JP5517541B2 - Hydrodesulfurization catalyst for hydrocarbon oil and method for producing the same - Google Patents
Hydrodesulfurization catalyst for hydrocarbon oil and method for producing the same Download PDFInfo
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- JP5517541B2 JP5517541B2 JP2009227465A JP2009227465A JP5517541B2 JP 5517541 B2 JP5517541 B2 JP 5517541B2 JP 2009227465 A JP2009227465 A JP 2009227465A JP 2009227465 A JP2009227465 A JP 2009227465A JP 5517541 B2 JP5517541 B2 JP 5517541B2
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- 239000003054 catalyst Substances 0.000 title claims description 162
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 15
- 229930195733 hydrocarbon Natural products 0.000 title claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 176
- 239000007864 aqueous solution Substances 0.000 claims description 68
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 59
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 239000011148 porous material Substances 0.000 claims description 38
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 36
- 239000003921 oil Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 28
- 230000000737 periodic effect Effects 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- -1 silicate ions Chemical class 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910001773 titanium mineral Inorganic materials 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 27
- 238000006477 desulfuration reaction Methods 0.000 description 25
- 230000023556 desulfurization Effects 0.000 description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 11
- 238000007865 diluting Methods 0.000 description 11
- 229910001388 sodium aluminate Inorganic materials 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 10
- 150000007524 organic acids Chemical class 0.000 description 10
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 5
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000002250 progressing effect Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
本発明は、炭化水素油の水素化脱硫触媒およびその製造方法に関し、さらに詳しくは、炭化水素油、特に軽油留分の水素化処理反応に使用され、高い脱硫活性を示すシリカ−チタニア−アルミナ担体に活性成分を担持した水素化脱硫触媒およびその製造方法に関する。 The present invention relates to a hydrodesulfurization catalyst for hydrocarbon oils and a method for producing the same, and more particularly to a silica-titania-alumina support that is used in a hydrotreating reaction of hydrocarbon oils, particularly gas oil fractions, and exhibits high desulfurization activity. The present invention relates to a hydrodesulfurization catalyst having an active component supported thereon and a method for producing the same.
従来、炭化水素油の水素化処理を目的として使用されてきた触媒には、アルミナ、アルミナ−シリカ、チタニア、アルミナ−チタニアなどの多孔性無機酸化物からなる担体に、周期表第ＶＩＡ族及び第ＶＩＩＩ族から選ばれた金属成分を担持した触媒が広く使用されている。
現在、環境保護の観点から燃料油の硫黄分の品質規制が強化されている。特に、軽油中の硫黄分は１０質量ｐｐｍ以下という厳しい規制となっている。このため、この規制に対応できるよう軽油超深度脱硫触媒の開発が進んでいる。
Conventionally, catalysts that have been used for the hydrotreatment of hydrocarbon oils include carriers of porous inorganic oxides such as alumina, alumina-silica, titania, alumina-titania, periodic table groups VIA and Catalysts carrying a metal component selected from Group VIII are widely used.
At present, the quality regulation of sulfur content in fuel oil is being strengthened from the viewpoint of environmental protection. In particular, the sulfur content in light oil is strictly regulated to 10 mass ppm or less. For this reason, development of a light oil ultra-deep desulfurization catalyst is progressing so that it can respond to this regulation.
チタニア担体は、アルミナ担体と比べ高脱硫性能を示すことが知られているが、一般的に比表面積が小さく、また高温での熱安定性が低いといった問題があった。チタニア含有触媒としては、チタニアゲルを用いてチタニア担体を調製する製法（特許文献１参照）、水溶性チタニア化合物をアルミナ担体に担持させアルミナ−チタニア担体を調製する製法（特許文献２参照）などが知られている。特許文献１に記載の触媒は、高価なチタニアが多く含有されており、従来のアルミナ担体を用いた触媒と比較して、価格が高くなると共に、嵩密度が高くなっていた。また、特許文献２に記載の触媒は、担体の吸水率分しかチタニアを担持できないため、チタニアを担体に高担持させるには担持工程を繰り返す必要があり、工業的に製造するには高価となっていた。また、アルミナ調製時にチタニアを混合させアルミナ中にチタニアを高分散させる製法（特許文献３参照）などもある。本製法は、チタニアをアルミナ中に高分散させることができるが、チタニアの含有量が増えるにつれチタニアの結晶化が進み易くなり比表面積が低下し、細孔分布のシャープネスが悪くなるという欠点があるうえ、これまで１０質量ｐｐｍ規制に対応できる十分な性能を有する触媒ではなかった。
The titania support is known to exhibit high desulfurization performance as compared with the alumina support, but generally has a problem that the specific surface area is small and the thermal stability at high temperature is low. Known titania-containing catalysts include a production method for preparing a titania carrier using titania gel (see Patent Document 1), a production method for preparing an alumina-titania carrier by supporting a water-soluble titania compound on an alumina carrier (see Patent Document 2), and the like. It has been. The catalyst described in
本発明の目的は、アルミナを主成分とし、シリカおよびチタニアを含有する高比表面積の担体を使用した安価で高性能な炭化水素油、特に軽油留分の水素化脱硫触媒およびその製造方法の提供にある。 An object of the present invention is to provide a low-cost and high-performance hydrocarbon oil, particularly a hydrodesulfurization catalyst for a gas oil fraction, and a method for producing the same, using a carrier having a high specific surface area containing alumina and silica and titania as a main component. It is in.
本発明者らは鋭意研究した結果、特定の構造を有するシリカ−チタニア−アルミナ担体を用い、かつ所定の性状を有する水素化脱硫触媒とすることにより、脱硫性能が大きく向上し、前記課題を達成し得ることを見出した。 As a result of diligent research, the inventors of the present invention have achieved a significant improvement in desulfurization performance by using a silica-titania-alumina support having a specific structure and a hydrodesulfurization catalyst having a predetermined property, thereby achieving the above object. I found out that I could do it.
即ち、本発明は、Ｘ線回折分析により測定されるアナターゼ型チタニア（１０１）面の結晶構造を示す回折ピーク面積及びルチル型チタニアの（１１０）面の結晶構造を示す回折ピーク面積の合計の面積が、γ−アルミナ（４００）面に帰属されるアルミニウム結晶構造を示す回折ピーク面積に対して、１／４以下であるシリカ−チタニア−アルミナ担体に、周期表第ＶＩＡ族及び第ＶＩＩＩ族から選ばれる少なくとも１種の金属成分を担持してなる炭化水素油の水素化脱硫触媒であって、（ａ）比表面積（ＳＡ）が１５０ｍ２／ｇ以上、（ｂ）全細孔容積（ＰＶｏ）が０．３０ｍｌ／ｇ以上、（ｃ）平均細孔直径（ＰＤ）が６〜１５ｎｍ（６０〜１５０Å）の範囲、および（ｄ）平均細孔径（ＰＤ）±３０％の細孔直径の細孔容積（ＰＶｐ）の占める割合が全細孔容積（ＰＶｏ）の７０％以上であることを特徴とする炭化水素油の水素化脱硫触媒に関する。 That is, the present invention is the total area of the diffraction peak area showing the crystal structure of the anatase titania (101) plane and the diffraction peak area showing the crystal structure of the (110) plane of rutile titania as measured by X-ray diffraction analysis. Is selected from the group VIA and the group VIII of the periodic table as a silica-titania-alumina support having a diffraction peak area of ¼ or less with respect to the diffraction peak area indicating the aluminum crystal structure attributed to the γ-alumina (400) plane. A hydrodesulfurization catalyst for hydrocarbon oil supporting at least one metal component, wherein (a) specific surface area (SA) is 150 m 2 / g or more, (b) total pore volume (PVo) is Pore volume of 0.30 ml / g or more, (c) average pore diameter (PD) in the range of 6 to 15 nm (60 to 150 mm), and (d) pore diameter of average pore diameter (PD) ± 30% (PVp About hydrodesulfurization catalyst for hydrocarbon oil, wherein the ratio of is more than 70% of the total pore volume (PVo).
また、本発明は、珪酸イオンの存在下で、塩基性アルミニウム塩水溶液と、チタニウム鉱酸塩及び酸性アルミニウム塩の混合水溶液とを、ｐＨが６．５〜９．５になるように混合して水和物を得る第１工程と、前記水和物を順次洗浄、成型、乾燥及び焼成して担体を得る第２工程と、前記担体に、周期表第ＶＩＡ族及び第ＶＩＩＩ族から選ばれる少なくとも１種の金属成分を担持する第３工程とを有することを特徴とする前記の炭化水素油の水素化脱硫触媒の製造方法に関する。 In the present invention, a basic aluminum salt aqueous solution and a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt are mixed in the presence of silicate ions so that the pH is 6.5 to 9.5. A first step for obtaining a hydrate, a second step for obtaining a carrier by washing, molding, drying and calcining the hydrate sequentially, and the carrier comprises at least one selected from Group VIA and Group VIII of the periodic table. And a third step of supporting one type of metal component. The present invention relates to a method for producing a hydrodesulfurization catalyst for hydrocarbon oils.
本発明の水素化脱硫触媒は、炭化水素油、特に軽油留分の水素化処理において高い脱硫活性を示し、極めて有効である。また、本発明の水素化脱硫触媒の製造方法においては、担体中にチタンを高分散することができるため、アルミナやシリカと比較して高価なチタンを比較的少ない量で高性能を示すことが可能となり、安価で高性能な触媒を得ることができる。 The hydrodesulfurization catalyst of the present invention exhibits high desulfurization activity in hydrotreating hydrocarbon oils, particularly gas oil fractions, and is extremely effective. Further, in the method for producing a hydrodesulfurization catalyst of the present invention, titanium can be highly dispersed in the support, and therefore, high performance can be achieved with a relatively small amount of expensive titanium compared to alumina or silica. This makes it possible to obtain an inexpensive and high-performance catalyst.
以下、本発明の好適な実施の形態について、詳細に説明する。
本発明の水素化脱硫触媒は、Ｘ線回折分析により測定されるアナターゼ型チタニア（１０１）面の結晶構造を示す回折ピーク面積及びルチル型チタニア（１１０）面の結晶構造を示す回折ピーク面積の合計の面積が、γ−アルミナ（４００）面に帰属されるアルミニウム結晶構造を示す回折ピーク面積に対して、１／４以下であるシリカ−チタニア−アルミナ担体に、周期表第ＶＩＡ族（ＩＵＰＡＣ 第６族）及び第ＶＩＩＩ族（ＩＵＰＡＣ 第８族〜第１０族）から選ばれる少なくとも１種の金属成分が担持されたものであり、かつ、比表面積（ＳＡ）が１５０ｍ２／ｇ以上、全細孔容積（ＰＶｏ）が０．３０ｍｌ／ｇ以上、平均細孔直径（ＰＤ）が６〜１５ｎｍ（６０〜１５０Å）の範囲、平均細孔径（ＰＤ）±３０％の細孔直径の細孔容積（ＰＶｐ）の占める割合が全細孔容積（ＰＶｏ）の７０％以上のものである。
Hereinafter, preferred embodiments of the present invention will be described in detail.
