JP2018126737A - ギ酸の脱水素化に用いる触媒、ギ酸の脱水素化方法、水素製造方法 - Google Patents
ギ酸の脱水素化に用いる触媒、ギ酸の脱水素化方法、水素製造方法 Download PDFInfo
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- JP2018126737A JP2018126737A JP2018023764A JP2018023764A JP2018126737A JP 2018126737 A JP2018126737 A JP 2018126737A JP 2018023764 A JP2018023764 A JP 2018023764A JP 2018023764 A JP2018023764 A JP 2018023764A JP 2018126737 A JP2018126737 A JP 2018126737A
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- formic acid
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 100
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 43
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000003446 ligand Substances 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims abstract 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 32
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001174 sulfone group Chemical group 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims 1
- 150000004675 formic acid derivatives Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- -1 alkoxide ion Chemical class 0.000 description 39
- 239000000243 solution Substances 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 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
- 230000006866 deterioration Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910001427 strontium ion Inorganic materials 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 229910052727 yttrium Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-M periodate Chemical compound [O-]I(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-M 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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Abstract
【解決手段】触媒は、式(22)で表されるピラゾール環とピリジン環とからなる2座配位子をもつ錯体、その異性体又は塩を有効成分として含む。
。
【選択図】なし
Description
さらに、本発明は、該触媒を用い高効率・簡便な操作・安価に実施できるギ酸の脱水素化による水素の製造方法を提供することとともに、燃料電池等の水素消費装置に必要な水素量を安定して連続的に供給できるように、一酸化炭素をふくまない高圧水素を製造する方法の提供を課題とする。
[1]式(1)で表される窒素原子が2個以上含まれた芳香族複素5員環からなる2座配位子、または式(2)で表される窒素原子が2個以上含まれた芳香族複素5員環と窒素原子が1個以上含まれた6員環からなる2座配位子をもつ錯体、その異性体、または塩を有効成分として含む、ギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
M1およびM2は、イリジウム、ロジウム、ルテニウム、コバルト、オスミニウム、ニッケル、鉄、パラジウムまたは白金の遷移金属であり、
X1〜X16は、それぞれ独立に、窒素または炭素であり、
R1〜R13は、それぞれ独立に、水素原子、アルキル基、ヒドロキシ基(-OH)、アルコキシ基(-OR)、ニトロ基、ハロゲン基、スルホン基、カルボン酸基、アルキルアミノ基、もしくはフェニル基、または、隣り合ったR同士で環を形成しても良く、置換基を有している場合は、前記置換基は1つでも複数でも良く、〔ただし、Xi(iが13から16)が窒素である場合、その窒素の位置のRiは存在しない。〕ただし、R1〜R6は、少なくとも1つが前記アルキル基、前記ヒドロキシ基(-OH)、前記アルコキシ基(-OR)、前記ニトロ基、前記ハロゲン基、前記スルホン基、前記カルボン酸基、前記アルキルアミノ基、もしくは前記フェニル基であるか、または、前記環を少なくとも1つ形成し、
L1およびL2は、芳香族性アニオン配位子、もしくは芳香族性配位子であり、置換基を有している場合は、前記置換基は1つでも複数でも良く、
Z1およびZ2は、任意の配位子であるか、または存在せず、
mおよびnは、正の整数、0、または負の整数である。
