JP6338218B2 - 有機基修飾ゼオライト触媒を用いた二酸化炭素からの炭化水素製造方法 - Google Patents
有機基修飾ゼオライト触媒を用いた二酸化炭素からの炭化水素製造方法 Download PDFInfo
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- JP6338218B2 JP6338218B2 JP2014258596A JP2014258596A JP6338218B2 JP 6338218 B2 JP6338218 B2 JP 6338218B2 JP 2014258596 A JP2014258596 A JP 2014258596A JP 2014258596 A JP2014258596 A JP 2014258596A JP 6338218 B2 JP6338218 B2 JP 6338218B2
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- Prior art keywords
- catalyst
- zeolite
- compound
- organic
- carbon dioxide
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- 239000003054 catalyst Substances 0.000 title claims description 161
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 111
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 92
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 54
- 229930195733 hydrocarbon Natural products 0.000 title claims description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 46
- 239000001569 carbon dioxide Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title description 22
- 230000008569 process Effects 0.000 title description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 153
- -1 silane compound Chemical class 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 32
- 238000003786 synthesis reaction Methods 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000000962 organic group Chemical group 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000002028 Biomass Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 150000002390 heteroarenes Chemical class 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 150000003606 tin compounds Chemical class 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 description 110
- 229910021536 Zeolite Inorganic materials 0.000 description 100
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000002894 organic compounds Chemical class 0.000 description 17
- 239000007787 solid Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000003993 interaction Effects 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001722 carbon compounds Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- YBNBOGKRCOCJHH-UHFFFAOYSA-N hydroxy-[4-[hydroxy(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C[Si](C)(O)C1=CC=C([Si](C)(C)O)C=C1 YBNBOGKRCOCJHH-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ULKGULQGPBMIJU-UHFFFAOYSA-N benzene;hydron;bromide Chemical compound Br.C1=CC=CC=C1 ULKGULQGPBMIJU-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- XUZDJUDKWXESQE-UHFFFAOYSA-N chromium copper zinc Chemical compound [Cr].