JPH0513706B2 - - Google Patents
Info
- Publication number
- JPH0513706B2 JPH0513706B2 JP59081961A JP8196184A JPH0513706B2 JP H0513706 B2 JPH0513706 B2 JP H0513706B2 JP 59081961 A JP59081961 A JP 59081961A JP 8196184 A JP8196184 A JP 8196184A JP H0513706 B2 JPH0513706 B2 JP H0513706B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- silica
- alumina
- group
- carrier
- 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
Links
- 239000003054 catalyst Substances 0.000 claims description 127
- 229910052751 metal Inorganic materials 0.000 claims description 103
- 239000002184 metal Substances 0.000 claims description 103
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 98
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 86
- 238000000034 method Methods 0.000 claims description 75
- 239000000377 silicon dioxide Substances 0.000 claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 150000002739 metals Chemical class 0.000 claims description 35
- 229910017052 cobalt Inorganic materials 0.000 claims description 30
- 239000010941 cobalt Substances 0.000 claims description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 230000000737 periodic effect Effects 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 description 62
- 239000011148 porous material Substances 0.000 description 61
- 238000006243 chemical reaction Methods 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 24
- 239000004215 Carbon black (E152) Substances 0.000 description 20
- 229930195733 hydrocarbon Natural products 0.000 description 20
- 150000002430 hydrocarbons Chemical class 0.000 description 20
- 238000006477 desulfuration reaction Methods 0.000 description 17
- 230000023556 desulfurization Effects 0.000 description 17
- 229910000428 cobalt oxide Inorganic materials 0.000 description 15
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- -1 but in this case Chemical compound 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000010426 asphalt Substances 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 229910052753 mercury Inorganic materials 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 8
- 238000007605 air drying Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical class [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 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 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
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000588731 Hafnia Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 2
- NGPGDYLVALNKEG-OLXYHTOASA-N diammonium L-tartrate Chemical compound [NH4+].[NH4+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O NGPGDYLVALNKEG-OLXYHTOASA-N 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
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-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
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 241001619461 Poria <basidiomycete fungus> Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B01J35/63—
-
- B01J35/64—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Description
本発明は、炭化水素油の水素化処理に使用され
る水素化処理触媒に関するものであり、特にシリ
カアルミナ又はシリカアルミナを含有する担体上
に周期表第族及び第Ｂ族金属を分散性よく担
持させ高活性の水素化処理用触媒を製造する方法
に関するものである。
本発明の説明において「水素化処理」とは、炭
素水素油と水素との接触による処理方法を称し、
比較的反応条件の苛酷度の低い水素化精製、比較
的苛酷度の高い若干の分解反応を伴う水素化精
製、水添異性化、水素化脱アルキル化及びその他
の水素の存在下における炭化水素油の反応を包含
するものである。例えば、常圧蒸留又は減圧蒸留
の留出油及び残渣油の水素化脱硫、水素化脱窒
素、及び水素化分解を含み、又灯油留分、軽油留
分、ワツクス、潤滑油留分の水素化精製等を包含
するものである。
本発明に従つて製造される触媒は、特に灯油留
分及び軽油留分の如き常圧蒸留による中質留出
油、減圧蒸留の重質留出油、アスフアルトを含有
する残渣油又はこれらの混合油の水素化脱硫を実
施するのに好適であるため、本明細書では特に水
素化脱硫に関連して説明する。
従来、石油精製時の水素化脱硫においては、ア
ルミナ担体に元素周期表第族金属及び／又は元
素周期表第Ｂ族金属の群から選択される一種又
は二種以上の金属を担持させて製造される、例え
ばコバルトモリブデン系又はニツケルモリブデン
系の水素化処理用触媒が広く使用されている。斯
る水素化処理用触媒の製造において最も重要なこ
とは、均一な組成のモリブデン−コバルト又はモ
リブデン−ニツケル粒子を担体に多量に（酸化物
として約20重量％）、しかも高度に分散した状態
で担持せしめることである。
水素化処理用触媒の製造法としては、従来(1)共
沈法、(2)混練法及び(3)含浸法が提案され又一般に
実施されている。しかしながら、共沈法は、前記
水素化処理用触媒のように活性金属成分が複数の
場合には、これら活性金属成分を均一に、しかも
再現性よく製造することが困難であるという欠点
を有している。混練法も又、前述のように活性金
属成分を複数有するような水素化処理用触媒にお
いて担体及び複数の活性金属成分を互いに十分に
近接させ、且つ均一で完全な混合をなすことが必
要であるが、該混練法ではこのような状態を達成
することが極めて困難であるという欠点を有して
いる。上記二方法に比べ、含浸法は、前述のよう
に活性金属成分を複数有するような水素化処理用
触媒、例えばアルミナを担体としたコバルトモリ
ブデン系触媒、又はニツケルモリブデン系触媒の
製造にはより適しているということができる。
含浸法による水素化処理用触媒の製造におい
て、通常担体としてはアルミナを使用し、モリブ
デンを先ずアルミナ担体に担持し（第１ステツ
プ）、次でコバルト又はニツケルを該活性金属と
モリブデンとの相互作用によりモリブデン−コバ
ルト又はモリブデン−ニツケルの微粒子として担
体に担持させる（第２ステツプ）方法（２段式含
浸法）が提案されているが、第１ステツプで約15
％ものモリブデンを高度に分散した状態でアルミ
ナ担体に担持せしめることは難しく、最終的に得
られる触媒の分散性も実質的に、該第１ステツプ
におけるモリブデンの分散状態で決つてしまい、
従つて活性の低下が余儀なくされる。
含浸法における前述のような欠点を解決するべ
く、第１ステツプにてコバルトと又はニツケルを
アルミナ担体に担持させ、次いでモリブデンを担
持させることも考えられるが、この場合には、コ
バルト又はニツケルの如き活性金属成分はアルミ
ナ担体上ではアルミナ担体と十分な相互作用を持
たず、活性を有さないCo3O4として塊状に凝集す
るか又はコバルトアルミネートを形成して不活性
となり、所望の性能を達成することができない。
又、含浸法によつて複数の活性金属を同時にア
ルミナ担体に担持させる方法は、担体内に各成分
を均一に分布せしめることが難しく、好ましいも
のではない。
以上のように、水素化処理用触媒のように、活
性金属成分の担持量が高い触媒で且つ複数成分の
活性金属を担持する場合に、各成分を均一な組成
で、且つ高度に分散した状態に担持することは、
従来の既知の方法では極めて困難である。
従つて、本発明の主たる目的は、元素周期表第
族金属及び第Ｂ族金属より成る水素化処理用
触媒の製造法において、元素周期表第族金属と
担体との結合力を利用して、両活性金属成分を分
散性よく担持することにより、高活性の水素化処
理用触媒を得る触媒の製造法を提供することであ
る。
本発明の更に他の目的は、シリカアルミナ又は
シリカアルミナを含有する担体上に、イオン交換
法を用いてコバルト又はニツケルを、分散性よく
且つ化学的均一性（担持されたコバルト又はニツ
ケルと担体との結合強さの均一性）を向上せしめ
て担持せしめることができ、従つて主活性金属成
分であるモリブデンを担体上に分散性及び均一性
よく担持せしめることのできる水素化処理用触媒
の製造法を提供することである。
本発明者等は、従来の諸製造法を改良するべく
種々研究、実験を行なつた結果、水素化処理用触
媒の活性金属成分であるコバルト及びニツケル
は、担体の酸性点に担持され、従来のアルミナ担
体に代えて、酸性点を有するシリカアルミナ担体
又はシリカアルミナ含有担体を使用することによ
り、コバルト又はニツケルを第１ステツプにて分
散性良く且つ安定に担持し得ることを見出した。
これは、シリカアルミナの酸性点に化学的結合力
によつてコバルト又はニツケルが担持されるから
だと考えられ、特にシリカアルミナ担体又はシリ
カアルミナ含有担体にコバルト又はニツケルをイ
オン交換法によつて担持させることによつてその
分散性を飛躍的に向上せしめ得ることを見出し
た。
更に又、上記の如くに第１ステツプにてコバル
ト又はニツケルが担持されたシリカアルミナ担体
又はシリカアルミナ含有担体に第２ステツプとし
てモリブデンを担持せしめることができ、このと
きモリブデンはコバルト又はニツケルとの結合力
によつてコバルト又はニツケルの囲りに担持さ
れ、モリブデン−コバルト又はモリブデン−ニツ
ケルの微粒子が均一に且つ高分散状態に担持され
ることが分つた。
上述のように、本発明者等は、担体としてシリ
カアルミナ又はシリカアルミナ含有物を使用した
場合コバルト及びニツケルはブロモータ（助触
媒）であり、同時にモリブデンのアンカーとして
機能し、活性金属成分であるモリブデンの分散
性、安定性を向上させる効果を有することを見出
した。本発明は斯る新しい知見に基づきなされた
ものである。
要約すると、本発明は担体としてシリカアルミ
ナ又はシリカアルミナ含有物を使用し、該担体上
に、先ず元素周期表第族金属の群から選択され
る一種又は二種以上の金属を担持させ、次で元素
周期表第Ｂ族金属の群から選択される一種又は
二種以上の金属から担持させることを特徴とする
水素化処理用触媒の製造法である。特に本発明に
よると、第族金属の担持量を少なくして良好な
触媒活性を得るという特徴を有する。
本発明による水素化処理用触媒の製造法におい
ては、アルミナ担体の代わりに酸性点を有するシ
リカアルミナ担体又はシリカアルミナ含有担体が
使用される。担体としてシリカアルミナ又はシリ
カアルミナ含有物を使用することによつて第１ス
