JP2008513204A - 有機剤を含む前駆体から作製されるバルクNi−Mo−W触媒 - Google Patents
有機剤を含む前駆体から作製されるバルクNi−Mo−W触媒 Download PDFInfo
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- JP2008513204A JP2008513204A JP2007532536A JP2007532536A JP2008513204A JP 2008513204 A JP2008513204 A JP 2008513204A JP 2007532536 A JP2007532536 A JP 2007532536A JP 2007532536 A JP2007532536 A JP 2007532536A JP 2008513204 A JP2008513204 A JP 2008513204A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 27
- 239000002243 precursor Substances 0.000 title description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 81
- 229910000510 noble metal Inorganic materials 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- 239000011593 sulfur Substances 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 238000005486 sulfidation Methods 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000003863 metallic catalyst Substances 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- UVKFSMBPRQBNCH-UHFFFAOYSA-M 4,4-diphenylbutan-2-yl-ethyl-dimethylazanium;bromide Chemical compound [Br-].C=1C=CC=CC=1C(CC(C)[N+](C)(C)CC)C1=CC=CC=C1 UVKFSMBPRQBNCH-UHFFFAOYSA-M 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 claims description 2
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 6
- 150000002823 nitrates Chemical class 0.000 claims 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 150000003842 bromide salts Chemical class 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011230 binding agent Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- -1 Molybdate anions Chemical class 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- 239000011733 molybdenum Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000005336 cracking Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 229910052698 phosphorus Chemical group 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011574 phosphorus Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry 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
