素化処理用触媒と重質油（ＶＧＯ、ＶＲ）および水素とを接触させる水素化分解において、分解率およびアスファルテン処理能の向上を実現し、ガス、軽質油（ナフサ、ケロシン、軽油および減圧軽油（ＶＧＯ））の収率増大、これらの硫黄、窒素含有量を大幅に低減し、またプロダクト中に含まれるセディメント含有量を大幅に低減させることができるなど著しく顕著な効果を奏するものである。
【００２７】
かくして、本発明に係る水素化処理用触媒は、細孔容積分布において前記の如きシャープな第一のピークを示すバイモダル構造を含む特異な細孔特性を有することから従来の水素化処理用触媒と同程度の高い触媒強度を維持した上で、水素化、水素化脱硫・脱窒素反応、水素化分解等において高度な活性および活性維持能を奏することが可能となった。つまり、本発明の水素化処理用触媒は、不要な直径の細孔の割合を低減させているため、すでに提案されたバイモダル構造を有する触媒と比較して強度が著しく向上しており、従来の水素化処理用触媒と同等程度の強度を維持することができる。触媒強度として例えば、平均側面強度として直径１．３ｍｍの円柱状ペレットでは１〜４ｌｂｓ／ｍｍ、直径１ｍｍの円柱状ペレットでは０．５〜３．０ｌｂｓ／ｍｍのものを得ることができる。また、すでに提案されたバイモダル構造を有する触媒と比較してＣＢＤ(Compacted-Bulk-Density)も増大するので触媒体積当たりの活性が著しく向上する、という特性を有するものである。
なお、触媒形状は、円柱状、粒状、または錠剤状その他断面が四つ葉状等の異形状を含め如何なるものでもよく、反応形式により任意に選択することができる。また、成形体のサイズは限定されるものではないが、通常直径０．５〜３ｍｍの範囲のものを採用することができる。
【００２８】
前記の如き特性値を有する水素化処理用触媒は、次に示す製造方法を採用することにより調製することができる。
すなわち、本発明に係る水素化処理用触媒の構成成分としてのシリカ−アルミナ系担体は、シリカ水和物ゲルおよびアルミナ水和物ゲルを各々調製しておき両者を混合する方法、水溶性アルミニウム化合物と水溶性ケイ素化合物との均一混合溶液に塩基性物質または酸性物質を添加して両者を共沈させる方法等を条件・操作を制御することにより採用することができるが、特に、本発明の水素化処理用触媒として必要な細孔構造および物性値を有し、アルミナ上にシリカが高度に分散したシリカ−アルミナ系担体を得るためには特定条件下において特定のアルミナ水和物ゲルを生成させた後、アルミナ水和物ゲル上にシリカ水和物ゲルを沈着させる方法が好適であり、具体的に例示すれば次の如くである。
【００２９】
酸性アルミニウム化合物または塩基性アルミニウム化合物の各水溶液からアルミナ水和物ゲルを酸性から中性またはアルカリ性へｐＨスウィングを行ないながらゲル化速度と再溶解速度を制御しながら所望の細孔構造が得られるようにアルミナ水和物ゲルを調製する第一工程と、前記工程にて生成したアルミナ水和物ゲル上に水溶性ケイ素化合物の水溶液を添加してシリカゲルを沈着させる第二工程とから構成される。第二工程においてアルミナ水和物ゲル上へのシリカ水和物ゲルを沈着させる際のｐＨをコントロールすることにより、シリカ水和物ゲルのゲル化速度を制御し、アルミナとシリカの結合を良好にしたシリカ層を形成させることが好ましい。
【００３０】
前記酸性アルミニウム化合物としてはアルミニウムの硫酸塩、塩化物、硝酸塩等が用いられる。また、塩基性アルミニウム化合物としては、アルミン酸ナトリウム、アルミン酸カリウム等が用いられる。
さらに具体的には、第一工程においてｐＨ１０以上の水酸化アルカリ化合物水溶液に酸性アルミニウム水溶液を１分以上で溶解導入することが好ましく、アルミナヒドロゲルの溶解・沈積速度を制御しながら最適なゲル粒径分布をつくることが必要であり、混合後、加温条件下で、適切な熟成処理を施しながら水酸化アルカリ化合物を添加し、ｐＨを調整し、アルミナ水和物ゲルを沈殿させる。水酸化アルカリ化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム等を挙げることができる。
【００３１】
また、第二工程においては、第一工程にて得られたアルミニウム水和物ゲルのスラリーに水溶性ケイ素化合物の水溶液を添加混合し、ｐＨ７〜１０の条件下で温度５０〜８０℃に保持しアルミナ水和物ゲル上にシリカ水和物ゲルを沈着させる。水溶性ケイ素化合物としてはアルカリ金属ケイ酸塩、テトラアルコキシシラン、オルソケイ酸エステル等を用いることができる。アルカリ金属ケイ酸塩としてはＮａ2Ｏ：ＳｉＯ2のモル比が１：２〜１：４の範囲のケイ酸ナトリウムの使用が好ましい。
また、アルミナ水和物ゲルへのシリカ水和物ゲルの沈着中または沈着後にアルミナゲルに対するシリカゲルの分散状態を著しく向上させるため、さらには所望のバイモダル細孔構造を形成させるためにｐＨ、温度および時間の制御下で熟成処理を行なう工程が設けられる。この熟成処理によりシリカ−アルミナ中のＳｉ原子の分散状態が著しく向上し、ブレンステッド酸量の増大および高比表面積化を実現することができる。
【００３２】
前記熟成工程にて得られたシリカ−アルミナヒドロゲルスラリーは、適量の水と酸を混合した状態でニーダーにより所定の直径および形態を有する触媒へと押出成形される。押出成形物ゲルの乾燥処理は、酸素の存在下または非存在下において常温〜約２００℃に加熱することにより行ない、また、その後の焼成処理は、酸素の存在下において約４００〜約８００℃、好ましくは、約６００〜約７００℃の範囲に加熱することにより行なう。乾燥および焼成処理によりＳｉが高分散した高ブレンステッド酸量、高比面積を有し、前記の特定の細孔構造を有するシリカ−アルミナ系担体を得ることができる。
【００３３】
次に、該シリカ−アルミナ系担体に水素化活性金属成分を担持させる。該金属成分の担持方法としては、担体を前記金属成分の可溶性塩の溶液に浸漬し、該金属成分を担体中に導入する含浸法または担体の製造の際、金属成分を同時に沈殿させる共沈法等を採用することができ、その他如何なる方法を使用しても差し支えがないが、操作上容易であり触媒物性の安定化維持に好都合な含浸法によることが好ましい。含浸操作としては担体を常温または常温以上で含浸溶液に浸漬して所望成分が十分担体中に含浸する条件下で保持する。含浸溶液の量および温度は、所望量の活性金属成分が担持されるように適宜調整することができる。また、活性金属成分の所望担持量により含浸溶液に浸漬する担体の量を決定することができる。
【００３４】
水素化活性金属成分の担体上への含浸担持は、一液含浸法または二液含浸法等のいずれの方法により行なってもよい。すなわち、二種以上の金属成分を担持するには、二種以上の金属成分をあらかじめ混合し、その混合溶液から同時に含浸（一液含浸法）するかまたは二種以上の金属成分の溶液を別々に調製し、逐次含浸していく（二液含浸法）こともできるわけであり、本発明の水素化処理用触媒の製造においては、これらの含浸方法を何ら限定するものではなく、いずれの方法も任意に採用することができるが、前記のシリカ−アルミナ担体上に先ず元素周期表第８族金属からなる群より選択される一種または二種以上の金属を担持させ（第一ステップ）、次いで、同表第６Ａ族金属からなる群より選択される一種または二種以上の金属を担持させる（第二ステップ）ことが好ましい。具体的には、第一ステップにおいて元素周期表第８族のコバルト、ニッケル、パラジウム、白金、オスミウム、イリジウム、ルテニウムおよびロジウム等からなる群より一種または二種以上が選択して使用される。好ましくは、コバルトおよびニッケルを単独または両者を組合せて使用することができる。また、第二ステップにおいては元素周期表第６Ａ族のクロム、モリブデンおよびタングステンからなる群より一種または二種以上が選択して使用される。好ましくはモリブデンおよびタングステンが単独でまたは両者を組合せて使用することができる。また所望に応じ、前記のような元素周期表第４Ｂ族、同表第７Ａ族の第三の金属を添加することもできる。
【００３５】
先に述べた金属成分を担体と同時に沈殿させる共沈法を採用する場合には水素化活性金属成分を含浸担持した担体は、押出成形、打状成形、転動造粒等の成形方法により成形した後、乾燥処理、さらに焼成処理を行なう。乾燥処理は、酸素の存在下または非存在下において、常温〜約２００℃に加熱することにより行ない、焼成処理は、酸素の存在下において約４００〜約８００℃、好ましくは約４５０〜約７００℃に３〜５時間加熱することにより行なうことができる。
【００３６】
次に、本発明に係る炭化水素油の水素化処理方法について説明する。
本発明に係る炭化水素油の水素化処理方法は、前記水素化処理油触媒の存在下において、炭化水素油を水素化処理条件下で水素と接触させる工程を包含するものである。
【００３７】
水素化処理に供される原料油としては、特に限定されるものではなく、常圧蒸留留出油、常圧蒸留残渣油、減圧蒸留留出油、減圧蒸留残渣油、分解軽油留分またはこれらの混合油等いずれも用いることができるが、特に、ナフサ、ケロシン、直留軽油、減圧軽油（ＶＧＯ）、および減圧残渣油を効率よく水素化処理に供することができる。減圧軽油は、常圧蒸留残渣油を減圧蒸留して得られる約３７０〜６１０℃の範囲の沸点を有する留出油であり、硫黄分、窒素分および金属分を相当量含有するものである。例えば、中東原油減圧軽油の一例を挙げるならば、約２〜約４重量％の硫黄分、約０．０３〜約０．２重量％の窒素分を含有する。また、残留炭素分を約１重量％程度含有する。分解軽油は、残渣油を熱分解して得られる約２００℃以上の沸点を有する分解油であり、例えば、残渣油のコーカーおよびビスブレーカー等から得られる。また、接触分解装置から得られるライトサイクルガスオイル（ＬＣＧＯ）およびヘビーサイクルガスオイル（ＨＣＧＯ）等も原料油として本発明の水素化処理方法に供することができる。本発明の水素化処理方法によれば、前記減圧軽油の水素化脱硫・脱窒素を効果的に行なうことができるが、特に、常圧残渣油または減圧残渣油の水素化分解を高分解率で円滑に行なうことができ、高品質製品を得ることができる。
【００３８】
水素化処理の反応条件は、ナフサ、ケロシン、直留軽油、減圧軽油（ＶＧＯ）および減圧残渣油（ＶＲ）が水素化処理される場合には脱硫率、脱窒素率等の目標値により適宜選択することができるが、次の反応条件を採用することができる。