[2]M1またはM2が、イリジウムである[1]記載のギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
[3]L1またはL2が、ペンタメチルシクロペンタジエニル配位子である[1]〜[2]のいずれか1項に記載のギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
[4]Z1またはZ2が、水分子、水素原子、アルコキシドイオン、水酸化物イオン、ハロゲン化物イオン、炭酸イオン、トリフルオロメタンスルホン酸イオン、硫酸イオン、硝酸イオン、ギ酸イオン、もしくは酢酸イオンであるか、または存在しない[1]〜[3]のいずれか1項に記載のギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
[5]前記錯体が下記式(3)または(4)で表される構造を有するものである[1]〜[4]のいずれか1項に記載のギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
[6]前記錯体が下記式(5)〜(12)のいずれかで表される構造を有するものである[5]に記載のギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
[7]前記錯体が下記式(13)〜(21)のいずれかで表される構造を有するものである[1]に記載のギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
[9][1]〜[7]のいずれか1項に記載の触媒の存在下、ギ酸または/およびギ酸塩を含む溶液と反応させることによってギ酸または/およびギ酸塩を脱水素化し水素を製造する方法。
[10]上記反応が、ギ酸または/およびギ酸塩の濃度2M以上で行われる[8]または[9]に記載の方法。
[11]上記反応が、ギ酸または/およびギ酸塩の濃度5M以上で行われる[8]、[9]、または[10]に記載の方法。
[12]上記反応が70℃以上の条件下で行われる[8]、[9]、[10]、[11]のいずれか1項に記載の方法。
[13]上記反応が80℃以上の条件下で行われる[8]、[9]、[10]、〜[12]のいずれか1項に記載の方法。
[14]上記反応が0.2MPa以上の条件下で行われる[8]、[9]、[10]、〜[13]のいずれか1項に記載の方法。
[15]上記反応が1MPa以上の条件下で行われる[8]、[9]、[10]、〜[14]のいずれか1項に記載の方法。
[錯体合成]
(一般式(1)または(2)で示される錯体触媒の硫酸塩の合成)
等量の[Cp*Ir(H2O)3]SO4と対応する配位子を水に溶解して、アルゴン気流下室温で12時間撹拌した。反応液を濾過し、ろ液を減圧下濃縮し、得られた生成物を減圧下50℃で12時間乾燥し、目的物を得た。
以下、得られた錯体触媒のスペクトルデータを示す。
下記式(22)のスペクトルデータを以下に示す。
下記式(23)のスペクトルデータを以下に示す。
下記式(24)のスペクトルデータを以下に示す。
下記式(25)のスペクトルデータを以下に示す。
下記式(26)のスペクトルデータを以下に示す。
下記式(27)のスペクトルデータを以下に示す。
(15)のスペクトルデータを以下に示す。
1H NMR(D2O,400MHz):7.38(s,1H),7.19(s,1H),6.01(s,1H),1.63(s,15H).1H NMR(DMSO-d6,400MHz):10.89(s,1H),7.86(s,1H),7.57(s,1H),6.12(s,1H),1.69(s,15H);ESI-MS(+):m/z505.2[M-H2O-H]+.
(16)のスペクトルデータを以下に示す。
1H NMR(D2O,400MHz):8.68(d,J=3.2Hz,1H),8.37(d,J=3.2Hz,1H),8.00(t,J=4.0Hz,1H),7.42(d,J=8Hz,1H),6.98(t,J=3.2Hz,2H),1.69(s,15H);13C NMR(D2O,125MHz):δ=164.09,146.86,145.24,143.88,132.22,112.45,110.61,101.99,89.77,8.97.ESI-MS(+):m/z488.1[M-H2O-H]+.
(17)のスペクトルデータを以下に示す。
1H NMR(DMSO-d6,400MHz):11.38(s,1H),8.65(s,1H),8.45(s,1H),7.03(s,1H),5.29(s,1H),1.73(s,15H);13C NMR(DMSO-d6,125MHz):169.56,168.59,145.18,133.44,111.97,96.26,87.89,8.83;ESI-MS:505.1[M-H2O-H]+. Anal. Calc. for C17H23IrN4O7S・0.5H2O: C 32.48, H 3.85, N 8.91. Found: C 32.62, H 3.63, N 8.66.
(18)のスペクトルデータを以下に示す。
1H NMR (D2O, 400 MHz): d = 7.38 (s, 1H), 7.19 (s, 1H), 6.01 (s, 1H), 1.63 (s, 15H). 1H NMR (d6-DMSO, 400 MHz): 10.89 (s, 1H), 7.86 (s, 1H), 7.57 (s, 1H), 6.12 (s, 1H), 1.69 (s, 15H). 13C NMR (d6-DMSO, 125 MHz): d =168.71, 157.91, 127.47, 123.18, 95.95, 87.73, 84.72, 55.90, 8.99. ESI-MS(+): m/z 505.2 [M−H2O−H]+.