The hydrodesulfurization catalyst of the present invention is the sum of the diffraction peak area showing the crystal structure of the anatase-type titania (101) plane and the diffraction peak area showing the crystal structure of the rutile-type titania (110) plane measured by X-ray diffraction analysis. The silica-titania-alumina support whose area is 1/4 or less with respect to the diffraction peak area showing the aluminum crystal structure attributed to the γ-alumina (400) plane is a group VIA (IUPAC No. 6) of the periodic table. Group) and at least one metal component selected from Group VIII (IUPAC Group 8 to Group 10) and a specific surface area (SA) of 150 m 2 / g or more, Pore volume with a volume (PVo) of 0.30 ml / g or more, an average pore diameter (PD) in the range of 6 to 15 nm (60 to 150 mm), and an average pore diameter (PD) of ± 30%. Proportion of (PVP) is of more than 70% of the total pore volume (PVo).
本発明の水素化脱硫触媒におけるシリカ−チタニア−アルミナ担体は、シリカを担体基準でＳｉＯ２として１〜１０質量％含有することが好ましく、２〜７質量％含有することがより好ましく、２〜５質量％含有することが更に好ましい。シリカ含有量が１質量％未満では、比表面積が低くなる上、担体を焼成する際にチタニア粒子が凝集しやすくなり、Ｘ線回折分析により測定されるアナターゼ型チタニア及びルチル型チタニアの結晶構造を示す回折ピーク面積が大きくなる。また、シリカの含有量が１０質量％を超える場合には、得られる担体の細孔分布のシャープネスが悪くなり所望の脱硫活性が得られないことがある。 The silica-titania-alumina carrier in the hydrodesulfurization catalyst of the present invention preferably contains 1 to 10% by mass, more preferably 2 to 7% by mass of silica as SiO 2 based on the carrier. More preferably, it is contained by mass%. When the silica content is less than 1% by mass, the specific surface area becomes low, and the titania particles tend to aggregate when the carrier is baked, and the crystal structures of anatase titania and rutile titania measured by X-ray diffraction analysis are obtained. The diffraction peak area shown increases. On the other hand, when the content of silica exceeds 10% by mass, the sharpness of the pore distribution of the obtained carrier is deteriorated and the desired desulfurization activity may not be obtained.
また、本発明でのシリカ−チタニア−アルミナ担体は、チタニアを担体基準でＴｉＯ２として３〜４０質量％含有することが好ましく、より好ましくは１５〜３５質量％、さらに好ましくは１５〜２５質量％含有するのが望ましい。チタニアの含有量が３質量％より少ない場合には、チタニア成分の添加効果が少なく、得られる触媒は所望の脱硫活性が得られないことがある。また、チタニアの含有量が４０質量％より多い場合には、触媒の機械的強度が低くなる虞がある上、担体を焼成したときにチタニア粒子の結晶化が進み易くなるため比表面積が低くなり、チタニア量を増やした分の経済性に見合うだけの脱硫性能が発揮されず、本発明目的である安価で高性能な触媒とならず好ましくない。 Further, the silica-titania-alumina carrier in the present invention preferably contains 3 to 40% by mass of titania as TiO 2 based on the carrier, more preferably 15 to 35% by mass, and further preferably 15 to 25% by mass. It is desirable to contain. When the titania content is less than 3% by mass, the addition effect of the titania component is small, and the obtained catalyst may not obtain the desired desulfurization activity. Further, when the titania content is more than 40% by mass, the mechanical strength of the catalyst may be lowered, and the crystallization of titania particles is facilitated when the support is fired, so that the specific surface area is lowered. The desulfurization performance corresponding to the economical efficiency of the increased titania amount is not exhibited, and it is not preferable because it is not an inexpensive and high-performance catalyst that is the object of the present invention.
さらに、本発明でのシリカ−チタニア−アルミナ担体は、アルミナを担体基準でＡｌ２Ｏ３として５０〜９６質量％含有することが好ましく、より好ましくは５８〜８３質量％、さらに好ましくは７０〜８３質量％含有するのが望ましい。ここで、アルミナの含有量が５０質量％未満の場合には、触媒劣化が大きくなる傾向にあるので好ましくない。また、アルミナの含有量が９６質量％より多い場合には、触媒性能が低下する傾向にあるため好ましくない。 Furthermore, the silica-titania-alumina carrier in the present invention preferably contains 50 to 96% by mass of alumina as Al 2 O 3 based on the carrier, more preferably 58 to 83% by mass, and still more preferably 70 to 83%. It is desirable to contain by mass. Here, when the content of alumina is less than 50% by mass, catalyst deterioration tends to increase, such being undesirable. Moreover, when there is more content of alumina than 96 mass%, since there exists a tendency for catalyst performance to fall, it is unpreferable.
本発明の水素化脱硫触媒は、前記のシリカ−チタニア−アルミナ担体に周期表第ＶＩＡ族（ＩＵＰＡＣ 第６族）及び第ＶＩＩＩ族（ＩＵＰＡＣ 第８族〜第１０族）から選ばれる少なくとも１種以上の金属成分が担持されたものである。
周期表第ＶＩＡ族の金属成分としては、モリブデン（Ｍｏ）、タングステン（Ｗ）等を例示することができ、周期表第ＶＩＩＩ族の金属成分としては、コバルト（Ｃｏ）、ニッケル（Ｎｉ）等を例示することができる。これらの金属成分は１種を単独で又は２種以上を組合せて用いても良い。触媒性能の点から、金属成分としては、ニッケル−モリブデン、コバルト−モリブデン、ニッケル−モリブデン−コバルト、ニッケル−タングステン、コバルト−タングステン、ニッケル−タングステン−コバルト等の組合せが好ましく、特に、ニッケル−モリブデン、コバルト−モリブデン、ニッケル−モリブデン−コバルトの組合せがより好ましい。
The hydrodesulfurization catalyst of the present invention is at least one selected from Group VIA (IUPAC Group 6) and Group VIII (IUPAC Group 8 to Group 10) of the periodic table on the silica-titania-alumina support. The metal component is supported.
Examples of the metal component of Group VIA of the periodic table include molybdenum (Mo) and tungsten (W). Examples of the metal component of Group VIII of the periodic table include cobalt (Co) and nickel (Ni). It can be illustrated. These metal components may be used alone or in combination of two or more. From the viewpoint of catalyst performance, the metal component is preferably a combination of nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten, cobalt-tungsten, nickel-tungsten-cobalt, etc. A combination of cobalt-molybdenum and nickel-molybdenum-cobalt is more preferable.
金属成分の担持量は、触媒基準で、酸化物として、１〜３５質量％の範囲が好ましく、１５〜３０質量％の範囲がさらに好ましい。特に、周期表第ＶＩＡ族の金属成分は、酸化物として、好ましくは１０〜３０質量％の範囲、より好ましくは１３〜２４質量％の範囲、周期表第ＶＩＩＩ族の金属成分は、酸化物として、好ましくは１〜１０質量％の範囲、より好ましくは２〜６質量％の範囲にあることが望ましい。 The supported amount of the metal component is preferably in the range of 1 to 35% by mass and more preferably in the range of 15 to 30% by mass as the oxide on the catalyst basis. In particular, the metal component of Group VIA of the periodic table is preferably in the range of 10 to 30% by mass, more preferably in the range of 13 to 24% by mass, and the metal component of Group VIII of the periodic table is as oxide. , Preferably it is in the range of 1-10% by mass, more preferably in the range of 2-6% by mass.
本発明の水素化脱硫触媒が周期表第ＶＩＡ族の金属成分を含有する場合は、酸を用いて該金属成分を溶解させることが好ましい。ここで酸としては、リン酸および／または有機酸を使用することが好ましい。
リン酸を用いる場合、周期表第ＶＩＡ族の金属成分１００質量％に対してリンは酸化物換算で３〜２５質量％のリン酸を担持させることが好ましく、より好ましくは１０〜１５質量％の範囲で担持されることが好ましい。担持量が２５質量％を超えると触媒性能が低下する傾向にあるので好ましくなく、３質量％未満だと担持金属溶液の安定性が悪くなり好ましくない。
また、有機酸を用いる場合、有機酸は好ましくは周期表第ＶＩＡ族の金属成分に対し３５〜７５質量％、より好ましくは５５〜６５質量％の範囲で担持されることが好ましい。有機酸が周期表第ＶＩＡ族の金属成分に対し７５質量％を超えると該金属成分を含有した溶液（以下、「担持金属含有溶液」ともいう。）の粘度が上がり、製造での含浸工程が困難になるため好ましくなく、３５質量％未満だと担持金属含有溶液の安定性が悪くなる上、触媒性能が低下する傾向にあり好ましくない。
When the hydrodesulfurization catalyst of the present invention contains a metal component of Group VIA of the periodic table, it is preferable to dissolve the metal component using an acid. Here, it is preferable to use phosphoric acid and / or an organic acid as the acid.
When using phosphoric acid, phosphorus preferably supports 3 to 25% by mass of phosphoric acid, more preferably 10 to 15% by mass based on 100% by mass of the metal component of Group VIA of the periodic table. It is preferable to be carried in a range. If the loading amount exceeds 25% by mass, the catalyst performance tends to decrease, which is not preferable. If the loading amount is less than 3% by mass, the stability of the supported metal solution deteriorates, which is not preferable.
When an organic acid is used, the organic acid is preferably supported in a range of 35 to 75% by mass, more preferably 55 to 65% by mass with respect to the metal component of Group VIA of the periodic table. When the organic acid exceeds 75% by mass relative to the metal component of Group VIA of the periodic table, the viscosity of the solution containing the metal component (hereinafter also referred to as “supported metal-containing solution”) increases, and the impregnation step in the production is performed. It is not preferable because it becomes difficult, and if it is less than 35% by mass, the stability of the supported metal-containing solution is deteriorated and the catalyst performance tends to be deteriorated.