テツプにて元素周期表第族金属を担持させて
も、該活性金属成分がシリカアルミナの酸性点に
結合することによつて分散性良く且つ安定に担持
される。このように、第１ステツプにて第族金
属を担体の酸性点上に分散性よく担持することに
より、主活性金属である元素周期表第Ｂ族金属
を第族金属の外側、つまり第族金属層の上に
担持することができ、水素化処理用触媒としては
極めて好適である。
一方、水素化処理、特に水素化脱硫及び水素化
脱窒素において触媒は所望の固体酸性度を保持さ
せることが重要であり、又担体中のシリカ含有量
によつて酸性制御が可能であることが知られてい
る。本発明においても、シリカアルミナ担体又は
シリカアルミナ含有担体のシリカ含有量が過大と
なつた場合には、水素化脱硫反応又は水素化脱窒
素反応において過度の分解反応に伴う水素消費量
の増大又はコークの生成等といつた好ましくない
反応を併発せしめることとなる。
従つて、本発明のより好ましい実施態様におい
てシリカアルミナ担体又はシリカアルミナ含有担
体中のシリカの含有量は２〜35重量％好ましくは
５〜30重量％、より好ましくは７〜12重量％の範
囲となすべきである。
又、シリカアルミナ担体の表面積及び細孔分布
は特に規定されるものではないが、触媒担体とし
て好ましい表面積、例えば50m2／ｇ以上、特に
200m2／ｇ以上が好適である。斯るシリカアルミ
ナ担体の製造法としては、アルミナ及びシリカの
ゲルを各々あらかじめ製造しておき両者を混合す
る方法、シリカゲルをアルミニウム化合物の溶液
に浸漬した後に、塩基性物質を適当量添加し、ア
ルミナゲルをシリカゲル上に沈着させる方法、又
は水溶性アルミニウム化合物と水溶性珪素化合物
との均一混合溶液に塩基性物質を添加し、両者を
共沈させる方法等を採用することができる。
担体上に第１ステツプにて担持させる水素化活
性金属成分は、元素周期表第族金属の群から選
択される一種又は二種以上の金属である。即ち、
第族の鉄、コバルト、ニツケル、パラジウム、
白金、オスミウム、イリジウム、ルテニウム及び
ロジウム等から一種又は二種以上を選択して使用
する。好ましくは、コバルト及びニツケルが単独
で又は両者を組合せて使用されるであろう。
第２ステツプにて担体に担持させる水素化活性
金属成分は、元素周期表第Ｂ族金属の群から選
択される一種又は二種以上の金属である。即ち、
第Ｂ族のクロム、モリブデン及びタングステン
から一種又は二種以上選択して使用される。好ま
しくはモリブデン及びタングステンが単独で又は
両者を組合せて使用されるであろう。又所望に応
じ、、第三の金属を添加することも可能であろう。
上記第族及び第Ｂ族の水素化活性金属成分
は、酸化物及び／又は硫化物として担持させるこ
とが好適である。斯る活性金属成分の担持量は、
本発明のより好ましい実施態様においては酸化物
として触媒基準で、第族金属は0.5〜20重量％、
好ましくは１〜８重量％、より好ましくは２〜５
重量％であり、第Ｂ族金属は５〜30重量％、好
ましくは８〜25重量％、より好ましくは15〜20重
量％である。第族金属を0.5重量％以下担持さ
せたのでは十分な触媒が得られず、又20重量％以
上では担体と結合しない遊離の金属成分が増加す
る。第族金属の遊離成分が増加すると、次で第
Ｂ族金属を担持させる場合に不活性の複合酸化
物が生成し、第Ｂ族金属の分散性を低下せし
め、触媒活性を低下させる。一方、第Ｂ族金属
が５重量％以下では活性が得られず、30重量％以
上では分散性が低下すると同時に第族金属の助
触媒効果が発揮されない。
本発明において、第１及び第２ステツプにおけ
る活性金属成分の担体への担持方法としては、担
体を前記金属の可溶性塩の水溶液に浸漬し、金属
成分を担体中に導入する含浸法を採用することが
できる。含浸操作としては、担体を常温又は常温
以上で含浸溶液に浸漬して所望成分が十分担体中
に含浸する条件に保持する。含浸溶液の量及び温
度は、所望量の金属が担持されるように適宜調整
することができる。担持量の如何により、含浸溶
液に浸漬する担体の量を決定する。
一方、本発明者等は、本発明に従つた触媒製造
法における第１ステツプはシリカアルミナ担体又
はシリカアルミナ含有担体表面上のプロトンと前
記金属イオンの交換をアンモニウムイオンを介し
て行なうイオン交換法が極めて好適であるという
ことを見出した。本発明をイオン交換法に基づき
実施すると、触媒の分散度は通常の含浸法触媒に
比べ著しく向上し、更に化学的均一性も向上する
ことが分つた。
イオン交換法に基づく触媒の製法は、活性金属
のアンミン錯塩溶液を調製し、該溶液にシリカア
ルミナ担体を浸漬し、該金属を担体に担持させる
ことによつて行なわれる。アンミン錯塩溶液の量
及び濃度は、所望量金属が担持されるように適宜
調整することができる。
水素化活性金属成分を担持した担体は、含浸溶
液から分離した後、乾燥及び焼成を行なう。乾燥
及び焼成の条件は、前記担体の場合の条件と同一
でよい。
触媒は、使用に先立ち予備硫化を行なうことが
好ましい。予備硫化は、反応塔のその場において
行なうことができる。すなわち、焼成した触媒を
含硫留出油と、温度；約150〜400℃、圧力（全
圧）；約５〜100Kg／cm2、液空間速度；約0.3〜
2.0V／HV及び約50〜1500／の水素含有ガス
の存在下において接触させ、硫化処理の終了後含
硫留出油を原料油に切替え原料油の脱硫に適当な
運転条件に設定し運転を開始する。硫化処理の方
法としては、以上の如き方法の他に、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又は
適当な留出油に添加してこれを触媒と接触させる
こともある。
本発明者等は、前述の如き本発明に従つた触媒
の製造法を研究し、種々の実験を行なつた結果、
本発明に係る触媒の製造法によるとシリカを約２
〜35重量％含有するアルミナ担体上に、元素周期
表第族金属の群から選択される一種又は二種以
上の金属及び元素周期表第Ｂ族金属の群から選
択される一種又は二種以上の金属を担持させて成
り、
30〜100Åの範囲の直径を有する細孔の容積
が０〜150Åの範囲の直径を有する細孔の容積
の70％以上
100〜300Åの範囲の直径を有する細孔の容積
が０〜300Åの範囲の直径を有する細孔の容積
の約30％以下（以上及びの細孔容積は窒素
吸着法により測定）
水銀圧入法により測定した150〜150000Åの
範囲の直径を有する細孔の容積が約0.005〜
0.25ml／ｇ、好ましくは0.1ml／ｇ以下
水銀圧入法により測定した150〜2000Åの範
囲の直径を有する細孔の容積が約0.01ml／ｇ以
下
窒素吸着法により測定した０〜300Åの範囲
の直径を有する細孔の容積が約0.30〜0.70ml／
ｇの範囲
比表面積が約200〜400m2／ｇの範囲である炭
化水素油の水素化処理用触媒を好適に製造し得
ることを見出した。又、該触媒は全細孔容積；
0.4〜0.9ml／ｇ、カサ密度；約0.5〜1.0ｇ／ml、
側面破壊強度；約0.8〜3.5Kg／mmであつた。
従来、残渣油の水素化脱硫方法は、石油燃料中
の硫黄化合物が燃焼により亜硫酸ガスとなり大気
汚染源の一つとなるに及んで、亜硫酸ガスの放散
量を低下させる目的で、積極的な開発が行なわ
れ、多数提案されている。例えば、アスフアルト
及び金属含有化合物を含有する炭化水素油の水素
化脱硫及び水素化脱窒素を行なうためには、使用
する水素化精製用触媒の細孔分布が活性及び活性
維持能に大きく影響を与えることを予想して、原
料油中のアスフアルト及び金属含有化合物の浸入
を防止するために細孔半径80Å以上の細孔容積を
全細孔容積の10％以下に抑えた細孔分布を有する
触媒を使用する方法（特公昭45−38142号公報）
又は前記同残渣油の水素化脱硫において半径120
Å以下の細孔の容積が10Å間隔で比較的均一に分
布した触媒を使用する方法（特公昭45−38143号
公報）等が知られている。又、約50〜100Åの範
囲の孔径を有する粒子の細孔容積を全容積の少な
くとも50％とし、０〜50Åの範囲の孔径を有する
細孔容積を最大25％とする原油又は抜頭原油の水
素化脱硫触媒も開示されている（特開昭47−
10356号公報）。
しかしながら、これらの水素化脱硫方法におい
ては、使用する触媒の細孔半径300Å以上のいわ
ゆるマクロポアーの細孔分布については十分検討
されておらず、その触媒性能に与える影響は無視
されている。すなわち、従来開示された技術は、
いわゆるミクロボアに重点が置かれているが、ミ
クロボアのみでは常圧蒸留残渣油、減圧蒸留軽油
及び減圧蒸留残渣油等の如き多量の硫黄分、窒素
分、金属分、アスフアルトおよびその他の不純物
を含有する炭化水素油の水素化精製の活性および
活性維持能を向上させることができない。
本発明者等は、触媒のミクロボアー及びマクロ
ボアーの両領域にわたる細孔分布が脱硫及び脱窒
素に多大の影響を与えることを見出した。即ち、
水銀圧入法により測定した細孔直径150〜2000Å
の細孔容積が約0.01ml／ｇ以下であり、且つ窒素
吸着法により測定した30〜100Åの範囲の直径を
有する細孔の容積が０〜150Åの範囲の直径を有
する細孔の容積の70％以上、好ましくは80％以
上、更に好ましくは90％以上であり、更に100〜
300Åの範囲の直径を有する細孔の容積が０〜300
Åの範囲の直径を有する細孔の容積の30％以下、
好ましくは20％以下である触媒が極めて顕著な脱
硫効果を発揮することを見出した。つまり水素化
精製用触媒の存在下における水素との接触におい
て重質炭化水素油、特に、残渣油に含有されるア
スフアルト及びレジン分が触媒の細孔に侵入し、
触媒の活性劣化の原因となることを防止するため
には、マクロボアーの細孔容積を低減させること
が必要である。
又、飽和炭化水素の炭素間開裂に伴う炭化水素
油の軽質化を抑制し、アスフアルト及びレジン分
による触媒の細孔の閉塞を防止するためには直径
30Å以下の細孔を低減することが好ましいわけで
ある。
アルミナシリカの如き固体酸は、炭化水素油の
脱硫反応及び脱窒素反応に適する触媒成分である
ことはすでに公知であるが、水素化精製において
は、前述の如く所望の固体酸性度を保持させるこ
とが肝要であり、この目的のためにはシリカ含有
量により酸性制御をなし得る。本発明者らは、担
体中シリカ含有量による酸性制御に基づく分解活
性の調整と共に触媒の細孔構造を特定することに
より、炭化水素油の水素化反応の接触能及び選択
性を調整できることを認めている。この種の選択
性は、炭化水素油の脱硫及び脱窒素において水素
消費量を節約し、かつ、反解反応に伴なう炭素分
の生成による触媒活性の低下を防止する効果を有
するものであり、極めて重要な役割を演ずる。
従つて、水素化脱硫反応又は水素化脱窒素反応
においては、前述の如く、過度の分解反応に伴う
水素消費量の増大又はコークの生成等を制御する
ためにはアルミナ含有担体中のシリカの含有量を
約２〜35重量％、好ましくは約５〜30重量％の範
囲となすべきである。
上記水素化処理用触媒は、窒素吸着法により測
定した直径30〜100Åの範囲に細孔が集中してい
るが、細孔は、全体としてかなり広範囲に分布し
たものである。
本発明により開示する触媒のこのような細孔分
布が炭化水素油の水素化脱硫において活性及び活
性維持能に顕著な効果を賦与する理由については
十分解明されていないが、細孔分布を比較的広範
囲となしたことにより、原料油中のアスフアル
ト、レジン分及び金属含有化合物が、触媒表面に
付着した際、細孔径の極めて小さい細孔は閉塞さ
れ、触媒の活性点は完全に隔離されるのに対し、
細孔径を特定範囲で大きくしておくと、金属含有
化合物すなわち、アスフアルト又はレジンが同様
に触媒表面に付着はするが、細孔を完全に閉塞せ
ず、次に触媒上に到達する炭化水素分子及び硫黄
分子を活性点に接近させることができ、従つて、
高性能を発揮するものと推定することができる。
本発明のより好ましい実施態様において使用す
る担体は、シリカを約２〜35重量％含有するアル
ミナ又はアルミナ含有物質である。アルミナ含有
物質としてはアルミナに他の担体物質を配合させ
て得られる組成物であり、例えば、マグネシア、
酸化カルシウム、ジルコニア、チタニア、ポリ
ア、ハフニア及び結晶性ゼオライト等の一種又は
二種以上をアルミナに配合することができる。前
記シリカは、前述の如く、触媒の固体酸性度の制
御には好適であるため、担体中約２〜35重量％、
好ましくは約５〜30重量％の範囲で使用する。更
に好ましいシリカ含有量は約７〜12重量％の範囲
にあることである。
シリカは、触媒に強酸点を賦与し、触媒の分解
活性を増大させるが、一方、例えば、マグネシア
は、アルミナ−シリカ等が有する強酸点を減少さ
せ、同時に弱酸点を増加させて触媒の選択性を向
上させる作用を有する。前記マグネシア、酸化カ
ルシウム、ジルコニア、、チタニア、ボリア、ハ
フニア及び結晶性ゼオライト等の耐火性無機酸化
物の配合量は、アルミナ−シリカに対して約１〜
10重量％の範囲が適当である。
アルミナとしては、γ−アルミナ、χ−アルミ
ナ又はη−アルミナのいずれか又はそれらの混合
体が好適である。シリカアルミナ担体又はシリカ
アルミナ含有担体の製造法は前述の通りである
が、ただ、ここに述べる水素化処理用触媒の製造
に当つては水素化処理用触媒として必要な細孔分
布及び特性値のものを得るようにアルミナ及びシ
リカの水和物の沈殿および熟成における温度、時
間等の製造条件の調整を行なう。
触媒の製造に使用する原料物質として水溶性化
合物、例えば、水溶性酸性アルミニウム化合物又
は水溶性アルカリ性アルミニウム化合物、具体的
には、アルミニウムの硫酸塩、塩化物、硝酸塩、
アルカリ金属アルミン酸塩及びアルミニウムアル
コキシドその他の無機塩又は有機塩を使用するこ
とができる。水溶性ケイ素化合物としては、アル
カリ金属ケイ酸塩（Na2O：SiO2＝１：２〜１：
４が好ましい。）。テトラアルコキシシラン、オル
ソケイ酸エステル等のケイ素含有化合物が適当で
ある。これらのアルミニウム及びケイ素の化合物
は、水溶液として使用することができ、水溶液の
濃度は、特に限定するものではなく、適宜決定し
て差し支えがないが、アルミニウム化合物溶液の