一般式(1)から(2)で示される錯体触媒を水に溶かした溶液を脱気した。1Mギ酸の水溶液(10mL)を脱気し、先に調整した触媒溶液を加えて、加熱撹拌した。発生するガス量をガスメーター(Shinagawa W-NK-05)で測定した。また、発生したガス成分は、ガスクロマトグラフィーGLサイエンス(GC390)で、水素は熱伝導度検出器(TCD)で、二酸化炭素および一酸化炭素はメタナイザーおよび水素炎イオン検出器(FID)を用いて測定した。その結果、水素と二酸化炭素は1:1の割合で発生し、一酸化炭素は検出できなかった(検出限界10ppm以下)。表1に示す反応の結果から、本発明で見出した5員環を含む配位子を有する触媒は、いずれも高い触媒活性を示した。また、非特許文献18で記載されているように、ギ酸の脱水素化反応において、触媒配位子上の置換基の電子供与性効果によって、触媒が活性されることが分かっている。この知見から、一般式(25)で示される錯体に4つのメチル基を導入した一般式(26)で示される錯体は、一般式(25)で示される錯体に比べて1.75倍高いTOF(触媒回転効率:1時間当たり触媒1分子が作用する基質(ギ酸)分子数)を示した。さらに、強い電子供与性を示す水酸基を導入すると、一般式(22)で示される無置換体に対し、水酸基を置換した一般式(15)で示される類似錯体は、5倍以上高いTOFを示した。
一般式(18)で示される錯体触媒を水に溶かした溶液を脱気した。80%ギ酸の水溶液(10mL)を脱気し、先に調整した触媒溶液(1μmol)を加えて、加熱撹拌した。150時間以上触媒反応が進行し、反応後ギ酸は完全に分解された。ガス発生の時間経過を図1に示す。本錯体触媒は、高濃度ギ酸溶液中でも1週間以上の触媒が劣化することなく、安定した触媒性能を発現することができた。
一般式(18)で示される錯体触媒を水に溶かした溶液を脱気した。pHを調整した1Mのギ酸/ギ酸ナトリウム(100/0から0/100)水溶液(10mL)を脱気して、先に調整した錯体溶液100μL(1μmol)を加えて、60℃で撹拌した。pHに依存した反応速度を図2に示す。
一般式(18)で示される錯体触媒(5μmol)を含んだ8Mのギ酸水溶液(50mL)脱気し、ガラスオートクレーブに入れた。反応容器を80℃で加熱撹拌し、2MPaに設定した背圧弁から発生するガス量とガスの比率を測定した(図3及び4)。この結果、触媒回転効率は1時間あたり34000回と極めて高い触媒性能を示した。また、水素と二酸化炭素は、ほぼ1:1の割合で発生し、反応後ギ酸は99%以上分解されていることを確認した。この結果は、高濃度ギ酸水溶液中、80℃の高温条件、2MPaの高圧の激しい反応条件でも、錯体触媒が劣化することなく、水素を生成することを示している。
一般式(28)で示される類似の無置換ビピリジン錯体触媒を用いたギ酸の脱水素化反応(1Mギ酸水溶液、反応温度60℃)では、TOFは30であった。本発明で見出した触媒は、同一反応条件下この値を大きく上回る高い触媒活性を示した。また、一般式(28)で示される錯体の配位子上に水酸基を置換して活性化させた一般式(29)で示される錯体触媒のTOFは1800であったことから、本発明により配位子上の5員環基本骨格だけで、優れた触媒性能を示す触媒を設計できることが分かった。実際、触媒配位子に水酸基を導入した一般式(18)で示される錯体触媒が最も高い触媒性能を示した。
特許文献12および13の一般式(30)(R=HまたはOH)で示されるギ酸脱水素化触媒は、1M以下でpH3.5に調整されたギ酸溶液および70℃以下の反応温度の最適反応条件では極めて高い反応速度を示す。しかし、これ以外の条件では、触媒性能が大きく低下する。また、反応後のギ酸の変換効率は50%と低い。一方で、2M以上のギ酸溶液あるいは/および80℃以上激しい反応条件では、1時間以内で触媒性能が著しく低下する。
Claims (4)
- 式(10)で表されるピラゾール環とピリジン環とからなる2座配位子をもつ錯体、その異性体、または塩を有効成分として含む、ギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
R7〜R13は、それぞれ独立に、水素原子、アルキル基、ヒドロキシ基(-OH)、アルコキシ基(-OR)、ニトロ基、ハロゲン基、スルホン基、カルボン酸基、アルキルアミノ基、もしくはフェニル基、または、隣り合ったR同士で環を形成しても良く、置換基を有している場合は、前記置換基は1つでも複数でも良く、ただし、R7〜R13は、少なくとも1つが前記ヒドロキシ基(-OH)、または、前記アルコキシ基(-OR)であり、
Z2は、任意の配位子であるか、または、存在せず、
nは、正の整数、0、または負の整数である。 - 前記錯体が下記式(16)、式(C)〜(H)のいずれかで表される構造を有するものである請求項1に記載のギ酸または/およびギ酸塩の脱水素化反応に用いる触媒。
- 請求項1または2に記載の触媒の存在下、ギ酸または/およびギ酸塩を含む溶液と反応させることによってギ酸または/およびギ酸塩を脱水素化する方法。
- 請求項1または2に記載の触媒の存在下、ギ酸または/およびギ酸塩を含む溶液と反応させることによってギ酸または/およびギ酸塩を脱水素化し水素を製造する方法。
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WO2011108730A1 (ja) * | 2010-03-04 | 2011-09-09 | 国立大学法人大阪大学 | 単核金属錯体、水素化還元触媒、脱水素用触媒、水素化還元生成物の製造方法、水素(h2)の製造方法および脱水素反応生成物の製造方法 |
WO2013125020A1 (ja) * | 2012-02-23 | 2013-08-29 | 関東化学株式会社 | 脱水素用触媒、該触媒を用いたカルボニル化合物および水素の製造方法 |
JP2013193983A (ja) * | 2012-03-19 | 2013-09-30 | National Institute Of Advanced Industrial Science & Technology | 二酸化炭素の水素化またはギ酸の脱水素化に用いる触媒、該触媒を用いる二酸化炭素の水素化方法、ギ酸の脱水素化方法、水素の貯蔵および製造方法 |
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EP3056273A4 (en) | 2017-08-09 |
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