なお、上記担体に、上記金属成分、あるいはさらにリンおよび／または有機酸を担持・含有させる方法は特に限定されず、上記金属成分を含む化合物、あるいはさらにリンを含む化合物および／または有機酸を用いた含浸法（平衡吸着法、ポアフィリング法、初期湿潤法）、イオン交換法等の公知の方法を用いることができる。ここで、含浸法とは、担体に活性金属を含む溶液を含浸させた後、乾燥、焼成する方法のことである。
含浸法では、周期表第ＶＩＡ族の金属成分と周期表第ＶＩＩＩ族の金属成分とを同時に担持することが好ましい。別々に金属を担持すると、脱硫活性または脱窒素活性が不充分になることがある。担持を含浸法により行う場合には、担体上での周期表第ＶＩＡ族の金属成分の分散性が高くなって、得られる触媒の脱硫活性および脱窒素活性がより高くなることから、酸の共存下、好ましくはリン酸または有機酸の共存下で行う。その際、周期表第ＶＩＡ族の金属成分１００質量％に対して３〜２５質量％のリン酸又は３５〜７５質量％の有機酸を添加することが好ましい。ここで、有機酸としてはカルボン酸化合物が好ましく、具体的にはクエン酸、リンゴ酸、酒石酸、グルコン酸などが挙げられる。
The method for supporting and containing the metal component or further phosphorus and / or organic acid on the carrier is not particularly limited, and a compound containing the metal component, or a compound containing phosphorus and / or an organic acid is used. Well-known methods such as an impregnation method (equilibrium adsorption method, pore filling method, initial wet method), ion exchange method and the like can be used. Here, the impregnation method is a method of impregnating a support containing a solution containing an active metal, followed by drying and firing.
In the impregnation method, it is preferable to simultaneously support a metal component of Group VIA of the periodic table and a metal component of Group VIII of the periodic table. If the metals are supported separately, the desulfurization activity or denitrification activity may be insufficient. When the loading is carried out by the impregnation method, the dispersibility of the metal component of Group VIA of the periodic table on the support becomes high, and the desulfurization activity and denitrogenation activity of the resulting catalyst become higher. The reaction is preferably carried out in the presence of phosphoric acid or organic acid. In that case, it is preferable to add 3-25 mass% phosphoric acid or 35-75 mass% organic acid with respect to 100 mass% of periodic table VIA group metal components. Here, the organic acid is preferably a carboxylic acid compound, and specific examples thereof include citric acid, malic acid, tartaric acid, and gluconic acid.
本発明の水素化脱硫触媒は、ＢＥＴ法で測定した比表面積（ＳＡ）が１５０ｍ２／ｇ以上であることが必要であり、好ましくは１７０ｍ２／ｇ以上である。比表面積（ＳＡ）が１５０ｍ２／ｇ未満では、脱硫反応の活性点が少なくなり、脱硫性能が低下する虞があるため好ましくない。一方、上限については特に制限はないが、比表面積（ＳＡ）が２５０ｍ２／ｇを超えると触媒強度が低下する傾向にあるので、２５０ｍ２／ｇ以下であることが好ましく、２３０ｍ２／ｇ以下がより好ましい。 The hydrodesulfurization catalyst of the present invention needs to have a specific surface area (SA) measured by the BET method of 150 m 2 / g or more, preferably 170 m 2 / g or more. If the specific surface area (SA) is less than 150 m 2 / g, the active point of the desulfurization reaction is decreased, and there is a possibility that the desulfurization performance may be deteriorated. On the other hand, the upper limit is not particularly limited, but when the specific surface area (SA) exceeds 250 m 2 / g, the catalyst strength tends to decrease. Therefore, the upper limit is preferably 250 m 2 / g or less, and 230 m 2 / g or less. Is more preferable.
また、本発明の水素化脱硫触媒は、水銀圧入法（水銀の接触角：１３５度、表面張力：４８０ｄｙｎ／ｃｍ）により測定した全細孔容積（ＰＶｏ）が０．３０ｍｌ／ｇ以上であることが必要であり、好ましくは０．３５ｍｌ／ｇ以上である。一方、上限については特に制限はないが、全細孔容積（ＰＶo）が０．６０ｍｌ／ｇを超えると触媒強度が低下する傾向にあるので、０．６０ｍｌ／ｇ以下であることが好ましく、０．５０ｍｌ／ｇ以下がより好ましい。 The hydrodesulfurization catalyst of the present invention has a total pore volume (PVo) measured by a mercury intrusion method (mercury contact angle: 135 degrees, surface tension: 480 dyn / cm) of 0.30 ml / g or more. Is preferably 0.35 ml / g or more. On the other hand, the upper limit is not particularly limited, but when the total pore volume (PVo) exceeds 0.60 ml / g, the catalyst strength tends to decrease. Therefore, the upper limit is preferably 0.60 ml / g or less. More preferably, it is 50 ml / g or less.
更に、本発明の水素化脱硫触媒は、平均細孔直径（ＰＤ）が６〜１５ｎｍ（６０〜１５０Å）の範囲であることが必要であり、好ましくは６．５〜１１ｎｍの範囲である。平均細孔直径（ＰＤ）が６ｎｍ未満では、細孔が小さいため、原料油との反応性が悪くなることがあり、また、１５ｎｍを超えるものは製造的に困難であると共に、比表面積が小さくなり、触媒性能が悪くなる傾向がある。なお、全細孔容積（ＰＶｏ）は、細孔直径が測定上の定量限界である４.１ｎｍ（４１Å）以上の細孔を表し、平均細孔直径（ＰＤ）は、全細孔容積（ＰＶｏ）の５０％に相当する細孔直径を表す。 Further, the hydrodesulfurization catalyst of the present invention needs to have an average pore diameter (PD) in the range of 6 to 15 nm (60 to 150 mm), preferably in the range of 6.5 to 11 nm. When the average pore diameter (PD) is less than 6 nm, the pores are small, so the reactivity with the raw material oil may be deteriorated, and those exceeding 15 nm are difficult to produce and the specific surface area is small. Therefore, the catalyst performance tends to deteriorate. The total pore volume (PVo) represents pores having a pore diameter of 4.1 nm (41 cm) or more, which is the quantification limit in measurement, and the average pore diameter (PD) is the total pore volume (PVo). ) Represents the pore diameter corresponding to 50%.
また、本発明の水素化脱硫触媒は、平均細孔直径（ＰＤ）±３０％の細孔直径を有する細孔容積（ＰＶｐ）の全細孔容積（ＰＶｏ）に対して占める割合（ＰＶｐ／ＰＶｏ）が７０％以上であることが必要であり、８０％以上であることが好ましく、その細孔分布はシャープである。ＰＶｐ／ＰＶｏが７０％未満では、触媒の細孔分布がブロードになり、所望の脱硫性能が得られないことがある。 In addition, the hydrodesulfurization catalyst of the present invention has a ratio (PVp / PVo) of the pore volume (PVp) having an average pore diameter (PD) ± 30% to the total pore volume (PVo). ) Must be 70% or more, preferably 80% or more, and its pore distribution is sharp. When PVp / PVo is less than 70%, the pore distribution of the catalyst becomes broad and the desired desulfurization performance may not be obtained.
また、本発明の水素化脱硫触媒の担体は、Ｘ線回折分析により測定されるアナターゼ型チタニア（１０１）面の結晶構造を示す回折ピーク面積及びルチル型チタニア（１１０）面の結晶構造を示す回折ピーク面積の合計の面積（以下、「チタニア回折ピーク面積」ともいう。）が、γ−アルミナ（４００）面に帰属されるアルミニウム結晶構造を示す回折ピーク面積（以下、「アルミナ回折ピーク面積」ともいう。）に対して、１／４以下であることが必要であり、１／５以下であるのが好ましく、１／６以下であるのがより好ましい。ここで、アルミナ回折ピーク面積に対するチタニア回折ピーク面積（チタニア回折ピーク面積／アルミナ回折ピーク面積）が１／４より大きい場合は、チタニアの結晶化が進み反応に有効な細孔が減少する。そのためチタニア量を増やしても、その経済性に見合う分の脱硫性能が発揮されず、本発明の目的である安価で高性能な触媒とならない。 Further, the carrier of the hydrodesulfurization catalyst of the present invention has a diffraction peak area showing the crystal structure of the anatase titania (101) plane and a diffraction structure showing the crystal structure of the rutile titania (110) plane measured by X-ray diffraction analysis. The total peak area (hereinafter also referred to as “titania diffraction peak area”) is a diffraction peak area (hereinafter referred to as “alumina diffraction peak area”) indicating the aluminum crystal structure attributed to the γ-alumina (400) plane. ), It is necessary to be 1/4 or less, preferably 1/5 or less, and more preferably 1/6 or less. Here, when the titania diffraction peak area with respect to the alumina diffraction peak area (titania diffraction peak area / alumina diffraction peak area) is larger than 1/4, crystallization of titania proceeds and pores effective for the reaction decrease. Therefore, even if the amount of titania is increased, the desulfurization performance corresponding to the economic efficiency is not exhibited, and the inexpensive and high-performance catalyst which is the object of the present invention is not obtained.
ここで、アナターゼ型チタニア（１０１）面の結晶構造を示す回折ピークは２θ＝２５．５°で測定したものであり、ルチル型チタニア（１１０）面の結晶構造を示す回折ピークは、２θ＝２７．５°で測定したものである。また、γ−アルミナ（４００）面に帰属されるアルミニウム結晶構造を示す回折ピークは２θ＝４５．９°で測定したものである。
それぞれの回折ピーク面積の算出方法は、Ｘ線回折装置でＸ線回折分析によって得られたグラフを最小二乗法によりフィッティングしベースライン補正を行い、最大ピーク値からベースラインまでの高さを求め（ピーク強度Ｗ）得られたピーク強度の半分の値（１／２Ｗ）のときのピーク幅（半値幅）を求め、この半値幅とピーク強度との積を回折ピーク面積とした。求めた各回折ピーク面積から、「チタニア回折ピーク面積／アルミナ回折ピーク面積」を算出した。
Here, the diffraction peak indicating the crystal structure of the anatase titania (101) plane was measured at 2θ = 25.5 °, and the diffraction peak indicating the crystal structure of the rutile titania (110) plane was 2θ = 27. Measured at 5 °. The diffraction peak showing the aluminum crystal structure attributed to the γ-alumina (400) plane is measured at 2θ = 45.9 °.
Each diffraction peak area is calculated by fitting a graph obtained by X-ray diffraction analysis with an X-ray diffractometer using the least square method and correcting the baseline to obtain the height from the maximum peak value to the baseline ( Peak intensity W) A peak width (half-value width) at a half value (1/2 W) of the obtained peak intensity was determined, and the product of this half-value width and peak intensity was defined as a diffraction peak area. From the obtained diffraction peak areas, “titania diffraction peak area / alumina diffraction peak area” was calculated.