[Zn].[Cu] XUZDJUDKWXESQE-UHFFFAOYSA-N 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- KQEIOCQUCGCMHX-UHFFFAOYSA-N diethyl(dimethyl)stannane Chemical compound CC[Sn](C)(C)CC KQEIOCQUCGCMHX-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VLNRSEGRGSDKLS-UHFFFAOYSA-N ethenyl-[4-[ethenyl(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C=C[Si](C)(C)C1=CC=C([Si](C)(C)C=C)C=C1 VLNRSEGRGSDKLS-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000012771 household material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Description
項1. メタノール合成触媒と有機基修飾ゼオライト触媒類を含む、一酸化炭素及び/又は二酸化炭素と水素を含む混合ガスから炭素数2以上の炭化水素を合成するための複合触媒。
項2. 前記有機基修飾ゼオライト触媒類が、ゼオライト触媒類と有機化合物を高温で反応させて得られるものである、項1に記載の複合触媒。
項3. 前記有機化合物が有機シラン化合物、有機ホウ素化合物、有機アルミニウム化合物、有機スズ化合物、有機含酸素化合物、芳香族化合物、ヘテロ芳香族化合物、脂肪族もしくは脂環式不飽和化合物からなる群から選ばれる少なくとも1種である、項2に記載の複合触媒。
項4. 一酸化炭素及び/又は二酸化炭素と水素を含む混合ガスを、項1〜3のいずれかに記載の複合触媒の存在下に反応させることを特徴とする、炭素数2以上の炭化水素の製造方法。
項5. 前記混合ガスが、一酸化炭素と水素を含む混合ガス、二酸化炭素と水素を含む混合ガス、一酸化炭素と二酸化炭素と水素を含む混合ガス、又はバイオマスガスである、項4に記載の炭化水素の製造方法。
本技術で、複合触媒に用いる銅−亜鉛−アルミニウム触媒は以下の方法で調製した。29gの硝酸銅(Cu(NO3)3・3H2O)、17.9gの硝酸亜鉛(Zn(NO3)2・6H2O)および7.5g硝酸アルミニウム(Al(NO3)3・9H2O)を200mLのイオン交換水に溶かした水溶液を、25.4gの炭酸ナトリウム(Na2CO3)を240mLのイオン交換水に溶かした水溶液へ、溶液温度を約80℃にしながら一度に加え、生成した混合溶液を80℃で1時間撹拌した。その後、生成した沈殿をろ別し、2Lのイオン交換水で5回洗浄した後、80℃で約12時間乾燥処理をした。得られた銅−亜鉛−アルミニウムの複合炭酸塩は、350℃で3時間焼成し、銅−亜鉛−アルミニウム触媒を得た。
事前にゼオライトベータ[HB(東ソー社製、HSZ−931HOA、SiO2/Al2O3=28.5]は500℃で6時間焼成し、吸着成分を除去した。このゼオライトベータ2.5gを150℃で3時間乾燥処理し、メタノール18.75mLに所定量のジシラン化合物[1,4-bis(hydroxydimethylsilyl)benzene]を溶解させた溶液へ加えて、30分間室温で撹拌の後、減圧下でメタノールを留去した。テフロン容器を内包したオートクレーブに移して密閉し、150℃、24時間加熱処理した。その後、150mLのメタノールで3回洗浄を行い、室温で2日以上空気乾燥させた。得られた有機基修飾ゼオライトの細孔構造は、Belsorp Mini(日本ベル社製)を用いた窒素吸着等温線より評価した。代表的な触媒の結果を表1に示す。
実施例2と同様の方法で、ジシラン化合物等を用いず、メタノールやトルエン等の有機溶媒のみをゼオライトに加え、30分間室温で撹拌の後、減圧下で有機溶媒を留去した。オートクレーブに移して密閉し、150℃、24時間加熱反応させた。その後、容器より回収した固体は、洗浄処理を行わず、室温で2日以上空気乾燥させた。得られた有機基修飾ゼオライトの細孔構造は、Belsorp Mini(日本ベル社製)を用いての窒素吸着等温線より評価した。代表的結果を表1に示す。
実施例1で調製した銅−亜鉛−アルミニウム触媒0.1gと実施例2および3で得たゼオライト触媒類0.9gをメノウ製乳鉢内で、100回混合することで、複合触媒を得た。