前記炭化水素油の水素化脱硫・水素化脱窒素等の水素化精製においては、特に軽油中に含有される脱硫反応の困難な４−メチルジベンゾチオフェンおよび４，６−ジメチルジベンゾチオフェンに代表される立体障害アルキル置換基を有する難脱ジベンゾチオフェン類の脱硫促進およびこの反応に対する活性劣化の抑制が不可欠であり、本発明の水素化処理方法によれば、特定の細孔領域に従来には提案されていない大きな細孔領域を設けた水素化処理用触媒を用いるものであり、これにより原料油のフィード拡散性の向上および予備水素化または水素化分解を促進することにより対象とする分子種をより小細孔・高比表面積細孔への拡散とその後の脱硫反応を容易にし、かつコーク劣化による細孔プラギングとこれに伴なう拡散障害を大幅に緩和することに成功したものである。拡散してきた難脱硫硫黄化合物は、細孔直径４０〜２００Åの範囲に細孔容積分布のピークを有する第一ピーク領域において高度に分散した水素化活性金属成分およびブレンステッド酸点およびルイス酸点により水素化脱硫が促進され、全体としてフィード拡散・水素化脱硫、活性劣化の大幅な抑制を図るものである。
【００４０】
軽油留分について前記の効果を奏することのできる反応条件を挙げると以下の如くである。
また、減圧軽油（ＶＧＯ）については、以下の条件での水素化処理が好ましい。
本発明の水素化処理方法によれば、重質油の水素化分解においても本発明に係る水素化処理用触媒を使用することにより、前記メカニズムは同様であり、減圧残渣油（ＶＲ留分）の大きな分子、特にレジンおよびアスファルテン分子に代表される巨大芳香族分子の触媒内の拡散を極めて容易にすると共にその細孔領域におけるＶＲ分子およびアスファルテン分子の予備的水素化および水素化分解を促進し、ここで水素化または水素化分解された分子はさらに小細孔・高比表面積領域へと拡散し、高度に分散された水素化活性金属およびブレンステッド酸、さらにはルイス酸点において水素化、水素化分解、水素化脱硫、水素化脱窒素反応が積極的に行なわれる。特に水素化分解プロセス（固定床、沸騰床、スラリー床）においては、高温での高転化率運転の場合には、水素化分解および熱分解と同時に脱水素や重縮合反応も起こり、プロダクト中にアスファルテンやセディメント固形物が生成・増大するため、これらによりリアクター内、下流の蒸留装置および配管類へのセディメント蓄積によるファウリングトラブルが発生し大きな問題となる。従って、重質油の水素化分解プロセスにおいては、コンバージョンのアップやセディメントの低減が非常に大きな課題である。通常、セディメント固形物質は、巨大アスファルテン分子が溶媒から過飽和状態で析出する溶解度現象で説明できる。非常に重縮合度が高く脱水素が進んだ巨大アスファルテン分子を十分に溶解させるためには、これを溶解する溶媒プロダクト成分はある程度芳香族性の高いものでなければならない。一方、このプロセスで得られるプロダクトについては、クリーン燃料への要求から水素化能を強化することにより、分解率、各留分の水素化脱硫、脱窒素、脱芳香族（水添）を進める必要がある。触媒の水素化能を向上させることによりプロダクトの硫黄、窒素および芳香族成分は低減できるものの、一方で、アスファルテンを溶解しているプロダクトの芳香族性低下に伴ない溶質であるアスファルテン分子が非常に多く析出し、セディメントの多量発生、ファウリングによる安定運転不可を招く。しかしながら、本発明に係る水素化処理用触媒を使用することにより、従来の触媒以上にアスファルテンを効率的に除去することが可能であるため、水素化能についてもさらに向上させることが可能となり、セディメントの抑制および安定運転を実現するだけでなく、プロダクトの水素化脱硫および脱窒素、脱芳香族化を強化することが可能となった。当該触媒は、特定の大細孔構造を持つ触媒表面に水素化活性金属、ブレンステッド酸およびルイス酸が高分散かつ均一に分布しており、転化率向上とセディメント低減、水素化能向上とを同時に成し遂げたものである。
【００４３】
減圧残渣油（ＶＲ）については、次の条件での水素化処理が好ましい。
炭化水素油の水素化処理を行なうにあたり、水素化処理用触媒は、固定床、流動床、移動床または沸騰床のいずれの形式でも使用することができ、任意に選択することができる。また二基以上の複数基の反応塔を結合して水素化処理を行ない、高度の脱硫率、脱窒素率、芳香族水添率を達成し、また、水素化分解活性を制御することもできる。
【００４５】
本発明に係る水素化処理方法においては、原料炭化水素油の水素化処理に前置の予備硫化処理を行なうことが好ましい。予備硫化は、焼成した触媒を反応塔内に充填した後、含硫留出油を反応塔に供給し、温度；１５０〜４００℃、圧力（全圧）；２０〜２００ｋｇ／ｃｍ2 、液空間速度；０．３〜２．０Ｖ／Ｈ／Ｖおよび水素含有ガスレイト；５０〜１５００リットル／リットルの反応条件下で接触させ、水素化活性金属成分の硫化処理を行ない、終了後含硫留出油を原料炭化水素油に切替え、水素化処理の運転を開始する。硫化処理の方法としては、前記の如き方法の他に、硫化水素その他の硫黄化合物を直接触媒と接触させるかまたは適当な含硫炭化水素油に添加してこれを触媒と接触させる方法を採用することもできる。
【００４６】
【実施例】
以下、実施例および比較例により本発明をさらに具体的に説明する。もっとも、本発明は、実施例等により何ら限定されるものではない。
なお、実施例等にて得られた触媒の細孔分布の測定に用いた水銀圧入法は、Ｐ．Ｈ．エメット他著「キヤタリシス」第１巻、第123頁（ラインホールド・バブリシング・カンパニー発行）（1959年）P.H.Emmett,et.al.“Catalysis"，Vol. 1, p123 (1959) (Reinhold PublishingCo.)、および触媒工学講座、第４巻、第69頁〜第78頁（地人書館発行）（昭和39年）に記載の方法を採用した。
細孔容積は、触媒に対する水銀の接触角を１３０゜、表面張力を４８５ダイン／ｃｍとし、すべての細孔は円筒形であると仮定して算出した。
また、比表面積は窒素吸着法により測定した。
【００４７】
実施例１（触媒Ａ）
純水３リットルを５０℃へ加温し、これに２Ｎ水酸化ナトリウム水溶液を５０ｍｌ加えることによりｐＨ＝１３へ調整した。硫酸アルミニウム（Ａｌ２（ＳＯ４） ３・１４Ｈ２Ｏ）４９５ｇを純水７１０ｇに溶解し、そしてこの水溶液を予め準備しておいた前記の加温された水酸化ナトリウム水溶液（ｐＨ＝１３）全量に３分間かけて混合した。得られた混合水溶液に２Ｎ水酸化ナトリウム水溶液９８０ｍｌを５分間かけて加えることによりｐＨ＝８．８へと変化させ、アルミナヒドロゲルを沈殿させた。このアルミニウムヒドロゲルを含む水溶液をｐＨ＝８．８に維持しながら５０℃で３０分間熟成処理した。
次に、純水２００ｇにケイ酸ナトリウム（ＪＩＳ３号水ガラス）５２ｇを溶解させてケイ酸ナトリウム水溶液を調製し、これを前記アルミナヒドロゲルを含む水溶液ヘ必要に応じ硝酸および／または水酸化ナトリウム水溶液を使用し、ｐＨ＝９．０を維持しながら添加した。この混合溶液を、シリカ高分散化を実現するため５０℃で３０分間熟成処理した。
ここで得られたスラリーを濾過し、その後、濾過後の濾液の残存Ｎａ量が５ｐｐｍ以下になるように炭酸アンモニウム水溶液で洗浄した。
洗浄後のシリカ−アルミナヒドロゲルに、水分および酸を添加し、粘度を調節しニーダーにより１．３ｍｍ直径の押出成形体（Ｅｘｔｒｕｄａｔｅ）に成形した。
得られた押出成形体（Ｅｘｔｒｕｄａｔｅ）を１２０℃で一昼夜乾燥し、その後７００℃で３時間空気中で焼成処理し、シリカ１５重量％のシリカ−アルミナ担体を得た。
次に、酢酸ニッケル４．４ｇ、酢酸コバルト１９．５ｇおよびクエン酸１０．０ｇを純水に溶解し、これにアンモニア水を加えることによりｐＨ＝８．８に調整し、金属塩含有水溶液を７０ｇ調製した。
この金属塩含有水溶液７０ｇを、前記シリカ−アルミナ担体７０ｇへ含浸担持させ、１２０℃で一昼夜乾燥した後、４５０℃で３時間空気中にて焼成処理することにより、ＮｉＣｏ／シリカ−アルミナ触媒を７５．５ｇ得た。
ヘプタモリブデン酸アンモニウム２６．１ｇを５０℃でアンモニア水４９．４ｍｌに溶解し、ｐＨ＝９．０のＭｏ塩水溶液を調製した。
前記の如くして得られたＮｉＣｏ／シリカ−アルミナ触媒７５．５ｇに、Ｍｏ塩水溶液７５．５ｇを含浸させ、１２０℃で一昼夜乾燥後、５００℃で３時間、空気中で焼成処理することにより、ＮｉＣｏＭｏ／シリカ−アルミナ触媒［Ａ］を得た。触媒［Ａ］の細孔容積分布および触媒特性を表１に示す。
最終的に得られた触媒［Ａ］５０ｇを使用し、固定床式水素化処理用高圧反応装置を用いて、下記の反応条件で軽油を原料油として水素化処理を行い脱硫活性を評価した。評価結果を表１に示す。
【００４８】
サルファイディング条件
10％ H2S/90％H2 ガスを触媒床に24リットル/hの流通速度で250℃で12時間流通させ、次いで、350℃に昇温し12時間流通させた。
原料油
軽油 (LGO-D)
硫黄分：1.5 wt％
窒素分：110 wtppm
評価運転条件
反応温度（℃）：343
反応圧力 (Psig-H2)：300
液空間速度 (V/H/V)：0.8
水素ガス／原料油比率（SCF/B）：550
【００４９】
実施例２（触媒Ｂ）
純水３リットルを５０℃へ加温し、これに２Ｎ水酸化ナトリウム水溶液を５０ｍｌ添加することによりｐＨ＝１３へ調整した。硫酸アルミニウム（Al2(SO4) 3・14H2O) ４９５ｇを純水７１０ｇに溶解し硫酸アルミニウム水溶液を調製した。硫酸アルミニウム水溶液を予め準備しておいた前記の加温された水酸化ナトリウム水溶液（ｐＨ＝１３）全量に３分間かけて混合した。得られた硫酸アルミニウム水溶液に２Ｎ水酸化ナトリウム水溶液１１００ｍｌを３分間で加えることによりｐＨを９．５に制御することによりアルミナヒドロゲルを沈殿させた。このアルミナヒドロゲルを含む水溶液をｐＨ９．５、５０℃で３０分間熟成処理した。
次に、純水２００ｇにケイ酸ナトリウム（ＪＩＳ３号水ガラス）５２ｇを溶解して調製したケイ酸ナトリウム水溶液を前記アルミナヒドロゲルを含む水溶液に必要に応じ硝酸および／または水酸化ナトリウム水溶液を使用し、ｐＨ＝９．０を維持しながら添加した。得られた混合水溶液を、シリカ高分散化を実現するため、５０℃で３０分間熟成処理した。