本発明の水素化脱硫触媒は、炭化水素油、特に軽油留分の水素化処理に好適に使用される。該触媒を使用した水素化脱硫処理は、固定床反応装置に触媒を充填して水素雰囲気下、高温高圧条件で行なわれる。
軽油留分としては、原油の常圧蒸留装置から得られる直留軽油、常圧蒸留装置から得られる直留重質油や残査油を減圧蒸留装置で処理して得られる減圧軽油、減圧重質軽油あるいは脱硫重油を接触分解して得られる接触分解軽油、減圧重質軽油あるいは脱硫重油を水素化分解して得られる水素化分解軽油等が挙げられる。
The hydrodesulfurization catalyst of this invention is used suitably for the hydroprocessing of hydrocarbon oil, especially a light oil fraction. The hydrodesulfurization treatment using the catalyst is carried out under a high-temperature and high-pressure condition in a hydrogen atmosphere by filling the catalyst in a fixed bed reactor.
Gas oil fractions include straight-run light oil obtained from a crude oil atmospheric distillation apparatus, straight-run heavy oil obtained from an atmospheric distillation apparatus and residual oil obtained by treating the crude oil with a vacuum distillation apparatus, Examples include catalytic cracking gas oil obtained by catalytic cracking of light diesel oil or desulfurized heavy oil, hydrocracked gas oil obtained by hydrocracking depressurized heavy gas oil or desulfurized heavy oil, and the like.
反応圧力（水素分圧）は３．０〜１５．０ＭＰａであることが好ましく、より好ましくは４．０〜１０．０ＭＰａである。反応圧力が３．０ＭＰａ未満では脱硫および脱窒素が著しく低下する傾向にあり、また、１５．０ＭＰａを超えると水素消費が大きくなり運転コストが増加するので好ましくない。
反応温度は３００〜４２０℃であることが好ましく、より好ましくは３２０〜３８０℃である。反応温度が３００℃未満では脱硫および脱窒素活性が著しく低下する傾向にあり実用的でない。また、反応温度が４２０℃を超えると触媒劣化が顕著になると共に、反応装置の耐熱温度（通常約４２５℃）に近づくため好ましくない。
液空間速度は特に制限されないが、０．５〜４．０ｈ−１であることが好ましく、より好ましくは０．５〜２．０ｈ−１である。液空間速度が０．５ｈ−１未満では処理量が低いので生産性が低くなり実用的ではない。また、液空間速度が４．０ｈ−１を超えると反応温度が高くなり、触媒劣化が速くなるので好ましくない。
水素／油比は１２０〜４２０ＮＬ／Ｌであることが好ましく、より好ましくは１７０〜３４０ＮＬ／Ｌである。水素／油比が１２０ＮＬ／Ｌ未満では脱硫率が低下するので好ましくない。また、４２０ＮＬ／Ｌを超えても脱硫活性に大きな変化がなく、運転コストが増加するだけなので好ましくない。
The reaction pressure (hydrogen partial pressure) is preferably 3.0 to 15.0 MPa, more preferably 4.0 to 10.0 MPa. If the reaction pressure is less than 3.0 MPa, desulfurization and denitrogenation tend to be remarkably reduced, and if it exceeds 15.0 MPa, hydrogen consumption increases and the operating cost increases, which is not preferable.
The reaction temperature is preferably 300 to 420 ° C, more preferably 320 to 380 ° C. If the reaction temperature is less than 300 ° C., the desulfurization and denitrification activities tend to be remarkably lowered, which is not practical. Further, when the reaction temperature exceeds 420 ° C., catalyst deterioration becomes remarkable, and it approaches the heat resistant temperature of the reaction apparatus (usually about 425 ° C.), which is not preferable.
But not liquid hourly space velocity particularly limited, is preferably a 0.5～4.0H -1, more preferably 0.5~2.0h -1. If the liquid space velocity is less than 0.5 h −1 , the throughput is low and the productivity is low, which is not practical. Further, if the liquid space velocity exceeds 4.0 h −1 , the reaction temperature is increased, and the catalyst deterioration is accelerated.
The hydrogen / oil ratio is preferably 120 to 420 NL / L, more preferably 170 to 340 NL / L. A hydrogen / oil ratio of less than 120 NL / L is not preferable because the desulfurization rate decreases. Moreover, even if it exceeds 420 NL / L, since there is no big change in desulfurization activity and only an operating cost increases, it is not preferable.
次に、本発明の水素化脱硫触媒の製造方法について説明する。
本発明の水素化脱硫触媒の製造方法は、珪酸イオンの存在下で、チタニウム鉱酸塩及び酸性アルミニウム塩の混合水溶液（以下、単に「混合水溶液」ともいう。）と、塩基性アルミニウム塩水溶液とを、ｐＨが６．５〜９．５になるように混合して水和物を得る第１工程と、前記水和物を順次洗浄、成型、乾燥、及び焼成して担体を得る第２工程と、前記担体に、周期表第ＶＩＡ族（ＩＵＰＡＣ 第６族）及び第ＶＩＩＩ族（ＩＵＰＡＣ 第８族〜第１０族）から選ばれる少なくとも１種の金属成分を担持する第３工程とを有する。以下、それぞれの工程について説明する。
Next, the manufacturing method of the hydrodesulfurization catalyst of this invention is demonstrated.
The method for producing a hydrodesulfurization catalyst of the present invention comprises a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt (hereinafter also simply referred to as “mixed aqueous solution”), a basic aluminum salt aqueous solution, in the presence of silicate ions. The first step of obtaining a hydrate by mixing the hydrate so that the pH is 6.5 to 9.5, and the second step of obtaining a carrier by sequentially washing, molding, drying and baking the hydrate And a third step of supporting at least one metal component selected from Group VIA (IUPAC Group 6) and Group VIII (IUPAC Group 8 to Group 10) on the carrier. Hereinafter, each process will be described.
（第１工程）
まず、珪酸イオンの存在下で、チタニウム鉱酸塩及び酸性アルミニウム塩の混合水溶液（これは酸性の水溶液である。）と、塩基性アルミニウム塩水溶液（これはアルカリ性の水溶液である。）とを、ｐＨが６．５〜９．５、好ましくは６．５〜８．５、より好ましくは６．５〜7．５になるように混合して、シリカ、チタニア及びアルミナを含む水和物を得る。
(First step)
First, in the presence of silicate ions, a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt (this is an acidic aqueous solution) and a basic aqueous aluminum salt solution (this is an alkaline aqueous solution), Mixing so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 7.5, to obtain a hydrate containing silica, titania and alumina. .
この工程では、（１）珪酸イオンを含む塩基性アルミニウム塩水溶液に、混合水溶液を添加する場合と、（２）珪酸イオンを含む混合水溶液に、塩基性アルミニウム塩水溶液を添加する場合とがある。
ここで、（１）の場合、塩基性アルミニウム塩水溶液に含有される珪酸イオンは、塩基性または中性のものが使用できる。塩基性の珪酸イオン源としては、珪酸ナトリウムなどの水中で珪酸イオンを生じる珪酸化合物が使用可能である。また、（２）の場合、チタニウム鉱酸塩及び酸性アルミニウム塩水溶液の混合液に含有される珪酸イオンは、酸性または中性のものが使用できる。酸性の珪酸イオン源としては、珪酸などの水中で珪酸イオンを生じる珪酸化合物が使用可能である。
In this step, (1) a mixed aqueous solution may be added to the basic aluminum salt aqueous solution containing silicate ions, and (2) a basic aluminum salt aqueous solution may be added to the mixed aqueous solution containing silicate ions.
Here, in the case of (1), the silicate ion contained in the basic aluminum salt aqueous solution can be basic or neutral. As the basic silicate ion source, a silicate compound that generates silicate ions in water such as sodium silicate can be used. In the case of (2), the silicate ions contained in the mixed solution of the titanium mineral acid salt and the acidic aluminum salt aqueous solution can be acidic or neutral. As the acidic silicate ion source, a silicate compound that generates silicate ions in water such as silicic acid can be used.
塩基性アルミニウム塩としては、アルミン酸ナトリウム、アルミン酸カリウムなどが好適に使用される。また、酸性アルミニウム塩としては、硫酸アルミニウム、塩化アルミニウム、硝酸アルミニウムなどが好適に使用され、チタニウム鉱酸塩としては、四塩化チタン、三塩化チタン、硫酸チタン、硝酸チタンなどが例示され、特に硫酸チタンは安価であるので好適に使用される。 As the basic aluminum salt, sodium aluminate, potassium aluminate or the like is preferably used. Further, as the acidic aluminum salt, aluminum sulfate, aluminum chloride, aluminum nitrate and the like are preferably used, and as the titanium mineral acid salt, titanium tetrachloride, titanium trichloride, titanium sulfate, titanium nitrate and the like are exemplified. Titanium is preferably used because it is inexpensive.
例えば、所定量の塩基性の珪酸イオンを含有する塩基性アルミニウム塩水溶液を攪拌機付きタンクに張り込み、通常４０〜９０℃、好ましくは５０〜７０℃に加温して保持し、この溶液の温度±５℃、好ましくは±２℃、より好ましくは±１℃に加温した所定量のチタニウム鉱酸塩及び酸性アルミニウム塩水溶液の混合水溶液をｐＨが６．５〜９．５、好ましくは６．５〜８．５、より好ましくは６．５〜７．５になるように、通常５〜２０分、好ましくは７〜１５分で連続添加し沈殿を生成させ、水和物のスラリーを得る。ここで、塩基性アルミニウム塩水溶液への混合水溶液の添加は、時間が長くなると擬ベーマイトの他にバイヤライトやギブサイトなどの好ましくない結晶物が生成することがあるので、１５分以下が望ましく、１３分以下がさらに望ましい。バイヤライトやギブサイトは、焼成した時に比表面積が低下するので、好ましくない。 For example, a basic aluminum salt aqueous solution containing a predetermined amount of basic silicate ions is placed in a tank equipped with a stirrer, and is usually kept at 40 to 90 ° C., preferably 50 to 70 ° C., and the temperature of this solution ± A mixed aqueous solution of a predetermined amount of a titanium mineral acid salt and an acidic aluminum salt aqueous solution heated to 5 ° C., preferably ± 2 ° C., more preferably ± 1 ° C. has a pH of 6.5 to 9.5, preferably 6.5. It is added continuously in 5 to 20 minutes, preferably 7 to 15 minutes so as to be ˜8.5, more preferably 6.5 to 7.5, to form a precipitate, thereby obtaining a hydrate slurry. Here, the addition of the mixed aqueous solution to the basic aluminum salt aqueous solution is desirably 15 minutes or less because undesirable crystals such as bayerite and gibbsite may be generated in addition to pseudoboehmite as time goes on. More preferably less than a minute. Bayerite and gibbsite are not preferred because their specific surface area decreases when fired.