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- AJRFYWWXFKNJHC-UHFFFAOYSA-N CCCCCCCCCCCC(C)(C)N(C)C Chemical compound CCCCCCCCCCCC(C)(C)N(C)C AJRFYWWXFKNJHC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910008938 W—Si Inorganic materials 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- TTZGICPOSYHERT-UHFFFAOYSA-N [Si](O)(O)(O)O.[Mo] Chemical compound [Si](O)(O)(O)O.[Mo] TTZGICPOSYHERT-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical compound CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- TXPMUPUOSOZCCS-UHFFFAOYSA-N hexadecyl(trimethyl)phosphanium Chemical compound CCCCCCCCCCCCCCCC[P+](C)(C)C TXPMUPUOSOZCCS-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IYFXESRMJKRSNZ-UHFFFAOYSA-L hydrogen carbonate;nickel(2+) Chemical compound [Ni+2].OC([O-])=O.OC([O-])=O IYFXESRMJKRSNZ-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 239000012685 metal catalyst precursor Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 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
- 239000012266 salt solution Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- IKANSXQHJXBNIN-UHFFFAOYSA-N trimethyl(octadecyl)phosphanium Chemical compound CCCCCCCCCCCCCCCCCC[P+](C)(C)C IKANSXQHJXBNIN-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
【選択図】なし
Description
(X)b(Mo)c(W)dOz
[式中、モル比b:(c+d)は0.5/1〜3/1であり、モル比c:dは>0.01/1、好ましくは>0.1/1であり、z=[2b+6(c+d)]/2である]
を有する前駆体から調製される。前駆体は、d=2.53および1.70ÅにX線回折ピークを有する。前駆体は、硫化されて、対応する活性化触媒が製造される。
(X)a(Mo1−xWx)b[(CH3CH2)dN(CH3)3]eOz
[式中、Xは一種以上の第VIII族非貴金属であり、dは10〜40の整数であり、xは0〜1であり、モル比e:aは≦2.0/1であり、z=((2a+6b)+e)/2であり、モル比a:(b)は0.5/1〜3/1である]
によって表されるバルク多元金属触媒組成物が提供される。前記触媒組成物は、スルフィド化後に、(Mo1−xWx)S2化学量論組成の積重ね層からなり、そのために平均積重ね高さは、10Å〜20Åである。
(X)a(Mo1−xWx)b[(CH3CH2)dN(CH3)3]eOz
[式中、Xは一種以上の第VIII族非貴金属であり、dは10〜40の整数であり、xは0〜1であり、モル比e:aは≦2.0/1であり、z=((2a+6b)+e)/2であり、モル比a:(b)は0.5/1〜3/1である]
によって表され、スルフィド化後の前記触媒は、(Mo1−xWx)S2積重ね層からなり、そのために平均積重ね高さは、10Å〜20Åである。
(X)a(Mo)b(W)cOz
[式中、b、c、およびdのモル比は0.1<(b+c)/a<10であり、z=[2a+6(b+c)]/2である]
から調製される。前駆体は、X線回折のピークを、d=2.53および1.70オングストロームに有する。
のアンモニウムまたはホスホニウムイオンである。本明細書で用いるのに適切なこれらの指向剤の限定しない例には、セチルトリメチルアンモニウム、セチルトリメチルホスホニウム、オクタデシルトリメチルホスホニウム、セチルピリジニウム、ミリスチルトリメチルアンモニウム、デシルトリメチルアンモニウム、ドデシルトリメチルアンモニウム、およびジメチルジドデシルアンモニウムが含まれる。上記のアンモニウムまたはホスホニウムイオンが誘導される化合物は、例えば、水酸化物、ハロゲン化物、シリケート、またはそれらの混合物であってもよい。