ここで得られたスラリーを、濾過後、濾液の残存Ｎａ量が５ｐｐｍ以下になるように炭酸アンモニウム水溶液で洗浄した後、実施例１の操作および条件と同一の操作および条件によりシリカ−アルミナ担体［Ｂ］を調製し、活性金属成分の担持についても実施例１の操作および条件と同一の操作および条件により、ＮｉＣｏＭｏ／シリカ−アルミナ触媒［Ｂ］を調製した。触媒［Ｂ］の細孔分布および触媒特性を表１に示す。
【００５０】
比較例１（触媒Ｃ）
純水２リットルを７０℃に加熱し、これに２Ｎ水酸化ナトリウムを５０ｍｌ加えることによりｐＨ＝１３へ調整した。硫酸アルミニウム(Al2(SO4) 3・14H2O) ）５２５ｇを純水７１０ｇに溶解し、そしてこの溶液を予め準備しておいた前記の加温された水酸化ナトリウム水溶液（ｐＨ＝１３）へ１０分間かけて混合した。次いで、混合水溶液に２Ｎ水酸化ナトリウム水溶液９５０ｍｌを１５分かけて加えることにより、混合溶液をｐＨ＝８．４に調整し、アルミナヒドロゲルを沈殿させた。このアルミナヒドロゲルを含む水溶液をｐＨ＝８．４、７０℃で３０分間熟成処理した。
ケイ酸ナトリウム（ＪＩＳ３号水ガラス）の添加条件については、ケイ酸ナトリウム３３ｇを純水２００ｇへ添加・溶解し、これをアルミナヒドロゲルを含む水溶液へｐＨ＝９で混合したこと以外は、全て実施例１と同様にしてシリカ含有量１０重量％のシリカ−アルミナ担体を調製した。その他の触媒調製条件を実施例１の条件と同一とし、ＮｉＣｏＭｏ／シリカ−アルミナ触媒［Ｃ］を調製した。
その他の触媒調製条件は、実施例１の条件と同一とし、ＮｉＣｏＭｏ／シリカ−アルミナ触媒［Ｃ］を調製した。
【００５１】
比較例２（触媒Ｄ）
純水１リットルを７０℃へ加温し、これに水酸化ナトリウム水溶液（ＮａＯＨ１６９ｇ、純水４２０ｇ）を加えることによりｐＨ＝１３へ調整した。硫酸アルミニウム（Ａｌ２（ＳＯ４）３・１４Ｈ２Ｏ）４６６ｇを純水７１０ｇに溶解し、そしてこの溶液を５秒間以内で、予め準備しておいた前記の加温水酸化ナトリウム水溶液（ｐＨ＝１３）全量へ混合した。得られた混合溶液に水酸化ナトリウム水溶液５００ｍｌを１分間以内に加えることにより混合溶液をｐＨ＝９．０に調整し、アルミナヒドロゲルを沈殿させた。このアルミナヒドロゲルを含む水溶液をｐＨ＝９．０に維持しながら、７０℃で６０分間熟成処理した。
次に、純水２１０ｇ中にケイ酸ナトリウム（ＪＩＳ３号水ガラス）６９ｇを溶解し、これを前記アルミナヒドロゲルを含む水溶液へ添加し、必要に応じて硝酸溶液を加えｐＨ＝９．０とした。この混合溶液をｐＨ＝９．０に維持しながら、７０℃で１８０分間熟成処理した。
得られたシリカアルミナヒドロゲルは、実施例１と同様な操作によって、シリ カ２０重量％の押出成形体（Ｅｘｔｒｕｄａｔｅ）担体とした。この担体に、酸化物として２０重量％のモリブデンが担持されるように、ヘプタモリブデン酸アンモニウム水溶液を含浸させ、その後１２０℃で一昼夜乾燥後、５５０℃で３時間焼成し、Ｍｏ／シリカ−アルミナ触媒を得た。
次に、酸化物として５重量％のコバルトが担持されるように、前記担体に酢酸コバルト水溶液を含浸させ、その後１２０℃で一昼夜乾燥後、４５０℃で３時間焼成し、ＣｏＭｏ／シリカ−アルミナ触媒［Ｄ］を得た。
触媒［Ｄ］の細孔特性は、表１に示すが、ＰＶ（１ｓｔｐｅａｋ±２０Å）／ＰＶ（４０〜２００）が４２％であり、５０％に達していない。また、ＰＶ（１ｓｔｐｅａｋ±１０Å）／ＰＶ（４０〜２００）も３０％に達しないものであり、また、半値巾は８０〜９０Åと巾広い分布をもち、細孔容積分布はブロードな形態である。従って、平均側面強度が０．３ｌｂｓ／ｍｍと著しく低いものであった。
【００５２】
【表１】
実施例３（触媒Ｅ）
実施例２のシリカ−アルミナ担体調製条件において、ケイ酸ナトリウム（ＪＩＳ３号水ガラス）の添加条件については、ケイ酸ナトリウム３３ｇを純水２００ｇへ添加・溶解し、これをアルミナヒドロゲルを含む水溶液へ混合することにより行なったこと以外は、実施例１と同じ手法でシリカ−アルミナヒドロゲル担体［Ｅ］を調製した。
得られたシリカ−アルミナヒドロゲルは、水分または酸の添加により粘度を調整し、ニーダーにより１．０ｍｍ直径の押出成形体（Ｅｘｔｒｕｄａｔｅ）に成形した。
得られた押出成形体（Ｅｘｔｒｕｄａｔｅ）を１２０℃で一昼夜乾燥し、その後７００℃で３時間空気中で焼成処理し、シリカ１０重量％のシリカ−アルミナ担体を得た。
次に、酢酸ニッケル７．６ｇ、ヘプタモリブデン酸アンモニウム１３．３ｇ、クエン酸１０．２ｇを純水に溶解し、これにアンモニア水を加えることによりｐＨ＝８．８に調整し、金属塩含有水溶液を１１０．７ｇ調製した。
この金属塩含有水溶液１１０．７ｇをシリカ−アルミナ担体［Ｅ］９０．０ｇへ含浸担持し、１２０℃で一昼夜乾燥した。その後、４００℃で３時間、空気中にて焼成することにより、ＮｉＭｏ／シリカ−アルミナ触媒［Ｅ］を１０３．１ｇ得た。
最終的に得られた触媒［Ｅ］を連続攪拌流通式の水素化処理用高圧反応装置を用いて、減圧残渣油（ＶＲ）を原料油として水素化分解処理を行ない、各種プロダクト性状を評価した。サルファイディング条件および評価運転条件は以下の通り。
【００５４】
サルファイディング条件
触媒160gを触媒床に充填後、160kg/cm2の圧力で減圧軽油(VGO)硫化処理用原料油(S=2.0wt.%、密度＝0.9194g/cc)を、185cc/hの割合で、また、100％ H2ガスを100SL/hの割合で200℃において12時間流通させ、次いで 280℃に昇温し12時間流通させ、さらに、340℃に昇温し1 2時間流通させ硫化処理を行なった。
原料油
減圧残渣油 VR-D（密度＝1.027、Ｓ＝3.86wt.%、Ｎ＝0.32wt%）
評価運転条件
圧力160kg/cm2、温度415℃で原料油を370cc/hの割合、水素ガスを270SL/hの割合でそれぞれ４日間流通させエージング処理をした後、温度 410℃で原料油を185cc/hの割合、水素ガス135 SL/hの割合でそれぞれ2日間流通させ評価し、その後温度を415℃へ昇温し2日間評価した。
【００５５】
実施例４（触媒Ｆ）
実施例２のシリカ−アルミナ担体調製条件において、硫酸アルミニウム水溶液を２分間でｐＨ＝９．５に調整した。また、アルミナヒドロゲルを沈積させたケイ酸ナトリウム（ＪＩＳ３号水ガラス）の添加条件については、ケイ酸ナトリウム３３ｇを純水２００ｇへ添加・溶解し、これをアルミナヒドロゲル水溶液へ混合したこと以外は、実施例２と同じ手法でシリカ−アルミナヒドロゲル担体［Ｆ］を調製した。得られたシリカ−アルミナヒドロゲルは、水分または酸の添加により粘度を調整し、ニーダーにより１．０ｍｍ直径の押出成形体（Ｅｘｔｒｕｄａｔｅ）に成形した。
得られた押出成形体（Ｅｘｔｒｕｄａｔｅ）を１２０℃で一昼夜乾燥し、その後７００℃で３時間空気中で焼成処理した。ここで得られたシリカ−アルミナ担体中のシリカ含有量は１０重量％であった。水素化活性金属担持以後の触媒調製および触媒評価条件については、実施例３の条件と同一の条件とした（触媒［Ｆ］）。触媒組成、細孔特性および評価結果緒を表２に示す。
【００５６】
比較例３（触媒Ｇ）
比較例１のシリカ−アルミナヒドロゲル担体を用い、実施例３にならって直径１．０ｍｍ 押出成形体(Extrudate)担体を調製し、乾燥・焼成によりシリカ−アルミナ担体を調製した。活性金属の担持は、実施例３と同様の手法で行ない、触媒［Ｇ］を調製した。触媒［Ｇ］について実施例３と同一の条件で水素化分解評価を実施した。触媒組成、細孔特性および評価結果を表２に示す。
以上の実施例および比較例から本発明に係る水素化処理用触媒が、前記構成要素（１）〜（９）を満たし、細孔容積分布において特定のバイモダル構造を有し、脱硫活性、水素化分解活性、セディメント抑制能等に顕著な効果を奏するのに対し、前記構成要素のいずれかを充足できない従来提案されている触媒は十分な効果を発揮できないことが明らかとなった。
【００５７】
【表２】
【発明の効果】
本発明に係る水素化処理用触媒が特定のバイモダルな細孔構造を有することにより、炭化水素油の触媒内への拡散をより容易にし、触媒活性劣化を大幅に低減することにより、ナフサやケロシン、軽油、減圧軽油（ＶＧＯ）と水素とを接触させてなる水素化処理において脱硫活性、脱窒素活性、芳香族水添活性を向上させることができる。また、特に、当該触媒と減圧軽油（ＶＧＯ）、減圧残渣油（ＶＲ）等の重質油および水素とを接触させてなる水素化分解プロセスにおいて、分解率（コンパージョン）およびアスファルテン処理能の向上を実現し、所望とするガス、軽質油（ナフサ、ケロシン、軽油および減圧軽油（ＶＧＯ））の収率向上、脱硫・脱窒素率の向上、セディメント含有量の大幅な低減を実現することができる。[0001]
[Technical field to which the invention belongs]
The present invention relates to a hydrocarbon oil hydrotreating catalyst and a hydrocarbon oil hydrotreating method using the same, and more particularly, a silica-alumina hydrotreating catalyst and a hydrocarbon oil using the same. In particular, the present invention relates to a method for hydrotreating fuel oil fractions such as naphtha, kerosene, light oil, vacuum gas oil (VGO), vacuum residue oil (VR) and the like.
In the present specification, “hydrotreatment” in the present invention is a general term for reactions caused by contact between hydrocarbon oil and hydrogen, and hydrodesulfurization, hydrodenitrogenation, and hydrogenation of hydrocarbon oil. Including dearomatization, hydroisomerization, hydrorefining and hydrocracking.