濃度は、約0.1〜4.0モルの範囲で採用することが
できる。アルミナ−シリカ担体又はその他の担体
物質を含有する触媒の好ましい製造法は、アルミ
ナとシリカとの共沈法であるが、沈着法及びゲル
混合法等も採用することができる。
上記水素化処理用触媒に好適なアルミナシリカ
担体の製造法の一態様を例示すれば、次の如くで
ある。
酸性アルミニウム水溶液（好ましくは約0.3〜
２モルの範囲）に水酸化アルカリ溶液を添加し、
PH6.0〜11.0の範囲で約50〜98℃に加熱した後ケ
イ酸アルカリの水溶液を加え、PHを約6.0〜11.0、
好ましくは約8.0〜10.5の範囲でヒドロゲル又は
ヒドロゾルを生成させ、又はアンモニア水、硝酸
又は酢酸等を適宜添加し、PHを調整しながらこの
懸濁液を約50〜98℃の温度に加熱して少なくとも
２時間保持する。この場合、オキシカルボン酸又
はその塩、例えば酒石酸、クエン酸その他の水酸
基多価カルボン酸及びアルカリ金属塩を添加する
と更に良好な触媒担体が得られる。又、アミノジ
カル酸及びその塩、例えばグルタミン酸、アスパ
ラギン酸及びその他のアミノ基含有多価カルボン
酸及びアルカリ金属塩を使用することができる。
これらの化合物はアルミニウム化合物１モルに対
し0.0002〜0.1モルの範囲で添加することができ
る。この処理が終了した後、沈殿を別し、酢酸
アルミニウム及び水で洗浄して不純物イオンを除
去し、乾燥及び焼成等の常法を採用して担体に仕
上げる。
乾燥は、酸素の存在下又は非存在下において、
常温−約200℃に加熱し、焼成は、酸素の存在下
において、約200〜800℃の範囲に加熱することに
より行なう。
担体上に担持させる水素化活性金属成分は前述
の通りである。特に、炭化水素油の水素化脱硫の
ためには、特に、第Ｂ族金属と第族金属との
組合せ、例えば、モリブデン−コバルト、モリブ
デン−ニツケル、タングステン−ニツケル、モリ
ブデン−コバルト−ニツケル又はタングステン−
コバルト−ニツケル等の組合せを好ましく使用す
ることができる。これらの活性金属成分に第3′の
金属、つまり元素周期表第族金属、例えばマン
ガン、及び第族金属、例え、錫、ゲルマニウム
等を添加して使用することもできる。これら第３
の金属は、第１ステツプの前に担体の前処理とし
て、又は第２ステツプの後に後処理として添加す
ることができる。
これら水素化活性金属成分は、酸化物及び／又
は硫化物として担持させることが好適である。
水素化活性金属成分は、前述したように第１及
び第２ステツプに分けて担体に担持される。
触媒の形状は、円筒状、粒状又は錠剤状その他
如何なるものでもよく、このような形状は、押出
成形、造粒成形等の成形法により得られる。成形
物の直径は0.5〜3.0mmの範囲が好ましい。
水素化活性金属成分を含浸した担体は、含浸溶
液を分離した後、水洗、乾燥及び焼成を行なう。
乾燥及び焼成の条件は、前記担体の場合の条件と
同一でよい。重質炭化水素油の水素化脱硫におい
て、触媒は、使用に先立ち、前述したように予備
硫化を行なうことが好ましい。
このようにして、製造される触媒は、前述の如
く、シリカを約２〜35重量％含有するアルミナ又
はアルミナ含有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成り、
30〜100Åの範囲の直径を有する細孔の容積
が０〜150Åの範囲の直径を有する細孔の容積
の70％以上
100〜300Åの範囲の直径を有する細孔の容積
が０〜300Åの範囲の直径を有する細孔の容積
の約30％以下（上記及びの細孔容積は窒素
吸着法により測定）
水銀圧入法により測定した150〜150000Åの
範囲の直径を有する細孔の容積が約0.005〜
0.25ml／ｇ、好ましくは0.1ml／ｇ以下
水銀圧入法により測定した150〜2000Åの範
囲の直径を有する細孔の容積が約0.01ml／ｇ以
下
窒素吸着法により測定した０〜300Åの範囲
の直径を有する細孔の容積が約0.30〜0.70ml／
ｇの範囲
及び
比表面積が約200〜400m2／ｇの範囲であるこ
とを特徴とするものであり全細孔容積；0.4〜
0.9ml／ｇ、カサ密度；約0.5〜1.0ｇ／ml、側面
破壊強度；約0.8〜3.5Kg／mmであつて、炭化水
素油の良好な水素化精製用触媒を実現する。
触媒の細孔容積の測定法として使用した窒素吸
着法及び水銀圧入法は、P.H.エメツト他著「キ
ヤタリシス」第１巻、第123頁（ラインホール
ド・パブリシング・カンパニー発行）（1959年）
P.H.Emmett，stal，“Catalysis”，１，123
（1959）（Reinhold Publishing Co.）、及び触媒
工学講座、第４巻、第69頁〜第78頁（地人書館発
行）（昭和39年）に記載の方法による。
水銀圧入法においては触媒に対する水銀の接触
角を140゜、表面張力を480ダイン／cmとし、すべ
ての細孔は円筒形であると仮定した。
窒素吸着法に対しては多分子層吸着に基づく補
正の方法が種々提案されており、その中でも
BJH法〔E.P.Barrett，L.G.Joyner and P.P.
Halnda，J.Amer.，Chem，Soc.，73，373
（1951）〕及びCI法〔R.W.Cranston and F.A.
Inkley，“Advances in Catalysis，”1X，143
（1957）（New York Academic Press）〕が一般
に用いられている。
本発明における細孔容積に係るデータは吸着等
温線の吸着側を使用し、DH法〔D.Dollimore
and G.R.Heal，J.Appl.，Chem.，14，109
（1964）〕によつて計算したものである。
本発明に従つて製造した触媒の使用による炭化
水素油の水素化脱硫の方法について述べる。
重質炭化水素油として減圧蒸留軽油、重質分解
油等を使用することができる。減圧蒸留軽油は、
常圧蒸留残渣油を減圧蒸留して得られる約250℃
〜560℃の範囲の沸点を有する留分を含有する留
出油であり、硫黄分、窒素分及び金属分を相当量
含有するものである。例えば、中東原油減圧蒸留
軽油の一例を挙げるならば、約２〜４重量％の硫
黄分、約0.05〜0.2重量％の窒素分を含有する。
又、残留炭素分を0.4〜５重量％含有する。
重質分解油は、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、
残渣油のコーキングおよびビスブレーキング等か
ら得られる軽油を使用することができる。
又、炭化水素油としては、硫黄分、窒素分、ア
スフアルト及び金属含有化合物を含有し、実質的
に約480℃以上に沸点を有するもので、原油の常
圧又は減圧蒸留残渣油を含有する。例えば、常圧
において約480℃以上の沸点を有する炭化水素成
分が約30〜100重量％の範囲の残渣油は、通常、
約１〜10重量％の硫黄分、約0.1〜１重量％の窒
素分、約10〜1000ppmの金属及び約１重量％の残
留炭素分（コンラドソン）を含有する。
前記水素化精製法の原料油としては、前記の如
き常圧蒸留残渣油、減圧蒸留残渣油、減圧蒸留軽
油重質分解油若しくは常圧蒸留軽油又はこれらの
混合油を使用することができる。
反応条件は、原料油の種類、脱硫率又は脱窒素
率等の如何により適宜選択することができる。す
なわち、反応温度；約350〜450℃、反応圧力；約
30〜200Kg／cm2、水素含有ガスレイト；約50〜
1500／、及び液空間速度；約0.2〜20V／
Ｈ／Ｖを採用する。水素含有ガス中の水素濃度
は、約60〜100％の範囲でよい。
本発明に従つて製造される触媒は、活性劣化が
小さく、苛酷度の低い反応条件、特に、低反応圧
においても高い脱硫率を達成することができる。
水素化脱硫を行なうにあたり、触媒は、固定
床、流動床又は移動床のいずれの形式でも使用す
ることができるが、装置面又は操作上からは固定
床を採用することが好ましい。又、二基以上の複
数基の反応塔を結合して水素化脱硫を行ない、高
度の脱硫率を達成することもできる。更に、本発
明触媒は、脱硫・脱窒素反応を主体とする主反応
塔に前置の金属除去を目的とするカード・ドラム
に充填使用することもできる。
次に、本発明の実施例について説明する。
実施例 １、２、３
硝酸コバルト13.9ｇを蒸留水70mlに溶解し、更
にこれにアンモニア80mlを加え、コバルトアンミ
ン錯塩溶液を得た。この溶液にシリカゲルアルミ
ナ担体（シリカ含有量10％）50ｇを16時間浸漬
し、コバルトを酸化コバルトとして５重量％担持
した。風乾後300℃で焼成したものを触媒Ａ（実施
例１）、500℃で焼成したものを触媒Ｂ（実施例
２）、600℃で焼成したものと触媒Ｃ（実施例３）
とする。
比較例 １、２
市販のアルミナ担体を用いて、実施例１と同様
の手順で、コバルトを酸化コバルトとして５重量
％担持した。焼成温度300℃のものを触媒Ｄ（比較
例１）、600℃のものを触媒Ｅ（比較例２）とする。
実施例１、２、３及び比較例１、２で得られた
触媒の、酸化コバルトの担持状態を知るため、昇
温還元法による分析を行なつた。手順はジエイ・
ダブリユ・ジエンキンス（J.W.Jenkins）
（CHEMTECH Vol 7316−320、（1977））らの方
法に依つた。その結果を第１図〜第５図に示す。
アルミナ担体上において酸化コバルトは、300
℃以下で還元を受ける状態（担体と結合を有しな
い酸化コバルト微粒子と考えられる）か、又は
700℃において還元を受けない状態（コバルトア
ルミネートのようにアルミナと強く結合した酸化
コバルトと考えられる）のいずれかの状態にあ
る。300℃焼成の触媒Ｄでは、大部分が前者であ
り、600℃焼成の触媒Ｅでは大部分が後者である。
中間の焼成温度においても、両者の比が変化する
のみであり、その他の状態の酸化コバルトは見出
されない。
一方、シリカアルミナ担体上では、アルミナ担
体の場合にみられた２つの状態の酸化コバルト
は、むしろ少なく、500〜700℃で還元を受ける酸
化コバルト（担体と中程度に結合した酸化コバル
ト）が大部分であり、焼成温度の影響はアルミナ
担体の場合に比べ小さい。
以上の結果は、シリカアルミナ担体と、脱硫触
媒用担体として広く用いられているアルミナとで
は、活性金属の一つである酸化コバルトの担持状
態が全く異なつていることを示しており、シリカ
アルミナ担体を用いる場合、このような特徴を生
かした新規な触媒製造法が可能であることを示唆
している。
比較例 ３
コバルトアンミン錯塩溶液の代わりに、硝酸コ
バルト水溶液を用いて実施例１と同様の手順、同
じシリカアルミナ担体を用いて、コバルトを酸化
コバルトとして5.0wt％担持した。焼成温度500℃
のものを触媒Ｆとする。
触媒Ｆの昇温還元法による分析結果を第６図に
示す。触媒Ｂに比べ、やや複雑なプロフイルを示
し、担持状態が不均一であることを示している。
比較例 ４、５、６、７
シリカを25％含有するシリカアルミナを担体と
して用い、４種のコバルトモリブデン触媒を製造
した。
触媒Ｇ（比較例４）−モリブデン酸アンモニウム
13.2ｇを50mlの３規定アンモニア水に溶
解。これにシリカアルミナ担体25ｇを浸漬
し、２時間放置後、液を捨てて、風乾す
る。550℃で焼成後比較例３と同様の手順
で、コバルトを担持する。風乾後550℃で
焼成して、触媒Ｇを得た。
触媒Ｈ（比較例５）−触媒Ｇと同様の手順でモリ
ブデンを担持した後、550℃で焼成し、更
に、実施例１と同様の手順でコバルトアン
ミン錯塩溶液を用いてコバルトを担持し
た。風乾後550℃で焼成して触媒Ｈを得た。
触媒Ｉ（比較例６）−硝酸コバルト13.9ｇを蒸留
水70mlに溶解。この溶液に、アンモニア80
mlを加える。これに更にモリブデン酸アン
モニウム26.4ｇを溶解した。この溶液にシ
リカアルミナ担体50ｇを浸漬し、２時間放
置後、液を捨て風乾した後、550℃で焼成
して触媒Ｉを得た。
触媒Ｊ（比較例７）−リンモリブデン酸280ｇをエ
タノール150mlに溶解。この溶液に硝酸コ
バルト27.7ｇを更に溶解した。この溶液に
シリカアルミナ担体50ｇを浸漬し、２時間
放置後、液を捨て、風乾した後、550℃で
焼成して触媒Ｊを得た。
実施例４、比較例８
触媒Ｋ（実施例４）−実施例１と同様の手順で
コバルトアンミン錯塩溶液を用いて、コバ
ルトを担持した。風乾後550℃で焼成し、
更にモリブデン酸アンモニウムの３規定ア
ンモニア溶液に浸漬して、モリブデンを担
持した。風乾後550℃で焼成して、触媒Ｋ
を得た。
触媒Ｌ（比較例８）−比較例３と同様の手順で
硝酸コバルト水溶液を用いてコバルトを担
持した。風乾後550℃で焼成し、更に実施
例４と同様にして、モリブデンを担持し、
触媒Ｌを得た。
触媒Ｇ、Ｈ、Ｉ、Ｊ、Ｋ、Ｌの脱硫活性をチオ
フエンの脱硫反応により調べた。
フイード組成はチオフエン5.5wt％、ピリジン
2.3wt％、ｎ−ヘキサン92.7wt％である。反応条
件は下記の通りである。
反応温度 300℃ 反応圧 大気圧
フイード流量 1.5W／Ｈ／Ｗ 水素／
フイードモル比 6.0
The present invention relates to a hydrotreating catalyst used in the hydrotreating of hydrocarbon oils, and in particular supports metals of group 3 and group B of the periodic table with good dispersion on silica alumina or a carrier containing silica alumina. The present invention relates to a method for producing a highly active hydrotreating catalyst. In the description of the present invention, "hydrotreatment" refers to a treatment method by contacting carbon hydrogen oil with hydrogen,