MoO3 28.8g(Mo 0.2モル)、およびタングステン酸H2WO4 50.0g(W 0.2モル)を水800ml中にスラリー化し(懸濁A)、90℃へ加熱した。ヒドロキシカルボン酸ニッケル2NiCO3 *3Ni(OH)2 *4H2O 70.6g(Ni 0.6モル)を、水200ml中に懸濁し、90℃へ加熱した(懸濁B)。懸濁Bを、懸濁Aに、時間60分でゆっくり添加し、得られた混合物を、連続的に撹拌をしながら、90℃で18時間保持した。この時間の終わりに、得られた懸濁を、ろ過し、固形分を、120℃で4〜8時間乾燥し、400℃で焼成した。収率は、その酸化物へ転化された全金属成分の計算重量を基準として99%であった。このバルク触媒前駆体の酸化物組成物のX線スペクトルを、本明細書の図1の上部軌跡として示す。
オクタデシルトリメチルアンモニウムがそこに組込まれた名目組成物Ni1Mo0.5W0.5酸化物の触媒前駆体を、次のように調製した。水500ccに、ヘプタモリブデン酸アンモニウム17.65g(Mo 0.10モル)およびメタタングステン酸アンモニウム24.5g(W 0.10モル)を溶解した。これに、臭化オクタデシルトリメチルアンモニウム58.9g(0.15モル)を添加した。これにより、pH5.7の溶液が得られた。この溶液を、90℃へ加熱し、ミルク状スラリーを形成した。これに、硝酸ニッケル58.15g(Ni 0.20モル)を添加した。これは、最初に、更なる水100cc中に溶解されている。全混合物を、次いで、還流コンデンサーおよび温度計を含む三口フラスコ中で、90℃へ加熱および撹拌し、その温度で1時間保持した。最終pHは、4.2と測定された。ろ過および120℃での乾燥の後、得られた固形物は、63.5gと秤量された。この前駆体のX線回折スペクトルを、本明細書の図1の下部軌跡として示す。
本明細書の実施例1および2からの触媒4〜6gを、120℃で乾燥し、石英ボートに入れ、これを、次には、水平の石英管中に挿入し、リンドバーグ[Lindberg]加熱炉に入れた。依然として室温のまま、H2S 10%/H2気流200cc/分を、15分間入れ、次いで温度を、H2S 10%/H2を200cc/分で流しながら、45分間で400℃へ昇温した。この気流を、400℃で2時間続けた。加熱を、次いで止め、得られた触媒を、H2S/H2気流中で室温へ冷却し、同じ気流下で、室温で30分間保持した。窒素300cc/分を、30分間入れた。その後、酸素1%/ヘリウム不活性化ガスを、室温で入れ、50cc/分で終夜流した。試料を、次いで加熱炉から取出した。得られたX線回折スペクトルを、二つの試料について測定し、本明細書の図2に示す。上部軌跡は、硫化された単味酸化物の試料であり、下部軌跡は、Ni−Mo−Wの硫化された酸化物−アミン界面活性剤(有機剤)前駆体である。図2においては、(002)ピーク(12゜)の広がりは、アミン界面活性剤を含む前駆体に対するものであることが、注目されるであろう。この広がりは、通常、硫化物シートの積重ね高さの減少の結果として生じる。
本明細書の実施例3の硫化前駆体の試料を、粉々に粉砕し(厚さ100mm未満)、穴あき炭素被覆されたTEMグリッド上に散布し、フィリップス[Phillips]CM200F装置の明視野TEM画像方式で検査した。硫化された前駆体の250〜350個の異なる結晶を検査し、積重ね高さを計数し、平均した。本明細書の図3aおよび3bは、これらの積重ね、並びに積重ね高さ測定の代表的なTEM顕微鏡写真を示す。このTEMデータは、有機剤含有硫化物前駆体(図3b)が、有機剤なしに調製されたもの(図3a)と比較した場合に、より低い積重ね高さの硫化物をもたらすことを明示する。
実施例3からの触媒組成物70mgを、メトラー[Mettler]TGA851熱天秤に充填した。これは、二次電子倍増管を装備したバルツアーズサーモスター[Balzers Thermostar]四重極質量分析計と組合わされた。触媒組成物を、空気流(50cc/分)中1気圧の全圧で、4℃/分で室温から600℃へ加熱した。18(H2O)、44(CO2)、および64(SO2)のm/eフラグンメントについて、MS信号(アンペア)を、重量変化と共にプロットし、本明細書の図4に示す。図4においては、硫化された有機剤前駆体からのCO2およびSO2ピークが、同時に、375℃で生じることが注目されるであろう。これは、硫化された有機剤相が、カルボ硫化物を形成することを示す。また、図4から、酸化物前駆体から調製された硫化物の酸化はCO2を全く生じないこと、および硫化物のピークはカルボ硫化物より実質的に高い温度で酸化することが注目されるであろう。これは、再度、[カルボ]硫化物の結晶子のサイズが、有機剤から調製された触媒上では、単味酸化物前駆体に対するより小さいことを示唆する。
本明細書の実施例1および2の触媒組成物の水素化脱硫活性を、硫黄592wppm、窒素100wppmを含む商業的な常圧留出油について、650psig(4,579kPa)、625゜F、および2LHSV(液空間速度)で評価した。結果を、次の表2に示す。
Claims (15)
- 次式:
(X)a(Mo1−xWx)b[(CH3CH2)dN(CH3)3]eOz
(式中、Xは一種以上の第VIII族非貴金属であり、dは10〜40の整数であり、xは0〜1であり、モル比e:aは≦2.0/1であり、z=((2a+6b)+e)/2であり、モル比a:(b)は0.5/1〜3/1である)
によって表されるバルク多元金属触媒組成物であって、