[0002]
[Prior art]
Conventionally, as a catalyst used for hydrotreating hydrocarbon oils such as petroleum, refractory inorganic oxides composed of alumina, silica-alumina, boria, magnesia, zirconia, and the like and mixed compositions thereof are used as a carrier, and the periodic table 6A Various hydrotreating catalysts on which active components containing Group metals, Group 8 metals and the like are supported have been proposed. For example, JP-A-61-287446 discloses a method for preparing a catalyst support after adding a basic compound to a mixed solution of alumina hydrate and colloidal silica to form a thickened gel, According to Japanese Patent Application Laid-Open No. 61-242039, a monolithic material having a porous oxide high surface support layer integrated with a sintered ceramic structure layer, comprising 50 to 93% by weight of alumina and 7 to 50% by weight of silica. A catalyst support is disclosed. Furthermore, a boria-silica-alumina as a carrier carries a Group 6A metal and / or Group 8 metal of the Periodic Table, and has an average pore diameter of 60 to 90 mm and an average pore diameter in the range of ± 10 mm. In addition to hydrorefining catalysts having a pore volume of 60% or more of the total pore volume (JP-A-8-89806), JP-A-9-276712 discloses an element on a support containing alumina, silica and magnesia. A hydrorefining catalyst having an average pore diameter of 190 to 350 mm and having a periodic table group 6A metal and / or a group 8 metal supported thereon has been proposed.
[0003]
Such hydrotreating catalysts are, for example, hydrodesulfurization, hydrodenitrogenation and hydrocracking of distillate or residual oil of atmospheric distillation and vacuum distillation, hydrorefining of lubricating oil fractions, water of wax fractions Used for hydroisomerization, etc., but in the hydrotreating of various hydrocarbon oils, the pore structure and pore distribution of the hydrotreating catalyst, and the acid properties and amount of the catalyst surface are important for the catalyst activity and the ability to maintain the activity. Has been recognized as a key factor. Therefore, for example, the present applicant also controls the pore volume in a specific region having a diameter of 300 mm or more as a low catalyst as a catalyst that exhibits high activity mainly in hydrodesulfurization, denitrogenation, aromatic hydrogenation, etc. of distillate. The present inventors have developed a hydroprocessing catalyst (Japanese Patent Publication No. 3-31496) in which a hydrogenation active component is supported on a silica-alumina carrier having a uniform pore distribution, and an invention relating to the hydroprocessing catalyst. It has a pore volume of 0.01 to 0.25 ml / g in a region having a pore diameter of 300 to 150,000 Å, and a pore volume of a region having a pore diameter of 300 to 600 の is a region having a diameter of 300 to 150,000 Å. A hydrogenation catalyst having a pore volume of 40% or more was proposed (Japanese Patent Laid-Open No. 8-89816). Further, JP-A-6-127931 has proposed a silica-alumina-based catalyst having a bimodal structure having a pore volume distribution peak in the range of pore diameters of 30 to 300 mm and 300 to 1500 mm, respectively.
[0004]
However, in recent years, it has become obligatory to produce clean fuel with a significantly reduced sulfur content (for gasoline and light oil, 50 ppm or less as S component) from the viewpoint of environmental protection, and in the future, production of sulfur-free fuel containing almost no sulfur. Therefore, it is inevitable that advanced desulfurization processing technology is required. In addition, research into the effects of fuel properties with greatly reduced aromatic components on automobile emissions has been actively promoted, and discussions are underway to reduce this in the future. In order to cope with such a situation, the conventionally proposed hydrotreating catalyst as described above is not necessarily in terms of desulfurization performance, denitrogenation performance, aromatic hydrogenation performance and hydrocracking performance, and further its activity maintenance ability. Development of a catalyst for hydrotreating with higher performance is indispensable. In particular, in the hydrocracking treatment of heavy oil, hydrocracking reaction and thermal cracking reaction occur when operating at a high cracking rate, while dehydrogenation and polycondensation reactions also occur vigorously, and asphaltenes and cediment solids are contained in the product Since these are generated and increased, fouling occurs due to accumulation of sediment in the reactor and downstream distillation apparatus and piping in the reactor, which causes serious problems in the operation of the apparatus. Therefore, in the hydrocracking process of heavy oil, it is necessary to improve the cracking rate, hydrodesulfurization, denitrogenation, and dearomatic activities by strengthening the hydrogenation ability of the catalyst due to the demand for clean fuel. On the other hand, however, there is a negative effect that the aromaticity of the product is lowered due to the improvement of hydrogenation ability, resulting in an increase in sediment due to the precipitation of dissolved large condensed aromatic compounds such as asphaltenes.
[0005]
As described above, in the conventional heavy oil hydrocracking process, there is a trade-off relationship between the enhancement of hydrogenation ability and the effect of reducing sedimentation. However, it is impossible to achieve both advanced hydrocracking and suppression of sediment formation at the same time, and there is an urgent need for the development of a hydrotreating catalyst having both of these performances.
[0006]
[Problems to be solved by the invention]
Accordingly, in view of the development status of hydrotreating catalysts as described above, the object of the present invention is to provide hydrogen having excellent desulfurization activity, denitrogenation activity, aromatic hydrogenation activity, and hydrocracking activity for various hydrocarbon oils. Catalyst for hydrotreating, especially hydrotreating catalyst excellent in hydrogenation and hydrodesulfurization / denitrogenation activity of light oil and vacuum gas oil (VGO) and advanced hydrogenation activity and sediment in heavy oil hydrocracking An object of the present invention is to provide a hydrotreating catalyst having both generation suppressing ability.
[0007]
[Means for Solving the Problems]
Therefore, the present inventors, as a result of intensive studies to solve the above problems, are hydrotreating catalysts in which at least one hydrogenation active metal component is supported on a silica-alumina-based carrier, In the pore volume distribution, hydrotreating catalyst with a specific bimodal pore structure is desulfurization activity, denitrogenation activity, aromatic hydrogenation activity and hydrocracking activity in hydrotreating heavy oil as well as light oil. In particular, it is found that high-quality clean fuel can be provided from heavy oil by a hydrotreating method using the hydrotreating catalyst, based on these findings. Reached completion.
[0008]
Thus, according to the present invention,
A hydrogenation having a structure in which a silica layer is formed on an alumina surface and containing at least one hydrogenation active metal component on a silica-alumina-based carrier containing 2 to 40% by weight of silica based on the total weight of the carrier. A catalyst for treatment,
In pore volume distribution measured by mercury porosimetry,
[0009]
(1) having a first peak of pore volume distribution in a pore diameter range of 40 to 200 mm;
(2) having a second peak of pore volume distribution in a pore diameter range of 200 to 2000 mm;
(3) The pore volume in a region having a pore diameter of 40 to 200 mm with respect to the total pore volume is 40 to
90%,
(4) The pore volume of the region having a pore diameter of 200 to 1000 mm with respect to the total pore volume is 10 to 10
60%,
(5) The pore volume of the region having a pore diameter of 1000 mm or more with respect to the total pore volume is 20% or less
And
(6) At the position of the first peak existing in the pore diameter range of 40 to 200 mm.
Corresponding pore diameters in the range of ± 20 mm are those having a pore diameter of 40 to 200 mm.
50% or more of the range pore volume,
(7) The average pore diameter is 60 to 150 mm,
Measured by nitrogen adsorption methodSpecific surface area of 150-400m2/ G
Hydrotreating catalyst characterized in that
Is provided.
[0010]
Further, according to the present invention, as a catalyst carrier suitable for a hydrotreating catalyst,
A silica-alumina-based carrier having a structure in which a silica layer is formed on an alumina surface and containing 2 to 40% by weight of silica based on the total weight of the carrier,
In pore volume distribution measured by mercury porosimetry,
[0011]
(1) It has a first peak of pore volume distribution in a pore diameter range of 40 to 200 mm,
(2) Has a second peak of pore volume distribution in the pore diameter range of 200 to 2000 mm,
(3) The pore volume of the pore diameter range of 40 to 200 mm relative to the total pore volume is 40 to 90%,
(4) The pore volume of the pore diameter range of 200 to 1000% with respect to the total pore volume is 10 to 60%,
(5) The pore volume of the region having a pore diameter of 1000 mm or more with respect to the total pore volume is 20% or less,
(6) A pore volume having a pore diameter in the range of ± 20 mm corresponding to the position of the first peak existing in the pore diameter in the range of 40 to 200 mm is a pore having a pore diameter in the range of 40 to 200 mm. 50% or more of the volume,
▲ 7 ▼ Average pore diameter is 60 ~ 150Å
A silica-alumina-based support characterized in that
Is provided.
[0012]
Furthermore, according to the present invention,
A hydrogenation having a structure in which a silica layer is formed on an alumina surface and containing at least one hydrogenation active metal component on a silica-alumina-based carrier containing 2 to 40% by weight of silica based on the total weight of the carrier. A catalyst for treatment, in the pore volume distribution measured by mercury porosimetry,
[0013]
(1) having a first peak of pore volume distribution in a pore diameter range of 40 to 200 mm;
(2) having a second peak of pore volume distribution in a pore diameter range of 200 to 2000 mm;
(3) The pore volume in a region having a pore diameter of 40 to 200 mm with respect to the total pore volume is 40 to
90%,
(4) The pore volume in the region having a pore diameter of 200 to 1000 mm with respect to the total pore volume is 10
~ 60%,
(5) The pore volume of the region having a pore diameter of 1000 mm or more with respect to the total pore volume is 20%.
And
(6) At the position of the first peak existing in the pore diameter range of 40 to 200 mm.
Corresponding pore diameters in the range of ± 20 mm are those having a pore diameter of 40 to 200 mm.
50% or more of the range pore volume,
(7) The average pore diameter is 60 to 150 mm,
Measured by nitrogen adsorption methodSpecific surface area of 150-400m2/ G
Hydrocarbon oil hydrotreating method comprising contacting hydrocarbon oil with hydrogen under hydrotreating conditions in the presence of a hydrotreating catalyst
Is provided.
[0014]
According to the present invention, the hydrotreating catalyst and the hydrotreating method of hydrocarbon oil using the hydrotreating catalyst are provided. As a more preferred embodiment, the following 1) to 14) are provided. Includes the following.
[0015]
1) At least one oxidation selected from the group consisting of magnesia, calcium oxide, boria, zirconia, titania, tria, ceria, hafnia and phosphorus oxide is a third carrier component that may be incorporated into the silica-alumina carrier. The catalyst for hydroprocessing, which is a product.
2) The catalyst for hydrogenation treatment, wherein the hydrogenation active metal component is a metal component composed of at least one group 6A metal component of the periodic table and at least one group 8 metal component.
3) The group 6A metal component of the periodic table is molybdenum and / or tungsten, and the group 8 metal component of the periodic table is from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. The hydrotreating catalyst, which is at least one metal component selected.
4) The hydrotreating catalyst in which the second peak is in the range of a pore diameter of 200 to 1500 mm.
5) The hydrotreating catalyst, wherein the pore volume in the region of the pore diameter of 40 to 200 mm is 45 to 80% with respect to the total pore volume.
6) The hydrotreating catalyst, wherein the pore volume in the region of the pore diameter of 200 to 1000 mm is 20 to 50% with respect to the total pore volume.
7) The hydrotreating catalyst, wherein the pore volume in the region having a pore diameter of 1000 mm or more is 15% or less with respect to the total pore volume.
8) The pore volume in the range of pore diameter ± 10 ± corresponding to the position of the first peak existing in the range of 40 to 200Å is the pore volume in the range of 40 to 200Å. 30% or more of the hydrotreating catalyst.
9) The specific surface area is 160 to 370 m2The hydrotreating catalyst which is / g.