Hydrocarbon oils in the presence of hydrogen such as hydrorefining with relatively less severe reaction conditions, hydrorefining with relatively more severe cracking reactions, hydroisomerization, hydrodealkylation, and other hydrocarbon oils in the presence of hydrogen. This includes the following reactions. Examples include hydrodesulfurization, hydrodenitrogenation, and hydrocracking of distillate oils and residual oils of atmospheric distillation or vacuum distillation, and hydrogenation of kerosene fractions, gas oil fractions, waxes, and lubricating oil fractions. This includes purification, etc. The catalyst produced according to the invention is suitable for use in medium distillate oils obtained by atmospheric distillation, such as kerosene fractions and gas oil fractions, heavy distillate oils obtained by vacuum distillation, asphalt-containing residue oils or mixtures thereof. Because it is suitable for carrying out hydrodesulfurization of oils, it will be described herein with particular reference to hydrodesulfurization. Conventionally, in hydrodesulfurization during petroleum refining, an alumina carrier is produced by supporting one or more metals selected from the group of group metals of the periodic table of elements and/or metals of group B of the periodic table of elements. For example, cobalt-molybdenum-based or nickel-molybdenum-based hydrotreating catalysts are widely used. The most important thing in the production of such hydrotreating catalysts is to use molybdenum-cobalt or molybdenum-nickel particles of uniform composition in a large amount (approximately 20% by weight as oxide) on a carrier and in a highly dispersed state. It is to make them bear the burden. As methods for producing hydrotreating catalysts, (1) a coprecipitation method, (2) a kneading method, and (3) an impregnation method have been proposed and generally practiced. However, the coprecipitation method has the disadvantage that when there are multiple active metal components, such as the above-mentioned hydrotreating catalyst, it is difficult to produce these active metal components uniformly and with good reproducibility. ing. As for the kneading method, as mentioned above, in a hydrotreating catalyst having a plurality of active metal components, it is necessary to bring the support and the plurality of active metal components sufficiently close to each other and to achieve uniform and complete mixing. However, this kneading method has the disadvantage that it is extremely difficult to achieve such a state. Compared to the above two methods, the impregnation method is more suitable for producing hydrotreating catalysts that have multiple active metal components, such as cobalt-molybdenum-based catalysts using alumina as a carrier, or nickel-molybdenum-based catalysts, as described above. It can be said that In the production of hydrotreating catalysts by the impregnation method, alumina is usually used as a carrier, molybdenum is first supported on the alumina carrier (first step), and then cobalt or nickel is added to the active metal and molybdenum interacts with each other. proposed a method (two-stage impregnation method) in which molybdenum-cobalt or molybdenum-nickel is supported on a carrier as fine particles (second step), but in the first step approximately 15
It is difficult to support molybdenum on an alumina carrier in a highly dispersed state, and the dispersibility of the final catalyst is also substantially determined by the dispersion state of molybdenum in the first step.
Therefore, a decrease in activity is inevitable. In order to solve the above-mentioned drawbacks of the impregnation method, it is possible to support cobalt or nickel on an alumina support in the first step, and then to support molybdenum, but in this case, cobalt or nickel, etc. The active metal component does not have sufficient interaction with the alumina support on the alumina support, and either aggregates into lumps as inactive Co 3 O 4 or forms cobalt aluminate, becoming inert and unable to achieve the desired performance. cannot be achieved. Further, the method of simultaneously supporting a plurality of active metals on an alumina carrier by impregnation is not preferred because it is difficult to uniformly distribute each component within the carrier. As mentioned above, when using a catalyst with a high amount of active metal components supported, such as a catalyst for hydrotreating, and supporting multiple active metal components, each component must be in a uniform composition and highly dispersed state. What it carries is
This is extremely difficult using conventional known methods. Therefore, the main object of the present invention is to provide a method for producing a hydrotreating catalyst comprising a group metal of the periodic table of the elements and a group B metal, by utilizing the bonding force between the metal of the group of the periodic table of the elements and a support. The object of the present invention is to provide a method for producing a highly active catalyst for hydrotreating by supporting both active metal components with good dispersion. Still another object of the present invention is to apply cobalt or nickel to silica alumina or a carrier containing silica alumina using an ion exchange method with good dispersibility and chemical uniformity (cobalt or nickel supported on the carrier and A method for producing a catalyst for hydrotreating, which can be supported with improved bond strength (uniformity of bond strength), and can therefore support molybdenum, which is a main active metal component, on a support with good dispersion and uniformity. The goal is to provide the following. The present inventors have conducted various studies and experiments to improve conventional manufacturing methods, and have found that cobalt and nickel, which are the active metal components of hydrotreating catalysts, are supported on the acidic sites of the carrier, It has been found that cobalt or nickel can be stably supported with good dispersibility in the first step by using a silica-alumina carrier having acidic points or a silica-alumina-containing carrier instead of the alumina carrier.