内径約1cmのステンレス製の触媒反応管に実施例4で作成した複合触媒を1g充填し、100%の水素を流速40mL/minの速度で流して、250℃で約16時間触媒を前還元処理した。その後に、反応ガスである二酸化炭素と水素の混合ガス(H2/CO2=3)を導入し、圧力0.98MPa、温度300℃、マスフローコントローラで制御したガス流速50mL/min(sccm)の条件下反応させ、1時間後に反応ガスを採取し、反応生成物等をオンラインのガスクロマトグラフィーにより分析した。この結果を表2に示す。表2の結果からわかるように、有機基を全く修飾していないゼオライトを用いた場合、C2+炭化水素の収率は約0.5%であったが、有機基を修飾したゼオライトからなる複合触媒では、C2+炭化水素収率は明らかに向上した。3%の有機シラン化合物を修飾したゼオライトを用いた場合、C2+炭化水素収率は8%以上となった。また、メタノールやトルエンのみを修飾した場合もC2+炭化水素収率の向上が見られ、トルエンの場合の収率は約8.5%であった。
実施例5と同様の方法で、反応ガスを二酸化炭素と水素の混合ガスに代えて、報告されているバイオマスガスの一つの組成である、二酸化炭素20%、一酸化炭素40%、水素30%、窒素10%の混合ガス(T. Hanaoka, T. Miyazawa, M. Nurunnabi, S. Hirata, K. Sakanishi, J. Jpn. Inst. Energy, 90, 1072 (2011))を、複合触媒を用いて、圧力0.98MPa、温度300℃、ガス流速50mL/minの条件下反応させた。この結果を表3に示す。表3の結果からわかるように、ジシラン化合物を全く修飾していないゼオライトを用いた場合、C2+炭化水素は約1.5%であったが、有機基を修飾したゼオライトからなる複合触媒ではC2+炭化水素収率は明らかに向上し、3%の有機シラン化合物を修飾したゼオライトを用いた場合はC2+炭化水素収率は4.7%となり、非修飾のゼオライトを用いた場合の収率と比べ、3倍以上になった。また、トルエンのみを修飾した場合もC2+炭化水素収率の向上が見られ、収率は約3.5%であった。
ゼオライトに修飾された有機化合物の状態を解析するために、ゼオライト粉末の拡散反射紫外可視スペクトルを測定した。日本分光社製の分光光度計V−550に積分球ISV−469を取り付けて、種々のゼオライト触媒類の拡散反射紫外可視スペクトルを測定した。図3に示す様に、実施例2で調製したジシラン化合物修飾ゼオライトには、ジシラン化合物由来の270nm近傍の吸収が観測された。また、この吸収と共に、ゼオライトやジシラン化合物にはない320〜330nmの吸収も観測された。表2で高い活性を示したゼオライト2〜5では、実施例2の処理によりジシラン化合物が単にゼオライト表面に吸着しただけではなく、この処理によりジシラン化合物から320〜330nmに吸収を持つ化合物が形成され、当該化合物によってゼオライトが修飾されていることがわかった。
日本分光社製の分光光度計V−550に積分球ISV−469を取り付けて、種々のゼオライト類の拡散反射紫外可視スペクトルを測定した。図4に示す様に、実施例3で調製したトルエン修飾ゼオライトには、トルエン由来の250〜260nmの吸収と共に、処理前のゼオライトにはない450nmに明確な吸収が観測された。一方、密閉容器を用い室温でトルエンを飽和吸着処理させたゼオライトには、トルエン由来の250〜260nmの吸収はあるものの、450nmには全く吸収は観測されなかった。表2で高い活性を示したゼオライト7では、実施例3の処理によりトルエンが単にゼオライト表面に吸着しただけではなく、この処理によりトルエンから450nmに吸収を持つ化合物が形成され、当該化合物によってゼオライトが修飾されていることがわかった。
島津製作所製の熱分析装置TGA−50を用い、白金セルにゼオライト試料を充填し、空気の30mL/minの気流下、昇温速度3℃/minで約20℃の室温から800℃まで温度を上げて重量減少をモニターし、150℃までの重量減少は吸着物の脱離による減少とし、また150〜600℃での重量減少分を修飾された有機成分に相当するものと考え、種々のゼオライトの有機成分量を解析した。有機基非修飾のゼオライト(ゼオライト1)の150〜600℃での減少量は0.972%であり、この減少量より多い分を修飾された有機化合物由来の有機成分とした。例えば、仕込み量10%で有機ジシラン化合物を修飾したゼオライト5において、同様に計算した150〜600℃での重量減少分は2.889%であるため、ゼオライト5中の修飾有機基の重量は1.917%とした。同様の計算で得られた結果は表1にまとめた。
Claims (4)
- メタノール合成触媒と有機基修飾ゼオライト触媒類を含み、前記有機基が有機シラン化合物、有機ホウ素化合物、有機アルミニウム化合物、有機スズ化合物、有機含酸素化合物、芳香族化合物、ヘテロ芳香族化合物、脂肪族もしくは脂環式不飽和化合物からなる群から選ばれる少なくとも1種に由来する、一酸化炭素及び/又は二酸化炭素と水素を含む混合ガスから炭素数2以上の炭化水素を合成するための複合触媒。
- 前記有機基が、有機シラン化合物に由来する請求項1に記載の複合触媒。
- 一酸化炭素及び/又は二酸化炭素と水素を含む混合ガスを、請求項1又は2に記載の複合触媒の存在下に反応させることを特徴とする、炭素数2以上の炭化水素の製造方法。
- 前記混合ガスが、一酸化炭素と水素を含む混合ガス、二酸化炭素と水素を含む混合ガス、一酸化炭素と二酸化炭素と水素を含む混合ガス、又はバイオマスガスである、請求項3に記載の炭化水素の製造方法。
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