10) Hydrogen having a structure in which a silica layer is formed on an alumina surface and having at least one hydrogenation active metal component supported on a silica-alumina-based carrier containing 2 to 40% by weight of silica based on the total weight of the carrier. A catalyst for hydrotreating treatment, in the pore characteristics of the catalyst,
(1) The first peak is in the range of a pore diameter of 40 to 200 mm,
(2) The second peak is in the range of a pore diameter of 200 to 1500 mm,
(3) The pore volume in the range of the pore diameter of 40 to 200 mm is 45 to 80% with respect to the total pore volume,
(4) The pore volume in the range of the pore diameter of 200 to 1000 mm is 20 to 50% with respect to the total pore volume,
(5) The pore volume in the range of the pore diameter of 1000 mm or more is 15% or less with respect to the total pore volume,
(6) A pore volume having a pore diameter in the range of ± 10Å corresponding to the position of the first peak existing in the pore diameter in the range of 40 to 200Å is a pore having a pore diameter in the range of 40 to 200Å. 30% or more of the volume,
(7) The average pore diameter is 60 to 150 mm,
(8) The total pore volume is 0.3 to 1.2 ml / g,
(9) The specific surface area is 160 to 370 m.2/ G
Said hydrotreating catalyst.
11) The hydrotreating method, wherein the hydrocarbon oil is a fuel oil fraction selected from the group consisting of naphtha, kerosene, light oil, and vacuum light oil.
12) The hydroprocessing method, wherein the hydrocarbon oil is a heavy oil selected from the group consisting of atmospheric distillation residue oil, vacuum distillation residue oil, vacuum gas oil and cracked gas oil.
13) The hydrotreating condition of the fuel oil fraction is
Hydrogen pressure (Psig): 100-3000
Hydrogen treat gas rate (SCF / B): 300-5000
Liquid space velocity (V / H / V): 0.1 ~ 4
Temperature (℃): 200 ~ 470
The said hydrotreating method which is the specific reaction conditions selected from these conditions.
14) The heavy oil hydrotreating conditions are:
Hydrogen pressure (Psig): 600-3000
Hydrogen treat gas rate (SCF / B): 500-5000
Liquid space velocity (V / H / V): 0.1-3
Temperature (℃): 350 ~ 470
The said hydrotreating method which is the specific reaction conditions selected from each of these conditions.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
One of the specificities of the hydrotreating catalyst of the present invention is that a highly dispersed silica layer is formed on the alumina surface, and the silica content is 2 to 40% by weight based on the total weight of the support, It lies in that at least one hydrogenation active metal component is supported on a silica-alumina-based support having a high specific surface area and containing a Bronsted acid.
[0017]
The second specificity is that the catalyst has a specific bimodal pore structure in the pore volume distribution of the hydrotreating catalyst. By having such a pore structure, as will be described later, light oil and vacuum gas oil (VGO) In the hydrodesulfurization, denitrogenation, and dearomatic reactions of)), the initial activity deterioration is suppressed and the activity is improved by improving the molecular diffusibility, and in the contact of various hydrocarbon oils including heavy oil with hydrogen. It is possible to perform a controlled hydrotreating reaction, and in particular, to realize a hydrotreating catalyst excellent in high hydrogenation performance and sediment suppression performance in heavy oil hydrotreating.
[0018]
The silica-alumina-based carrier as a constituent component of the hydrotreating catalyst according to the present invention has a structure in which a silica layer is formed on the surface of alumina as a nucleus, and the silica component in the silica-alumina carrier is a catalyst component. It is suitable for control and improvement of solid acidity, can remarkably improve the dispersibility of the hydrogenation active metal component, and can impart a relatively strong acid point to the catalyst to increase the decomposition activity. Therefore, the silica content can be appropriately selected depending on the type of reaction and the reaction conditions of the hydrotreating process, but the hydrogen consumption accompanying excessive decomposition reaction for hydrodesulfurization reaction and hydrodenitrogenation reaction. From the viewpoint of controlling an appropriate cracking reaction in hydrogenolysis, it can be employed in a range of 2 to 40% by weight based on the total weight of the support. In particular, 4 to 20% by weight for hydrorefining such as hydrodesulfurization reaction and 5 to 25% by weight for hydrocracking can be selected as more preferable ranges. When the silica content exceeds 40% by weight, the decomposition of the raw material oil proceeds excessively, resulting in a problem that the coke-up becomes intense. As the alumina component in the silica-alumina carrier, any of γ-alumina, χ-alumina, η-alumina, or a mixture thereof is suitable. The form of the alumina component is not particularly limited as long as it gives the specific pore structure and pore volume distribution and characteristic values as the constituent components of the hydrotreating catalyst of the present invention. It can be preferably used.
[0019]
The silica-alumina carrier is selected from the group consisting of other refractory inorganic oxides such as magnesia, calcium oxide, boria, zirconia, titania, tria, ceria, hafnia, phosphorus oxide and crystalline zeolite. 1 type, or 2 or more types can be contained as a 3rd component.
[0020]
Therefore, specifically, silica-alumina-magnesia, silica-alumina-calcium oxide, silica-alumina-boria, silica-alumina-zirconia, silica-alumina-titania, silica-alumina-tria, silica-alumina-ceria, Examples thereof include silica-alumina-based carriers such as silica-alumina-hafnia, silica-alumina-phosphorus oxide, silica-alumina-crystalline zeolite, silica-alumina-phosphorus oxide-boria and the like. The content of the refractory inorganic oxide as the third component is suitably in the range of 0.1 to 10% by weight based on the total weight of the carrier. These refractory inorganic oxides, such as magnesia, can improve the selectivity of the catalyst by decreasing the relatively strong acid point of silica-alumina and the like and at the same time increasing the weak acid point.
[0021]
Next, the pore structure of the hydrotreating catalyst according to the present invention will be described. The catalyst has one or more peaks in the pore volume distribution in both the relatively small pore size region and the large pore size region. In particular, it has at least the following components (1) to (9) in the pore structure or pore volume distribution measured by mercury porosimetry. The characteristic points of each element will be described below.
[0022]
Element (1) has a first peak of pore volume distribution in the pore diameter range of 40-200 mm. In this case, the catalyst having the first peak in a region having a pore diameter of 200 mm or more has a problem that the specific surface area is lowered and high activity cannot be obtained. On the other hand, it is difficult to produce a catalyst having a peak in a region having a pore diameter of 40 mm or less, and it is not realistic to obtain a catalyst having the effects required by the present invention. In addition, the peak which exists in the range of 40-200 mm of pore diameters may be branched into two or more.
Element (2) has a second peak of pore volume distribution in the pore diameter range of 200 to 2000 mm. The position of the second peak is particularly preferably in the range of the pore diameter of 200 to 1500 mm. This provides high selectivity for heavy oil hydrocracking reactions to molecular species of specific sizes (giant aromatic molecules such as asphaltenes and resins), and moderate cracking rates and hydrogenation, hydrodesulfurization, and denitrification. It is possible to control the basics of improving the desulfurization and denitrification reactions of diesel oil and vacuum diesel oil and maintaining their activity, and also exhibiting hydrogenation performance and sediment suppression ability at a high cracking rate in heavy oil hydrocracking. It is estimated that If the position of the second peak is more than 2000 mm in pore diameter, the catalyst strength is remarkably lowered, and there is a possibility that it cannot be used. The peak at a pore diameter of 200 to 2000 mm may be branched into two or more as long as it is within the range.
Element (3) The pore volume of the pore diameter range of 40 to 200 mm where the first peak is present is 40 to 90%, preferably 45 to 80% of the total pore volume. If the pore volume in the pore diameter range of 40 to 200 mm does not reach 40%, the number of large pores increases, causing a problem of catalyst strength. On the other hand, if it exceeds 90%, the desired large pore region is too small. The expected activity may not be obtained.
Element (4) The pore volume with a pore diameter in the range of 200-1000 mm occupies 10-60%, preferably 20-50% of the total pore volume. If the pore volume in the region of the pore diameter of 200 to 1000 mm does not reach 10%, the pores with large pore diameters will be too small. Cannot be obtained. In addition, the catalyst strength is remarkably lowered, and there is a fear that it cannot be used.
Element (5) The volume of pores having a pore diameter of 1000 mm or more is controlled to 20% or less, preferably 15% or less of the total pore volume. When the pore volume exceeds 20%, a difficulty occurs in maintaining the catalyst strength.
Element (6) A pore volume having a pore diameter in the range of ± 20 mm corresponding to the position of the first peak existing in the range of the pore diameter of 40 to 200 mm is small in the range of the pore diameter of 40 to 200 mm. One of the most specific elements of the pore characteristics of the hydrotreating catalyst according to the present invention is 50% or more of the pore volume. A particularly preferable pore structure is one having a pore volume in the range of pore diameter ± 10 mm corresponding to the position of the first peak of 30% or more of the pore volume in the range of 40 to 200 mm.
The pore characteristics are such that the pore volume distribution related to the first peak is sharp in the pore diameter range of 40 to 200 mm, and there are many uniform pores centering on pores having a diameter corresponding to the peak position. It shows what to do. As a result, the full width at half maximum of the first peak is 70 cm or less, preferably 50 cm or less.
If the pore volume in the range of the pore diameter of ± 20 mm corresponding to the position of the first peak is less than 50%, pores having an inappropriate diameter will increase excessively, leading to a significant decrease in strength, and Δ due to catalyst powdering. Occurrence of P and fouling hinders stable device operation in actual production. In addition, the catalyst becomes a high-capacity catalyst having a total pore volume exceeding 1.2 ml / g, which causes a problem that the CBD (Compacted Bulk Density) of the catalyst is remarkably lowered and the reactor volume activity is lowered.
When the peak is branched, the pore volume corresponding to the peak position is calculated by adopting the pore diameter corresponding to the peak position and calculating the pore volume of ± 20 cm.
Element (7) The average pore diameter is in the range of 60 to 150 mm.
Element (8) has a total pore volume of 0.3 to 1.2 ml / g, preferably 0.35 to 0.95 ml / g.
Element (9) specific surface area 150-400m2/ G, which realizes a high specific surface area.
[0023]
As the hydrogenation active metal component of the hydrotreating catalyst according to the present invention, at least one metal selected from the group consisting of Group 6A metals and Group 8 metals of the Periodic Table can be used. That is, one or more metals can be selected from the group consisting of Group 6A chromium, molybdenum and tungsten, Group 8 cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium and rhodium. . For hydrodesulfurization, hydrodenitrogenation, hydrocracking, hydrodearomatic, etc. of hydrocarbon oils, a combination of at least one group 6A metal and at least one group 8 metal of the periodic table is required. For example, a combination of molybdenum-cobalt, molybdenum-nickel, tungsten-nickel, molybdenum-cobalt-nickel, tungsten-cobalt-nickel, molybdenum-tungsten-cobalt-nickel, or the like is preferable.
Further, these active metal components can be used by adding a Group 7A metal of the periodic table, for example, manganese and a Group 4B metal, for example, tin, germanium or lead.
These hydrogenation active metal components are preferably supported as oxides and / or sulfides, and the sulfides can be formed on the catalyst by a presulfidation treatment of the catalyst as described below.