（第２工程）
第１工程で得られた水和物のスラリーを、所望により熟成した後、洗浄して副生塩を除き、シリカ、チタニア及びアルミナを含む水和物のスラリーを得る。得られた水和物のスラリーを、所望によりさらに加熱熟成した後、慣用の手段により、例えば、加熱捏和して成型可能な捏和物とした後、押出成型などにより所望の形状に成型し、通常７０〜１５０℃、好ましくは９０〜１３０℃で乾燥した後、更に４００〜８００℃、好ましくは４５０〜６００℃で、０．５〜１０時間、好ましくは２〜５時間焼成して、シリカ、チタニア及びアルミナを含むシリカ−チタニア−アルミナ担体を得る。
(Second step)
The hydrate slurry obtained in the first step is aged as desired, and then washed to remove by-product salts to obtain a hydrate slurry containing silica, titania and alumina. The obtained hydrate slurry is further heat-aged if desired, and then, by conventional means, for example, heat-kneaded to form a kneaded product, which is then molded into a desired shape by extrusion molding or the like. In general, after drying at 70 to 150 ° C., preferably 90 to 130 ° C., it is further calcined at 400 to 800 ° C., preferably 450 to 600 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours to obtain silica. A silica-titania-alumina support containing titania and alumina is obtained.
（第３工程）
得られたシリカ−チタニア−アルミナ担体に、周期表第ＶＩＡ族及び第ＶＩＩＩ族から選ばれた少なくとも１種の金属成分を上述したとおり、慣用の手段（含浸法、浸漬法など）で担持した後、通常４００〜８００℃、好ましくは４５０〜６００℃で、０．５〜１０時間、好ましくは２〜５時間焼成し、本発明の水素化脱硫触媒を製造する。
金属成分の原料としては、例えば、硝酸ニッケル、炭酸ニッケル、硝酸コバルト、炭酸コバルト、三酸化モリブデン、モリブデン酸アンモン、パラタングステン酸アンモンなどが好ましく使用される。
(Third step)
After loading the obtained silica-titania-alumina support with at least one metal component selected from Group VIA and Group VIII of the periodic table by conventional means (impregnation method, dipping method, etc.) as described above. In general, it is calcined at 400 to 800 ° C., preferably 450 to 600 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours to produce the hydrodesulfurization catalyst of the present invention.
As a raw material for the metal component, for example, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, and ammonium paratungstate are preferably used.
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらのものに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
［実施例１：水素化脱硫触媒ａの調製］
容量が１００Ｌのスチームジャケット付のタンクに、Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液８．１６ｋｇを入れ、イオン交換水４１ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液１．８０ｋｇを攪拌しながら添加し、６０℃に加温して、塩基性アルミニウム塩水溶液を作成した。また、Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液７．３８ｋｇを１３ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液と、ＴｉＯ２濃度換算で３３質量％の硫酸チタン１．８２ｋｇを１０ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合し、６０℃に加温して、混合水溶液を作成した。塩基性アルミニウム塩水溶液が入ったタンクに、ローラーポンプを用いて混合水溶液をｐＨが７．２となるまで一定速度で添加（添加時間：１０分）し、シリカ、チタニア、及びアルミナを含有する水和物スラリーａを調製した。
[Example 1: Preparation of hydrodesulfurization catalyst a]
A tank with a steam jacket with a capacity of 100 L is charged with 8.16 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 41 kg of ion-exchanged water, and then 5 mass% silicic acid in terms of SiO 2 concentration. 1.80 kg of sodium solution was added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Further, 10 kg of an acidic aluminum salt aqueous solution obtained by diluting 7.38 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 13 kg of ion-exchanged water, and 1.82 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration. The aqueous solution of titanium mineral salt dissolved in the ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution. Water containing silica, titania, and alumina is added to the tank containing the basic aqueous aluminum salt solution at a constant rate using a roller pump until the pH is 7.2 (addition time: 10 minutes). A Japanese slurry a was prepared.
得られた水和物スラリーａを攪拌しながら６０℃で１時間熟成した後、平板フィルターを用いて脱水し、更に、０．３質量％アンモニア水溶液１５０Ｌで洗浄した。洗浄後のケーキ状のスラリーをＡｌ２Ｏ３濃度換算で１０質量％となるようにイオン交換水で希釈した後、１５質量％アンモニア水でｐＨを１０．５に調整した。これを還流機付熟成タンクに移し、攪拌しながら９５℃で１０時間熟成した。熟成終了後のスラリーを脱水し、スチームジャケットを備えた双腕式ニーダーにて練りながら所定の水分量まで濃縮捏和した。得られた捏和物を押出成型機にて直径が１．８ｍｍの円柱形状に成型し、１１０℃で乾燥した。乾燥した成型品は電気炉で５５０℃の温度で３時間焼成し、担体ａを得た。担体ａは、シリカがＳｉＯ２濃度換算で３質量％（担体基準）、チタニアがＴｉＯ２濃度換算で２０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で７７質量％（担体基準）含有されていた。 The obtained hydrate slurry a was aged at 60 ° C. for 1 hour with stirring, dehydrated using a flat plate filter, and further washed with 150 L of a 0.3 mass% aqueous ammonia solution. The cake-like slurry after washing was diluted with ion-exchanged water so as to be 10% by mass in terms of Al 2 O 3 concentration, and then the pH was adjusted to 10.5 with 15% by mass ammonia water. This was transferred to an aging tank equipped with a reflux machine and aged at 95 ° C. for 10 hours with stirring. The slurry after completion of aging was dehydrated and concentrated and kneaded to a predetermined moisture content while kneading with a double-arm kneader equipped with a steam jacket. The obtained kneaded product was molded into a cylindrical shape having a diameter of 1.8 mm by an extrusion molding machine and dried at 110 ° C. The dried molded product was baked in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain a carrier a. As for the carrier a, silica is 3% by mass in terms of SiO 2 (support standard), titania is 20% by mass in terms of TiO 2 (support standard), and aluminum is 77% by mass in terms of Al 2 O 3 concentration (support standard). Contained.
また、担体ａをリガク社製のＸ線回折装置ＲＩＮＴ２１００にて、Ｘ線回折分析を行った（以下の実施例についても同様である）。その結果を図１に示す。ここで、得られたグラフを最小二乗法によりフィッティングし、ベースライン補正を行い２θ＝２５．５°に示されるアナターゼ型チタニア（１０１）面に帰属されるピークの半値幅を求め、この半値幅とベースラインからのピーク強度との積をアナターゼ型チタニア回折ピーク面積とした。同様に２θ＝２７．５°に示されるルチル型チタニア（１１０）面に帰属されるピークの半減値を求め、この半減値とベースラインからのピーク強度との積をルチル型チタニア回折ピーク面積とした。ここで、アナターゼ型チタニア回折ピーク面積とルチル型チタニア回折ピーク面積との合計の面積を、チタニア回折ピーク面積とした。なお、担体ａにおいては、ルチル型チタニアのピークは検出されなかった。更に、２θ＝４５．９°に示されるγ−アルミナ（４００）面に帰属されるピークの半減値を求め、この半減値とベースラインからのピーク強度との積をアルミナ回折ピーク面積とした。担体ａは、アナターゼ型チタニア及びルチル型チタニアの結晶構造を示す回折ピーク面積が、アルミニウムに帰属される結晶構造を示す回折ピーク面積に対して、１／８であった（チタニア回折ピーク面積／アルミナ回折ピーク面積＝１／８。以下同様）。 Further, the carrier a was subjected to X-ray diffraction analysis with an RINT2100 X-ray diffractometer manufactured by Rigaku (the same applies to the following examples). The result is shown in FIG. Here, the obtained graph was fitted by the least square method, the baseline was corrected, and the half width of the peak attributed to the anatase-type titania (101) surface indicated by 2θ = 25.5 ° was obtained. And the peak intensity from the baseline was defined as the anatase titania diffraction peak area. Similarly, the half value of the peak attributed to the rutile-type titania (110) plane shown at 2θ = 27.5 ° is obtained, and the product of this half-value and the peak intensity from the baseline is the rutile-type titania diffraction peak area. did. Here, the total area of the anatase type titania diffraction peak area and the rutile type titania diffraction peak area was defined as the titania diffraction peak area. In carrier a, no rutile-type titania peak was detected. Further, the half value of the peak attributed to the γ-alumina (400) plane shown at 2θ = 45.9 ° was determined, and the product of this half value and the peak intensity from the baseline was defined as the alumina diffraction peak area. In carrier a, the diffraction peak area showing the crystal structure of anatase titania and rutile type titania was 1/8 of the diffraction peak area showing the crystal structure belonging to aluminum (titania diffraction peak area / alumina). Diffraction peak area = 1/8.
更に、三酸化モリブデン３０６ｇと炭酸コバルト６８ｇとを、イオン交換水５００ｍｌに懸濁させ、この懸濁液を９５℃で５時間液容量が減少しないように適当な還流措置を施して加熱した後、リン酸６８ｇを加えて溶解させ、含浸液を作製した。この含浸液を、担体ａ１０００ｇに噴霧含浸させた後、２５０℃で乾燥し、更に電気炉にて５５０℃で１時間焼成して水素化脱硫触媒ａ（以下、単に「触媒ａ」ともいう。以下の実施例についても同様である。）を得た。触媒ａの金属成分は、ＭｏＯ３が２２質量％（触媒基準）で、ＣｏＯが３質量％（触媒基準）で、Ｐ２Ｏ５が３質量％（触媒基準）であった。触媒ａの性状を表１に示す。 Further, 306 g of molybdenum trioxide and 68 g of cobalt carbonate were suspended in 500 ml of ion-exchanged water, and the suspension was heated at 95 ° C. for 5 hours so that the liquid volume did not decrease, and then heated. 68 g of phosphoric acid was added and dissolved to prepare an impregnation solution. The impregnating solution is spray impregnated on 1000 g of support a, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to be hydrodesulfurized catalyst a (hereinafter also simply referred to as “catalyst a”. The same applies to the examples of the above. The metal component of the catalyst a was 22% by mass of MoO 3 (based on catalyst), 3% by mass of CoO (based on catalyst), and 3% by mass of P 2 O 5 (based on catalyst). Table 1 shows the properties of the catalyst a.