This is thought to be because cobalt or nickel is supported on the acidic sites of silica alumina by chemical bonding force, and in particular, cobalt or nickel is supported on a silica alumina support or a silica alumina-containing support by an ion exchange method. It has been found that, in particular, the dispersibility can be dramatically improved. Furthermore, molybdenum can be supported in the second step on the silica-alumina carrier or silica-alumina-containing support on which cobalt or nickel was supported in the first step as described above, and in this case, molybdenum is bonded with cobalt or nickel. It was found that fine particles of molybdenum-cobalt or molybdenum-nickel were supported in a uniform and highly dispersed state by being supported around the cobalt or nickel by force. As mentioned above, the present inventors have discovered that when silica alumina or a silica alumina-containing material is used as a support, cobalt and nickel act as bromotors (cocatalysts) and at the same time function as anchors for molybdenum, which is an active metal component. It has been found that it has the effect of improving the dispersibility and stability of. The present invention has been made based on this new knowledge. To summarize, the present invention uses silica alumina or a silica alumina-containing material as a support, and first supports one or more metals selected from the group of metals of Group Group of the Periodic Table of Elements on the support, and then This is a method for producing a catalyst for hydrotreating, characterized in that it is supported on one or more metals selected from the Group B metals of the Periodic Table of Elements. In particular, the present invention is characterized in that good catalytic activity is obtained by reducing the amount of group metal supported. In the method for producing a hydrotreating catalyst according to the present invention, a silica-alumina carrier or a silica-alumina-containing carrier having acidic sites is used instead of an alumina carrier. Even if a group metal of the Periodic Table of Elements is supported in the first step by using silica-alumina or a silica-alumina-containing material as a carrier, the active metal component binds to the acidic sites of the silica-alumina and thereby It has good dispersibility and is stably supported. In this way, by supporting the Group metal on the acidic points of the carrier with good dispersion in the first step, the Group B metal of the periodic table, which is the main active metal, is transferred to the outside of the Group metal, that is, the Group metal It can be supported on a layer and is extremely suitable as a catalyst for hydrotreating. On the other hand, in hydrotreating, especially hydrodesulfurization and hydrodenitrogenation, it is important that the catalyst maintains the desired solid acidity, and it is possible to control the acidity by adjusting the silica content in the carrier. Are known. In the present invention, when the silica content of the silica-alumina carrier or the silica-alumina-containing carrier becomes excessive, hydrogen consumption may increase due to excessive decomposition reaction in the hydrodesulfurization reaction or hydrodenitrogenation reaction, or coke may be generated. This may lead to undesirable reactions such as the formation of Therefore, in a more preferred embodiment of the present invention, the content of silica in the silica-alumina support or silica-alumina-containing support ranges from 2 to 35% by weight, preferably from 5 to 30% by weight, more preferably from 7 to 12% by weight. It should be done. Further, the surface area and pore distribution of the silica alumina carrier are not particularly defined, but the surface area is preferably 50 m 2 /g or more as a catalyst carrier, particularly
200 m 2 /g or more is suitable. Methods for producing such a silica-alumina carrier include a method in which alumina and silica gels are each prepared in advance and then mixed together, and a method in which silica gel is immersed in a solution of an aluminum compound, and then an appropriate amount of a basic substance is added to form alumina gel. A method of depositing a gel on silica gel, a method of adding a basic substance to a homogeneous mixed solution of a water-soluble aluminum compound and a water-soluble silicon compound, and co-precipitating the two, etc. can be adopted. The hydrogenation-active metal component supported on the carrier in the first step is one or more metals selected from the group of metals of Group Group of the Periodic Table of the Elements. That is,
Group iron, cobalt, nickel, palladium,
One or more selected from platinum, osmium, iridium, ruthenium, rhodium, etc. are used. Preferably cobalt and nickel will be used alone or in combination. The hydrogenation active metal component supported on the carrier in the second step is one or more metals selected from the group B metals of the periodic table of elements. That is,
One or more selected from Group B chromium, molybdenum, and tungsten are used. Preferably molybdenum and tungsten will be used alone or in combination. It would also be possible to add a third metal if desired. The hydrogenation-active metal components of Groups and Groups B are preferably supported as oxides and/or sulfides. The amount of active metal component supported is
In a more preferred embodiment of the present invention, the group metal is 0.5 to 20% by weight on a catalyst basis as an oxide;
Preferably 1 to 8% by weight, more preferably 2 to 5% by weight
% by weight, and the Group B metal is 5-30% by weight, preferably 8-25% by weight, more preferably 15-20% by weight. If the group metal is supported at less than 0.5% by weight, a sufficient catalyst cannot be obtained, and if it is supported at more than 20% by weight, the amount of free metal components that are not bonded to the support increases. When the free component of the group metal increases, an inert composite oxide is generated when the group B metal is subsequently supported, which reduces the dispersibility of the group B metal and reduces the catalytic activity. On the other hand, if the Group B metal is less than 5% by weight, no activity will be obtained, and if it is more than 30% by weight, the dispersibility will decrease and at the same time the promoter effect of the Group B metal will not be exhibited. In the present invention, as a method for supporting the active metal component on the carrier in the first and second steps, an impregnation method is adopted in which the carrier is immersed in an aqueous solution of a soluble salt of the metal and the metal component is introduced into the carrier. I can do it. In the impregnation operation, the carrier is immersed in an impregnating solution at room temperature or above room temperature, and maintained under conditions such that the desired component is sufficiently impregnated into the carrier. The amount and temperature of the impregnating solution can be adjusted as appropriate to support the desired amount of metal. The amount of carrier to be immersed in the impregnating solution is determined depending on the amount of carrier supported. On the other hand, the present inventors have discovered that the first step in the catalyst production method according to the present invention is an ion exchange method in which protons on the surface of a silica-alumina carrier or a silica-alumina-containing carrier are exchanged with the metal ions via ammonium ions. It has been found that this is extremely suitable. It has been found that when the present invention is carried out based on the ion exchange method, the degree of dispersion of the catalyst is significantly improved compared to a conventional impregnation method catalyst, and the chemical uniformity is also improved. A method for producing a catalyst based on an ion exchange method is carried out by preparing an ammine complex salt solution of an active metal, immersing a silica alumina carrier in the solution, and supporting the metal on the carrier. The amount and concentration of the ammine complex salt solution can be adjusted as appropriate so that a desired amount of metal is supported. The carrier carrying the hydrogenation-active metal component is separated from the impregnating solution and then dried and calcined. The drying and calcination conditions may be the same as those for the carrier. The catalyst is preferably presulfided before use. Presulfurization can be carried out in situ in the reaction column. That is, the calcined catalyst is mixed with sulfur-containing distillate oil at a temperature of approximately 150 to 400°C, a pressure (total pressure) of approximately 5 to 100 Kg/cm 2 , and a liquid hourly space velocity of approximately 0.3 to 400°C.
Contact is made in the presence of hydrogen-containing gas of 2.0V/HV and about 50 to 1500V, and after the sulfidation treatment is completed, the sulfur-containing distillate is switched to feedstock oil, and the operating conditions are set to suitable for desulfurization of the feedstock oil, and operation is started. Start. In addition to the methods described above, the sulfurization treatment may be carried out by directly contacting hydrogen sulfide or other sulfur compounds with the catalyst, or by adding it to a suitable distillate and bringing it into contact with the catalyst. The present inventors have researched the method for producing the catalyst according to the present invention as described above, and have conducted various experiments.
According to the method for producing a catalyst according to the present invention, about 2 silica
~35% by weight of an alumina support containing one or more metals selected from the group of group metals of the periodic table of the elements and one or more types of metals selected from the group of group B metals of the periodic table of the elements. The volume of the pores having a diameter in the range of 30 to 100 Å is 70% or more of the volume of the pores having a diameter in the range of 0 to 150 Å. Approximately 30% or less of the volume of pores with a diameter in the range of 0 to 300 Å (the pore volume is measured by nitrogen adsorption method); The pore volume is approximately 0.005 ~
0.25 ml/g or less, preferably 0.1 ml/g or less The volume of pores with a diameter in the range of 150 to 2000 Å measured by mercury porosimetry is approximately 0.01 ml/g or less The volume of pores in the range of 0 to 300 Å measured by nitrogen adsorption method The volume of the pores with a diameter is approximately 0.30-0.70ml/
It has been found that it is possible to suitably produce a catalyst for hydrotreating hydrocarbon oil having a specific surface area in the range of about 200 to 400 m 2 /g. In addition, the catalyst has a total pore volume;
0.4-0.9ml/g, bulk density: approx. 0.5-1.0g/ml,
Side breaking strength: approximately 0.8 to 3.5 kg/mm. Conventionally, hydrodesulfurization methods for residual oil have been actively developed with the aim of reducing the amount of sulfur dioxide released, as sulfur compounds in petroleum fuel become sulfur dioxide gas when burned, becoming a source of air pollution. Many proposals have been made. For example, in order to perform hydrodesulfurization and hydrodenitrogenation of hydrocarbon oil containing asphalt and metal-containing compounds, the pore distribution of the hydrorefining catalyst used greatly affects the activity and ability to maintain activity. In anticipation of this, we developed a catalyst with a pore distribution in which the volume of pores with a pore radius of 80 Å or more is suppressed to 10% or less of the total pore volume in order to prevent the infiltration of asphalt and metal-containing compounds in the feedstock oil. Method of use (Special Publication No. 45-38142)
Or a radius of 120 in the hydrodesulfurization of the same residual oil.
A method using a catalyst in which the volume of pores of Å or less is relatively uniformly distributed at intervals of 10 Å (Japanese Patent Publication No. 38143/1983) is known. Also, hydrogen of crude oil or crude oil without oil, in which the pore volume of particles having a pore size in the range of about 50 to 100 Å is at least 50% of the total volume, and the pore volume of particles having a pore size in the range of 0 to 50 Å is at most 25%. A desulfurization catalyst has also been disclosed (Japanese Unexamined Patent Application Publication No. 1973-
Publication No. 10356). However, in these hydrodesulfurization methods, the pore distribution of so-called macropores with a pore radius of 300 Å or more of the catalyst used has not been sufficiently studied, and its influence on catalyst performance is ignored. That is, the conventionally disclosed technology is
The focus is on so-called micro-pores, but micro-pores alone contain large amounts of sulfur, nitrogen, metals, asphalt, and other impurities, such as atmospheric distillation residue oil, vacuum distillation gas oil, vacuum distillation residue oil, etc. It is not possible to improve the activity and ability to maintain activity in hydrorefining hydrocarbon oil. The inventors have discovered that the pore distribution across both the microbore and macrobore regions of the catalyst has a profound effect on desulfurization and denitrification. That is,
Pore diameter 150-2000Å measured by mercury intrusion method
The pore volume of the pores is about 0.01 ml/g or less, and the volume of pores with a diameter in the range of 30 to 100 Å measured by a nitrogen adsorption method is 70% of the volume of pores with a diameter in the range of 0 to 150 Å. % or more, preferably 80% or more, more preferably 90% or more, and furthermore 100 to
The volume of pores with diameters ranging from 0 to 300 Å
Not more than 30% of the volume of pores with a diameter in the range of Å,
It has been found that a catalyst containing preferably 20% or less exhibits a very significant desulfurization effect. In other words, upon contact with hydrogen in the presence of a hydrorefining catalyst, heavy hydrocarbon oil, especially the asphalt and resin components contained in the residual oil, enter the pores of the catalyst.
In order to prevent deterioration of catalyst activity, it is necessary to reduce the pore volume of the macrobore. In addition, in order to suppress the lightening of hydrocarbon oil due to carbon-to-carbon cleavage of saturated hydrocarbons, and to prevent the clogging of the pores of the catalyst by asphalt and resin components, the diameter
Therefore, it is preferable to reduce pores of 30 Å or less. It is already known that solid acids such as alumina silica are suitable catalyst components for desulfurization and denitrification reactions of hydrocarbon oils, but in hydrorefining, it is necessary to maintain the desired solid acidity as described above. is important, and for this purpose acidity can be controlled by controlling the silica content. The present inventors have recognized that the catalytic ability and selectivity of the hydrogenation reaction of hydrocarbon oil can be adjusted by adjusting the cracking activity based on acidic control by controlling the silica content in the carrier and by specifying the pore structure of the catalyst. ing. This type of selectivity has the effect of saving hydrogen consumption in desulfurization and denitrification of hydrocarbon oils, and preventing a decrease in catalyst activity due to the generation of carbon components accompanying the reaction. , plays a very important role. Therefore, in the hydrodesulfurization reaction or hydrodenitrogenation reaction, as mentioned above, the content of silica in the alumina-containing carrier is necessary to control the increase in hydrogen consumption or the generation of coke due to excessive decomposition reaction. The amount should range from about 2 to 35% by weight, preferably from about 5 to 30%. Although the pores of the above-mentioned hydrotreating catalyst are concentrated in a diameter range of 30 to 100 Å as measured by the nitrogen adsorption method, the pores are distributed over a fairly wide range as a whole. The reason why such a pore distribution of the catalyst disclosed by the present invention imparts a remarkable effect on the activity and activity maintenance ability in hydrodesulfurization of hydrocarbon oil is not fully elucidated. Because of this, when asphalt, resin content, and metal-containing compounds in the feedstock oil adhere to the catalyst surface, the extremely small pores are blocked and the active sites of the catalyst are completely isolated. For,
If the pore size is increased within a certain range, metal-containing compounds, i.e., asphalt or resin, will adhere to the catalyst surface as well, but will not completely block the pores, and the hydrocarbon molecules that will then reach the catalyst. and sulfur molecules can be brought close to the active site, thus
It can be estimated that it exhibits high performance. In a more preferred embodiment of the invention, the support used is an alumina or alumina-containing material containing about 2-35% by weight silica. The alumina-containing material is a composition obtained by blending alumina with other carrier materials, such as magnesia,
One or more of calcium oxide, zirconia, titania, poria, hafnia, crystalline zeolite, etc. can be blended with alumina. As mentioned above, the silica is suitable for controlling the solid acidity of the catalyst, so it is contained in the carrier in an amount of about 2 to 35% by weight.
It is preferably used in a range of about 5 to 30% by weight. A more preferred silica content is in the range of about 7-12% by weight. Silica provides strong acid sites to the catalyst and increases the decomposition activity of the catalyst. On the other hand, for example, magnesia reduces the strong acid sites of alumina-silica, etc., and at the same time increases weak acid sites, increasing the selectivity of the catalyst. It has the effect of improving The amount of the refractory inorganic oxides such as magnesia, calcium oxide, zirconia, titania, boria, hafnia, and crystalline zeolite is about 1 to 1 to alumina-silica.