[0024]
The content of the hydrogenation active metal component of Group 8 and Group 6A of the periodic table is 0.5 to 30% by weight, preferably 1 to 10% by weight, based on the total weight of the catalyst as the oxide for Group 8 metal. And for Group 6A metals it is 5-30% by weight, preferably 8-25% by weight. If the Group 8 metal does not reach 0.5% by weight, sufficient desulfurization / denitrogenation activity cannot be obtained, and the hydrodearomatic and hydrogenation ability cannot be sufficiently exhibited. On the other hand, if it exceeds 30% by weight, the free metal component that does not bind to the carrier increases, and a group 6A metal and an inactive composite oxide are formed. As a result, the dispersibility of the group 6A metal is lowered. Will occur. Further, if the Group 6A metal is less than 5% by weight, desulfurization / denitrogenation activity cannot be obtained. On the other hand, if it exceeds 30% by weight, the dispersibility of the metal component is lowered and the Group 8 metal promoter effect is not exhibited. The evil that occurs.
[0025]
As described above, the hydrotreating catalyst according to the present invention comprises the silica-alumina carrier and a hydrogenation active metal component supported on the carrier, and has a specific surface area of 150 to 400 mm.2/ G and a total pore volume of 0.3 to 1.2 ml / g, a first peak of pore volume distribution in a specific pore diameter range of 40 to 200 mm, and a pore diameter of 200 to In addition to having a second peak in the range of 2000 Å and exhibiting unique pore characteristics in each of the two pore diameter regions, the first peak is a sharp shape that was first embodied by the present inventors. It is what has.
[0026]
This hydrogenation active metal component and pore structure provide unexpected effects in hydrocarbon oil hydroprocessing, making it easier to diffuse hydrocarbon oil into the catalyst and greatly reducing catalyst activity degradation. Therefore, desulfurization activity, denitrification activity, and aromatic hydrogenation activity can be greatly improved in hydrorefining in which naphtha, kerosene, straight-run gas oil, vacuum gas oil (VGO) and hydrogen are brought into contact with each other. . Further, in hydrocracking where the hydrotreating catalyst according to the present invention is contacted with heavy oil (VGO, VR) and hydrogen, the cracking rate and asphaltene treatment performance are improved, and gas, light oil (naphtha, Kerosene, diesel oil and vacuum gas oil (VGO)) yield increase, these sulfur and nitrogen content can be greatly reduced, and the content of sediment contained in the product can be significantly reduced. It plays.
[0027]
Thus, the hydrotreating catalyst according to the present invention has a unique pore characteristic including a bimodal structure exhibiting the sharp first peak as described above in the pore volume distribution. While maintaining the same high catalyst strength, it has become possible to exhibit high activity and ability to maintain activity in hydrogenation, hydrodesulfurization / denitrogenation reaction, hydrocracking, and the like. In other words, the hydrotreating catalyst of the present invention has a significantly improved strength compared with the catalyst having the bimodal structure already proposed because the proportion of pores having unnecessary diameters is reduced. The strength comparable to that of the hydrotreating catalyst can be maintained. For example, the catalyst strength can be 1 to 4 lbs / mm for a cylindrical pellet having a diameter of 1.3 mm as the average side strength, and 0.5 to 3.0 lbs / mm for a cylindrical pellet having a diameter of 1 mm. Further, since the CBD (Compacted-Bulk-Density) increases as compared with the catalyst having the bimodal structure already proposed, the activity per catalyst volume is remarkably improved.
The catalyst shape may be any shape including a columnar shape, a granular shape, a tablet shape, or any other shape such as a quadrilateral cross section, and can be arbitrarily selected depending on the reaction mode. Further, the size of the molded body is not limited, but one having a diameter in the range of 0.5 to 3 mm can be employed.
[0028]
The hydrotreating catalyst having the above characteristic values can be prepared by employing the following production method.
That is, the silica-alumina-based carrier as a constituent of the hydrotreating catalyst according to the present invention is a method of preparing a silica hydrate gel and an alumina hydrate gel and mixing them together, a water-soluble aluminum compound A method of adding a basic substance or an acidic substance to a homogeneous mixed solution of water and a water-soluble silicon compound to co-precipitate both can be adopted by controlling conditions and operations. In order to obtain a silica-alumina-based support having a pore structure and physical properties necessary as a catalyst for hydrotreating and having silica highly dispersed on alumina, a specific alumina hydrate gel is formed under specific conditions. Thereafter, a method of depositing a silica hydrate gel on an alumina hydrate gel is suitable, and a specific example is as follows.
[0029]
It is possible to obtain the desired pore structure while controlling the gelation rate and re-dissolution rate while pH swinging the alumina hydrate gel from acidic to neutral or alkaline from each aqueous solution of acidic aluminum compound or basic aluminum compound The first step of preparing an alumina hydrate gel and the second step of adding an aqueous solution of a water-soluble silicon compound onto the alumina hydrate gel produced in the previous step to deposit silica gel. By controlling the pH at which the silica hydrate gel is deposited on the alumina hydrate gel in the second step, the gelation rate of the silica hydrate gel is controlled, and the bond between alumina and silica is improved. It is preferable to form a silica layer.
[0030]
As the acidic aluminum compound, aluminum sulfate, chloride, nitrate and the like are used. Further, as the basic aluminum compound, sodium aluminate, potassium aluminate or the like is used.
More specifically, it is preferable to dissolve and introduce the acidic aluminum aqueous solution into the aqueous alkali hydroxide compound solution having a pH of 10 or more in the first step in 1 minute or more, and the optimum gel particle size while controlling the dissolution / deposition rate of the alumina hydrogel. It is necessary to create a distribution. After mixing, an alkali hydroxide compound is added under warming conditions while performing an appropriate aging treatment, pH is adjusted, and an alumina hydrate gel is precipitated. Examples of the alkali hydroxide compound include sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like.
[0031]
In the second step, an aqueous solution of a water-soluble silicon compound is added to and mixed with the aluminum hydrate gel slurry obtained in the first step, and maintained at a temperature of 50 to 80 ° C. under a pH of 7 to 10. A silica hydrate gel is deposited on the alumina hydrate gel. As the water-soluble silicon compound, alkali metal silicate, tetraalkoxysilane, orthosilicate ester and the like can be used. As alkali metal silicate, Na2O: SiO2It is preferable to use sodium silicate in a molar ratio of 1: 2 to 1: 4.
In order to significantly improve the dispersion state of the silica gel relative to the alumina gel during or after the deposition of the silica hydrate gel on the alumina hydrate gel, and further to form the desired bimodal pore structure, the pH, temperature and A step of performing aging treatment under the control of time is provided. By this aging treatment, the dispersion state of Si atoms in the silica-alumina is remarkably improved, and an increase in the Bronsted acid amount and an increase in the specific surface area can be realized.
[0032]
The silica-alumina hydrogel slurry obtained in the aging step is extruded into a catalyst having a predetermined diameter and shape by a kneader in a state where an appropriate amount of water and acid are mixed. The extrudate gel is dried by heating to room temperature to about 200 ° C. in the presence or absence of oxygen, and the subsequent baking treatment is performed at about 400 to about 800 ° C. in the presence of oxygen. Preferably, the heating is performed in the range of about 600 to about 700 ° C. A silica-alumina-based carrier having a high Bronsted acid amount and a high specific area in which Si is highly dispersed and having the specific pore structure can be obtained by drying and baking treatment.
[0033]
Next, the hydrogenation active metal component is supported on the silica-alumina carrier. As a method for supporting the metal component, an impregnation method in which the support is immersed in a solution of a soluble salt of the metal component and the metal component is introduced into the support, or a coprecipitation method in which the metal component is simultaneously precipitated during the manufacture of the support. Any other method can be used, but it is preferable to use an impregnation method that is easy in operation and convenient for maintaining the stability of catalyst physical properties. In the impregnation operation, the support is immersed in an impregnation solution at normal temperature or above normal temperature, and is maintained under the condition that the desired component is sufficiently impregnated in the support. The amount and temperature of the impregnation solution can be appropriately adjusted so that a desired amount of the active metal component is supported. Further, the amount of the carrier immersed in the impregnation solution can be determined by the desired loading amount of the active metal component.
[0034]
Impregnation and loading of the hydrogenation active metal component onto the support may be performed by any method such as a one-component impregnation method or a two-component impregnation method. That is, in order to carry two or more metal components, two or more metal components are mixed in advance and impregnated simultaneously from the mixed solution (one-component impregnation method) or two or more metal component solutions are separated. In the production of the hydrotreating catalyst of the present invention, these impregnation methods are not limited in any way, and any method can be used. Can be arbitrarily employed, but one or more metals selected from the group consisting of Group 8 metals of the periodic table of elements are first supported on the silica-alumina support (first step), and then It is preferable to support one or more metals selected from the group consisting of Group 6A metals in the same table (second step). Specifically, in the first step, one or more kinds selected from the group consisting of cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium, rhodium and the like of Group 8 of the periodic table are used. Preferably, cobalt and nickel can be used alone or in combination. In the second step, one or more kinds selected from the group consisting of chromium, molybdenum and tungsten of Group 6A of the periodic table are used. Preferably, molybdenum and tungsten can be used alone or in combination. If desired, a third metal of Group 4B and Group 7A of the periodic table can be added as described above.
[0035]
When the coprecipitation method in which the metal component described above is precipitated simultaneously with the carrier is adopted, the carrier impregnated and supported with the hydrogenation active metal component is molded by a molding method such as extrusion molding, punching molding or rolling granulation. After that, a drying process and a baking process are performed. The drying treatment is performed by heating to normal temperature to about 200 ° C. in the presence or absence of oxygen, and the baking treatment is performed at about 400 to about 800 ° C., preferably about 450 to about 700 ° C. in the presence of oxygen. For 3 to 5 hours.
[0036]
Next, the hydrotreating method for hydrocarbon oil according to the present invention will be described.
The hydrotreating method for hydrocarbon oil according to the present invention includes a step of bringing a hydrocarbon oil into contact with hydrogen under hydrotreating conditions in the presence of the hydrotreating oil catalyst.
[0037]
There are no particular limitations on the feedstock used in the hydrotreating process, and atmospheric distillation distillate oil, atmospheric distillation residue oil, vacuum distillation residue oil, vacuum distillation residue oil, cracked gas oil fraction or these In particular, naphtha, kerosene, straight-run gas oil, vacuum gas oil (VGO), and vacuum residue oil can be efficiently subjected to hydroprocessing. The vacuum gas oil is a distillate having a boiling point in the range of about 370 to 610 ° C. obtained by subjecting an atmospheric distillation residue oil to vacuum distillation, and contains a considerable amount of sulfur, nitrogen and metal. For example, one example of Middle Eastern crude oil vacuum gas oil contains about 2 to about 4% by weight of sulfur and about 0.03 to about 0.2% by weight of nitrogen. Further, the residual carbon content is about 1% by weight. The cracked light oil is a cracked oil having a boiling point of about 200 ° C. or higher obtained by pyrolyzing the residual oil, and is obtained from, for example, a residual oil coker and a bisbreaker. Moreover, light cycle gas oil (LCGO), heavy cycle gas oil (HCGO), etc. obtained from a catalytic cracking apparatus can also be used for the hydroprocessing method of this invention as raw material oil. According to the hydrotreating method of the present invention, the hydrodesulfurization / denitrogenation of the vacuum gas oil can be carried out effectively. In particular, the hydrocracking of the atmospheric residue oil or the vacuum residue oil can be performed at a high decomposition rate. It can be performed smoothly and a high quality product can be obtained.