［実施例２：水素化脱硫触媒ｂの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液８．４９ｋｇを入れ、イオン交換水３７ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液１．８０ｋｇを攪拌しながら添加し、６０℃に加温して作製した塩基性アルミニウム塩水溶液と、（２）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液１０．６２ｋｇを１９ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、ＴｉＯ２濃度換算で３３質量％の硫酸チタン０．９１ｋｇを５ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｂを調製した点が、実施例１と異なる。
[Example 2: Preparation of hydrodesulfurization catalyst b]
(1) Add 8.49 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 37 kg of ion-exchanged water, and then stir 1.80 kg of 5 mass% sodium silicate solution in terms of SiO 2 concentration. And the basic aluminum salt aqueous solution prepared by heating to 60 ° C., and (2) an acid obtained by diluting 10.62 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 19 kg of ion-exchanged water. A mixed aqueous solution prepared by mixing an aqueous solution of aluminum salt and an aqueous solution of titanium mineral acid obtained by dissolving 0.91 kg of 33 wt% titanium sulfate in terms of TiO 2 concentration in 5 kg of ion-exchanged water has a constant pH. The difference from Example 1 is that the hydrate slurry b was prepared by adding until 7.2.
実施例１と同様にして、水和物スラリーｂから担体ｂを調製した。担体ｂは、ＳｉＯ２濃度が３質量％（担体基準）、ＴｉＯ２濃度が１０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で８７質量％（担体基準）であった。
また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、アナターゼ型チタニア及びルチル型チタニアの結晶構造を示す回折ピークが検出されず、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／４未満であった。
実施例１と同様にして、担体ｂから触媒ｂを製造した。触媒ｂは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表１に触媒ｂの性状を示す。
In the same manner as in Example 1, carrier b was prepared from hydrate slurry b. In the carrier b, the SiO 2 concentration was 3% by mass (carrier standard), the TiO 2 concentration was 10% by mass (carrier standard), and the aluminum was 87% by mass in terms of Al 2 O 3 (carrier standard).
Further, as a result of X-ray diffraction analysis (not shown) as in Example 1, a diffraction peak showing the crystal structure of anatase titania and rutile titania was not detected, and titania diffraction peak area / alumina diffraction peak area Was less than ¼.
In the same manner as in Example 1, catalyst b was produced from carrier b. The catalyst b contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst b.
［実施例３：水素化脱硫触媒ｃの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液７．８２ｋｇを入れ、イオン交換水４４ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液１．８０ｋｇを攪拌しながら添加し、６０℃に加温して作製した塩基性アルミニウム塩水溶液と、（２）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液４．１４ｋｇを７ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、ＴｉＯ２濃度換算で３３質量％の硫酸チタン２．７３ｋｇを１５ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｃを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｃから担体ｃを調製した。担体ｃは、ＳｉＯ２濃度が３質量％（担体基準）、ＴｉＯ２濃度が３０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で６７質量％（担体基準）であった。
また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／５であった。
実施例１と同様にして、担体ｃから触媒ｃを製造した。触媒ｃは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表１に触媒ｃの性状を示す。
[Example 3: Preparation of hydrodesulfurization catalyst c]
(1) 7.82 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was added, diluted with 44 kg of ion-exchanged water, and then 1.80 kg of 5 mass% sodium silicate solution in terms of SiO 2 concentration was stirred. And the basic aluminum salt aqueous solution prepared by heating to 60 ° C. and (2) an acid obtained by diluting 4.14 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 7 kg of ion-exchanged water. A mixed aqueous solution prepared by mixing an aqueous aluminum salt solution and an aqueous titanium mineral salt solution obtained by dissolving 2.73 kg of 33 wt% titanium sulfate in terms of TiO 2 concentration in 15 kg of ion-exchanged water has a pH at a constant rate. The point which added until it became 7.2 and the hydrate slurry c was prepared differs from Example 1. FIG.
In the same manner as in Example 1, carrier c was prepared from hydrate slurry c. In the carrier c, the SiO 2 concentration was 3% by mass (carrier standard), the TiO 2 concentration was 30% by mass (carrier standard), and the aluminum was 67% by mass (carrier standard) in terms of Al 2 O 3 concentration.
Moreover, as a result of performing X-ray diffraction analysis in the same manner as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/5.
In the same manner as in Example 1, catalyst c was produced from support c. The catalyst c contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst c.
［比較例１：水素化脱硫触媒ｄの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液８．８２ｋｇを入れ、イオン交換水３４ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液１．８０ｋｇを攪拌しながら添加し、６０℃に加温して作製した塩基性アルミニウム塩水溶液に、（２）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液１３．８６ｋｇを２５ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｄを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｄから担体ｄを調製した。担体ｄは、ＳｉＯ２濃度が３質量％（担体基準）、ＴｉＯ２濃度が０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で９７質量％（担体基準）であった。
また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、アナターゼ型チタニア及びルチル型チタニアの結晶構造を示す回折ピークが検出されず、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／４未満であった。
更に、実施例１と同様にして、担体ｄから触媒ｄを製造した。触媒ｄは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表１に触媒ｄの性状を示す。
[Comparative Example 1: Preparation of hydrodesulfurization catalyst d]
(1) After putting 8.82 kg of 22% by mass sodium aluminate aqueous solution in terms of Al 2 O 3 concentration and diluting with 34 kg of ion-exchanged water, 1.80 kg of 5% by mass sodium silicate solution in terms of SiO 2 concentration was stirred. To the basic aluminum salt aqueous solution prepared by heating to 60 ° C. and (2) acidified by diluting 13.86 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 25 kg of ion-exchanged water. The point that the aqueous solution of aluminum salt was added at a constant rate until the pH reached 7.2 to prepare the hydrate slurry d was different from Example 1.
In the same manner as in Example 1, carrier d was prepared from hydrate slurry d. In the carrier d, the SiO 2 concentration was 3% by mass (carrier standard), the TiO 2 concentration was 0% by mass (carrier standard), and the aluminum was 97% by mass in terms of Al 2 O 3 concentration (carrier standard).
Further, as a result of X-ray diffraction analysis (not shown) as in Example 1, a diffraction peak showing the crystal structure of anatase titania and rutile titania was not detected, and titania diffraction peak area / alumina diffraction peak area Was less than ¼.
Further, in the same manner as in Example 1, a catalyst d was produced from the carrier d. The catalyst d contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst d.
［比較例２：水素化脱硫触媒ｅの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液７．０９ｋｇを入れ、イオン交換水４７ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液１．８０ｋｇを攪拌しながら添加し、６０℃に加温して作製した塩基性アルミニウム塩水溶液に、（２）ＴｉＯ２濃度換算で３３質量％の硫酸チタン４．０９ｋｇを２３ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｅを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｅから担体ｅを調製した。担体ｅは、ＳｉＯ２濃度が３質量％（担体基準）、ＴｉＯ２濃度が４５質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で５２質量％（担体基準）であった。
また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／３であった。
更に、実施例１と同様にして、担体ｅから触媒ｅを製造した。触媒ｅは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表１に触媒ｅの性状を示す。
[Comparative Example 2: Preparation of hydrodesulfurization catalyst e]
(1) Add 7.09 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 47 kg of ion-exchanged water, and then stir 1.80 kg of 5 mass% sodium silicate solution in terms of SiO 2 concentration. (2) Titanium mineral salt obtained by dissolving 4.09 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration in 23 kg of ion-exchanged water. The point that the aqueous solution was added at a constant rate until the pH became 7.2 to prepare the hydrate slurry e was different from Example 1.
In the same manner as in Example 1, carrier e was prepared from hydrate slurry e. In the carrier e, the SiO 2 concentration was 3% by mass (carrier standard), the TiO 2 concentration was 45% by mass (carrier standard), and the aluminum was 52% by mass (carrier standard) in terms of Al 2 O 3 concentration.
Moreover, as a result of conducting an X-ray diffraction analysis in the same manner as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/3.
Further, in the same manner as in Example 1, a catalyst e was produced from the carrier e. The catalyst e contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 1 shows the properties of the catalyst e.
［実施例４：水素化脱硫触媒ｆの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液７．７９ｋｇを入れ、イオン交換水４０ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液４．２０ｋｇを攪拌しながら添加し、６０℃に加温して作製した塩基性アルミニウム塩水溶液と、（２）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液６．８１ｋｇを１２ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、ＴｉＯ２濃度換算で３３質量％の硫酸チタン１．８２ｋｇを１０ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｆを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｆから担体ｆを調製した。担体ｆは、ＳｉＯ２濃度が７質量％（担体基準）、ＴｉＯ２濃度が２０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で７３質量％（担体基準）であった。
また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／８であった。
更に、実施例１と同様にして、担体ｆから触媒ｆを製造した。触媒ｆは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表２に触媒ｆの性状を示す。
[Example 4: Preparation of hydrodesulfurization catalyst f]
(1) Add 7.79 kg of 22% by mass sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 40 kg of ion-exchanged water, and then stir 4.20 kg of 5% by mass sodium silicate solution in terms of SiO 2 concentration. The basic aluminum salt aqueous solution prepared by heating and heating to 60 ° C., and (2) an acid obtained by diluting 6.81 kg of a 7 mass% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 12 kg of ion-exchanged water A mixed aqueous solution prepared by mixing an aqueous aluminum salt solution and an aqueous titanium mineral salt solution in which 1.82 kg of 33 mass% titanium sulfate in terms of TiO 2 concentration is dissolved in 10 kg of ion-exchanged water, has a pH at a constant rate. The difference from Example 1 is that hydrate slurry f was prepared by adding until 7.2.
In the same manner as in Example 1, the carrier f was prepared from the hydrate slurry f. In the carrier f, the SiO 2 concentration was 7% by mass (carrier standard), the TiO 2 concentration was 20% by mass (carrier standard), and the aluminum was 73% by mass (carrier standard) in terms of Al 2 O 3 concentration.
Moreover, as a result of performing X-ray diffraction analysis in the same manner as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/8.
Further, a catalyst f was produced from the carrier f in the same manner as in Example 1. The catalyst f contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of the catalyst f.