A range of 10% by weight is suitable. As the alumina, γ-alumina, χ-alumina, η-alumina, or a mixture thereof is suitable. The method for producing the silica-alumina support or the silica-alumina-containing support is as described above. The manufacturing conditions such as temperature and time for precipitation and aging of alumina and silica hydrates are adjusted to obtain the desired product. Water-soluble compounds, such as water-soluble acidic aluminum compounds or water-soluble alkaline aluminum compounds, specifically, aluminum sulfates, chlorides, nitrates,
Alkali metal aluminates and aluminum alkoxides and other inorganic or organic salts can be used. As the water-soluble silicon compound, alkali metal silicate (Na 2 O:SiO 2 =1:2-1:
4 is preferred. ). Silicon-containing compounds such as tetraalkoxysilanes and orthosilicate esters are suitable. These aluminum and silicon compounds can be used as an aqueous solution, and the concentration of the aqueous solution is not particularly limited and may be determined as appropriate, but the concentration of the aluminum compound solution is about 0.1 to 4.0 mol. It can be adopted within the range of A preferred method for producing a catalyst containing an alumina-silica carrier or other carrier material is a co-precipitation method of alumina and silica, but deposition methods, gel mixing methods, etc. can also be employed. An example of an embodiment of the method for producing an alumina-silica carrier suitable for the above hydrotreating catalyst is as follows. Acidic aluminum aqueous solution (preferably about 0.3~
2 molar range) by adding an alkali hydroxide solution,
After heating to about 50 to 98℃ in the pH range of 6.0 to 11.0, add an aqueous solution of alkali silicate to adjust the pH to about 6.0 to 11.0.
Preferably, a hydrogel or hydrosol is produced in the range of about 8.0 to 10.5, or by adding aqueous ammonia, nitric acid, acetic acid, etc. as appropriate, and heating this suspension to a temperature of about 50 to 98 °C while adjusting the pH. Hold for at least 2 hours. In this case, an even better catalyst support can be obtained by adding oxycarboxylic acid or a salt thereof, such as tartaric acid, citric acid, other hydroxyl polyhydric carboxylic acids, and alkali metal salts. It is also possible to use aminodical acids and their salts, such as glutamic acid, aspartic acid and other amino group-containing polycarboxylic acids and alkali metal salts.
These compounds can be added in an amount of 0.0002 to 0.1 mol per mol of the aluminum compound. After this treatment is completed, the precipitate is separated, washed with aluminum acetate and water to remove impurity ions, and finished into a carrier by conventional methods such as drying and calcination. Drying is carried out in the presence or absence of oxygen,
It is heated to room temperature - about 200°C, and firing is carried out by heating in the range of about 200 to 800°C in the presence of oxygen. The hydrogenation-active metal component supported on the carrier is as described above. In particular, for the hydrodesulphurization of hydrocarbon oils, combinations of group B metals and group metals, such as molybdenum-cobalt, molybdenum-nickel, tungsten-nickel, molybdenum-cobalt-nickel or tungsten-nickel, are particularly suitable.
Combinations such as cobalt-nickel can be preferably used. It is also possible to add 3' metals to these active metal components, ie, metals from Group 1 of the Periodic Table of the Elements, such as manganese, and metals from Group 3, such as tin, germanium, etc. These third
The metal can be added as a pre-treatment of the support before the first step or as a post-treatment after the second step. These hydrogenation active metal components are preferably supported as oxides and/or sulfides. The hydrogenation active metal component is supported on the carrier in the first and second steps as described above. The shape of the catalyst may be cylindrical, granular, tablet, or any other shape, and such a shape can be obtained by a molding method such as extrusion molding or granulation molding. The diameter of the molded product is preferably in the range of 0.5 to 3.0 mm. The carrier impregnated with the hydrogenation-active metal component is washed with water, dried and calcined after the impregnation solution is separated.
The drying and calcination conditions may be the same as those for the carrier. In hydrodesulfurization of heavy hydrocarbon oil, the catalyst is preferably presulfurized as described above before use. The catalyst thus produced comprises at least one hydrogenation-active metal component supported on an alumina or alumina-containing support containing about 2 to 35% by weight of silica, as described above, The volume of pores with a diameter in the range 70% or more of the volume of pores with a diameter in the range 0 to 150 Å The volume of pores with a diameter in the range 100 to 300 Å has a diameter in the range 0 to 300 Å Approximately 30% or less of the volume of pores (the above pore volumes are measured by nitrogen adsorption method) The volume of pores with a diameter in the range of 150 to 150,000 Å measured by mercury porosimetry is approximately 0.005 to
0.25 ml/g or less, preferably 0.1 ml/g or less The volume of pores with a diameter in the range of 150 to 2000 Å measured by mercury porosimetry is approximately 0.01 ml/g or less The volume of pores in the range of 0 to 300 Å measured by nitrogen adsorption method The volume of the pores with a diameter is approximately 0.30-0.70ml/
It is characterized by having a specific surface area of about 200 to 400 m 2 /g, and a total pore volume of 0.4 to 400 m 2 /g.
0.9 ml/g, bulk density: about 0.5 to 1.0 g/ml, side breaking strength: about 0.8 to 3.5 Kg/mm, and realizes a good catalyst for hydrorefining hydrocarbon oil. The nitrogen adsorption method and mercury intrusion method used to measure the pore volume of catalysts are described in "Catalysis" by PH Emmet et al., Vol. 1, p. 123 (Reinhold Publishing Company) (1959).
PHEmmett, stal, “Catalysis”, 1 , 123
(1959) (Reinhold Publishing Co.) and by the method described in Catalyst Engineering Course, Vol. 4, pp. 69-78 (published by Chijinshokan) (1968). In the mercury intrusion method, the contact angle of mercury to the catalyst was 140°, the surface tension was 480 dynes/cm, and all pores were assumed to be cylindrical. Various correction methods based on multimolecular layer adsorption have been proposed for the nitrogen adsorption method, among which
BJH method [EPBarrett, LGJoyner and PP
Halnda, J. Amer., Chem, Soc., 73 , 373
(1951)] and the CI Act [RWCranston and FA
Inkley, “Advances in Catalysis,” 1X , 143.
(1957) (New York Academic Press)] is commonly used. The data regarding the pore volume in the present invention is obtained by using the adsorption side of the adsorption isotherm, and using the DH method [D.Dollimore
and GRHeal, J.Appl., Chem., 14 , 109
(1964)]. A method for hydrodesulfurization of hydrocarbon oils using a catalyst prepared according to the present invention is described. As the heavy hydrocarbon oil, vacuum distilled light oil, heavy cracked oil, etc. can be used. Vacuum distilled light oil is
Approximately 250℃ obtained by vacuum distillation of atmospheric distillation residue oil
It is a distillate oil containing a fraction having a boiling point in the range of ~560°C, and contains considerable amounts of sulfur, nitrogen, and metals. For example, an example of vacuum distilled gas oil from Middle East crude oil contains about 2 to 4% by weight of sulfur and about 0.05 to 0.2% by weight of nitrogen.
It also contains 0.4 to 5% by weight of residual carbon. Heavy cracked oil is obtained by thermally decomposing residual oil.
It is a cracked oil with a boiling point of 200℃ or higher, for example,
Light oil obtained from residual oil coking, visbreaking, etc. can be used. Further, the hydrocarbon oil contains sulfur, nitrogen, asphalt, and metal-containing compounds, has a boiling point substantially above about 480°C, and contains residual oil from normal pressure or vacuum distillation of crude oil. For example, residual oil containing about 30 to 100% by weight of hydrocarbon components having a boiling point of about 480°C or higher at normal pressure is usually
It contains about 1-10% by weight sulfur, about 0.1-1% by weight nitrogen, about 10-1000 ppm metals and about 1% by weight residual carbon (Conradson). As the raw material oil for the hydrorefining method, the above-mentioned atmospheric distillation residue oil, vacuum distillation residue oil, vacuum distillation gas oil heavy cracked oil, atmospheric distillation gas oil, or a mixture thereof can be used. The reaction conditions can be appropriately selected depending on the type of raw oil, desulfurization rate, denitrification rate, etc. That is, reaction temperature: approximately 350 to 450°C, reaction pressure: approximately
30-200Kg/cm 2 , hydrogen-containing gas rate; approx. 50-
1500/, and liquid space velocity; approximately 0.2~20V/
Adopt H/V. The hydrogen concentration in the hydrogen-containing gas may range from about 60 to 100%. The catalyst produced according to the present invention exhibits little activity deterioration and can achieve a high desulfurization rate even under less severe reaction conditions, particularly at lower reaction pressures. In carrying out hydrodesulfurization, the catalyst can be used in any of a fixed bed, fluidized bed, or moving bed format, but it is preferable to use a fixed bed from the standpoint of equipment and operation. Furthermore, a high desulfurization rate can be achieved by combining two or more reaction towers to perform hydrodesulfurization. Furthermore, the catalyst of the present invention can also be used to fill a card drum for the purpose of removing metals before a main reaction tower mainly for desulfurization and denitrification reactions. Next, examples of the present invention will be described. Examples 1, 2, 3 13.9 g of cobalt nitrate was dissolved in 70 ml of distilled water, and 80 ml of ammonia was added thereto to obtain a cobalt ammine complex salt solution. 50 g of a silica gel alumina carrier (silica content: 10%) was immersed in this solution for 16 hours to support 5% by weight of cobalt as cobalt oxide. Catalyst A (Example 1) was calcined at 300°C after air drying, Catalyst B (Example 2) was calcined at 500°C, and Catalyst C (Example 3) was calcined at 600°C.
shall be. Comparative Examples 1 and 2 Using a commercially available alumina carrier, 5% by weight of cobalt was supported as cobalt oxide in the same manner as in Example 1. The catalyst with a firing temperature of 300°C is designated as Catalyst D (Comparative Example 1), and the one with a firing temperature of 600°C is designated as Catalyst E (Comparative Example 2). In order to find out the state of cobalt oxide supported on the catalysts obtained in Examples 1, 2, and 3 and Comparative Examples 1 and 2, an analysis was performed using a temperature programmed reduction method. The procedure is J.
Davriu Jenkins (JWJenkins)
(CHEMTECH Vol 7316-320, (1977)) et al. The results are shown in FIGS. 1 to 5. Cobalt oxide on an alumina support
℃ or below (considered to be cobalt oxide fine particles that do not have a bond with a carrier), or
It is in a state where it does not undergo reduction at 700°C (it is thought to be cobalt oxide strongly bonded to alumina, such as cobalt aluminate). Catalyst D, which was fired at 300°C, was mostly the former, and Catalyst E, which was fired at 600°C, was mostly the latter.
Even at intermediate firing temperatures, only the ratio between the two changes, and cobalt oxide in other states is not found. On the other hand, on the silica-alumina support, the two states of cobalt oxide observed in the case of the alumina support are rather small, and the cobalt oxide that undergoes reduction at 500-700°C (cobalt oxide moderately bound to the support) is large. The effect of firing temperature is smaller than in the case of alumina carriers. The above results show that the supported state of cobalt oxide, which is one of the active metals, is completely different between the silica alumina carrier and alumina, which is widely used as a carrier for desulfurization catalysts. This suggests that it is possible to create a new catalyst production method that takes advantage of these characteristics. Comparative Example 3 In place of the cobalt ammine complex salt solution, an aqueous cobalt nitrate solution was used, and 5.0 wt% of cobalt was supported as cobalt oxide using the same procedure as in Example 1 and using the same silica alumina support. Firing temperature 500℃
This is designated as catalyst F. The analysis results of catalyst F by the temperature programmed reduction method are shown in FIG. Compared to catalyst B, it showed a slightly more complex profile, indicating that the supported state was non-uniform. Comparative Examples 4, 5, 6, 7 Four types of cobalt-molybdenum catalysts were produced using silica alumina containing 25% silica as a carrier. Catalyst G (Comparative Example 4) - Ammonium Molybdate
Dissolve 13.2g in 50ml of 3N ammonia water. 25 g of silica-alumina carrier is immersed in this, and after being left for 2 hours, the liquid is discarded and air-dried. After firing at 550°C, cobalt was supported in the same manner as in Comparative Example 3. After air drying, it was calcined at 550°C to obtain catalyst G. Catalyst H (Comparative Example 5) - After supporting molybdenum in the same manner as in Catalyst G, it was calcined at 550°C, and further, cobalt was supported in the same manner as in Example 1 using a cobalt ammine complex salt solution. After air drying, catalyst H was obtained by calcining at 550°C. Catalyst I (Comparative Example 6) - 13.9 g of cobalt nitrate was dissolved in 70 ml of distilled water. Add 80% ammonia to this solution.