[0038]
The hydrotreating reaction conditions are appropriately selected according to target values such as desulfurization rate and denitrogenation rate when naphtha, kerosene, straight-run gas oil, vacuum gas oil (VGO) and vacuum residue oil (VR) are hydrotreated. The following reaction conditions can be employed.
In hydrorefining such as hydrodesulfurization and hydrodenitrogenation of the hydrocarbon oil, it is represented by 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene, which are particularly difficult to desulfurize, contained in light oil. It is essential to promote desulfurization of refractory dibenzothiophenes having a sterically hindered alkyl substituent and to suppress the deterioration of the activity for this reaction. This is a catalyst for hydroprocessing that has a large pore region that is not present, which improves the feed diffusibility of the feedstock and promotes prehydrogenation or hydrocracking to further increase the molecular species of interest. Facilitates diffusion into small pores and high specific surface area pores, and subsequent desulfurization, and greatly reduces pore plugging due to coke degradation and associated diffusion barriers One in which was able to sum. Diffused hardly-desulfurized sulfur compounds are composed of highly dispersed hydrogenated active metal components and Bronsted acid points and Lewis acid points in the first peak region having a pore volume distribution peak in the pore diameter range of 40 to 200 mm. Hydrodesulfurization is promoted, and as a whole, feed diffusion, hydrodesulfurization, and active deterioration are greatly suppressed.
[0040]
The reaction conditions that can achieve the above-described effects on the light oil fraction are as follows.
Moreover, about the vacuum gas oil (VGO), the hydrogenation process on the following conditions is preferable.
According to the hydrotreating method of the present invention, the mechanism is the same in the hydrocracking of heavy oil by using the hydrotreating catalyst according to the present invention, and a vacuum residue oil (VR fraction) is used. Greatly facilitates the diffusion of large molecules in the catalyst, especially macroaromatic molecules represented by resin and asphaltene molecules, and promotes preliminary hydrogenation and hydrogenolysis of VR and asphaltene molecules in the pore region. Here, the hydrogenated or hydrocracked molecules further diffuse into the small pore / high specific surface area region, and are hydrogenated at highly dispersed hydrogenated active metals and Bronsted acids, as well as at Lewis acid sites. Hydrocracking, hydrodesulfurization, and hydrodenitrogenation are actively carried out. Especially in hydrocracking processes (fixed bed, boiling bed, slurry bed), in the case of high conversion operation at high temperatures, dehydrogenation and polycondensation reactions occur simultaneously with hydrocracking and thermal cracking in the product. Since asphaltene and sediment solids are generated and increased, fouling troubles due to accumulation of sediment in the reactor and downstream distillation apparatus and piping occur, which becomes a serious problem. Therefore, in the heavy oil hydrocracking process, increasing conversion and reducing sedimentation are very important issues. Usually, the cement solid substance can be explained by a solubility phenomenon in which giant asphaltenes molecules are precipitated from a solvent in a supersaturated state. In order to sufficiently dissolve a huge asphaltene molecule having a very high degree of polycondensation and advanced dehydrogenation, the solvent product component for dissolving it must be somewhat aromatic. On the other hand, for the products obtained by this process, it is necessary to advance the cracking rate, hydrodesulfurization, denitrogenation, and dearomatization (hydrogenation) of each fraction by strengthening the hydrogenation capacity from the demand for clean fuel There is. Although the sulfur, nitrogen, and aromatic components of the product can be reduced by improving the hydrogenation ability of the catalyst, on the other hand, the asphaltene molecule, which is a solute accompanying the decrease in aromaticity of the product dissolving asphaltene, is very high. A large amount of precipitation occurs, causing a large amount of sediment and inability to operate stably due to fouling. However, by using the hydrotreating catalyst according to the present invention, it is possible to more efficiently remove asphaltenes than conventional catalysts, so that it is possible to further improve the hydrogenation ability, As a result, it has become possible to strengthen the hydrodesulfurization, denitrogenation, and dearomatization of products. In this catalyst, hydrogenation active metals, Bronsted acids and Lewis acids are highly dispersed and evenly distributed on the surface of the catalyst having a specific large pore structure, improving conversion, reducing sedimentation, and improving hydrogenation ability. It was achieved at the same time.
[0043]
About the vacuum residue oil (VR), the hydrogenation process on the following conditions is preferable.
In carrying out the hydrotreating of hydrocarbon oil, the hydrotreating catalyst can be used in any form of a fixed bed, a fluidized bed, a moving bed or a boiling bed, and can be arbitrarily selected. It is also possible to combine two or more reaction towers and perform hydrogenation treatment to achieve high desulfurization rate, denitrogenation rate, and aromatic hydrogenation rate, and to control hydrocracking activity. .
[0045]
In the hydrotreating method according to the present invention, it is preferable to perform a preliminary sulfidation treatment before the hydrotreating of the raw hydrocarbon oil. In the preliminary sulfidation, the calcined catalyst is charged into the reaction tower, and then the sulfur-containing distillate is supplied to the reaction tower. Temperature: 150 to 400 ° C., pressure (total pressure): 20 to 200 kg / cm2Liquid space velocity; 0.3-2.0 V / H / V and hydrogen-containing gas rate; contacted under reaction conditions of 50-1500 liters / liter to sulfidize the hydrogenated active metal component, and after completion Switch distillate oil to raw hydrocarbon oil and start hydrotreatment. In addition to the method described above, a method of bringing hydrogen sulfide or other sulfur compound into direct contact with the catalyst or adding it to an appropriate sulfur-containing hydrocarbon oil and bringing it into contact with the catalyst is adopted as the sulfurization method. You can also.
[0046]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples.
In addition, the mercury intrusion method used for the measurement of the pore distribution of the catalyst obtained in Examples and the like is described in P.I. H. Emmet et al., “Kyatalysis”, Volume 1, page 123 (published by Linehold Publishing Company) (1959) PHEmmett, et.al. “Catalysis”, Vol. 1, p123 (1959) (Reinhold Publishing Co.) And the method described in Catalyst Engineering Course, Vol. 4, pages 69-78 (published by Jinjinshokan) (Showa 39).
The pore volume was calculated on the assumption that the contact angle of mercury with the catalyst was 130 °, the surface tension was 485 dynes / cm, and all the pores were cylindrical.
The specific surface area was measured by a nitrogen adsorption method.
[0047]
Example 1 (Catalyst A)
3 liters of pure water was heated to 50 ° C., and adjusted to pH = 13 by adding 50 ml of 2N aqueous sodium hydroxide solution thereto. Aluminum sulfate (Al2(SO4)3・ 14H2495 g of O) was dissolved in 710 g of pure water, and this aqueous solution was mixed with the entire amount of the previously heated aqueous sodium hydroxide solution (pH = 13) prepared in advance over 3 minutes. By adding 980 ml of 2N sodium hydroxide aqueous solution over 5 minutes to the obtained mixed aqueous solution, the pH was changed to 8.8, and alumina hydrogel was precipitated. The aqueous solution containing this aluminum hydrogel was aged at 50 ° C. for 30 minutes while maintaining pH = 8.8.
Next, 52 g of sodium silicate (JIS No. 3 water glass) is dissolved in 200 g of pure water to prepare an aqueous solution of sodium silicate, and this is added to an aqueous solution containing the alumina hydrogel with nitric acid and / or aqueous sodium hydroxide as required. And added while maintaining pH = 9.0. This mixed solution was aged at 50 ° C. for 30 minutes in order to achieve high dispersion of silica.
The slurry obtained here was filtered, and then washed with an aqueous ammonium carbonate solution so that the residual Na amount in the filtrate after filtration was 5 ppm or less.
Silica-alumina hydrogel after washingInAdd moisture and acidShiThen, the viscosity was adjusted, and it was molded into an extruded product (Extrudate) having a diameter of 1.3 mm by a kneader.
The obtained extruded product (Extrudate) was dried at 120 ° C. for a whole day and night, and then calcined in the air at 700 ° C. for 3 hours to obtain a silica-alumina carrier having 15% by weight of silica.
Next, 4.4 g of nickel acetate, 19.5 g of cobalt acetate and 10.0 g of citric acid were dissolved in pure water, and ammonia water was added thereto to adjust the pH to 8.8. Prepared.
70 g of this metal salt-containing aqueous solution was impregnated and supported on 70 g of the silica-alumina carrier, dried overnight at 120 ° C., and then calcined in the air at 450 ° C. for 3 hours to obtain 75 NiCo / silica-alumina catalyst. .5 g was obtained.
26.1 g of ammonium heptamolybdate was dissolved in 49.4 ml of aqueous ammonia at 50 ° C. to prepare a Mo salt aqueous solution having a pH of 9.0.
75.5 g of the NiCo / silica-alumina catalyst obtained as described above was impregnated with 75.5 g of an aqueous Mo salt solution, dried overnight at 120 ° C., and then calcined in air at 500 ° C. for 3 hours. NiCoMo / silica-alumina catalyst [A] was obtained. The pore volume distribution and catalyst characteristics of the catalyst [A] are shown in Table 1.
Using 50 g of the finally obtained catalyst [A], hydrogenation treatment was carried out using light oil as a raw material under the following reaction conditions using a fixed bed type high-pressure reactor for hydrotreatment, and desulfurization activity was evaluated. The evaluation results are shown in Table 1.
[0048]
Sulfiding conditions
10% H2S / 90% H2The gas was passed through the catalyst bed at a flow rate of 24 liter / h for 12 hours at 250 ° C., then heated to 350 ° C. and passed for 12 hours.
Raw oil
Light oil (LGO-D)
Sulfur content: 1.5 wt%
Nitrogen content: 110 wtppm
Evaluation operating conditions
Reaction temperature (° C): 343
Reaction pressure (Psig-H2): 300
Liquid space velocity (V / H / V): 0.8
Hydrogen gas / raw oil ratio (SCF / B): 550
[0049]
Example 2 (Catalyst B)
3 liters of pure water was heated to 50 ° C., and adjusted to pH = 13 by adding 50 ml of 2N sodium hydroxide aqueous solution thereto. Aluminum sulfate (Al2(SOFour)Three・ 14H2O) 495 g was dissolved in 710 g of pure water to prepare an aqueous aluminum sulfate solution. An aqueous solution of aluminum sulfate was mixed in advance with the entire amount of the aqueous sodium hydroxide solution (pH = 13) prepared in advance over 3 minutes. Alumina hydrogel was precipitated by controlling the pH to 9.5 by adding 1100 ml of 2N aqueous sodium hydroxide solution over 3 minutes to the obtained aqueous aluminum sulfate solution. This aqueous solution containing alumina hydrogel was aged at pH 9.5 and 50 ° C. for 30 minutes.
Next, an aqueous sodium silicate solution prepared by dissolving 52 g of sodium silicate (JIS No. 3 water glass) in 200 g of pure water uses nitric acid and / or sodium hydroxide aqueous solution as necessary for the aqueous solution containing the alumina hydrogel, It was added while maintaining pH = 9.0. The obtained mixed aqueous solution was aged at 50 ° C. for 30 minutes in order to realize high silica dispersion.
The slurry obtained here was filtered, washed with an aqueous ammonium carbonate solution so that the residual Na amount in the filtrate was 5 ppm or less, and then subjected to the same operation and conditions as in Example 1 using a silica-alumina carrier [ B] was prepared, and the NiCoMo / silica-alumina catalyst [B] was prepared by the same operation and conditions as in Example 1 with respect to loading of the active metal component. Table 1 shows the pore distribution and catalyst characteristics of the catalyst [B].