［実施例５：水素化脱硫触媒ｇの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液７．５２ｋｇを入れ、イオン交換水４０ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液６．００ｋｇを攪拌しながら添加し、６０℃に加温して作製した塩基性アルミニウム塩水溶液と、（２）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液６．３８ｋｇを１１ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、ＴｉＯ２濃度換算で３３質量％の硫酸チタン１．８２ｋｇを１０ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｇを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｇから担体ｇを調製した。担体ｇは、ＳｉＯ２濃度が１０質量％（担体基準）、ＴｉＯ２濃度が２０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で７０質量％（担体基準）であった。
また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／８であった。
更に、実施例１と同様にして、担体ｇから触媒ｇを製造した。触媒ｇは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表２に触媒ｇの性状を示す。
[Example 5: Preparation of hydrodesulfurization catalyst g]
(1) Add 7.52 kg of 22% by mass sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 40 kg of ion-exchanged water, and then stir 6.00 kg of 5% by mass sodium silicate solution in terms of SiO 2 concentration. The basic aluminum salt aqueous solution prepared by heating and heating to 60 ° C., and (2) an acid obtained by diluting 6.38 kg of a 7% by mass aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 11 kg of ion-exchanged water A mixed aqueous solution prepared by mixing an aqueous aluminum salt solution and an aqueous titanium mineral salt solution in which 1.82 kg of 33 mass% titanium sulfate in terms of TiO 2 concentration is dissolved in 10 kg of ion-exchanged water, has a pH at a constant rate. The difference from Example 1 is that hydrate slurry g was prepared by adding until 7.2.
In the same manner as in Example 1, carrier g was prepared from hydrate slurry g. The carrier g had a SiO 2 concentration of 10% by mass (carrier standard), a TiO 2 concentration of 20% by mass (carrier standard), and aluminum in terms of Al 2 O 3 concentration of 70% by mass (carrier standard).
Moreover, as a result of performing X-ray diffraction analysis in the same manner as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/8.
Further, in the same manner as in Example 1, catalyst g was produced from carrier g. Catalyst g contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of catalyst g.
［比較例３：水素化脱硫触媒ｈの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液８．４３ｋｇを入れ、イオン交換水４１ｋｇで希釈後、６０℃に加温して作製した塩基性アルミニウム塩水溶液と、（２）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液７．８１ｋｇを１４ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、ＴｉＯ２濃度換算で３３質量％の硫酸チタン１．８２ｋｇを１０ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｈを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｈから担体ｈを調製した。担体ｈは、ＳｉＯ２濃度が０質量％（担体基準）、ＴｉＯ２濃度が２０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で８０質量％（担体基準）であった。また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／４であった。
更に、実施例１と同様にして、担体ｈから触媒ｈを製造した。触媒ｈは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表２に触媒ｈの性状を示す。
[Comparative Example 3: Preparation of hydrodesulfurization catalyst h]
(1) A basic aluminum salt aqueous solution prepared by adding 8.43 kg of a 22% by mass sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluting with 41 kg of ion-exchanged water and heating to 60 ° C., (2 ) 10 kg of an acidic aluminum salt aqueous solution obtained by diluting 7.81 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 14 kg of ion-exchanged water and 1.82 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration The hydrate slurry h was prepared by adding a mixed aqueous solution prepared by mixing an aqueous solution of titanium mineral salt dissolved in ion-exchanged water to a pH of 7.2 at a constant rate. Different from Example 1.
The carrier h was prepared from the hydrate slurry h in the same manner as in Example 1. In the carrier h, the SiO 2 concentration was 0% by mass (carrier standard), the TiO 2 concentration was 20% by mass (carrier standard), and the aluminum was 80% by mass (carrier standard) in terms of Al 2 O 3 concentration. Moreover, as a result of performing X-ray diffraction analysis in the same manner as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/4.
Further, a catalyst h was produced from the carrier h in the same manner as in Example 1. The catalyst h contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of catalyst h.
［比較例４：水素化脱硫触媒ｉの調製］
（１）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液７．０７ｋｇを入れ、イオン交換水４０ｋｇで希釈後、ＳｉＯ２濃度換算で５質量％の珪酸ナトリウム溶液９．００ｋｇを攪拌しながら添加し、６０℃に加温して作製した塩基性アルミニウム塩水溶液と、（２）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液５．６７ｋｇを１０ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、ＴｉＯ２濃度換算で３３質量％の硫酸チタン１．８２ｋｇを１０ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液とを混合して作製した混合水溶液とを、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｉを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｉから担体ｉを調製した。担体ｉは、ＳｉＯ２濃度が１５質量％（担体基準）、ＴｉＯ２濃度が２０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で６５質量％（担体基準）であった。
また、実施例１と同様にＸ線回折分析を行った結果（図示せず）、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／８であった。
更に、実施例１と同様にして、担体ｉから触媒ｉを製造した。触媒ｉは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表２に触媒ｉの性状を示す。
[Comparative Example 4: Preparation of hydrodesulfurization catalyst i]
(1) Add 7.07 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, dilute with 40 kg of ion-exchanged water, and then stir 9.00 kg of 5 mass% sodium silicate solution in terms of SiO 2 concentration. The basic aluminum salt aqueous solution prepared by heating and heating to 60 ° C., and (2) an acid obtained by diluting 5.67 kg of 7 mass% aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 10 kg of ion-exchanged water An aqueous solution of aluminum salt and a mixed aqueous solution prepared by mixing 1.82 kg of 33 wt% titanium sulfate in terms of TiO 2 concentration with 10 kg of ion-exchanged water and mixed with an aqueous solution of titanium mineral salt at a constant speed Is different from Example 1 in that the hydrate slurry i was prepared by adding the hydrate slurry to 7.2.
In the same manner as in Example 1, carrier i was prepared from hydrate slurry i. The carrier i had a SiO 2 concentration of 15% by mass (carrier standard), a TiO 2 concentration of 20% by mass (carrier standard), and an aluminum content of 65% by mass in terms of Al 2 O 3 (carrier standard).
Moreover, as a result of performing X-ray diffraction analysis in the same manner as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/8.
Further, in the same manner as in Example 1, catalyst i was produced from carrier i. The catalyst i contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 2 shows the properties of catalyst i.
［実施例６：水素化脱硫触媒ｊの調製］
担体は実施例１の担体ａを用いた。
三酸化モリブデン２７８ｇと炭酸コバルト１１４ｇとを、イオン交換水５００ｍｌに懸濁させ、この懸濁液を９５℃で５時間液容量が減少しないように適当な還流措置を施して加熱した後、リン酸６８ｇと硝酸７６ｇとを加えて溶解させ、含浸液を作製した。この含浸液を、担体ａ１０００ｇに噴霧含浸させた後、２５０℃で乾燥し、更に電気炉にて５５０℃で１時間焼成して水素化脱硫触媒ｊを得た。触媒ｊの金属成分は、ＭｏＯ３が２０質量％（触媒基準）で、ＣｏＯが５質量％（触媒基準）で、Ｐ２Ｏ５が３質量％（触媒基準）であった。触媒ｊの性状を表３に示す。
[Example 6: Preparation of hydrodesulfurization catalyst j]
The carrier a of Example 1 was used as the carrier.
After suspending 278 g of molybdenum trioxide and 114 g of cobalt carbonate in 500 ml of ion-exchanged water and heating this suspension at 95 ° C. for 5 hours so that the liquid volume does not decrease, the suspension is heated, and then phosphoric acid. 68 g and 76 g of nitric acid were added and dissolved to prepare an impregnating solution. This impregnating solution was spray impregnated on 1000 g of carrier a, dried at 250 ° C., and further calcined at 550 ° C. for 1 hour in an electric furnace to obtain hydrodesulfurization catalyst j. The metal components of the catalyst j were 20% by mass of MoO 3 (catalyst reference), 5% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 3 shows the properties of the catalyst j.
［実施例７：水素化脱硫触媒ｋの調製］
担体は実施例１の担体ａを用いた。
三酸化モリブデン２７８ｇと炭酸コバルト１１４ｇとを、イオン交換水５００ｍｌに懸濁させ、この懸濁液を９５℃で５時間液容量が減少しないように適当な還流措置を施して加熱した後、リン酸６８ｇとリンゴ酸１７４ｇとを加えて溶解させ、含浸液を作製した。この含浸液を、担体ａ１０００ｇに噴霧含浸させた後、２５０℃で乾燥し、更に電気炉にて５５０℃で１時間焼成して水素化脱硫触媒ｋを得た。触媒ｋの金属成分は、ＭｏＯ３が２０質量％（触媒基準）で、ＣｏＯが５質量％（触媒基準）で、Ｐ２Ｏ５が３質量％（触媒基準）であった。触媒ｋの性状を表３に示す。
[Example 7: Preparation of hydrodesulfurization catalyst k]
The carrier a of Example 1 was used as the carrier.
After suspending 278 g of molybdenum trioxide and 114 g of cobalt carbonate in 500 ml of ion-exchanged water and heating the suspension at 95 ° C. for 5 hours so that the liquid volume does not decrease, phosphoric acid is added. 68 g and 174 g of malic acid were added and dissolved to prepare an impregnation solution. This impregnating solution was spray impregnated on 1000 g of support a, dried at 250 ° C., and further calcined at 550 ° C. for 1 hour in an electric furnace to obtain a hydrodesulfurization catalyst k. The metal component of the catalyst k was 20% by mass of MoO 3 (catalyst reference), 5% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Properties of catalyst k are shown in Table 3.
［実施例８：水素化脱硫触媒ｌの調製］
担体は実施例１の担体ａを用いた。
三酸化モリブデン２６７ｇと炭酸コバルト１０９ｇとを、イオン交換水５００ｍｌに懸濁させ、この懸濁液を９５℃で５時間液容量が減少しないように適当な還流措置を施して加熱した後、リンゴ酸１６７ｇを加えて溶解させ、含浸液を作製した。この含浸液を、担体ａ１０００ｇに噴霧含浸させた後、２５０℃で乾燥し、更に電気炉にて５５０℃で１時間焼成して水素化脱硫触媒ｌを得た。触媒ｌの金属成分は、ＭｏＯ３が２０質量％（触媒基準）で、ＣｏＯが５質量％（触媒基準）で、Ｐ２Ｏ５が０質量％（触媒基準）であった。触媒ｌの性状を表３に示す。
[Example 8: Preparation of hydrodesulfurization catalyst 1]
The carrier a of Example 1 was used as the carrier.