Add ml. Further, 26.4 g of ammonium molybdate was dissolved in this. 50 g of a silica-alumina carrier was immersed in this solution, and after being left for 2 hours, the solution was discarded, air-dried, and then calcined at 550° C. to obtain catalyst I. Catalyst J (Comparative Example 7) - 280 g of phosphomolybdic acid was dissolved in 150 ml of ethanol. 27.7 g of cobalt nitrate was further dissolved in this solution. 50 g of silica-alumina carrier was immersed in this solution, left for 2 hours, the solution was discarded, air-dried, and then calcined at 550° C. to obtain catalyst J. Example 4, Comparative Example 8 Catalyst K (Example 4) - Cobalt was supported using a cobalt ammine complex salt solution in the same manner as in Example 1. After air drying, it is fired at 550℃.
Furthermore, it was immersed in a 3N ammonia solution of ammonium molybdate to support molybdenum. After air drying, calcinate at 550℃ to prepare catalyst K.
I got it. Catalyst L (Comparative Example 8) - Cobalt was supported using a cobalt nitrate aqueous solution in the same manner as in Comparative Example 3. After air drying, it was fired at 550°C, and molybdenum was supported in the same manner as in Example 4.
Catalyst L was obtained. The desulfurization activities of catalysts G, H, I, J, K, and L were investigated by desulfurization reaction of thiophene. Feed composition is 5.5wt% thiophene, pyridine
2.3wt%, n-hexane 92.7wt%. The reaction conditions are as follows. Reaction temperature 300℃ Reaction pressure Atmospheric pressure Feed flow rate 1.5W/H/W Hydrogen/
Feed molar ratio 6.0
【表】
以上の結果、シリカを含有するアルミナ担体に
おいて本発明による触媒Ｋが、他の方法によつて
調製された触媒Ｇ、Ｈ、Ｉ、Ｊ、Ｌに比べ大巾に
高活性であることがわかる。
比較例９、実施例５〜12
シリカ含有量の異なる９種類のシリカアルミナ
担体を用いてニツケルモリブデン触媒（Ｍ〜Ｕ）
を調製した。担持手順は、ニツケルアンミン錯塩
を用いたことを除いて、実施例４（触媒Ｋ）と同
様である。
これらの触媒の性能を中東系減圧留出油の脱硫
反応により評価した。反応条件は下記の通りであ
る。
反応温度（℃） 320
反応圧力（Kg／cm2） 50
触媒充填量（ml） 12
フイード流量（Ｖ／Ｈ／Ｖ） 0.8
H2／フイード比（SCF／Ｂ） 2500[Table] The above results show that catalyst K according to the present invention has significantly higher activity on an alumina support containing silica than catalysts G, H, I, J, and L prepared by other methods. I understand. Comparative Example 9, Examples 5 to 12 Nickel-molybdenum catalysts (M to U) using nine types of silica-alumina supports with different silica contents
was prepared. The loading procedure was similar to Example 4 (Catalyst K), except that a nickel ammine complex salt was used. The performance of these catalysts was evaluated by desulfurization reaction of Middle Eastern vacuum distillate oil. The reaction conditions are as follows. Reaction temperature (℃) 320 Reaction pressure (Kg/cm 2 ) 50 Catalyst loading amount (ml) 12 Feed flow rate (V/H/V) 0.8 H 2 /feed ratio (SCF/B) 2500
【表】
上記結果から、本発明による調製法が、シリカ
を2wt％以上35wt％以下含有するシリカアルミナ
担体を使用するコバルトモリブデン又はニツケル
モリブデン触媒の脱硫および／あるいは脱窒素活
性の向上に効果が大きいことがわかる。
実施例 13
モリブデンの代わりにタングステンを使用した
こと以外実施例７と同一の条件及び操作で触媒Ｗ
を調製した。タングステンの担持にはタングステ
ン酸アンモニウムを蒸留水に溶解した溶液を使用
した。触媒Ｗの結果は表３に示される。本発明に
従つたNi−Ｗ系の触媒も又優れた脱硫率及び脱
窒素率を示すことが分る。
実施例 14
純水4.8を約70℃に加熱し、これに水酸化ナ
トリウム溶液（NaOH233.6ｇ、純水587ｇ）、硫
酸アルミニウム水溶液（硫酸アルミニウム644.5
ｇ、純水987ｇ）を加えた後、酒石酸二アンモニ
ウムをアルミナ１に対して２ミリモルになるよう
にその水溶液を加え、水酸化ナトリウム溶液また
は硝酸溶液でPHを8.8〜9.2に調節し、約70℃で約
１時間熟成した。これに、ケイ酸ナトリウム水溶
液（３号水ガラス42.5ｇ、純水129.4ｇ）を加え
必要に応じて硝酸溶液を加え、PHを約９とし、温
度約70℃で３時間熟成した。
生じた泥漿を過し、別したケーキは、1.5
％炭酸アンモニウム溶液で再泥漿化し、過した
後、液のナトリウム濃度が5ppm以下になるま
で炭酸アンモニウム溶液で洗浄した。これを、
100℃で16時間乾燥した後、純水及び少量の酢酸
を加え、成型可能な含水量になるまで乾燥しなが
ら混練し、押出し型成型機により、1.5mmφの円
柱状に成型した。成型されたペレツトは、100℃
で16時間乾燥し、さらに600℃で３時間焼成して
担体とした。
一方、硝酸ニツケルを蒸留水に溶解し、更にこ
れにアンモニアを加えて調製したニツケルアンミ
ン錯塩溶液を使用した以外は実施例７と同一の方
法でニツケル及びモリブデンを担持した。即ち、
このニツケルアンミン錯塩溶液に前述のシリカア
ルミナ担体（シリカ含有量10重量％）50ｇを16時
間浸漬し、ニツケルを酸化ニツケルとして４重量
％担持した。ニツケルを担持した担体を風乾し、
次いで550℃で焼成した後３規定モリブデン酸ア
ンモニウム水溶液に浸漬してモリブデンを酸化モ
リブデンとして14重量％担持した。これを風乾
後、550℃で焼成し触媒を得た。これを触媒Ｘと
する。この触媒の物理性状を次に示す。
物理性状
比表面積（m2／ｇ） 265
かさ密度（ｇ／ml） 0.72
側面破壊強度（Kg／mm） 1.6
触媒粒径（最長）（mm） 1.6
細孔容積（ml／ｇ）
細孔直径
30Å以下 0.002
30〜100Å 0.389
100〜300Å 0.072
０〜150Å 0.0425
０〜300Å 0.463
600Å以下（窒素ガス吸着法） 0.525
150〜150000Å（水銀圧入法） 0.021
150〜2000Å（水銀圧入法） 0.008
PV（30〜100）／PV（０〜150）×100 91.5
PV（100〜300）／PV（０〜300）×100 15.3
実施例５〜12の触媒Ｎ〜Ｕは試作したシリカアル
ミナ担体を使用して調製され、例えばシリカ含有
量が10重量％である実施例７の触媒Ｐは次のよう
な物理的性状を有していた。
物理性状
比表面積（m2／ｇ） 219
かさ密度（ｇ／ml） 0.70
側面破壊強度（Kg／mm） 1.5
触媒粒径（最長）（mm） 1.5
細孔容積（ml／ｇ）
細孔直径
30Å 0.058
30〜100Å 0.189
100〜300Å 0.118
０〜150Å 0.284
０〜300Å 0.365
600Å以下 0.517
150〜150000Å 0.026
150〜2000Å 0.013
PV（30〜100）／PV（０〜150）×100 66.5
PV（100〜300）／PV（０〜300）×100 32.3
表３を見ると、特定の細孔分布を有した触媒Ｘ
が他の細孔分布を有した触媒Ｐより優れた脱硫率
及び脱窒素率を有することが分る。
実施例 15
硝酸コバルト9.7ｇ及び硝酸ニツケル1.4ｇを蒸
留水70mlに溶解し、更に、これにアンモニア80ml
を加え、コバルト・ニツケル混合アンミン錯塩溶
液を得た。この溶液にシリカ10重量％を含有する
シリカアルミナ担体50ｇを16時間浸漬し、コバル
ト及びニツケルを酸化物として各々3.5重量％及
び0.5重量％を担持した。風乾、焼成後３規定モ
リブデン酸アンモニウム水溶液に浸漬して、モリ
ブデンを酸化物として14重量％担持し、触媒Ｙを
得た。[Table] From the above results, the preparation method according to the present invention is highly effective in improving the desulfurization and/or denitrification activity of cobalt molybdenum or nickel molybdenum catalysts using a silica alumina support containing 2 wt% or more and 35 wt% or less of silica. I understand that. Example 13 Catalyst W was prepared under the same conditions and operations as in Example 7 except that tungsten was used instead of molybdenum.
was prepared. A solution of ammonium tungstate dissolved in distilled water was used to support tungsten. The results for catalyst W are shown in Table 3. It can be seen that the Ni--W based catalyst according to the present invention also exhibits excellent desulfurization and denitrification rates. Example 14 Heating 4.8 g of pure water to about 70°C, adding sodium hydroxide solution (233.6 g of NaOH, 587 g of pure water) and aqueous aluminum sulfate solution (644.5 g of aluminum sulfate)
g, 987 g of pure water), then add diammonium tartrate in an aqueous solution of 2 mmol per 1 alumina, adjust the pH to 8.8 to 9.2 with sodium hydroxide solution or nitric acid solution, and add about 70 g of diammonium tartrate. It was aged for about 1 hour at ℃. To this, a sodium silicate aqueous solution (42.5 g of No. 3 water glass, 129.4 g of pure water) was added, a nitric acid solution was added as needed, the pH was adjusted to about 9, and the mixture was aged at a temperature of about 70° C. for 3 hours. Strain the resulting slurry and separate the cake, 1.5
% ammonium carbonate solution, filtered, and washed with ammonium carbonate solution until the sodium concentration of the solution was 5 ppm or less. this,
After drying at 100°C for 16 hours, pure water and a small amount of acetic acid were added, the mixture was kneaded while drying until the water content reached a moldable level, and the mixture was molded into a 1.5 mm diameter cylinder using an extrusion molding machine. Molded pellets are heated to 100℃
The mixture was dried for 16 hours at 600°C, and then fired at 600°C for 3 hours to obtain a carrier. On the other hand, nickel and molybdenum were supported in the same manner as in Example 7, except that a nickel ammine complex salt solution prepared by dissolving nickel nitrate in distilled water and adding ammonia thereto was used. That is,
50 g of the aforementioned silica-alumina carrier (silica content: 10% by weight) was immersed in this nickel ammine complex salt solution for 16 hours to support 4% by weight of nickel as nickel oxide. The carrier carrying nickel is air-dried,
Next, it was calcined at 550° C. and then immersed in a 3N aqueous ammonium molybdate solution to support 14% by weight of molybdenum as molybdenum oxide. This was air-dried and then calcined at 550°C to obtain a catalyst. This will be referred to as catalyst X. The physical properties of this catalyst are shown below. Physical properties Specific surface area (m 2 /g) 265 Bulk density (g/ml) 0.72 Side fracture strength (Kg/mm) 1.6 Catalyst particle diameter (longest) (mm) 1.6 Pore volume (ml/g) Pore diameter 30Å Less than 0.002 30-100Å 0.389 100-300Å 0.072 0-150Å 0.0425 0-300Å 0.463 Less than 600Å (Nitrogen gas adsorption method) 0.525 150-150000Å (Mercury intrusion method) 0.021 150-2000Å (Mercury intrusion method) 0.008 PV (30~100 ) / PV (0 to 150) × 100 91.5 PV (100 to 300) / PV (0 to 300) × 100 15.3 Catalysts N to U of Examples 5 to 12 were prepared using experimentally produced silica alumina supports, For example, catalyst P of Example 7 with a silica content of 10% by weight had the following physical properties. Physical properties Specific surface area (m 2 /g) 219 Bulk density (g/ml) 0.70 Side fracture strength (Kg/mm) 1.5 Catalyst particle diameter (longest) (mm) 1.5 Pore volume (ml/g) Pore diameter 30Å 0.058 30~100Å 0.189 100~300Å 0.118 0~150Å 0.284 0~300Å 0.365 600Å or less 0.517 150~150000Å 0.026 150~2000Å 0.013 PV (30~100)/PV (0~15 0)×100 66.5 PV(100~300) /PV(0~300)×100 32.3 Looking at Table 3, it can be seen that catalyst
It can be seen that the catalyst P has a better desulfurization rate and denitrification rate than catalyst P having other pore distributions. Example 15 9.7 g of cobalt nitrate and 1.4 g of nickel nitrate were dissolved in 70 ml of distilled water, and 80 ml of ammonia was added to this.