スルフィド化後の前記触媒組成物は、(Mo1−xWx)S2化学量論組成の積み重ね層からなり、そのために平均積み重ね高さは、10Å〜20Åであることを特徴とするバルク多元金属触媒組成物。 - 前記モル比a:bは、0.75/1〜1.5/1であることを特徴とする請求項1に記載の触媒組成物。
- dは、16〜20であり、eは、0.5〜1.5であることを特徴とする請求項1に記載の触媒組成物。
- Xは、NiおよびCoからなる群から選択されることを特徴とする請求項1に記載の触媒組成物。
- 次式:
(X)a(Mo1−xWx)b[(CH3CH2)dN(CH3)3]eOz
(式中、Xは一種以上の第VIII族非貴金属であり、dは10〜40の整数であり、xは0〜1であり、モル比e:aは≦2.0/1であり、z=((2a+6b)+e)/2であり、モル比a:(b)は0.5/1〜3/1である)
によって表される触媒前駆体組成物の調製方法であって、
(a)第VIII族非貴金属水溶性塩の第一の水溶液を調製する工程;
(b)MoおよびW水溶性塩を含む第二の水溶液を調製する工程;
(c)前記第一および第二の両水溶液を、温度60℃〜150℃に加熱する工程;
(d)有効量の有機剤を前記第二の水溶液に添加する工程;
(e)前記工程(d)の前記第二の水溶液の少なくとも一部を、前記第一の水溶液に導入する工程;および
(f)前記工程(e)の得られた溶液を、前記触媒前駆体組成物の沈殿を生じるのに効果的な温度に加熱する工程
を含むことを特徴とする触媒前駆体組成物の調製方法。 - 前記第VIII族非貴金属の塩は、硝酸塩、硝酸塩、臭化物、塩化物および酢酸塩からなる群から選択されることを特徴とする請求項5に記載の調製方法。
- 前記Mo塩は、ジモリブデン酸アンモニウム、トリ−、テトラ−、ヘプター、オクターおよびテトラデカ−モリブデン酸アンモニウムからなる群から選択され、前記W塩は、パラ−、メタ−、ヘキサ−およびポリタングステン酸アンモニウムであることを特徴とする請求項5に記載の調製方法。
- 前記有機剤は、芳香族アミン、環式脂肪族アミンおよび多環式脂肪族アミンからなる群から選択されることを特徴とする請求項5に記載の調製方法。
- 前記触媒前駆体組成物は、適切な触媒形状で成形され、乾燥され、酸素の存在下に温度100℃〜600℃で焼成されることを特徴とする請求項5に記載の調製方法。
- 前記成形され、乾燥され、焼成された触媒付形物は、元素硫黄、硫化水素および多硫化物からなる群から選択される硫黄含有化合物の存在下に、硫化条件で硫化されることを特徴とする請求項9に記載の調製方法。
- 水素処理条件における炭化水素原料材の水素処理方法であって、
前記原料材を、水素処理条件で、次式:
(X)a(Y)b[(CH3CH2)cN(CH3)3]dOz
(式中、Xは第VIII族非貴金属であり、YはMoおよびWからなる群から選択され、cは10〜40の整数であり、モル比a:bは0.5/1〜3/1である)
によって表される触媒前駆体組成物から誘導されるバルク多元金属触媒組成物の存在下に反応させる工程
を含み、
前記触媒組成物は、スルフィド化後、積み重ね層(Y)S2からなり、そのために平均積み重ね高さは、10Å〜20Åであることを特徴とする炭化水素原料の水素処理方法。 - 前記水素処理は、水素化脱金属、水素化脱ロウ、水素化処理、水素添加、水素化脱硫、水素化脱窒素、水素化脱芳香族、水素異性化および水素化分解からなる群から選択されることを特徴とする請求項11に記載の水素処理方法。
- 前記炭化水素原料材は、全および抜頭石油原油、常圧および減圧残油、プロパン脱瀝残油、サイクル油、流動接触分解塔底油、軽油、軽質〜重質留出油、水素化分解油、水素化処理油、脱ロウ油、スラックワックス、フィッシャー−トロプシュワックス、ラフィネート、ナフサおよびそれらの混合物からなる群から選択されることを特徴とする請求項11に記載の水素処理方法。
- 前記水素処理は、温度200℃〜450℃、水素圧5〜300バール(500〜30,000kPa)、液空間速度0.05〜10時−1および水素処理ガス比200〜10,000標準立法フィート/バレルで行われ、かつ二段以上で実施され、前記二つ以上の段は、同じまたは異なる水素処理工程であり得ることを特徴とする請求項11に記載の水素処理方法。
- 前記第VIII族非貴金属は、NiおよびCoからなる群から選択されることを特徴とする請求項5〜14のいずれかに記載の調製方法または水素処理方法。
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JP2015532618A (ja) * | 2012-09-05 | 2015-11-12 | シェブロン ユー.エス.エー. インコーポレイテッド | 水素化変換多金属触媒及びそれを調製する方法 |
JP2020502290A (ja) * | 2016-11-22 | 2020-01-23 | シェブロン ユー.エス.エー. インコーポレイテッド | 自己担持多金属触媒上のナフテン環開環 |
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