After 267 g of molybdenum trioxide and 109 g of cobalt carbonate were suspended in 500 ml of ion-exchanged water, this suspension was heated at 95 ° C. for 5 hours so that the liquid volume did not decrease, and then heated, followed by malic acid. 167 g was added and dissolved to prepare an impregnating solution. This impregnating solution was spray impregnated on 1000 g of carrier a, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst l. The metal component of the
［実施例９：水素化脱硫触媒ｍの調製］
担体は実施例１の担体ａを用いた。
三酸化モリブデン３０６ｇと炭酸ニッケル７６ｇとを、イオン交換水５００ｍｌに懸濁させ、この懸濁液を９５℃で５時間液容量が減少しないように適当な還流措置を施して加熱した後、リン酸６８ｇを加えて溶解させ、含浸液を作製した。この含浸液を、担体ａ１０００ｇに噴霧含浸させた後、２５０℃で乾燥し、更に電気炉にて５５０℃で１時間焼成して水素化脱硫触媒ｍを得た。触媒ｍの金属成分は、ＭｏＯ３が２２質量％（触媒基準）で、ＮｉＯが３質量％（触媒基準）で、Ｐ２Ｏ５が３質量％（触媒基準）であった。触媒ｍの性状を表３に示す。
[Example 9: Preparation of hydrodesulfurization catalyst m]
The carrier a of Example 1 was used as the carrier.
After suspending 306 g of molybdenum trioxide and 76 g of nickel carbonate in 500 ml of ion-exchanged water and heating this suspension at 95 ° C. for 5 hours so that the liquid volume does not decrease, phosphoric acid is added. 68 g was added and dissolved to prepare an impregnating solution. The impregnating solution was impregnated with 1000 g of carrier a by spraying, dried at 250 ° C., and further calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrodesulfurization catalyst m. The metal components of the catalyst m were 22% by mass of MoO 3 (catalyst reference), 3% by mass of NiO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 3 shows the properties of the catalyst m.
［実施例１０：水素化脱硫触媒ｎの調製］
（１）Ａｌ２Ｏ３濃度換算で７質量％の硫酸アルミニウム水溶液７．１７ｋｇを１３ｋｇのイオン交換水で希釈した酸性アルミニウム塩水溶液、及び、ＴｉＯ２濃度換算で３３質量％の硫酸チタン１．８２ｋｇを１０ｋｇのイオン交換水に溶解したチタニウム鉱酸塩水溶液を混合し、さらにＳｉＯ２濃度換算で４．８質量％珪酸液１．８８ｋｇを混合して作製した混合水溶液に、（２）Ａｌ２Ｏ３濃度換算で２２質量％のアルミン酸ナトリウム水溶液８．２２ｋｇを入れ、イオン交換水４１ｋｇで希釈後、６０℃に加温して作製した塩基性アルミニウム塩水溶液を、一定速度でｐＨが７．２となるまで添加して、水和物スラリーｎを調製した点が、実施例１と異なる。
実施例１と同様にして、水和物スラリーｎから担体ｎを調製した。担体ｎは、ＳｉＯ２濃度が３質量％（担体基準）、ＴｉＯ２濃度が２０質量％（担体基準）、アルミニウムがＡｌ２Ｏ３濃度換算で７７質量％（担体基準）であった。また、実施例１と同様に担体ｎのＸ線回折分析を行った結果（図示せず）、チタニア回折ピーク面積／アルミナ回折ピーク面積は１／７であった。
実施例１と同様にして、担体ｎから触媒ｎを製造した。触媒ｎは、ＭｏＯ３を２２質量％（触媒基準）、ＣｏＯを３質量％（触媒基準）、Ｐ２Ｏ５を３質量％（触媒基準）含有していた。表３に触媒ｎの性状を示す。
[Example 10: Preparation of hydrodesulfurization catalyst n]
(1) An acidic aluminum salt aqueous solution obtained by diluting 7.17 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 13 kg of ion-exchanged water, and 1.82 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration Was mixed with an aqueous solution of titanium mineral salt dissolved in 10 kg of ion-exchanged water, and further mixed with 1.88 kg of a 4.8% by mass silicic acid solution in terms of SiO 2 concentration. (2) Al 2 O A basic aluminum salt aqueous solution prepared by adding 8.22 kg of 22 mass% sodium aluminate aqueous solution in terms of 3 concentrations, diluted with 41 kg of ion-exchanged water, and heated to 60 ° C. has a pH of 7.2 at a constant rate. The difference from Example 1 is that the hydrate slurry n was added until
In the same manner as in Example 1, carrier n was prepared from hydrate slurry n. The carrier n had a SiO 2 concentration of 3% by mass (carrier standard), a TiO 2 concentration of 20% by mass (carrier standard), and aluminum 77% by mass (based on the carrier) in terms of Al 2 O 3 concentration. Further, as a result of X-ray diffraction analysis of the carrier n as in Example 1 (not shown), the titania diffraction peak area / alumina diffraction peak area was 1/7.
In the same manner as in Example 1, catalyst n was produced from carrier n. The catalyst n contained 22% by mass of MoO 3 (catalyst reference), 3% by mass of CoO (catalyst reference), and 3% by mass of P 2 O 5 (catalyst reference). Table 3 shows the properties of catalyst n.
［試験例１］
触媒ａ〜ｎを使用して、次の性状を有する原料油をザイテル社製の水素化脱硫装置により水素化処理した。ここで、生成油の硫黄分が７質量ｐｐｍとなる温度（以下、「反応温度」という）を求め、各触媒の脱硫性能を比較した。なお、水素化処理反応は以下の条件で行った。この結果を表１〜３に示す。
《原料油の性状》
原料油 ：直留軽油（沸点範囲２０８〜３９０℃）
密度＠１５℃ ：０．８４９３ｇ／ｃｍ３
硫黄分 ：１．３２質量％
窒素分 ：１０５質量ｐｐｍ
《反応条件》
液空間速度 ：１．０ｈｒ−１
水素圧力 ：４．９ＭＰa
水素／油比 ：２５０ＮＬ／Ｌ
[Test Example 1]
Using the catalysts a to n, a raw material oil having the following properties was hydrotreated with a hydrodesulfurization apparatus manufactured by Zeitel. Here, the temperature (hereinafter referred to as “reaction temperature”) at which the sulfur content of the product oil becomes 7 mass ppm was determined, and the desulfurization performance of each catalyst was compared. The hydrotreatment reaction was performed under the following conditions. The results are shown in Tables 1-3.
<Properties of raw oil>
Raw material oil: straight run diesel oil (boiling point range 208-390 ° C)
Density @ 15 ° C .: 0.8493 g / cm 3
Sulfur content: 1.32% by mass
Nitrogen content: 105 ppm by mass
<Reaction conditions>
Liquid space velocity: 1.0 hr −1
Hydrogen pressure: 4.9 MPa
Hydrogen / oil ratio: 250 NL / L
表１は、担体中のチタニア量の影響を確認した結果である。担体中のチタニア量が増えると脱硫性能が向上するが、４０％を超えると細孔分布のシャープネスが悪くなるため性能が低下した。表２は、担体中のシリカ量の影響を確認した結果である。担体中のシリカ量も１０％を超えると細孔分布のシャープネスが悪くなるため性能が低下した。表３は担持する金属成分の影響を確認した結果である。ニッケル−モリブデン、コバルト−モリブデンいずれも高い脱硫性能を有している。また、金属成分と同時にリン酸および／または有機酸を含有しても高い脱硫性能を有している結果となった。さらに、担体調製の際に酸溶液を塩基性溶液に添加する製法と塩基性溶液に酸溶液に添加する製法といずれも高い脱硫性能を示した。
以上の結果により、本発明の触媒は、生成油の硫黄分が７質量ｐｐｍとなる温度が低く、脱硫活性に優れていることが分かった。また、本発明の担体は、安価なアルミナが主成分であり従来のアルミナ及びアルミナシリカ系触媒と比較して大幅に生産コストが向上せず、安価で高性能な触媒であると言える。
Table 1 shows the results of confirming the influence of the amount of titania in the carrier. When the amount of titania in the support increases, the desulfurization performance improves, but when it exceeds 40%, the sharpness of the pore distribution deteriorates and the performance deteriorates. Table 2 shows the results of confirming the influence of the amount of silica in the support. When the amount of silica in the carrier also exceeds 10%, the sharpness of the pore distribution deteriorates and the performance deteriorates. Table 3 shows the results of confirming the influence of the supported metal component. Both nickel-molybdenum and cobalt-molybdenum have high desulfurization performance. Moreover, even if it contained phosphoric acid and / or organic acid simultaneously with the metal component, it resulted in having high desulfurization performance. Furthermore, both the production method of adding the acid solution to the basic solution and the production method of adding the acid solution to the basic solution during the carrier preparation showed high desulfurization performance.
From the above results, it was found that the catalyst of the present invention has a low temperature at which the sulfur content of the product oil becomes 7 mass ppm and is excellent in desulfurization activity. Further, the carrier of the present invention is an inexpensive and high-performance catalyst whose main component is inexpensive alumina and does not significantly increase the production cost as compared with conventional alumina and alumina-silica catalysts.
本発明の水素化脱硫触媒は、特に軽油留分の水素化処理において高い脱硫活性を有し、産業上きわめて有用である。 The hydrodesulfurization catalyst of the present invention has a high desulfurization activity particularly in the hydrotreatment of a light oil fraction, and is extremely useful industrially.
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| JP2009227465A JP5517541B2 (en) | 2009-09-30 | 2009-09-30 | Hydrodesulfurization catalyst for hydrocarbon oil and method for producing the same |
| US13/498,165 US9067191B2 (en) | 2009-09-30 | 2010-09-14 | Hydrodesulfurization catalyst for hydrocarbon oil, process of producing same and method for hydrorefining |
| EP10820343.1A EP2484745B1 (en) | 2009-09-30 | 2010-09-14 | Hydrodesulfurization catalyst for a hydrocarbon oil, manufacturing method therefor, and hydrorefining method |
| CN201080044048.2A CN102575175B (en) | 2009-09-30 | 2010-09-14 | Hydrodesulfurization catalyst for a hydrocarbon oil, manufacturing method therefor, and hydrorefining method |
| PCT/JP2010/065785 WO2011040224A1 (en) | 2009-09-30 | 2010-09-14 | Hydrodesulfurization catalyst for a hydrocarbon oil, manufacturing method therefor, and hydrorefining method |
| SG2012018552A SG179173A1 (en) | 2009-09-30 | 2010-09-14 | Hydrodesulfurization catalyst for a hydrocarbon oil, manufacturing method therefor, and hydrorefining method |
| DK10820343.1T DK2484745T3 (en) | 2009-09-30 | 2010-09-14 | HYDRO DEVULATION CATALYST FOR A CARBOHYDRATE OIL, METHOD OF MANUFACTURE AND PROCEDURE FOR HYDRO REFINING |
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| JP6284403B2 (en) | 2014-03-27 | 2018-02-28 | Ｊｘｔｇエネルギー株式会社 | Hydrocarbon oil hydrodesulfurization catalyst |
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