JPH06198184A - Production of hydrodesulfurization catalyst - Google Patents
Production of hydrodesulfurization catalystInfo
- Publication number
- JPH06198184A JPH06198184A JP4361064A JP36106492A JPH06198184A JP H06198184 A JPH06198184 A JP H06198184A JP 4361064 A JP4361064 A JP 4361064A JP 36106492 A JP36106492 A JP 36106492A JP H06198184 A JPH06198184 A JP H06198184A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- gel
- aluminum
- periodic table
- hydrodesulfurization
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 230000000737 periodic effect Effects 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 15
- 230000023556 desulfurization Effects 0.000 claims abstract description 15
- -1 aluminum alkoxide Chemical class 0.000 claims abstract description 13
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000013522 chelant Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims description 38
- 239000004480 active ingredient Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 abstract description 44
- 239000000843 powder Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000010304 firing Methods 0.000 abstract description 9
- 150000002739 metals Chemical class 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- HJWSYAYJPBVLQT-UHFFFAOYSA-M aluminum butan-1-olate 3-oxobutanoate Chemical compound [Al+3].CCCC[O-].CCCC[O-].CC(=O)CC([O-])=O HJWSYAYJPBVLQT-UHFFFAOYSA-M 0.000 description 1
- KEBBHXFLBGHGMA-UHFFFAOYSA-K aluminum;4-ethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O KEBBHXFLBGHGMA-UHFFFAOYSA-K 0.000 description 1
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
- BHGPTGSAHKMFSZ-UHFFFAOYSA-M aluminum;octadecanoate;oxygen(2-) Chemical compound [O-2].[Al+3].CCCCCCCCCCCCCCCCCC([O-])=O BHGPTGSAHKMFSZ-UHFFFAOYSA-M 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 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
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、従来の水素化脱硫触媒
に比べて、脱硫活性が飛躍的に向上した炭化水素油用水
素化脱硫触媒を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrodesulfurization catalyst for hydrocarbon oil, which has a drastically improved desulfurization activity as compared with conventional hydrodesulfurization catalysts.
【０００２】[0002]
【従来の技術】炭化水素油は、一般に硫黄化合物を含
み、それらの油を燃料として使用した場合には、硫黄化
合物中に存在する硫黄が、硫黄酸化物に転化して大気中
に排出される。このような硫黄化合物を含む炭化水素油
は、燃焼した場合の大気汚染を考慮すれば、硫黄含有量
ができるだけ少ないことが望ましい。この硫黄含有量の
低減化は、炭化水素油を接触水素化脱硫することによっ
て達成することができる。2. Description of the Related Art Hydrocarbon oils generally contain sulfur compounds, and when these oils are used as fuel, the sulfur present in the sulfur compounds is converted into sulfur oxides and discharged into the atmosphere. . It is desirable that the hydrocarbon oil containing such a sulfur compound has as low a sulfur content as possible in consideration of air pollution when burned. This reduction in sulfur content can be achieved by catalytically hydrodesulfurizing hydrocarbon oils.
【０００３】最近、酸性雨あるいは窒素酸化物や硫黄酸
化物などに起因する環境問題が地球的規模で取り上げら
れ、現状の技術レベル以上での硫黄分の除去が望まれて
いる。炭化水素油中の硫黄分をより低下させることは、
炭化水素油の接触水素化脱硫反応の際の運転条件、例え
ば、ＬＨＳＶ、温度、圧力を過酷にすることで、ある程
度達成することができる。しかし、このような技法で
は、反応に用いる装置をより耐圧性のものに増強する必
要があるのみならず、触媒上に炭素質が析出し、触媒の
活性を急速に低下させる。特に、炭化水素油が軽質留分
の場合、色相安定性や貯蔵安定性などの性状面での悪影
響も大きい。このように、運転条件での深度な脱硫に
は、限度がある。したがって、最も良い方策は、格段に
優れた脱硫活性を有する触媒を開発することである。Recently, environmental problems caused by acid rain, nitrogen oxides, sulfur oxides, etc. have been taken up on a global scale, and it has been desired to remove sulfur components at a level higher than the current technical level. To further reduce the sulfur content in hydrocarbon oils,
It can be achieved to some extent by making the operating conditions in the catalytic hydrodesulfurization reaction of hydrocarbon oil, for example, LHSV, temperature and pressure severe. However, in such a technique, not only the apparatus used for the reaction needs to be increased in pressure resistance, but also carbonaceous matter is deposited on the catalyst, which rapidly reduces the activity of the catalyst. In particular, when the hydrocarbon oil is a light fraction, it has great adverse effects on properties such as hue stability and storage stability. Thus, there is a limit to deep desulfurization under operating conditions. Therefore, the best strategy is to develop a catalyst with significantly better desulfurization activity.
【０００４】ところで、従来、水素化脱硫触媒を調製す
る一般的な方法として、（１）周期律表第ＶＩＩＩ族金
属塩、およびＣｒやＭｏなどの周期律表第ＶＩＢ族金属
塩の水溶液を担体に含浸させた後、乾燥し、焼成する
「含浸法」、（２）アルミナあるいはアルミナゲルを分
散した水溶液中に、周期律表第ＶＩＢ族金属塩および周
期律表第ＶＩＩＩ族金属塩の水溶液を加え、金属化合物
を沈澱させる「共沈澱法」、（３）アルミナあるいはア
ルミナゲル、周期律表第ＶＩＢ族金属塩および周期律表
第ＶＩＩＩ族金属塩の水溶液の混合ペーストを混練しな
がら加熱し、水分除去を行う「混練法」、がある（「触
媒調製化学」尾崎萃編、講談社サイエンティフィック、
２０５頁〜２５２頁）。By the way, conventionally, as a general method for preparing a hydrodesulfurization catalyst, (1) a metal salt of Group VIII of the Periodic Table and an aqueous solution of a metal salt of Group VIB of the Periodic Table such as Cr and Mo are used as a carrier. "Impregnation method" of impregnating with, drying and calcining, (2) Aqueous solution of Group VIB of the periodic table and Group VIII metal salt of the periodic table in an aqueous solution in which alumina or alumina gel is dispersed. In addition, “coprecipitation method” for precipitating a metal compound, (3) heating while mixing a mixed paste of an aqueous solution of alumina or alumina gel, Group VIB metal salt of the periodic table and Group VIII metal salt of the periodic table, There is a “kneading method” for removing water (“Catalyst Preparation Chemistry” edited by Kan Ozaki, Kodansha Scientific,
205-252).
【０００５】しかし、これらの方法では、比較的多量の
金属化合物を分散良く担体上に担持させることが困難で
ある。たとえ過剰の触媒金属化合物を担体に担持させる
ことができたとしても、これらの方法では、触媒の比表
面積を減少させるため、触媒の脱硫活性向上に限界があ
る。However, according to these methods, it is difficult to support a relatively large amount of metal compound on a carrier with good dispersion. Even if an excessive amount of the catalytic metal compound can be supported on the carrier, these methods reduce the specific surface area of the catalyst, and therefore, there is a limit in improving the desulfurization activity of the catalyst.
【０００６】そこで、本発明者らは、接触水素化脱硫反
応の際の運転条件の過酷度を上げることなく、生成油の
硫黄含有量を、例えば、軽油で０．０５ｗｔ％程度、Ｖ
ＧＯで０．０８〜０．１０ｗｔ％程度、常圧残油で０．
６〜０．８ｗｔ％程度にまで低減することのできる水素
化脱硫触媒として、先の出願において、第ＶＩＩＩ族金
属、第ＶＩＢ金属およびアルミニウムを含む金属酸化物
の複合物であって、その金属量が従来の水素化脱硫触媒
に比して、はるかに高い触媒と、その製造法とを提案し
た（特開昭３−２７５１４２号公報参照−以下、この提
案を「先願」と記す−）。この触媒は、Ｘ線回折パター
ンにおいて実質的にγ−Ａｌ２Ｏ３のピークを示さず、
また活性金属を多量に含有するにもかかわらず、高い表
面積をも有するため、運転条件を過酷にすることなく、
通常の運転条件下で、極めて高い脱硫活性を示す。[0006] Therefore, the inventors of the present invention have determined that the sulfur content of the produced oil is, for example, about 0.05 wt% of diesel oil, V without increasing the severity of the operating conditions during the catalytic hydrodesulfurization reaction.
About 0.08 to 0.10 wt% for GO, and 0.1% for atmospheric residual oil.
As a hydrodesulfurization catalyst that can be reduced to about 6 to 0.8 wt%, in the previous application, a composite of a metal oxide containing a Group VIII metal, a VIB metal and aluminum, the metal content of which is Proposed a catalyst much higher than the conventional hydrodesulfurization catalyst and a method for producing the same (see JP-A-3-275142-hereinafter, this proposal is referred to as "prior application"). This catalyst shows substantially no γ-Al 2 O 3 peak in the X-ray diffraction pattern,
In addition, even though it contains a large amount of active metal, it also has a high surface area, so without making the operating conditions severe,
It exhibits extremely high desulfurization activity under normal operating conditions.
【０００７】[0007]
【発明が解決しようとする課題】しかし、上記した先願
の方法で水素化脱硫触媒を製造すると、ゲルを焼成する
際に、ゲルより溶媒などの揮発性成分や低沸点成分が蒸
発し、爆発や火災の原因となったり、触媒の製造環境を
汚染するなどの問題を生じることがある。また、製造さ
れる触媒は、焼成前の条件（特に、乾燥《脱溶剤》条
件）次第で、細孔容積が約０．４ｃｃ／ｇ以下、側面破
壊強度が約１．０ポンド（以下、「Ｌｂｓ」と記す）／
ｍｍ以下となるのみならず、成形性が低下して押出しに
よる成形が不可能になるなどの問題が生じることもあ
る。その原因としては、生成した有効成分（スラリー）
を乾燥させてゲル化する段階において、焼成重量減少率
（以下、「ＬＯＩ」と記す）を調節するのが困難である
ことが考えられる。However, when the hydrodesulfurization catalyst is produced by the above-mentioned method of the prior application, when the gel is fired, volatile components such as a solvent and low-boiling components evaporate from the gel and explode. It may cause a fire or cause problems such as polluting the catalyst production environment. Further, the produced catalyst has a pore volume of about 0.4 cc / g or less and a side fracture strength of about 1.0 lb (hereinafter, referred to as " Lbs ”) /
Not only is it less than mm, but there is also a problem that the moldability is lowered and molding by extrusion becomes impossible. The cause is generated active ingredient (slurry)
It is considered difficult to control the baking weight loss rate (hereinafter referred to as “LOI”) in the step of drying and gelling.
【０００８】すなわち、触媒の細孔容積、あるいは側面
破壊強度などの触媒強度は、焼成により揮発性成分や低
沸点成分が消失する量の影響を受け、ゲルの成形性は、
該ゲル中に存在している揮発性成分や低沸点成分の量に
依存すると推測される。したがって、良好な物性、延い
ては高い脱硫活性を有する触媒を得るには、焼成前の原
料において、揮発性成分や低沸点成分の量、言い換えれ
ばＬＯＩが適性な値となっていることが必要となる。That is, the pore volume of the catalyst or the catalyst strength such as lateral fracture strength is influenced by the amount of volatile components and low-boiling components disappeared by calcination, and the gel moldability is
It is presumed that it depends on the amounts of volatile components and low-boiling components present in the gel. Therefore, in order to obtain a catalyst having good physical properties and, by extension, high desulfurization activity, it is necessary that the amount of volatile components and low-boiling components, that is, LOI, be an appropriate value in the raw material before calcination. Becomes
【０００９】そこで、本発明者らは、ＬＯＩを適性なも
のとすることにより、前述した先願の脱硫触媒を、良好
な物性を有して、したがって高い脱硫活性を有して、安
定して製造することのできる方法を、別途提案している
（同日付け特許出願の「炭化水素油用水素化脱硫触媒の
製法」参照−以下、この提案を「別途提案」と記す
−）。Therefore, the present inventors have made the LOI suitable so that the desulfurization catalyst of the above-mentioned prior application has good physical properties, and therefore has a high desulfurization activity and is stable. A method that can be produced is separately proposed (see "Production method of hydrodesulfurization catalyst for hydrocarbon oil" in the patent application dated on the same day-hereinafter, this proposal is referred to as "separate proposal").
【００１０】この別途提案では、ＬＯＩを適性にするた
めの手法として、前記した有効成分（スラリー）を乾燥
させてゲル化する際の乾燥度合、言い換えれば、溶媒
（有機溶剤や水）の除去程度や、溶媒に溶解している揮
発性成分や低沸点成分の除去程度を調整する手法を採用
している。In this separate proposal, as a method for making the LOI suitable, the degree of drying when the above-mentioned active ingredient (slurry) is dried and gelled, in other words, the removal degree of the solvent (organic solvent or water) Alternatively, a method of adjusting the degree of removal of volatile components and low boiling components dissolved in a solvent is adopted.
【００１１】ただし、この乾燥度合を調整する手法にお
いては、次のようなことが懸念される。例えば、上記の
スラリーを濾過濃縮した後、風乾や加熱により乾燥度合
を調整する方法を採用する場合は、ゲルの表面は早期に
乾燥して適性なＬＯＩとなっていても、ゲルの内部では
乾燥が不十分で、ゲル全体としては適性なＬＯＩになっ
ておらず、これをさらに風乾しようとしても、表面が乾
燥しているため、内部の乾燥が不可能となることがあ
る。また、他の調整法を採用する場合にあっては、運転
条件を微調整する必要が生じることがあり、操作性を困
難にする。However, in the method of adjusting the degree of dryness, there is a concern as follows. For example, when the method of adjusting the degree of dryness by air-drying or heating after filtering and concentrating the above-mentioned slurry, even if the surface of the gel is dried early to have an appropriate LOI, the inside of the gel is dried. Is insufficient and the gel does not have an appropriate LOI as a whole, and even if it is air-dried further, the inside may not be dried because the surface is dried. Further, in the case of adopting another adjustment method, it may be necessary to finely adjust the operating conditions, which makes operability difficult.
【００１２】本発明は、以上の諸点を考慮してなされた
もので、より簡単な操作で、容易に適性なＬＯＩを確実
に得ることができ、この結果として、前述した先願の脱
硫触媒を良好な物性、延いては高い脱硫活性を有して、
安定して製造することのできる方法を提案することを目
的とする。The present invention has been made in consideration of the above points, and it is possible to easily and surely obtain a suitable LOI by a simpler operation. As a result, the desulfurization catalyst of the above-mentioned prior application can be obtained. It has good physical properties and, by extension, high desulfurization activity,
It is intended to propose a method that can be stably manufactured.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、上記目的
を達成するために、検討を重ねた結果、（１）脱硫用触
媒などとして使用される複合酸化物系触媒においては、
該触媒の製造工程で派生的に生じる触媒粉末を、該粉末
の処理の容易化と、材料コストの低減とを目的として、
原料に混合している事実があることに着目し、（２）前
述した先願の水素化脱硫触媒の製造工程で生じる触媒粉
末を、該触媒焼成前のゲルに混合してみたところ、意外
にも、該触媒粉末の添加量を調整するのみで、ＬＯＩの
調整が極めて容易に行うことができるとの知見を得た。The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, (1) in a complex oxide catalyst used as a desulfurization catalyst or the like,
The catalyst powder derived from the manufacturing process of the catalyst is used for the purpose of facilitating the treatment of the powder and reducing the material cost.
Paying attention to the fact that it is mixed with the raw material, (2) When the catalyst powder produced in the manufacturing process of the hydrodesulfurization catalyst of the above-mentioned prior application was mixed with the gel before the catalyst was calcined, it was unexpectedly found. Also, it was found that the LOI can be adjusted extremely easily only by adjusting the addition amount of the catalyst powder.
【００１４】本発明は、この知見に基づいてなされたも
ので、（ａ）アルミニウムアルコキシド、アルミニウム
キレート化合物、環状アルミニウムオリゴマーのうちの
少なくとも１つと、（ｂ）周期律表第ＶＩＢ族金属の少
なくとも１種と、（ｃ）周期律表第ＶＩＩＩ族金属の少
なくとも１種との混合物を溶媒中において混合し、この
混合によって生じる有効成分を乾燥してゲルとし、これ
を焼成して、周期律表第ＶＩＢ族金属、周期律表第ＶＩ
ＩＩ族金属およびアルミニウムを含む複合酸化物からな
る水素化脱硫触媒を製造する方法であって、前記の焼成
前のゲルに、焼成後の水素化脱硫触媒を添加した後、焼
成することを特徴とする水素化脱硫触媒の製造法を要旨
とする。The present invention has been made based on this finding, and comprises (a) at least one of an aluminum alkoxide, an aluminum chelate compound and a cyclic aluminum oligomer, and (b) at least one of Group VIB metals of the periodic table. A mixture of the seed and (c) at least one Group VIII metal in the Periodic Table is mixed in a solvent, and the active ingredient produced by this mixing is dried to a gel, which is then calcined to give a gel. Group VIB metal, Periodic Table VI
A method for producing a hydrodesulfurization catalyst comprising a composite oxide containing a Group II metal and aluminum, comprising adding the hydrodesulfurization catalyst after firing to the gel before firing and then firing. The gist is a method for producing a hydrodesulfurization catalyst.
【００１５】本発明の製造方法においては、上記の
（ａ），（ｂ），（ｃ）成分を溶媒中にて混合し、その
有効成分を乾燥し、さらに焼成するもので、これにより
製造される触媒は、実質上周期律表第ＶＩＢ族金属、周
期律表第ＶＩＩＩ族金属およびアルミニウムよりなる複
合酸化物である。上記（ａ），（ｂ），（ｃ）の３成分
の混合は、これらの３成分の１種または２種を含む２種
または３種の原料溶液を混合することが好ましく、その
態様としては、例えば、後述する「Ａ法」〜「Ｄ法」な
どがある。なお、上記（ｂ），（ｃ）の２成分の化合物
は、原料溶液の調製に用いる溶媒（水または有機溶媒）
に可溶なものであればどのような化合物でもよい。In the production method of the present invention, the above-mentioned components (a), (b) and (c) are mixed in a solvent, the active ingredient thereof is dried and further calcined. The catalyst is a composite oxide consisting essentially of Group VIB metal of the periodic table, Group VIII metal of the periodic table, and aluminum. The mixing of the three components (a), (b), and (c) is preferably performed by mixing two or three raw material solutions containing one or two of these three components. For example, there are "Method A" to "Method D" which will be described later. The two-component compounds of (b) and (c) above are the solvent (water or organic solvent) used for preparing the raw material solution.
Any compound may be used as long as it is soluble in.
【００１６】「Ａ法」：先ず、上記（ａ）成分と上記
（ｂ）成分とを、これらを溶解し得る有機溶媒に溶解し
た溶液を、一定時間混合攪拌し、均一溶液とする。次い
で、この均一溶液に上記（ｃ）成分の水溶液を加えて混
合し、これによって生じる有効成分を乾燥し、焼成す
る。[Method A]: First, a solution prepared by dissolving the above-mentioned component (a) and the above-mentioned component (b) in an organic solvent capable of dissolving them is mixed and stirred for a certain period of time to form a uniform solution. Then, the aqueous solution of the component (c) is added to and mixed with the homogeneous solution, and the active ingredient thus produced is dried and calcined.
【００１７】「Ｂ法」：先ず、上記（ａ）成分と上記
（ｃ）成分とを、これらを溶解し得る有機溶媒に溶解し
た溶液を、一定時間混合攪拌し、均一溶液とする。次い
で、この均一溶液に上記（ｂ）成分の水溶液を加えて混
合し、これによって生じる有効成分を乾燥し、焼成す
る。"Method B": First, a solution prepared by dissolving the above-mentioned component (a) and the above-mentioned component (c) in an organic solvent capable of dissolving them is mixed and stirred for a certain period of time to form a uniform solution. Then, the aqueous solution of the above-mentioned component (b) is added to and mixed with this homogeneous solution, and the active ingredient thus produced is dried and calcined.
【００１８】「Ｃ法」：（ａ）成分を、これを溶解し得
る有機溶媒に溶解した溶液に（ｂ）成分と（ｃ）成分の
混合水溶液を加えて混合し、これによって生じる有効成
分を乾燥し、焼成する。"Method C": The component (a) is mixed with a solution prepared by dissolving the component (a) in an organic solvent capable of dissolving the component (b) and the component (c), and the resulting mixture is mixed with the active ingredient. Dry and bake.
【００１９】「Ｄ法」：先ず、（ａ）成分と（ｂ）成分
と（ｃ）成分とを、これらを溶解し得る有機溶媒に溶解
した溶液を、一定時間混合攪拌し、均一溶液とする。次
いで、この均一溶液に水を加えて混合し、これにより生
じる有効成分を乾燥し、焼成する。[Method D]: First, a solution prepared by dissolving the components (a), (b) and (c) in an organic solvent capable of dissolving them is mixed and stirred for a certain period of time to form a uniform solution. . Next, water is added to this homogeneous solution and mixed, and the active ingredient thus produced is dried and calcined.
【００２０】本発明においては、アルミニウムアルコキ
シド、アルミニウムキレート化合物、環状アルミニウム
オリゴマーの少なくとも１つを必須成分（すなわち、
（ａ）成分、以下、「アルミニウム成分」と記すことも
ある）として用いるが、これらのアルミニウム成分の１
部に代えて、ケイ素、チタン、ジルコニウム、ホウ素、
ガリウム、マグネシウム、ハフニウムのアルコキシド、
キレート化合物、環状オリゴマー（以下、これらを「代
替成分」と記すこともある）から選ばれる少なくとも１
種を用いることもできる。その代替割合は、どのような
割合でもよいが、一般には、酸化物換算で、アルミニウ
ム成分９０〜９５重量部に対し、代替成分５〜１０重量
部がよい。In the present invention, at least one of aluminum alkoxide, aluminum chelate compound and cyclic aluminum oligomer is an essential component (ie,
(A) component, hereinafter also referred to as “aluminum component”), but one of these aluminum components is used.
Instead of parts, silicon, titanium, zirconium, boron,
Gallium, magnesium, hafnium alkoxide,
At least one selected from a chelate compound and a cyclic oligomer (hereinafter, these may be referred to as “substitute components”)
Seeds can also be used. The replacement ratio may be any ratio, but generally, 5 to 10 parts by weight of the replacement component is preferable with respect to 90 to 95 parts by weight of the aluminum component in terms of oxide.
【００２１】アルミニウムアルコキシドとしては、どの
ようなアルミニウムアルコキシドも使用可能であるが、
乾燥などの容易さからアルコキシ基の炭素数が１〜５の
アルコキシドが好ましい。具体的には、アルミニウムメ
トキシド、アルミニウムエトキシド、アルミニウムイソ
プロポキシド、アルミニウム−ｎ−ブトキシド、アルミ
ニウム−ｓｅｃ−ブトキシドなどを挙げることができ
る。これらのアルミニウムアルコキシドは、チーグラー
法により調製したものを用いることができる。Any aluminum alkoxide can be used as the aluminum alkoxide.
An alkoxide having 1 to 5 carbon atoms in the alkoxy group is preferred because it is easy to dry. Specific examples include aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-sec-butoxide and the like. As these aluminum alkoxides, those prepared by the Ziegler method can be used.
【００２２】アルミニウムキレート化合物としては、市
販品のアルミニウムエチルアセトアセテートジイソプロ
ピレート、アルミニウムアセトアセテートジブトキシ
ド、アルミニウムトリス（アセチルアセトネート）、ア
ルミニウムビスエチルアセトアセテートモノアセチルア
セトネートなどが使用できる。Commercially available aluminum ethyl acetoacetate diisopropylate, aluminum acetoacetate dibutoxide, aluminum tris (acetylacetonate), aluminum bisethylacetoacetate monoacetylacetonate and the like can be used as the aluminum chelate compound.
【００２３】環状アルミニウムオリゴマーは、公知の方
法、例えば、アルミニウムアルコキシドを部分的に加水
分解することなどにより得ることができる。このように
して得られる環状アルミニウムオリゴマーは、一般に、
環状アルミニウムオキサイドアルキレートと呼ばれ、化
１の一般式で示される。The cyclic aluminum oligomer can be obtained by a known method, for example, by partially hydrolyzing an aluminum alkoxide. The cyclic aluminum oligomer thus obtained is generally
It is called a cyclic aluminum oxide alkylate and is represented by the general formula of Chemical formula 1.
【００２４】[0024]
【化１】 [Chemical 1]
【００２５】化１の式において、Ｒはアルキル基であ
り、炭素数２〜４のアルキル基が好ましく、特にイソプ
ロピル基であることが好ましい。In the formula (1), R is an alkyl group, preferably an alkyl group having 2 to 4 carbon atoms, and particularly preferably an isopropyl group.
【００２６】化１の一般式で示される環状アルミニウム
オキサイドアルキレートは、さらにステアリン酸などの
種々の脂肪酸と反応させると、化２の一般式で示される
脂肪酸型となった環状アルミニウムオリゴマーとするこ
とができる。When the cyclic aluminum oxide alkylate represented by the general formula of Chemical formula 1 is further reacted with various fatty acids such as stearic acid, the cyclic aluminum oxide alkylate becomes a fatty acid type cyclic aluminum oligomer represented by the general formula of Chemical formula 2. You can
【００２７】[0027]
【化２】 [Chemical 2]
【００２８】化２の式において、Ｒ′は１価の脂肪族炭
化水素基であり、好ましくは炭素数１３〜１９の１価の
脂肪族炭化水素基であり、特に炭素数１７の１価の脂肪
族炭化水素基が好ましく、これは一般に環状アルミニウ
ムオキサイドステアレートと呼ばれている。In the formula (2), R'is a monovalent aliphatic hydrocarbon group, preferably a monovalent aliphatic hydrocarbon group having 13 to 19 carbon atoms, and particularly a monovalent aliphatic hydrocarbon group having 17 carbon atoms. Aliphatic hydrocarbon groups are preferred and are commonly referred to as cyclic aluminum oxide stearate.
【００２９】本発明の（ｂ）成分である周期律表第ＶＩ
Ｂ族金属は、好ましくはクロム、モリブデン、タングス
テンであり、さらに好ましくはモリブデン、タングステ
ンを用いる。これらの第ＶＩＢ族金属の化合物は、前述
のとおり、有機溶媒または水に可溶であることが必要で
あり、例えば、硝酸塩、塩化物、酢酸塩、アルコキシ
ド、アセチルアセトナート、これら金属の酸のアンモニ
ウム塩などが用いられる。なお、第ＶＩＢ族金属化合物
を水溶液として用いる場合には、例えば、パラモリブデ
ン酸アンモニウム、重クロム酸アンモニウム、パラタン
グステン酸アンモニウムなどをイオン交換水に溶解させ
たものが好ましい。Periodic table VI of the component (b) of the present invention
The Group B metal is preferably chromium, molybdenum or tungsten, more preferably molybdenum or tungsten. As described above, these Group VIB metal compounds must be soluble in an organic solvent or water, and examples thereof include nitrates, chlorides, acetates, alkoxides, acetylacetonates, and acids of these metals. An ammonium salt or the like is used. When the Group VIB metal compound is used as an aqueous solution, for example, ammonium paramolybdate, ammonium dichromate, and ammonium paratungstate are preferably dissolved in ion-exchanged water.
【００３０】本発明の（ｃ）成分である周期律表第ＶＩ
ＩＩ族金属は、鉄、コバルト、ニッケル、ルテニウム、
ロジウム、パラジウム、オスミウム、イリジウム、白金
の全てを用いることができるが、好ましくは鉄族金属の
コバルト、ニッケルを用いる。これらの第ＶＩＩＩ族金
属の化合物も、前述のとおり、有機溶媒または水に可溶
であることが必要であり、例えば、硝酸塩、塩化物、酢
酸塩、アルコキシド、アセチルアセトナート、これら金
属の酸のアンモニウム塩などが用いられる。なお、第Ｖ
ＩＩＩ族金属化合物を水溶液として用いる場合には、例
えば、硝酸コバルト６水和物、塩化コバルト６水和物、
硝酸ニッケル６水和物、塩化ニッケル６水和物などをイ
オン交換水に溶解させたものが好ましい。Periodic Table VI, which is the component (c) of the present invention
Group II metals include iron, cobalt, nickel, ruthenium,
Rhodium, palladium, osmium, iridium, and platinum can all be used, but iron group metals cobalt and nickel are preferably used. As described above, these Group VIII metal compounds also need to be soluble in organic solvents or water, and examples thereof include nitrates, chlorides, acetates, alkoxides, acetylacetonates, and acids of these metals. An ammonium salt or the like is used. The Vth
When the Group III metal compound is used as an aqueous solution, for example, cobalt nitrate hexahydrate, cobalt chloride hexahydrate,
It is preferable to dissolve nickel nitrate hexahydrate, nickel chloride hexahydrate and the like in ion-exchanged water.
【００３１】以上の（ａ），（ｂ），（ｃ）成分を溶解
させるための有機溶媒は、これらを均一溶液としたり、
後のゲル化などを円滑にするために用いられる。これら
の有機溶媒は、（ａ）〜（ｃ）成分を溶解し得るもので
あればよく、アルコール類、エーテル類、ケトン類、芳
香族類を用いることができ、好ましくは、アセトン、メ
タノール、エタノール、ｎ−プロパノール、ｉｓｏ−プ
ロパノール、ｎ−ブタノール、ｔｅｒｔ−ブタノール、
ｓｅｃ−ブタノール、ヘキサノール、ベンゼン、トルエ
ン、キシレン、ジエチルエーテル、テトラヒドロフラ
ン、ジオキサンなどが挙げられ、これらは単独で、また
は混合して使用することができる。なお、これらの有機
溶媒の使用量は、（ａ），（ｂ），（ｃ）各成分が溶解
するに十分な量であればよい。The above-mentioned organic solvents for dissolving the components (a), (b) and (c) are used as a homogeneous solution,
It is used to facilitate later gelation. Any of these organic solvents may be used as long as it can dissolve the components (a) to (c), and alcohols, ethers, ketones, and aromatics can be used, preferably acetone, methanol, and ethanol. , N-propanol, iso-propanol, n-butanol, tert-butanol,
Examples thereof include sec-butanol, hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane and the like, and these can be used alone or in a mixture. The amount of these organic solvents used may be an amount sufficient to dissolve the components (a), (b) and (c).
【００３２】前述のＡ法〜Ｄ法における（ａ）〜（ｃ）
成分の混合割合は、酸化物として触媒基準で、（ｂ）成
分は約１０〜６０重量％、好ましくは約３〜２０重量％
であり、（ｃ）成分は約３〜２０、好ましくは約５〜１
８重量％であり、（ａ）成分は、〔１００−（ｂ）成分
−（ｃ）成分〕重量％である。(A) to (c) in the above methods A to D
The mixing ratio of the components is about 10 to 60% by weight, and preferably about 3 to 20% by weight of the component (b) as an oxide.
And the component (c) is about 3-20, preferably about 5-1.
8% by weight, and the component (a) is [100- (b) component- (c) component]% by weight.
【００３３】なお、以上のＡ法〜Ｄ法において、各種の
有機溶媒混合液に（ｂ），（ｃ）成分の水溶液を混合す
る場合、あるいは（ｂ），（ｃ）成分の水溶液を調製す
る場合、リン酸、硝酸、塩酸などの酸、好ましくはリン
酸を添加することにより、（ｂ），（ｃ）成分の溶解性
が良好となったり、製品触媒の強度が高められるなどの
効果を奏することができる。酸の添加量は、微量でよ
く、好ましくは、酸化物換算で、（ａ）成分からもたら
されるアルミナに対し、約０．５〜５重量％とすること
が適している。多すぎると、製品触媒の活性が低下する
のみならず、強度はそれほど向上せず、不経済となる。In the above methods A to D, when the aqueous solutions of the components (b) and (c) are mixed with various organic solvent mixed solutions, or the aqueous solutions of the components (b) and (c) are prepared. In this case, by adding an acid such as phosphoric acid, nitric acid or hydrochloric acid, preferably phosphoric acid, it is possible to improve the solubility of the components (b) and (c) and increase the strength of the product catalyst. Can play. The amount of the acid added may be very small, and is preferably about 0.5 to 5% by weight in terms of oxide, based on the alumina obtained from the component (a). If it is too large, not only the activity of the product catalyst is lowered, but also the strength is not improved so much, which is uneconomical.
【００３４】以上の（ａ）〜（ｃ）成分の混合方法は、
Ａ法〜Ｄ法において、通常の攪拌方法を用い、均一にな
るまで充分に攪拌すればよい。このときの温度条件は、
好ましくは約２０〜３００℃、さらに好ましくは約５０
〜２００℃であり、この程度の温度条件であれば、通
常、十数分〜約１時間の攪拌で均一溶液となる。The mixing method of the above components (a) to (c) is as follows:
In Method A to Method D, a conventional stirring method may be used and sufficient stirring may be performed until uniform. The temperature condition at this time is
Preferably about 20 to 300 ° C., more preferably about 50.
˜200 ° C. Under this temperature condition, a uniform solution is usually obtained by stirring for a few ten minutes to about 1 hour.
【００３５】なお、Ａ法〜Ｄ法において、各種の有機溶
媒混合液に（ｂ），（ｃ）成分の水溶液や水を添加する
場合は、好ましくは徐々に行い、さらに好ましくは滴下
による方法がよい。一度に添加すると、反応が十分に行
われず、したがって得られる触媒は、各々の金属酸化物
の分布が不均一となり好ましくない。In the methods A to D, when the aqueous solution of the components (b) and (c) or water is added to various organic solvent mixed liquids, it is preferably carried out gradually, more preferably by the dropping method. Good. If added all at once, the reaction is not sufficiently carried out, and thus the resulting catalyst is not preferable because the distribution of each metal oxide is non-uniform.
【００３６】以上のようにして（ａ）〜（ｃ）成分を溶
媒（有機溶媒や水）中で混合することにより、有効成分
が生成する。さらに攪拌を続けると、スラリー状とな
る。スラリー状となった有効成分を取り出す方法として
は、どのような方法でもよく、例えば、ロータリーエバ
ポレーターを用い、減圧下、約５０〜２００℃で溶媒を
除去し、ゲルを得る方法がある。また、濾紙による濾過
にて有効成分を取り出し、加熱濃縮してゲルを得る方法
などの公知の手段を用いることができる。By mixing the components (a) to (c) in a solvent (organic solvent or water) as described above, the active ingredient is produced. When the stirring is further continued, a slurry is formed. Any method may be used as a method for extracting the active ingredient in the form of a slurry, and for example, there is a method in which a solvent is removed under reduced pressure at about 50 to 200 ° C. using a rotary evaporator to obtain a gel. Further, a known means such as a method of obtaining a gel by extracting an active ingredient by filtration with a filter paper and concentrating it by heating can be used.
【００３７】上記のようにして得られたゲルに、焼成後
の触媒（説明の便宜上、以下、「焼成触媒」と記す）、
好ましくはその粉末を添加する。焼成触媒の粉末の添加
量は、添加した後のもののＬＯＩが約５５〜７５％、好
ましくは約５８〜６５％となるような量とすることがよ
く、具体的には、ゲルの乾燥度合によって多少異なる
が、上記のような有効成分の通常の取り出し方法で、か
つ通常採用されている条件で得られるゲルにおいては、
約２〜１０重量％、好ましくは約４〜７重量％とするこ
とが適している。すなわち、約２重量％未満であると、
ＬＯＩが約８０％より多くなってしまい、約１０重量％
より多いと、ＬＯＩが約５５％未満となってしまうから
である。On the gel obtained as described above, a catalyst after calcination (hereinafter, referred to as "calcination catalyst" for convenience of description),
Preferably the powder is added. The addition amount of the powder of the calcining catalyst may be such that the LOI of the powder after addition is about 55 to 75%, preferably about 58 to 65%. Specifically, it depends on the dryness of the gel. Although slightly different, in the gel obtained by the usual method for taking out the active ingredient as described above, and under the conditions usually adopted,
Suitably about 2-10% by weight, preferably about 4-7% by weight. That is, if it is less than about 2% by weight,
LOI is more than about 80%, about 10% by weight
This is because the LOI becomes less than about 55% when the amount is larger.
【００３８】なお、ＬＯＩは、実際には、焼成前のゲル
の重量α（本発明では、有効成分から得られるゲルの重
量α１と、添加した焼成触媒の粉末の重量α２との合計
量）と焼成後の製品触媒の重量βとから、ＬＯＩ＝１０
０−（β／α）×１００（％）の式により算出されるも
のである。したがって、本発明では、この式からＬＯＩ
が約５５〜８０％となるように、ゲルの重量α１に見合
った焼成触媒の粉末の重量α２を添加すればよく、この
重量α２が合計量αに対して約２〜１０重量％であるこ
とを意味している。The LOI is actually the weight α of the gel before calcination (in the present invention, the total amount of the weight α1 of the gel obtained from the active ingredient and the weight α2 of the powder of the added calcination catalyst). From the weight β of the product catalyst after calcination, LOI = 10
It is calculated by the formula of 0- (β / α) × 100 (%). Therefore, in the present invention, from this equation, the LOI
So as to be about 55-80%, the weight α2 of the powder of the calcining catalyst corresponding to the weight α1 of the gel may be added, and this weight α2 is about 2 to 10% by weight with respect to the total amount α. Means
【００３９】また、本発明において、ゲルのＬＯＩが、
別途提案のものよりやや高めの約５５〜８０％とする理
由は、焼成触媒の粉末が混合されることにより、ゲルの
成形性において、あるいは製品触媒の物性の発現性にお
いて、別途提案のものと若干異なる挙動を示すと推測さ
れるからである。因みに、後述の実施例（特に、図３）
に示すように、ゲルの成形性は、ゲルのＬＯＩが約５８
〜７０％の範囲内にある場合がかなり良好であり、製品
触媒の物性（表面積、細孔容積、側面破壊強度）は、ゲ
ルのＬＯＩが約５５〜８０％の範囲内にある場合が良好
となっている。In the present invention, the LOI of the gel is
The reason why the ratio is about 55 to 80%, which is slightly higher than that of the separately proposed one, is that the mixture of the powder of the calcined catalyst causes the gel moldability or the physical properties of the product catalyst to be expressed, and is differently proposed. This is because it is assumed that the behavior is slightly different. Incidentally, the embodiment described later (in particular, FIG. 3)
As shown in, the gel moldability is such that the gel LOI is about 58.
˜70% range is fairly good, and the physical properties of the product catalyst (surface area, pore volume, side rupture strength) are good when the LOI of the gel is in the range of about 55-80%. Has become.
【００４０】さらに、上記の焼成触媒としては、粉末状
のものが好ましく、本発明の製造方法で得られる製品触
媒を粉砕したものを使用してもよいし、この製品触媒を
得る工程あるいは先願や別途提案の製造工程で派生的に
生じる微粉末（例えば、ゲルを長尺紐状に成形し、これ
を焼成した後、破砕して適当な大きさのもののみを製品
触媒とするが、製品触媒になり得ないほど微細に破砕さ
れてしまったものなど）などを使用することもできる。
これら以外にも、（ａ）〜（ｃ）成分から得られる複合
酸化物からなる水素化脱硫触媒の粉末であれば、従来法
で得られる触媒あるいは市販の触媒などどのようなもの
も使用することができる。ただし、添加されるゲルから
得られる焼成触媒の組成に近似した組成を有する焼成触
媒の粉末を添加することが好ましい。Further, as the above-mentioned calcination catalyst, powdery one is preferable, and a product catalyst obtained by the production method of the present invention may be pulverized, and a step for obtaining this product catalyst or the prior application Or a fine powder that is derived from the separately proposed manufacturing process (for example, a gel is formed into a long string, fired, and then crushed to make only an appropriate size the product catalyst. It is also possible to use, for example, those that have been finely crushed so that they cannot be used as a catalyst.
In addition to these, any powder such as a catalyst obtained by a conventional method or a commercially available catalyst may be used as long as it is a powder of a hydrodesulfurization catalyst composed of a composite oxide obtained from the components (a) to (c). You can However, it is preferable to add a powder of a calcining catalyst having a composition similar to that of the calcining catalyst obtained from the added gel.
【００４１】また、上記の焼成触媒の粉末の大きさは、
特に制限はないが、ゲルとの均一な混合状態を得て、Ｌ
ＯＩを容易な操作でかつ確実により適性な値とするため
には、約０．１〜１０００μｍ、好ましくは約０．５〜
１００μｍの範囲内に入っているものを使用することが
望ましい。The size of the powder of the above calcined catalyst is
Although there is no particular limitation, a uniform mixed state with the gel is obtained, and L
In order to make the OI a more appropriate value by an easy operation, it is about 0.1-1000 μm, preferably about 0.5-.
It is desirable to use those having a thickness within the range of 100 μm.
【００４２】以上のような焼成触媒の粉末が添加された
可塑性を有するゲルは、必要に応じて空気中にて、約２
００〜８００℃の温度で、約１〜２４時間焼成すること
により、水素化脱硫触媒となる。The gel having plasticity, to which the powder of the calcining catalyst as described above is added, is about 2% in air if necessary.
A hydrodesulfurization catalyst is obtained by calcining at a temperature of 00 to 800 ° C for about 1 to 24 hours.
【００４３】なお、本発明において、焼成触媒を混合さ
せる前のゲルを、そのまま焼成して得られる周期律表第
ＶＩＢ族金属、周期律表第ＶＩＩＩ族金属およびアルミ
ニウムを含む複合酸化物（すなわち、前述の本発明者ら
による先願の触媒）は、Ｘ線回折パターンで実質的にγ
−Ａｌ２Ｏ３のピークを示さない。これは、製造方法の
特徴に起因するものと推測される。因みに、従来より水
素化脱硫触媒の製造方法として汎用されている「含浸
法」、「共沈澱法」、「混練法」により得られる触媒で
は、Ｘ線回折パターンでγ−Ａｌ２Ｏ３のピークを示
す。このことからして、本発明のゲルをそのまま焼成し
て得られる上記の複合酸化物と、従来の汎用方法で得ら
れる触媒とは、構造が全く異なることが明らかである。
参考までに、本発明のゲルをそのまま焼成して得られる
触媒と従来の含浸法で得られる触媒の通常の条件下での
Ｘ線回折パターンを、図１および図２に示す。図１が本
発明のゲルをそのまま焼成して得られる触媒〔組成（大
略）：ＣｏＯ１５ｗｔ％，ＭｏＯ３４５ｗｔ％，Ａｌ２
Ｏ３４０ｗｔ％〕のＸ線回折パターン、図２が従来法で
得られる触媒〔組成（大略）：ＣｏＯ５ｗｔ％，ＭｏＯ
３１５ｗｔ％，Ａｌ２Ｏ３８０ｗｔ％〕のＸ線回折パタ
ーンである。したがって、本発明において、ゲルに混合
する焼成触媒として、先願や別途提案の製造方法で得ら
れる製品触媒などを使用すれば、本発明の製品触媒も、
当然にＸ線回折パターンで実質的にγ−Ａｌ２Ｏ３のピ
ークを示さないが、従来より汎用されている例えば含浸
法などで得られる製品触媒を使用すれば、本発明の製品
触媒は、Ｘ線回折パターンでγ−Ａｌ２Ｏ３のピークが
現れる場合がある。In the present invention, the composite oxide containing the metal of Group VIB of the Periodic Table, the metal of Group VIII of the Periodic Table obtained by directly calcining the gel before mixing the calcining catalyst (ie, The catalyst of the above-mentioned prior application by the present inventors) is substantially γ in the X-ray diffraction pattern.
No peak -Al 2 O 3. It is speculated that this is due to the characteristics of the manufacturing method. By the way, in the catalysts obtained by the "impregnation method", "coprecipitation method" and "kneading method" which have been widely used as a conventional method for producing a hydrodesulfurization catalyst, the peak of γ-Al 2 O 3 in the X-ray diffraction pattern Indicates. From this, it is clear that the above-mentioned composite oxide obtained by directly firing the gel of the present invention and the catalyst obtained by the conventional general-purpose method have completely different structures.
For reference, the X-ray diffraction patterns of the catalyst obtained by calcining the gel of the present invention as it is and the catalyst obtained by the conventional impregnation method under normal conditions are shown in FIGS. 1 and 2. FIG. 1 shows a catalyst obtained by firing the gel of the present invention as it is [composition (roughly): CoO 15 wt%, MoO 345 wt%, Al 2
O 3 40 wt%] X-ray diffraction pattern, FIG. 2 shows catalyst obtained by conventional method [composition (roughly): CoO 5 wt%, MoO
3 15 wt%, Al 2 O 3 80 wt%] X-ray diffraction pattern. Therefore, in the present invention, if a product catalyst obtained by a prior application or a separately proposed production method is used as the calcining catalyst to be mixed with the gel, the product catalyst of the present invention is also
Naturally, the X-ray diffraction pattern does not substantially show the peak of γ-Al 2 O 3 , but if a product catalyst obtained by, for example, an impregnation method which has been widely used in the past is used, the product catalyst of the present invention is A peak of γ-Al 2 O 3 may appear in the X-ray diffraction pattern.
【００４４】また、本発明で得られる触媒は、必要に応
じて、約１５０〜７００℃の条件下で硫化処理を行い活
性化した後に、水素化脱硫反応に用いられる。Further, the catalyst obtained in the present invention is used for hydrodesulfurization reaction after being activated by performing a sulfurization treatment under the condition of about 150 to 700 ° C., if necessary.
【００４５】以上のようにして製造される水素化脱硫触
媒は、従来のものに比べ、はるかに高い量の活性金属を
含有しているのみならず、焼成前のゲルに焼成触媒の粉
末が添加されてＬＯＩを適性値としているため、高い量
の活性金属を含有する割には大きい表面積と細孔容積と
を有し、かつ高い側面破壊強度などの触媒強度をも有し
ている。また、焼成触媒が添加されている上記の可塑性
を有するゲルは、上記の焼成前に押出成形などにより、
所望の形状に成形されるが、このときの成形性も極めて
良好であり、所望形状に容易に成形することができる。The hydrodesulfurization catalyst produced as described above not only contains a much higher amount of active metal than the conventional one, but also the powder of the calcining catalyst is added to the gel before calcination. Since the LOI is set to an appropriate value, it has a large surface area and pore volume despite containing a high amount of active metal, and also has high catalyst strength such as side fracture strength. In addition, the gel having the above-mentioned plasticity to which the calcination catalyst is added is extruded before the above-mentioned calcination,
Although it is molded into a desired shape, the moldability at this time is also very good, and it can be easily molded into a desired shape.
【００４６】[0046]
実施例１ 反応容器中で、アルミニウム−ｉｓｏ−プロポキシド４
３．６３ｋｇと、コバルトアセチルアセトナート９．５
ｋｇとを、ｉｓｏ−プロパノール４４０ｋｇに溶解させ
た溶液を、８０℃で、１時間攪拌した。また、別に、モ
リブデン酸アンモニウム１３．３５ｋｇを、イオン交換
水８１．４ｋｇの中で、攪拌し、溶解させた。上記のｉ
ｓｏ−プロパノール溶液を５０℃に冷却し、ラインミキ
サー中に、このｉｓｏ−プロパノール溶液と、上記のモ
リブデン酸アンモニウム水溶液とを、それぞれ９０リッ
トル（以下、「Ｌ」と記す）／ｈ、３０Ｌ／ｈの速度で
滴下した。ここで１時間攪拌を行った後、８０℃に昇温
し、３時間の熟成を行った。その後、再び、ラインミキ
サーにかけて１．５時間攪拌を行った。生成したスラリ
ーを、通常のフィルタープレスで濾過したものと、
圧搾式フィルタープレスで濾過したものとの２種類の方
法で、濾過濃縮、焼成触媒粉混入成型、乾燥して可塑性
のあるゲルとした。Example 1 Aluminum-iso-propoxide 4 in a reaction vessel
3.63 kg and cobalt acetylacetonate 9.5
A solution obtained by dissolving 1 kg and 440 kg of iso-propanol was stirred at 80 ° C. for 1 hour. Separately, 13.35 kg of ammonium molybdate was stirred and dissolved in 81.4 kg of ion-exchanged water. I above
The so-propanol solution was cooled to 50 ° C., and the iso-propanol solution and the above ammonium molybdate aqueous solution were respectively added to the line mixer in an amount of 90 liters (hereinafter, referred to as “L”) / h, 30 L / h. Was dropped at a rate of. After stirring for 1 hour, the temperature was raised to 80 ° C. and aging was performed for 3 hours. Then, the mixture was again put into the line mixer and stirred for 1.5 hours. The resulting slurry, filtered with a normal filter press,
A gel having plasticity was obtained by filtering and concentrating, mixing with calcined catalyst powder and molding, and drying by two types of methods, one that was filtered by a compression type filter press.
【００４７】上記のの方法で得られたゲル（以下、
「ゲル」と記す）およびの方法で得られたゲル（以
下、「ゲル」と記す）のＬＯＩを、次の要領で求め
た。ゲル，の一部をそれぞれ焼成して得た触媒（以
下、ゲルから得られた触媒を「焼成触媒」と記し、
ゲルから得られた触媒を「焼成触媒」と記す）の重
量βと、ゲル，の重量αとから、前述した式により
ＬＯＩを算出した。この結果、ゲルのＬＯＩは、８０
％であり、ゲルのＬＯＩは、７０％であった。The gel obtained by the above method (hereinafter,
The LOI of the gel (hereinafter referred to as "gel") and the gel obtained by the method (hereinafter referred to as "gel") was determined in the following manner. A catalyst obtained by calcining a part of the gel, respectively (hereinafter, the catalyst obtained from the gel is referred to as “calcining catalyst”,
The LOI was calculated from the weight β of the catalyst obtained from the gel as “calcined catalyst”) and the weight α of the gel by the above-mentioned formula. As a result, the LOI of the gel is 80
% And the LOI of the gel was 70%.
【００４８】上記のゲル，に、それぞれ上記の焼成
触媒，を微粉砕した粒径０．５〜１００μｍの範囲
内の書生触媒粉（焼成触媒ととを等量づつ混合した
ものを使用）を、種々の割合で添加したものを、押出成
形機にて柱状物に成形した後、空気中で、４５０℃で、
４時間焼成して、いずれもＣｏＯ（１５ｗｔ％）−Ｍｏ
Ｏ３（４５ｗｔ％）−Ａｌ２Ｏ３（４０ｗｔ％）の組成
を有する複合金属酸化物からなる水素化脱硫触媒を得
た。The above-mentioned gel was finely pulverized with the above-mentioned calcination catalyst, and a gramocatalyst powder (using a mixture of the calcination catalyst and the calcining catalyst in equal amounts) having a particle size of 0.5 to 100 μm was used. What was added in various proportions, after being molded into a columnar product with an extruder, in air at 450 ℃,
After firing for 4 hours, CoO (15 wt%)-Mo
A hydrodesulfurization catalyst composed of a composite metal oxide having a composition of O 3 (45 wt%)-Al 2 O 3 (40 wt%) was obtained.
【００４９】これらの水素化脱硫触媒の物性を測定し、
結果を図３に示す。図３中、（Ａ）は、焼成触媒の粉末
の添加量と、ゲルのＬＯＩとの関係を示すグラフ、
（Ｂ）は、水素化脱硫触媒の表面積（ＳＡ）と、ゲルの
ＬＯＩとの関係を示すグラフ、（Ｃ）は、水素化脱硫触
媒の細孔容積（ＰＶ）と、ゲルのＬＯＩとの関係を示す
グラフ、（Ｄ）は、水素化脱硫触媒の側面破壊強度（Ｓ
ＣＳ）と、ゲルのＬＯＩとの関係を示すグラフである。
また、図３中、曲線１が、ゲルと、該ゲルから得ら
れた水素化脱硫触媒（以下、「水素化脱硫触媒」と記
す）のデータを示し、曲線２が、ゲルと、該ゲルか
ら得られた水素化脱硫触媒（以下、「水素化脱硫触媒
」と記す）のデータを示している。The physical properties of these hydrodesulfurization catalysts were measured,
The results are shown in Fig. 3. In FIG. 3, (A) is a graph showing the relationship between the addition amount of the powder of the calcining catalyst and the LOI of the gel,
(B) is a graph showing the relationship between the surface area (SA) of the hydrodesulfurization catalyst and the LOI of the gel, and (C) is the relationship between the pore volume (PV) of the hydrodesulfurization catalyst and the LOI of the gel. (D) is a graph showing the side fracture strength (S) of the hydrodesulfurization catalyst.
It is a graph which shows the relationship between CS) and LOI of a gel.
In FIG. 3, curve 1 shows the data of the gel and the hydrodesulfurization catalyst obtained from the gel (hereinafter referred to as “hydrodesulfurization catalyst”), and curve 2 shows the data of the gel and the gel. The data of the obtained hydrodesulfurization catalyst (hereinafter, referred to as "hydrodesulfurization catalyst") are shown.
【００５０】図３から明らかなように、焼成触媒粉の添
加量を約２〜１０重量％としたものでは、ＬＯＩが、ゲ
ルで約７８〜７０％、ゲルで約６８〜６０％となる
ことが判る。そして、この範囲内で焼成触媒粉を添加し
たもののゲルの成形性は、特に、ゲルが良好であっ
た。また、図３から明らかなように、表面積（ＳＡ）
は、水素化脱硫触媒で約２６０〜２８０ｍ２／ｇ、水
素化脱硫触媒で約２３０〜２５０ｍ２／ｇとなり、細
孔容積（ＰＶ）は、水素化脱硫触媒で約０．７〜０．
９ミリリットル（以下、「ｍＬ」と記す）／ｇ、水素化
脱硫触媒で約０．５５〜０．５８ｍＬ／ｇとなり、側
面破壊強度（ＳＣＳ）は、水素化脱硫触媒で約１．０
〜１．６Ｌｂｓ／ｍｍ、水素化脱硫触媒で約０．５〜
１．６ｍＬとなり、いずれも高い脱硫活性を示すことが
推測できる。As is clear from FIG. 3, when the addition amount of the calcined catalyst powder is about 2 to 10% by weight, the LOI is about 78 to 70% for gel and about 68 to 60% for gel. I understand. The gel moldability of the gel to which the calcined catalyst powder was added within this range was particularly good. Further, as is clear from FIG. 3, the surface area (SA)
Is about at hydrodesulfurization catalyst 260~280m 2 / g, about 230~250m 2 / g becomes in hydrodesulfurization catalyst, the pore volume (PV) is about at hydrodesulfurization catalyst from 0.7 to 0.
9 ml (hereinafter, referred to as “mL”) / g, the hydrodesulfurization catalyst has a side breakdown strength (SCS) of about 0.55 to 0.58 mL / g, and the hydrodesulfurization catalyst has a side fracture strength (SCS) of about 1.0.
~ 1.6 Lbs / mm, about 0.5 ~ with hydrodesulfurization catalyst
It will be 1.6 mL, and it can be inferred that all exhibit high desulfurization activity.
【００５１】これらに対し、焼成触媒粉を添加しないも
のでは、水素化脱硫触媒，の物性はいずれも良好で
あったが、ゲル，のＬＯＩはいずれも高く、ゲル
では良好な成形性を示したが、ゲルでは成形性に劣っ
ていた。また、焼成触媒の添加量が約１０重量％より多
いものでは、ゲル，ともＬＯＩが徐々に小さくなっ
て、成形性が次第に低下した。しかも、水素化脱硫触媒
，の物性においては、水素化脱硫触媒の細孔容積
は大きくなっているが、水素化脱硫触媒の細孔容積は
やや低くなる傾向がみられ、表面積および側面破壊強度
は、水素化脱硫触媒，ともかなり小さくなっている
ことが判る。On the other hand, in the case where the calcined catalyst powder was not added, the physical properties of the hydrodesulfurization catalyst, were all good, but the LOI of the gel was high, and the gel showed good moldability. However, the gel was inferior in moldability. Further, when the addition amount of the calcining catalyst was more than about 10% by weight, the gel and the LOI gradually decreased, and the formability gradually decreased. Moreover, in the physical properties of the hydrodesulfurization catalyst, the pore volume of the hydrodesulfurization catalyst is large, but the pore volume of the hydrodesulfurization catalyst tends to be slightly low, and the surface area and the lateral fracture strength are It can be seen that both the hydrodesulfurization catalysts are considerably smaller.
【００５２】[0052]
【発明の効果】以上詳述したように、本発明では、焼成
触媒の粉末を添加するため、焼成前のゲルのＬＯＩを極
めて容易に適性値にすることができ、この結果、次のよ
うな効果を、常時、安定して奏することができる。 （１）ゲルの成形性を良好なものとすることができると
ともに、該ゲル焼成時の危険度を減少させることができ
る。 （２）従来の触媒に比べ、高い金属含有量となり、かつ
大きい表面積および細孔容積を有するのみならず、高い
触媒強度をも有することができる。 このため、炭化水素油の水素化脱硫反応時において、反
応物（炭化水素油）の触媒の細孔内拡散が十分となって
高い脱硫率を得ることができるとともに、工業上必要な
充填量や充填密度に耐える触媒強度をも持つ上、触媒寿
命も伸び、経済的効果が莫大となる。As described above in detail, in the present invention, since the powder of the calcination catalyst is added, the LOI of the gel before calcination can be adjusted to an appropriate value very easily. As a result, the following results are obtained. The effect can be constantly and stably exhibited. (1) The moldability of the gel can be improved, and the risk of firing the gel can be reduced. (2) In addition to having a high metal content and having a large surface area and pore volume, it can have high catalyst strength as compared with conventional catalysts. Therefore, during hydrodesulfurization reaction of hydrocarbon oil, diffusion of the reactant (hydrocarbon oil) in the pores of the catalyst becomes sufficient and a high desulfurization rate can be obtained. In addition to having the catalyst strength to withstand the packing density, the catalyst life is extended, and the economic effect becomes enormous.
【図１】焼成触媒混合前のゲルをそのまま焼成して得ら
れる触媒のＸ線回折パターンを示す図である。FIG. 1 is a diagram showing an X-ray diffraction pattern of a catalyst obtained by directly calcining a gel before mixing with a calcining catalyst.
【図２】従来の含浸法で得られる触媒のＸ線回折パター
ンを示す図である。FIG. 2 is a diagram showing an X-ray diffraction pattern of a catalyst obtained by a conventional impregnation method.
【図３】焼成触媒の粉末の添加量と、ゲルのＬＯＩ、お
よび製品水素化脱硫触媒の物性との関係を示すグラフで
ある。FIG. 3 is a graph showing the relationship between the amount of calcination catalyst powder added, the gel LOI, and the physical properties of the product hydrodesulfurization catalyst.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤川 貴志 埼玉県幸手市権現堂1134−２ (72)発明者 千代田 修 埼玉県幸手市権現堂1134−２ (72)発明者 薄井 一司 千葉県野田市岩名１−62−10 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Fujikawa 1134-2, Gongen-do, Satte City, Saitama Prefecture (72) Inventor Osamu Chiyoda, 1134-2, Gongen-do, Satte City, Saitama Prefecture Kaiji Usui, Noda, Chiba Prefecture Ichiname 1-62-10
Claims (1)
ミニウムキレート化合物、環状アルミニウムオリゴマー
のうちの少なくとも１つと、（ｂ）周期律表第ＶＩＢ族
金属の少なくとも１種と、（ｃ）周期律表第ＶＩＩＩ族
金属の少なくとも１種との混合物を有機溶媒中において
混合し、この混合によって生じる有効成分を乾燥してゲ
ルとし、これを焼成して、周期律表第ＶＩＢ族金属、周
期律表第ＶＩＩＩ族金属およびアルミニウムを含む複合
酸化物からなる水素化脱硫触媒を製造する方法であっ
て、 前記の焼成前のゲルに、焼成後の水素化脱硫触媒を添加
した後、焼成することを特徴とする水素化脱硫触媒の製
造法。1. An aluminum alkoxide, an aluminum chelate compound, and a cyclic aluminum oligomer (a), (b) at least one metal of Group VIB of the Periodic Table, and (c) Group VIII of the Periodic Table. A mixture with at least one metal is mixed in an organic solvent, and the active ingredient produced by this mixing is dried to give a gel, which is then calcined to give a metal of Group VIB of the periodic table or a metal of Group VIII of the periodic table. A method for producing a hydrodesulfurization catalyst comprising a complex oxide containing aluminum and aluminum, wherein the gel before calcination is added with a hydrodesulfurization catalyst after calcination, and then calcination is performed. Manufacturing method of desulfurization catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4361064A JPH06198184A (en) | 1992-12-30 | 1992-12-30 | Production of hydrodesulfurization catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4361064A JPH06198184A (en) | 1992-12-30 | 1992-12-30 | Production of hydrodesulfurization catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06198184A true JPH06198184A (en) | 1994-07-19 |
Family
ID=18472048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4361064A Pending JPH06198184A (en) | 1992-12-30 | 1992-12-30 | Production of hydrodesulfurization catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06198184A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004511326A (en) * | 2000-07-12 | 2004-04-15 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method of preparing mixed metal catalyst based on additives |
-
1992
- 1992-12-30 JP JP4361064A patent/JPH06198184A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004511326A (en) * | 2000-07-12 | 2004-04-15 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Method of preparing mixed metal catalyst based on additives |
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