[0050]
Comparative Example 1 (Catalyst C)
2 liters of pure water was heated to 70 ° C., and 50 ml of 2N sodium hydroxide was added thereto to adjust the pH to 13. Aluminum sulfate (Al2(SOFour)Three・ 14H2O)) 525 g was dissolved in 710 g of pure water, and this solution was mixed with the previously prepared warmed aqueous sodium hydroxide solution (pH = 13) over 10 minutes. Subsequently, 950 ml of 2N sodium hydroxide aqueous solution was added to the mixed aqueous solution over 15 minutes to adjust the mixed solution to pH = 8.4, and alumina hydrogel was precipitated. This aqueous solution containing alumina hydrogel was aged at pH = 8.4 and 70 ° C. for 30 minutes.
Regarding the addition conditions of sodium silicate (JIS No. 3 water glass), all examples were carried out except that 33 g of sodium silicate was added and dissolved in 200 g of pure water, and this was mixed with an aqueous solution containing alumina hydrogel at pH = 9. In the same manner as in No. 1, a silica-alumina support having a silica content of 10% by weight was prepared. Other catalyst preparation conditions were the same as those in Example 1, and a NiCoMo / silica-alumina catalyst [C] was prepared.
Other catalyst preparation conditions were the same as those in Example 1, and a NiCoMo / silica-alumina catalyst [C] was prepared.
[0051]
Comparative Example 2 (Catalyst D)
1 liter of pure water was heated to 70 ° C., and an aqueous sodium hydroxide solution (169 g of NaOH, 420 g of pure water) was added thereto to adjust to pH = 13. Aluminum sulfate (Al2(SO4)3・ 14H2O) 466 g was dissolved in 710 g of pure water and this solution was prepared in advance within 5 seconds.AboveMix to total volume of warm aqueous sodium hydroxide (pH = 13). By adding 500 ml of an aqueous sodium hydroxide solution within 1 minute to the obtained mixed solution, the mixed solution was adjusted to pH = 9.0, and alumina hydrogel was precipitated. The aqueous solution containing the alumina hydrogel was aged at 70 ° C. for 60 minutes while maintaining the pH at 9.0.
Next, 69 g of sodium silicate (JIS No. 3 water glass) was dissolved in 210 g of pure water, and this was added to an aqueous solution containing the alumina hydrogel, and a nitric acid solution was added to adjust the pH to 9.0 as necessary. The mixed solution was aged at 70 ° C. for 180 minutes while maintaining pH = 9.0.
The obtained silica-alumina hydrogel was treated in the same manner as in Example 1 to give a 20% by weight silica extrudate support. This support was impregnated with an aqueous solution of ammonium heptamolybdate so that 20% by weight of molybdenum as an oxide was supported, then dried at 120 ° C. for a whole day and night, and calcined at 550 ° C. for 3 hours to obtain a Mo / silica-alumina catalyst. Got.
Next, the support was impregnated with an aqueous cobalt acetate solution so that 5% by weight of cobalt was supported as an oxide, then dried at 120 ° C. for 24 hours, and then calcined at 450 ° C. for 3 hours to obtain a CoMo / silica-alumina catalyst. [D] was obtained.
The pore characteristics of the catalyst [D] are shown in Table 1, but PV (1stpeak ± 20 cm) / PV (40 to 200) is 42% and does not reach 50%. PV (1stpeak ± 10 cm) / PV (40 to 200) does not reach 30%, and the half-value width has a wide distribution of 80 to 90 cm, and the pore volume distribution is broad. Therefore, the average side surface strength was as extremely low as 0.3 lbs / mm.
[0052]
[Table 1]
Example 3 (Catalyst E)
In the conditions for preparing silica-alumina support of Example 2, sodium silicate (JIS No. 3 water glass) was added by adding and dissolving 33 g of sodium silicate in 200 g of pure water, and mixing this into an aqueous solution containing alumina hydrogel. A silica-alumina hydrogel carrier [E] was prepared in the same manner as in Example 1 except that this was done.
The obtained silica-alumina hydrogel was adjusted in viscosity by addition of water or acid, and formed into an extruded product (Extrudate) having a diameter of 1.0 mm by a kneader.
The obtained extruded product (Extrudate) was dried at 120 ° C. for a whole day and night, and then calcined in the air at 700 ° C. for 3 hours to obtain a silica-alumina carrier having 10% by weight of silica.
Next, 7.6 g of nickel acetate, 13.3 g of ammonium heptamolybdate, and 10.2 g of citric acid are dissolved in pure water, and the pH is adjusted to 8.8 by adding ammonia water thereto. 110.7g of was prepared.
110.7 g of this metal salt-containing aqueous solution was impregnated and supported on 90.0 g of a silica-alumina carrier [E], and dried at 120 ° C. overnight. Then, 103.1g of NiMo / silica-alumina catalyst [E] was obtained by baking in the air at 400 degreeC for 3 hours.
The finally obtained catalyst [E] was hydrocracked using a reduced pressure residue oil (VR) as a raw oil using a continuous stirring flow type high-pressure reactor for hydroprocessing, and various product properties were evaluated. . Sulfiding conditions and evaluation operation conditions are as follows.
[0054]
Sulfiding conditions
160kg / cm after packing 160g of catalyst in the catalyst bed2Gas oil (VGO) for sulfurization treatment (S = 2.0wt.%, Density = 0.9194g / cc) at a rate of 185cc / h and 100% H2The gas was circulated at a rate of 100 SL / h for 12 hours at 200 ° C., then heated to 280 ° C. for 12 hours, further heated to 340 ° C. and circulated for 12 hours for sulfiding treatment.
Raw oil
Vacuum residue oil VR-D (Density = 1.027, S = 3.86wt.%, N = 0.32wt%)
Evaluation operating conditions
Pressure 160kg / cm2After aging treatment by circulating the raw oil at a rate of 370cc / h and hydrogen gas at a rate of 270SL / h for 4 days at a temperature of 415 ° C, the raw material oil at a temperature of 410 ° C at a rate of 185cc / h and hydrogen gas 135 Evaluation was made by circulating for 2 days at a rate of SL / h, and then the temperature was raised to 415 ° C. and evaluated for 2 days.
[0055]
Example 4 (Catalyst F)
Under the silica-alumina carrier preparation conditions of Example 2, the aqueous aluminum sulfate solution was adjusted to pH = 9.5 in 2 minutes. Moreover, about the addition conditions of the sodium silicate (JIS3 water glass) which deposited the alumina hydrogel, it implemented except having added and melt | dissolved 33 g of sodium silicate in the pure water 200g, and mixed this with the alumina hydrogel aqueous solution. A silica-alumina hydrogel support [F] was prepared in the same manner as in Example 2. The obtained silica-alumina hydrogel was adjusted in viscosity by addition of water or acid, and formed into an extruded product (Extrudate) having a diameter of 1.0 mm by a kneader.
The obtained extruded product (Extrudate) was dried at 120 ° C. overnight, and then calcined in air at 700 ° C. for 3 hours. The silica content in the silica-alumina support obtained here was 10% by weight. The catalyst preparation and catalyst evaluation conditions after supporting the hydrogenation active metal were the same as those in Example 3 (catalyst [F]). Table 2 shows the catalyst composition, pore characteristics and evaluation results.
[0056]
Comparative Example 3 (Catalyst G)
Using the silica-alumina hydrogel support of Comparative Example 1, an extruded support (extrudate) having a diameter of 1.0 mm was prepared according to Example 3, and a silica-alumina support was prepared by drying and firing. The active metal was supported in the same manner as in Example 3 to prepare catalyst [G]. The hydrocracking evaluation was performed on the catalyst [G] under the same conditions as in Example 3. Table 2 shows the catalyst composition, pore characteristics, and evaluation results.
From the above examples and comparative examples, the hydrotreating catalyst according to the present invention satisfies the components (1) to (9), has a specific bimodal structure in the pore volume distribution, and has a desulfurization activity and hydrogenation. It has been clarified that a conventionally proposed catalyst that cannot satisfy any of the above-described constituent elements cannot exhibit a sufficient effect, while having a remarkable effect on decomposition activity, ability to suppress sediment, and the like.
[0057]
[Table 2]
【The invention's effect】
The hydrotreating catalyst according to the present invention has a specific bimodal pore structure, thereby facilitating diffusion of hydrocarbon oil into the catalyst and greatly reducing deterioration of catalytic activity, thereby reducing naphtha and kerosene. Further, desulfurization activity, denitrogenation activity, and aromatic hydrogenation activity can be improved in a hydrotreating process in which light oil, vacuum gas oil (VGO) and hydrogen are brought into contact with each other. In particular, in a hydrocracking process in which the catalyst is contacted with heavy oil such as reduced pressure gas oil (VGO), reduced pressure residue oil (VR) and hydrogen, the decomposition rate (composition) and asphaltene treatment performance are improved. To achieve the desired gas and light oil (naphtha, kerosene, light oil and vacuum gas oil (VGO)) yield, desulfurization / denitrogenation rate, and drastic reduction of sediment content. .
Claims (2)
（１）細孔直径４０〜２００Åの範囲に細孔容積分布の第一のピークを有し、
（２）細孔直径２００〜２０００Åの範囲に細孔容積分布の第二のピークを有し、
（３）全細孔容積に対する細孔直径４０〜２００Åの領域の細孔容積が４０〜９０％
であり、
（４）全細孔容積に対する細孔直径２００〜１０００Åの領域の細孔容積が１０〜
６０％であり、
（５）全細孔容積に対する細孔直径１０００Å以上の領域の細孔容積が２０％以下
であり、
（６）前記細孔直径４０〜２００Åの範囲に存在する前記第一のピークの位置に対応す
る細孔直径±２０Åの範囲の細孔容積が、前記細孔直径４０〜２００Åの範囲の
細孔容積の５０％以上であり、
（７）平均細孔直径が６０〜１５０Åであり、
窒素吸着法により測定される比表面積が１５０〜４００ｍ２／ｇ
であることを特徴とする水素化処理用触媒。Hydrogenation having a structure in which a silica layer is formed on an alumina surface, and containing at least one hydrogenation active metal component on a silica-alumina-based carrier containing 2 to 40% by weight of silica based on the total weight of the carrier. A catalyst for treatment, in the pore volume distribution measured by mercury porosimetry,
(1) having a first peak of pore volume distribution in a pore diameter range of 40 to 200 mm;
(2) having a second peak of pore volume distribution in a pore diameter range of 200 to 2000 mm;
(3) The pore volume in the region having a pore diameter of 40 to 200 mm with respect to the total pore volume is 40 to 90%.
And
(4) The pore volume of the region having a pore diameter of 200 to 1000 mm with respect to the total pore volume is 10 to 10
60%,
(5) The pore volume of the region having a pore diameter of 1000 mm or more with respect to the total pore volume is 20% or less,
(6) The pore volume in the range of pore diameter ± 20 mm corresponding to the position of the first peak existing in the range of the pore diameter of 40 to 200 mm is small in the range of the pore diameter of 40 to 200 mm. More than 50% of the pore volume,
(7) The average pore diameter is 60 to 150 mm,
Specific surface area measured by nitrogen adsorption method is 150 to 400 m 2 / g
A catalyst for hydrotreating characterized by the above.
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