was added to obtain a cobalt/nickel mixed ammine complex salt solution. 50 g of a silica-alumina carrier containing 10% by weight of silica was immersed in this solution for 16 hours to support 3.5% by weight and 0.5% by weight of cobalt and nickel as oxides, respectively. After air-drying and calcination, it was immersed in a 3N ammonium molybdate aqueous solution to support 14% by weight of molybdenum as an oxide, yielding catalyst Y.
【表】
実施例 16〜26
水素化活性金属の担持量を変え、水素化活性金
属の担持量と触媒活性との関係を調べた。その結
果を表４に示す。表４から、本発明において第
族金属の担持量は0.5〜20重量％、第Ｂ族金属
の担持量は５〜30重量％がより有効であることが
分る。[Table] Examples 16 to 26 The amount of hydrogenation-active metal supported was varied and the relationship between the amount of hydrogenation-active metal supported and catalytic activity was investigated. The results are shown in Table 4. Table 4 shows that in the present invention, it is more effective to carry the group metal in an amount of 0.5 to 20% by weight, and to carry the group B metal in an amount of 5 to 30% by weight.
【表】
実施例 27
前記触媒Ｙを使用して中東系原油の常圧軽油留
分を原料油にして以下の反応条件で水素化処理を
行なつたところ良好な結果を得た。
反応条件
反応温度（℃） 300
反応圧力（Kg／cm3Ｇ） 10
液空間速度（Ｖ／Ｈ／Ｖ） 0.8
水素対原料油の流量比（SCF／Ｂ） 800
原料油性状
比 重15／４℃ 0.8437
イオウ含有量（重量％） 1.07
窒素含有量（ppm） 58[Table] Example 27 Good results were obtained when hydrogenation treatment was carried out using the above-mentioned catalyst Y and the atmospheric pressure gas oil fraction of Middle Eastern crude oil as a feedstock under the following reaction conditions. Reaction conditions Reaction temperature (℃) 300 Reaction pressure (Kg/cm 3 G) 10 Liquid hourly space velocity (V/H/V) 0.8 Hydrogen to feedstock flow rate ratio (SCF/B) 800 Feedstock oil property ratio Gravity 15/4 °C 0.8437 Sulfur content (wt%) 1.07 Nitrogen content (ppm) 58
第１図〜第３図は、シリカアルミナ担体を使用
し、本発明の方法に従いイオン交換法による第１
ステツプ処理後の酸化コバルトの担持状態を示す
ための昇温還元法に基づく分析結果を示すグラフ
である。第４図及び第５図は、アルミナ担体を使
用し、イオン交換法によりコバルトを担持させた
触媒の酸化コバルトの担持状態を示すための昇温
還元法に基づく分析結果を示すグラフである。第
６図は、シリカアルミナ担体を使用し、含浸法に
よる第１ステツプ処理後の酸化コバルトの担持状
態を示すための昇温還元法に基づく分析結果を示
すグラフである。
Figures 1 to 3 show the results of the first ion-exchange process using a silica-alumina support and according to the method of the present invention.
2 is a graph showing analysis results based on a temperature programmed reduction method to show the supported state of cobalt oxide after step treatment. FIGS. 4 and 5 are graphs showing analysis results based on a temperature programmed reduction method to show the state of cobalt oxide supported on a catalyst in which cobalt was supported by an ion exchange method using an alumina carrier. FIG. 6 is a graph showing the analysis results based on the temperature programmed reduction method to show the supported state of cobalt oxide after the first step treatment by the impregnation method using a silica alumina carrier.
Claims (1)
ナ含有物を使用し、該担体を、先ず元素周期表第
族金属の群から選択される一種又は二種以上の
金属アンミン錯塩溶液中に浸漬し、該金属をイオ
ン交換法にて担持させ、次で風乾及び焼成した後
更に元素周期表第Ｂ族金属の群から選択される
一種又は二種以上の金属の可溶性塩の溶液中に浸
漬し、該金属を含浸法で更に担持させて成る水素
化触媒の製造法。 ２ 元素周期表第族金属はニツケル及びコバル
トから成り、元素周期表第Ｂ族金属はモリブデ
ン及びタングステンから成る特許請求の範囲第１
項記載の方法。 ３ 担体はシリカを２〜35重量％含有して成る特
許請求の範囲第１項記載の方法。 ４ 担体はシリカを５〜30重量％含有して成る特
許請求の範囲第１項記載の方法。 ５ 担体はシリカを７〜12重量％含有して成る特
許請求の範囲第１項記載の方法。 ６ 元素周期表第族金属は酸化物として0.5〜
20重量％含有され、元素周期表第Ｂ族金属は酸
化物として５〜30重量％含有するようにした特許
請求の範囲第３項、第４項又は第５項記載の方
法。 ７ 元素周期表第族金属は酸化物として１〜８
重量％含有され、元素周期表第Ｂ族金属は酸化
物として８〜25重量％含有するようにした特許請
求の範囲第３項、第４項又は第５項記載の方法。 ８ 元素周期表第族金属は酸化物として２〜５
重量％含有され、元素周期表第Ｂ族金属は酸化
物として15〜20重量％含有するようにした特許請
求の範囲第３項、第４項又は第５項記載の方法。[Scope of Claims] 1. A silica-alumina or silica-alumina-containing material is used as a carrier, and the carrier is first immersed in a solution of one or more metal ammine complex salts selected from the group of group metals of the periodic table of elements. The metal is supported by an ion exchange method, then air-dried and calcined, and then immersed in a solution of a soluble salt of one or more metals selected from the group B metals of the periodic table of the elements. , a method for producing a hydrogenation catalyst comprising further supporting the metal by an impregnation method. 2. The metals of group B of the periodic table of the elements consist of nickel and cobalt, and the metals of group B of the periodic table of the elements consist of molybdenum and tungsten.
The method described in section. 3. The method according to claim 1, wherein the carrier contains 2 to 35% by weight of silica. 4. The method according to claim 1, wherein the carrier contains 5 to 30% by weight of silica. 5. The method according to claim 1, wherein the carrier contains 7 to 12% by weight of silica. 6 Group metals of the Periodic Table of Elements are 0.5~ as oxides.
The method according to claim 3, 4 or 5, wherein the metal of Group B of the Periodic Table of Elements is contained in an amount of 5 to 30% by weight as an oxide. 7 Group metals of the periodic table of elements are 1 to 8 as oxides.
The method according to claim 3, 4 or 5, wherein the metal of group B of the periodic table is contained in an amount of 8 to 25% by weight as an oxide. 8 Group metals of the Periodic Table of Elements are 2 to 5 as oxides.
5. The method according to claim 3, 4 or 5, wherein the Group B metal of the periodic table of elements is contained in an amount of 15 to 20% by weight as an oxide.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59081961A JPS60225645A (en) | 1984-04-25 | 1984-04-25 | Preparation of hydrogenating treatment catalyst |
| JP59133072A JPS6115739A (en) | 1984-04-25 | 1984-06-29 | Hydrogenating-treatment catalyst |
| CA000479461A CA1249570A (en) | 1984-04-25 | 1985-04-18 | Hydrotreating catalyst and process of manufacture |
| EP85302790A EP0160475B1 (en) | 1984-04-25 | 1985-04-22 | Hydrotreating catalyst and process of manufacture |
| DE8585302790T DE3583356D1 (en) | 1984-04-25 | 1985-04-22 | HYDROGEN TREATMENT CATALYST AND METHOD FOR PRODUCING THE SAME. |
| ES542525A ES8608567A1 (en) | 1984-04-25 | 1985-04-24 | Hydrotreating catalyst and process of manufacture. |
| AU41693/85A AU570794B2 (en) | 1984-04-25 | 1985-04-24 | Hydrotreating catalyst and process of manufacture |
| NO851641A NO851641L (en) | 1984-04-25 | 1985-04-24 | HYDRO-TREATMENT CATALYST AND PREPARATION thereof |
| FI851626A FI851626L (en) | 1984-04-25 | 1985-04-24 | VAETEBEHANDLINGSKATALYT OCH DESS FRAMSTAELLNINGSMETOD. |
| AR30020085A AR241872A1 (en) | 1984-04-25 | 1985-04-25 | A hydro-treatment catalyst and the procedure for producing it. |
| KR1019850002793A KR850007568A (en) | 1984-04-25 | 1985-04-25 | Hydroprocessing catalyst and preparation method thereof |
| US07/084,467 US4837193A (en) | 1984-04-25 | 1987-08-10 | Hydrotreating catalyst and process of manufacture |
| JP4166874A JPH0772273B2 (en) | 1984-04-25 | 1992-06-01 | Hydroprocessing method for hydrocarbon oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59081961A JPS60225645A (en) | 1984-04-25 | 1984-04-25 | Preparation of hydrogenating treatment catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60225645A JPS60225645A (en) | 1985-11-09 |
| JPH0513706B2 true JPH0513706B2 (en) | 1993-02-23 |
Family
ID=13761097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59081961A Granted JPS60225645A (en) | 1984-04-25 | 1984-04-25 | Preparation of hydrogenating treatment catalyst |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS60225645A (en) |
| KR (1) | KR850007568A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0968764A4 (en) | 1997-11-18 | 2001-10-17 | Tonen Corp | Hydrotreating catalyst and processes for hydrotreating hydrocarbon oil with the same |
| JP4930741B2 (en) * | 2001-03-21 | 2012-05-16 | 荒川化学工業株式会社 | Method for producing hydrogenated petroleum resin and hydrogenation catalyst used in the production method |
-
1984
- 1984-04-25 JP JP59081961A patent/JPS60225645A/en active Granted
-
1985
- 1985-04-25 KR KR1019850002793A patent/KR850007568A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR850007568A (en) | 1985-12-07 |
| JPS60225645A (en) | 1985-11-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |