JP2015074619A - Method for producing alcohol compound - Google Patents
Method for producing alcohol compound Download PDFInfo
- Publication number
- JP2015074619A JP2015074619A JP2013210728A JP2013210728A JP2015074619A JP 2015074619 A JP2015074619 A JP 2015074619A JP 2013210728 A JP2013210728 A JP 2013210728A JP 2013210728 A JP2013210728 A JP 2013210728A JP 2015074619 A JP2015074619 A JP 2015074619A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- catalyst
- compound
- metal
- yield
- 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.)
- Granted
Links
- -1 alcohol compound Chemical class 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 133
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 41
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 29
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 25
- 239000010948 rhodium Substances 0.000 claims abstract description 24
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 19
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 15
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims abstract description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000000737 periodic effect Effects 0.000 claims abstract description 13
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 11
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 10
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 10
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 126
- 239000000470 constituent Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 146
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 76
- 239000001384 succinic acid Substances 0.000 description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- 239000000243 solution Substances 0.000 description 55
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 54
- ONDSBJMLAHVLMI-UHFFFAOYSA-N trimethylsilyldiazomethane Chemical compound C[Si](C)(C)[CH-][N+]#N ONDSBJMLAHVLMI-UHFFFAOYSA-N 0.000 description 38
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 33
- 239000011521 glass Substances 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 28
- 239000000706 filtrate Substances 0.000 description 27
- 238000004817 gas chromatography Methods 0.000 description 27
- 239000012528 membrane Substances 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 27
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 26
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 20
- 239000011591 potassium Substances 0.000 description 20
- 229960003975 potassium Drugs 0.000 description 20
- 229910052700 potassium Inorganic materials 0.000 description 20
- 235000007686 potassium Nutrition 0.000 description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 19
- 230000032050 esterification Effects 0.000 description 19
- 238000005886 esterification reaction Methods 0.000 description 19
- 229910052708 sodium Inorganic materials 0.000 description 19
- 239000011734 sodium Substances 0.000 description 19
- 235000011121 sodium hydroxide Nutrition 0.000 description 19
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 17
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 12
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 11
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000004310 lactic acid Substances 0.000 description 9
- 235000014655 lactic acid Nutrition 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 229910002839 Pt-Mo Inorganic materials 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 6
- 235000019798 tripotassium phosphate Nutrition 0.000 description 6
- ZYSSNSIOLIJYRF-UHFFFAOYSA-H Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl Chemical compound Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl ZYSSNSIOLIJYRF-UHFFFAOYSA-H 0.000 description 5
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 5
- 229940040102 levulinic acid Drugs 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- ALHHYLLHZKAXCW-UHFFFAOYSA-H dipotassium;platinum(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[K+].[K+].[Pt+4] ALHHYLLHZKAXCW-UHFFFAOYSA-H 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- XZQYTGKSBZGQMO-UHFFFAOYSA-I rhenium pentachloride Chemical compound Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 4
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 4
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- BYHYTWGFYKDDCE-UHFFFAOYSA-H Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl.N.N Chemical compound Cl[Ir](Cl)(Cl)(Cl)(Cl)Cl.N.N BYHYTWGFYKDDCE-UHFFFAOYSA-H 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 3
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 3
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YOUIDGQAIILFBW-UHFFFAOYSA-J Tungsten(IV) chloride Inorganic materials Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 3
- DGVVPRHPLWDELQ-UHFFFAOYSA-N acetic acid;samarium Chemical compound [Sm].CC(O)=O.CC(O)=O.CC(O)=O DGVVPRHPLWDELQ-UHFFFAOYSA-N 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 3
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 3
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
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- 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 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
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- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
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- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
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- 239000000843 powder Substances 0.000 description 3
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- PKCZMSFDSKIUAK-UHFFFAOYSA-H [Na].[Na].[Ir](Cl)(Cl)(Cl)(Cl)(Cl)Cl Chemical compound [Na].[Na].[Ir](Cl)(Cl)(Cl)(Cl)(Cl)Cl PKCZMSFDSKIUAK-UHFFFAOYSA-H 0.000 description 2
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- GOJZFZCBZKSZIW-UHFFFAOYSA-H [Ru](Cl)(Cl)(Cl)(Cl)(Cl)Cl.[K].[K] Chemical compound [Ru](Cl)(Cl)(Cl)(Cl)(Cl)Cl.[K].[K] GOJZFZCBZKSZIW-UHFFFAOYSA-H 0.000 description 2
- MNGBVVXSJNCWMI-UHFFFAOYSA-H [Ru](Cl)(Cl)(Cl)(Cl)(Cl)Cl.[Na].[Na] Chemical compound [Ru](Cl)(Cl)(Cl)(Cl)(Cl)Cl.[Na].[Na] MNGBVVXSJNCWMI-UHFFFAOYSA-H 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- AEETWQIZFGAMIM-UHFFFAOYSA-K azane;trichlororuthenium;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ru+3] AEETWQIZFGAMIM-UHFFFAOYSA-K 0.000 description 2
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
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- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 2
- WTVAYLQYAWAHAX-UHFFFAOYSA-J cerium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ce+4] WTVAYLQYAWAHAX-UHFFFAOYSA-J 0.000 description 2
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- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 2
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- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 2
- LDMNYTKHBHFXNG-UHFFFAOYSA-H disodium;platinum(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Pt+4] LDMNYTKHBHFXNG-UHFFFAOYSA-H 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 2
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- NCDCLPBOMHPFCV-UHFFFAOYSA-N hexyl hexanoate Chemical compound CCCCCCOC(=O)CCCCC NCDCLPBOMHPFCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 description 1
- SECPZKHBENQXJG-BQYQJAHWSA-N palmitelaidic acid Chemical compound CCCCCC\C=C\CCCCCCCC(O)=O SECPZKHBENQXJG-BQYQJAHWSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- FWIYBTVHGYLSAZ-UHFFFAOYSA-I pentaiodoniobium Chemical compound I[Nb](I)(I)(I)I FWIYBTVHGYLSAZ-UHFFFAOYSA-I 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- SNPHNDVOPWUNON-UHFFFAOYSA-J platinum(4+);tetrabromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Pt+4] SNPHNDVOPWUNON-UHFFFAOYSA-J 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 description 1
- WXBOMIKEWRRKBB-UHFFFAOYSA-N rhenium(iv) oxide Chemical compound O=[Re]=O WXBOMIKEWRRKBB-UHFFFAOYSA-N 0.000 description 1
- BSMABMYXKITCBS-UHFFFAOYSA-K rhenium;triiodide Chemical compound [I-].[I-].[I-].[Re] BSMABMYXKITCBS-UHFFFAOYSA-K 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003317 samarium compounds Chemical class 0.000 description 1
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- MISXNQITXACHNJ-UHFFFAOYSA-I tantalum(5+);pentaiodide Chemical compound [I-].[I-].[I-].[I-].[I-].[Ta+5] MISXNQITXACHNJ-UHFFFAOYSA-I 0.000 description 1
- GCPVYIPZZUPXPB-UHFFFAOYSA-I tantalum(v) bromide Chemical compound Br[Ta](Br)(Br)(Br)Br GCPVYIPZZUPXPB-UHFFFAOYSA-I 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- IYWTUWKWQJIZPO-UHFFFAOYSA-J tetrabromoiridium Chemical compound Br[Ir](Br)(Br)Br IYWTUWKWQJIZPO-UHFFFAOYSA-J 0.000 description 1
- BSGFBYZRPYAMRQ-UHFFFAOYSA-H tetrabromoplatinum(2+) dibromide Chemical compound Br[Pt](Br)(Br)(Br)(Br)Br BSGFBYZRPYAMRQ-UHFFFAOYSA-H 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RNJPWBVOCUGBGY-UHFFFAOYSA-J tetraiodoplatinum Chemical compound [I-].[I-].[I-].[I-].[Pt+4] RNJPWBVOCUGBGY-UHFFFAOYSA-J 0.000 description 1
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- YPFBRNLUIFQCQL-UHFFFAOYSA-K tribromomolybdenum Chemical compound Br[Mo](Br)Br YPFBRNLUIFQCQL-UHFFFAOYSA-K 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
- GCZKMPJFYKFENV-UHFFFAOYSA-K triiodogold Chemical compound I[Au](I)I GCZKMPJFYKFENV-UHFFFAOYSA-K 0.000 description 1
- XQKBFQXWZCFNFF-UHFFFAOYSA-K triiodosamarium Chemical compound I[Sm](I)I XQKBFQXWZCFNFF-UHFFFAOYSA-K 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- UXVOMHPBSSIGNQ-UHFFFAOYSA-I tungsten(v) bromide Chemical compound Br[W](Br)(Br)(Br)Br UXVOMHPBSSIGNQ-UHFFFAOYSA-I 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 150000003747 ytterbium compounds Chemical class 0.000 description 1
- LSSJSIMBIIVSTN-UHFFFAOYSA-K ytterbium(3+);triiodide Chemical compound I[Yb](I)I LSSJSIMBIIVSTN-UHFFFAOYSA-K 0.000 description 1
- QNLXXQBCQYDKHD-UHFFFAOYSA-K ytterbium(iii) bromide Chemical compound Br[Yb](Br)Br QNLXXQBCQYDKHD-UHFFFAOYSA-K 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- 229910000350 zirconium(IV) sulfate Inorganic materials 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
- XLMQAUWIRARSJG-UHFFFAOYSA-J zirconium(iv) iodide Chemical compound [Zr+4].[I-].[I-].[I-].[I-] XLMQAUWIRARSJG-UHFFFAOYSA-J 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
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、アルコール化合物の製造方法に関する。 The present invention relates to a method for producing an alcohol compound.
従来、カルボン酸化合物から対応するアルコール化合物を製造する方法としては、カルボン酸をエステル化した後に、還元する方法が広く知られていた。しかしながら、還元するに先立ちカルボキシル基をエステル化する必要があった。そのため、カルボン酸化合物をエステル化することなく、直接アルコール化合物を製造する方法が望まれている。 Conventionally, as a method for producing a corresponding alcohol compound from a carboxylic acid compound, a method in which the carboxylic acid is esterified and then reduced is widely known. However, it was necessary to esterify the carboxyl group prior to the reduction. Therefore, a method for directly producing an alcohol compound without esterifying the carboxylic acid compound is desired.
カルボン酸化合物から直接アルコール化合物を製造する方法としては、例えば、下記の(1)〜(3)の方法が知られている。
(1)過酸化物により酸化された炭素上にパラジウム/銀/レニウムが担持された触媒の存在下、マレイン酸を還元して1,4−ブタンジオールを製造する方法(例えば、特許文献1参照)。
(2)パラジウム/銀/レニウム/金属(M)が炭素に担持された触媒の存在下、マレイン酸を還元して1,4−ブタンジオールを製造する方法(例えば、特許文献2参照)。
(3)過酸化水素で処理された活性炭に、ルテニウム/スズ/白金が担持された触媒の存在下、コハク酸、グルタル酸、アジピン酸の混合物を還元して、対応するジオールを製造する方法(例えば、特許文献3参照)。
As a method for producing an alcohol compound directly from a carboxylic acid compound, for example, the following methods (1) to (3) are known.
(1) A method for producing 1,4-butanediol by reducing maleic acid in the presence of a catalyst in which palladium / silver / rhenium is supported on carbon oxidized by peroxide (see, for example, Patent Document 1) ).
(2) A method for producing 1,4-butanediol by reducing maleic acid in the presence of a catalyst in which palladium / silver / rhenium / metal (M) is supported on carbon (see, for example, Patent Document 2).
(3) A method for producing a corresponding diol by reducing a mixture of succinic acid, glutaric acid and adipic acid in the presence of a catalyst in which ruthenium / tin / platinum is supported on activated carbon treated with hydrogen peroxide ( For example, see Patent Document 3).
しかしながら、上記特許文献1の方法では、触媒の製造に先立って、炭素担体と酸化剤とを接触させて酸化された炭素担体を使用しなければならず、酸化されていない炭素担体は、触媒活性が低いことが比較例において明確に開示されている(例えば、実施例2と比較例Bの対比)。そのため、触媒の製造が煩雑となるという問題があった。
更に、当該触媒においては、LHSV(液体空間速度)や反応温度によって、生成物が大きく変化するため、反応条件を限定して設定する必要があった(段落番号[0045]と[0046]の対比)
However, in the method of Patent Document 1 described above, a carbon support that has been oxidized by bringing a carbon support into contact with an oxidizing agent must be used prior to the production of the catalyst. Is clearly disclosed in the comparative example (for example, comparison between Example 2 and Comparative Example B). Therefore, there has been a problem that the manufacture of the catalyst becomes complicated.
Furthermore, in the catalyst, since the product greatly varies depending on LHSV (liquid space velocity) and reaction temperature, it is necessary to set reaction conditions in a limited manner (Contrast between paragraph numbers [0045] and [0046]). )
また、特許文献2の方法では、第4成分の金属(M;アルミニウム、鉄、コバルト)が触媒活性の必須の構成要件となっており(参考例1、実施例1及び比較例の対比)、参考例1及び2(触媒の使用前の処理)を参酌しても触媒の製造が煩雑であるという問題があった。 Further, in the method of Patent Document 2, the fourth component metal (M; aluminum, iron, cobalt) is an indispensable constituent requirement for the catalytic activity (comparison of Reference Example 1, Example 1 and Comparative Example), Even if Reference Examples 1 and 2 (treatment before using the catalyst) are taken into account, there is a problem that the production of the catalyst is complicated.
一方、特許文献3においては、活性炭を予め過酸化水素などで処理しなければならないという問題の他、特許文献1と同様な問題も存在していた。 On the other hand, in Patent Document 3, there is a problem similar to Patent Document 1 in addition to the problem that activated carbon must be previously treated with hydrogen peroxide or the like.
以上提案されている上記いずれの触媒を使用した還元反応においても、例えば、ジカルボン酸化合物を還元した場合には、不完全還元体であるヒドロキシカルボン酸化合物が残存、環状エステル化合物、環状エーテル化合物などが生成してしまうという問題も残っていた。 In the reduction reaction using any of the above-mentioned catalysts proposed above, for example, when a dicarboxylic acid compound is reduced, the hydroxycarboxylic acid compound that is an incompletely reduced form remains, a cyclic ester compound, a cyclic ether compound, etc. There was still a problem of generating.
そこで、本発明は、特定の構成成分からなる触媒を用いることによって、カルボン酸化合物を出発原料として、高い反応速度で、高収率且つ高選択的にアルコール化合物を製造することが可能とする、工業的生産に適用し得るアルコール化合物の製造方法を提供することを課題とする。 Therefore, the present invention makes it possible to produce an alcohol compound with high yield and high selectivity at a high reaction rate using a carboxylic acid compound as a starting material by using a catalyst comprising specific constituent components. It is an object of the present invention to provide a method for producing an alcohol compound that can be applied to industrial production.
本発明の課題は、水素源の存在下、カルボン酸化合物と、
ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の金属化合物(A)と、
周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)と、
を混合し、還元処理して得られる触媒とを接触させることを特徴とする、アルコール化合物の製造方法によって解決される。
An object of the present invention is to provide a carboxylic acid compound in the presence of a hydrogen source,
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold A metal compound (A) of
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
This is solved by a method for producing an alcohol compound, which comprises contacting the catalyst with a catalyst obtained by reduction and mixing.
本発明により、カルボン酸化合物を還元して、高い反応速度で、高収率且つ高選択的に上記カルボン酸化合物に対応するアルコール化合物を製造することが可能な触媒及び当該触媒の製造方法を提供することができる。また、本発明では、上述の触媒を用いることによって、高い反応速度で、高収率且つ高選択的にアルコール化合物を製造することが可能であり、工業的生産に適用し得るアルコール化合物の製造方法を提供する。 The present invention provides a catalyst capable of reducing a carboxylic acid compound to produce an alcohol compound corresponding to the carboxylic acid compound with high reaction rate and high yield, and a method for producing the catalyst. can do. Further, in the present invention, by using the above-mentioned catalyst, it is possible to produce an alcohol compound with high reaction rate, high yield and high selectivity, and a method for producing an alcohol compound that can be applied to industrial production. I will provide a.
以下、本発明について具体的に説明する。
(触媒)
本発明の触媒は、
ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の金属化合物(A)と、
周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル(B2)化合物と、
を混合し、還元処理して得られる触媒である。
以下、本発明の触媒を製造する際の構成成分について説明する。なお、以下、各構成成分を混合させてものを「混合物」と称することもある。
Hereinafter, the present invention will be specifically described.
(catalyst)
The catalyst of the present invention comprises
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold A metal compound (A) of
A metal oxide (B1) or metal carbonyl (B2) compound containing a metal of Group 5, 6 or 7 of the periodic table;
Is a catalyst obtained by mixing and reducing.
Hereafter, the component at the time of manufacturing the catalyst of this invention is demonstrated. In addition, hereinafter, a mixture of each component may be referred to as a “mixture”.
(ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の金属化合物(A))
ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の金属化合物(A)としては、例えば、
三塩化ロジウム、六塩化ロジウム三アンモニウム、六塩化ロジウム三カリウム、六塩化ロジウム三ナトリウム、三硝酸ロジウム、ヘキサヒドロキシロジウム(III)酸三ナトリウム、ヘキサヒドロキシロジウム(III)酸三カリウム、ヘキサヒドロキシロジウム(IV)酸二ナトリウム、ヘキサヒドロキシロジウム(IV)酸二カリウムなどのロジウム化合物;
三塩化イリジウム、三臭化イリジウム、四塩化イリジウム、四臭化イリジウム、イリジウム酸アンモニウム塩、ヘキサアンミンイリジウム三塩化物、ペンタアンミンクロロイリジウム二塩化物、六塩化イリジウム三アンモニウム、六塩化イリジウム三カリウム、六塩化イリジウム三ナトリウム、四塩化イリジウム二アンモニウム、六塩化イリジウム二アンモニウム、六塩化イリジウム二カリウム、六塩化イリジウム酸、六塩化イリジウム二ナトリウム、ヘキサヒドロキシイリジウム(IV)酸二ナトリウム、ヘキサヒドロキシイリジウム(IV)酸二カリウムなどのイリジウム化合物;
二塩化白金、四塩化白金、六塩化白金酸、二臭化白金、四臭化白金、六臭化白金酸、二ヨウ化白金、四ヨウ化白金、二塩化白金二アンモニウム、六塩化白金二アンモニウム、六塩化白金二アンモニウム、四塩化白金二アンモニウム、六塩化白金二ナトリウム、四塩化白金二カリウム、六塩化白金二カリウム、二臭化白金二アンモニウム、四臭化白金二カリウム、六臭化白金二アンモニウム、六ヨウ化白金酸ナトリウム、六ヨウ化白金酸カリウム、酸化白金、ヘキサヒドロキソ白金酸水素、水酸化白金、ヘキサヒドロキシ白金酸ナトリウム、ヘキサヒドロキシ白金(IV)酸カリウムなどの白金化合物;
三塩化ルテニウム、三臭化ルテニウム、五塩化ルテニウム二アンモニウム、六塩化ルテニウム三アンモニウム、六塩化ルテニウム二カリウム、六塩化ルテニウム二ナトリウム、六臭化ルテニウム三カリウム、六臭化ルテニウム二カリウム、過ルテニウム酸カリウム、過ルテニウム酸(テトラプロピルアンモニウム)、過ルテニウム酸(テトラブチルアンモニウム)、テトラオキソルテニウム(VI)酸二カリウム、テトラオキソルテニウム(VI)酸二ナトリウム、テトラヒドロキシルテニウム(IV)化合物などのルテニウム化合物;
五塩化タンタル、五臭化タンタル、五ヨウ化タンタル、タンタルペンタエチラート、タンタル酸ナトリウム、タンタル酸カリウム等のタンタル化合物;
三塩化レニウム、五塩化レニウム、三ヨウ化レニウム、過レニウム酸アンモニウム、過レニウム酸カリウム、過レニウム酸ナトリウム、六塩化レニウム三カリウム、六塩化レニウム二カリウム、七酸化二レニウム等のレニウム化合物;
二塩化パラジウム、二臭化パラジウム、二ヨウ化パラジウム、二酢酸パラジウム、二硝酸パラジウム、硫酸パラジウム、酸化パラジウム、ヘキサヒドロキシパラジウム(IV)酸二ナトリウム、ヘキサヒドロキシパラジウム(IV)酸二カリウム、水酸化パラジウム
等のパラジウム化合物;
三塩化ランタン、三臭化ランタン、三ヨウ化ランタン、三硝酸ランタン、リン酸ランタン、三硫酸二ランタン、三炭酸二ランタン、ギ酸ランタン等のランタン化合物;
塩化第一セリウム、臭化第一セリウム、三シュウ酸二セリウム、三硝酸セリウム、四水酸化セリウム、三炭酸二セリウム、硝酸第一セリウムアンモニウム、硝酸第二セリウムアンモニウム、リン酸セリウム、硫酸第一セリウム、硫酸第二セリウム等のセリウム化合物;
三塩化サマリウム、三酢酸サマリウム、三シュウ酸二サマリウム、三硝酸サマリウム、三炭酸二サマリウム、三ヨウ化サマリウム、硫酸サマリウム等のサマリウム化合物;
三塩化イッテルビウム、三臭化イッテルビウム、三硝酸イッテルビウム、三硫酸二イッテルビウム、三酢酸イッテルビウム、三シュウ酸二イッテルビウム、三ヨウ化イッテルビウム、リン酸イッテルビウム等のイッテルビウム化合物;
三塩化ルテチウム、三酢酸ルテチウム、三シュウ酸二ルテチウム、三硝酸ルテチウム、硫酸ルテチウム等のルテチウム化合物;
四塩化ジルコニウム、四臭化ジルコニウム、四ヨウ化ジルコニウム、四硝酸ジルコニウム、二硫酸ジルコニウム等のジルコニウム化合物;
四塩化ハフニウム、四臭化ハフニウム、四ヨウ化ハフニウム、四硝酸ハフニウム、二硫酸ハフニウム等のハフニウム化合物;
五塩化ニオブ、五臭化ニオブ、五ヨウ化ニオブ、五(シュウ酸水素)ニオブ、ニオブペンタエチラート、ニオブペンタ−n−ブチラート、三酸化ナトリウムニオブ等のニオブ化合物;
三塩化モリブデン、五塩化モリブデン、三臭化モリブデン、テトラコサオキソヘプタモリブデン(VI)酸アンモニウム、テトラオキソモリブデン(VI)酸カリウム、テトラオキソモリブデン(VI)酸ナトリウム等のモリブデン化合物;
四塩化タングステン、六塩化タングステン、五臭化タングステン、ケイタングステン酸、ケイタングステン酸カリウム、ケイタングステン酸ナトリウム、パラタングステン酸アンモニウム、タングステン酸カリウム等のタングステン化合物;
二塩化コバルト、二臭化コバルト、二ヨウ化コバルト、二フッ化コバルト、二硝酸コバルト、酸化コバルト、リン酸コバルト、二酢酸コバルト、トリヒドロキシコバルト(III)、ギ酸第一コバルト、クエン酸第一コバルト等のコバルト化合物;
二塩化ニッケル、二臭化ニッケル、二ヨウ化ニッケル、シュウ酸ニッケル、二硝酸ニッケル、二水酸化ニッケル等のニッケル化合物;
一塩化銅、二塩化銅、二塩化銅二アンモニウム、ギ酸第二銅、一臭化銅、二臭化銅、硝酸銅、リン酸銅、硫酸銅、酢酸銅、炭酸銅、シュウ酸銅等の銅化合物;
一塩化金、三塩化金、四塩化金酸、三臭化金、三ヨウ化金、水酸化金、四塩化金カリウム、四臭化金ナトリウム、四臭化金酸等の金化合物;
が挙げられ、好ましくは、
三塩化ロジウム、三硝酸ロジウム、三塩化イリジウム、四塩化イリジウム、イリジウム酸アンモニウム塩、六塩化イリジウム三ナトリウム、四塩化イリジウム二アンモニウム、六塩化イリジウム二アンモニウム、六塩化イリジウム二カリウム、六塩化イリジウム酸、六塩化イリジウム二ナトリウム、二塩化白金、四塩化白金、六塩化白金酸、ヘキサヒドロキソ白金酸水素、水酸化白金、ヘキサヒドロキシ白金酸ナトリウム、ヘキサヒドロキシ白金(IV)酸カリウム、三塩化ルテニウム、五塩化ルテニウム二アンモニウム、六塩化ルテニウム三アンモニウム、六塩化ルテニウム二カリウム、六塩化ルテニウム二ナトリウム、過ルテニウム酸カリウム、過ルテニウム酸(テトラプロピルアンモニウム)、過ルテニウム酸(テトラブチルアンモニウム)、テトラオキソルテニウム(VI)酸二カリウム、テトラオキソルテニウム(VI)酸二ナトリウム、五塩化タンタル、タンタル酸カリウム、三塩化レニウム、五塩化レニウム、過レニウム酸アンモニウム、過レニウム酸カリウム、過レニウム酸ナトリウム、七酸化二レニウム、二塩化パラジウム、二酢酸パラジウム、二硝酸パラジウム、水酸化パラジウム、三塩化ランタン、三硝酸ランタン、リン酸ランタン、三炭酸二ランタン、ギ酸ランタン、塩化第一セリウム、三硝酸セリウム、四水酸化セリウム、三炭酸二セリウム、リン酸セリウム、三塩化サマリウム、三酢酸サマリウム、三硝酸サマリウム、三塩化イッテルビウム、三硝酸イッテルビウム、三酢酸イッテルビウム、リン酸イッテルビウム、三塩化ルテチウム、三酢酸ルテチウム、三硝酸ルテチウム、四塩化ジルコニウム、四硝酸ジルコニウム、四塩化ハフニウム、四硝酸ハフニウム、五塩化ニオブ、三酸化ナトリウムニオブ、三塩化モリブデン、五塩化モリブデン、テトラコサオキソヘプタモリブデン(VI)酸アンモニウム、テトラオキソモリブデン(VI)酸カリウム、テトラオキソモリブデン(VI)酸ナトリウム、四塩化タングステン、六塩化タングステン、ケイタングステン酸、ケイタングステン酸カリウム、ケイタングステン酸ナトリウム、パラタングステン酸アンモニウム、タングステン酸カリウム、二塩化コバルト、二硝酸コバルト、リン酸コバルト、二酢酸コバルト、二塩化ニッケル、二硝酸ニッケル、二水酸化ニッケル、一塩化銅、二塩化銅、硝酸銅、リン酸銅、酢酸銅、一塩化金、三塩化金、四塩化金酸、水酸化金、四塩化金カリウムが挙げられ、更に好ましくは、
三塩化ロジウム、三硝酸ロジウム、三塩化イリジウム、四塩化イリジウム、塩化イリジウム酸、二塩化白金、四塩化白金、六塩化白金酸、水酸化白金、三塩化ルテニウム、過ルテニウム酸カリウム、過ルテニウム酸(テトラプロピルアンモニウム)、五塩化タンタル、タンタル酸カリウム、三塩化レニウム、五塩化レニウム、過レニウム酸アンモニウム、過レニウム酸カリウム、七酸化二レニウム、二塩化パラジウム、二酢酸パラジウム、二硝酸パラジウム、三塩化ランタン、三硝酸ランタン、塩化第一セリウム、三硝酸セリウム、三塩化サマリウム、三酢酸サマリウム、三硝酸サマリウム、三塩化イッテルビウム、三硝酸イッテルビウム、三酢酸イッテルビウム、三塩化ルテチウム、三酢酸ルテチウム、三硝酸ルテチウム、四塩化ジルコニウム、四硝酸ジルコニウム、四塩化ハフニウム、四硝酸ハフニウム、五塩化ニオブ、三酸化ナトリウムニオブ、三塩化モリブデン、五塩化モリブデン、テトラコサオキソヘプタモリブデン(VI)酸アンモニウム、テトラオキソモリブデン(VI)酸カリウム、テトラオキソモリブデン(VI)酸ナトリウム、四塩化タングステン、六塩化タングステン、ケイタングステン酸、ケイタングステン酸カリウム、ケイタングステン酸ナトリウム、パラタングステン酸アンモニウム、二塩化コバルト、二硝酸コバルト、二酢酸コバルト、二塩化ニッケル、二硝酸ニッケル、二水酸化ニッケル、一塩化銅、二塩化銅、硝酸銅、酢酸銅、一塩化金、三塩化金、四塩化金酸、四塩化金カリウム、が使用される。
(At least 2 selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold. Seed metal compound (A))
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold As the metal compound (A), for example,
Rhodium trichloride, Rhodium triammonium chloride, Tripotassium hexachloride, Trisodium hexachloride, Rhodium trinitrate, Rhodium trinitrate, Trisodium hexahydroxyrhodium (III), Tripotassium hexahydroxyrhodium (III), Hexahydroxyrhodium ( IV) Rhodium compounds such as disodium acid, dihydroxy potassium hexahydroxyrhodium (IV);
Iridium trichloride, iridium tribromide, iridium tetrachloride, iridium tetrabromide, ammonium iridate, hexaammine iridium trichloride, pentaammine chloroiridium dichloride, iridium hexachloride triammonium hexachloride iridium trichloride, Trisodium iridium hexachloride, diammonium iridium tetrachloride, diammonium iridium hexachloride, iridium hexachloride, dipotassium hexachloride, iridium hexachloride, iridium hexachloride disodium, disodium hexahydroxyiridium (IV), hexahydroxyiridium (IV ) Iridium compounds such as dipotassium acid;
Platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, platinum dibromide, platinum tetrabromide, platinum hexabromide acid, platinum diiodide, platinum tetraiodide, diammonium platinum dichloride, diammonium platinum hexachloride , Platinum hexachloride diammonium, platinum diammonium tetrachloride, platinum disodium hexachloride, dipotassium tetrachloride, dipotassium hexachlorochloride, diammonium platinum dibromide, dipotassium tetrabromide tetrachloride, platinum dibromide Platinum compounds such as ammonium, sodium hexaiodide platinate, potassium hexaiodide platinate, platinum oxide, hydrogen hexahydroxoplatinate, platinum hydroxide, sodium hexahydroxyplatinate, potassium hexahydroxyplatinate (IV);
Ruthenium trichloride, ruthenium tribromide, ruthenium diammonium pentachloride, ruthenium triammonium hexachloride, ruthenium hexachloride dipotassium, ruthenium hexachloride disodium, ruthenium hexabromide tripotassium, ruthenium hexabromide dipotassium perruthenate Ruthenium such as potassium, perruthenic acid (tetrapropylammonium), perruthenic acid (tetrabutylammonium), dipotassium tetraoxoruthenium (VI), disodium tetraoxoruthenium (VI), tetrahydroxyruthenium (IV) compounds Compound;
Tantalum compounds such as tantalum pentachloride, tantalum pentabromide, tantalum pentaiodide, tantalum pentaethylate, sodium tantalate, potassium tantalate;
Rhenium compounds such as rhenium trichloride, rhenium pentachloride, rhenium triiodide, ammonium perrhenate, potassium perrhenate, sodium perrhenate, tripotassium hexachlororhenium, dipotassium rhenium hexachloride, dirhenium heptoxide;
Palladium dichloride, palladium dibromide, palladium diiodide, palladium diacetate, palladium dinitrate, palladium sulfate, palladium oxide, disodium hexahydroxypalladium (IV), dipotassium hexahydroxypalladium (IV), hydroxylated Palladium compounds such as palladium;
Lanthanum compounds such as lanthanum trichloride, lanthanum tribromide, lanthanum triiodide, lanthanum trinitrate, lanthanum phosphate, dilanthanum trisulfate, dilanthanum tricarbonate, lanthanum formate;
Cerium chloride, cerium bromide, cerium trioxalate, cerium trinitrate, cerium tetrahydroxide, cerium tricarbonate, cerium ammonium nitrate, cerium ammonium nitrate, cerium ammonium nitrate, cerium phosphate, primary sulfate Cerium compounds such as cerium and ceric sulfate;
Samarium compounds such as samarium trichloride, samarium triacetate, samarium trioxalate, samarium trinitrate, samarium tricarbonate, samarium triiodide, samarium sulfate;
Ytterbium compounds such as ytterbium trichloride, ytterbium tribromide, ytterbium trinitrate, diytterbium trisulfate, ytterbium triacetate, ytterbium trioxalate, ytterbium triiodide, ytterbium phosphate;
Lutetium compounds such as lutetium trichloride, lutetium triacetate, dilutetium trioxalate, lutetium trinitrate, lutetium sulfate;
Zirconium compounds such as zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, zirconium tetranitrate, zirconium disulfate;
Hafnium compounds such as hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide, hafnium tetranitrate, hafnium disulfate;
Niobium compounds such as niobium pentachloride, niobium pentabromide, niobium pentaiodide, niobium penta (hydrogen oxalate), niobium pentaethylate, niobium penta-n-butyrate, sodium niobium trioxide;
Molybdenum compounds such as molybdenum trichloride, molybdenum pentachloride, molybdenum tribromide, ammonium tetracosaoxoheptamolybdate (VI), potassium tetraoxomolybdenum (VI), sodium tetraoxomolybdate (VI);
Tungsten compounds such as tungsten tetrachloride, tungsten hexachloride, tungsten pentabromide, silicotungstic acid, potassium silicotungstate, sodium silicotungstate, ammonium paratungstate, potassium tungstate;
Cobalt dichloride, cobalt dibromide, cobalt diiodide, cobalt difluoride, cobalt dinitrate, cobalt oxide, cobalt phosphate, cobalt diacetate, trihydroxycobalt (III), cobaltous formate, citric acid first Cobalt compounds such as cobalt;
Nickel compounds such as nickel dichloride, nickel dibromide, nickel diiodide, nickel oxalate, nickel dinitrate, nickel dihydroxide;
Copper monochloride, copper dichloride, copper diammonium dichloride, cupric formate, copper monobromide, copper dibromide, copper nitrate, copper phosphate, copper sulfate, copper acetate, copper carbonate, copper oxalate, etc. Copper compounds;
Gold compounds such as gold monochloride, gold trichloride, gold tetrachloride, gold tribromide, gold triiodide, gold hydroxide, gold tetrachloride, sodium tetrabromide, sodium tetrabromide, etc .;
And preferably,
Rhodium trichloride, rhodium trinitrate, iridium trichloride, iridium tetrachloride, ammonium iridate, iridium hexachloride, trisodium iridium tetrachloride, diammonium iridium hexachloride, diammonium iridium hexachloride, dipotassium iridium hexachloride, iridium hexachloride, Iridium hexachloride disodium, platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, hydrogen hexahydroxoplatinate, platinum hydroxide, sodium hexahydroxyplatinate, potassium hexahydroxyplatinate (IV), ruthenium trichloride, pentachloride Ruthenium diammonium, ruthenium hexachloride triammonium, ruthenium hexachloride dipotassium, ruthenium hexachloride disodium, potassium perruthenate, perruthenate (tetrapropylammonium), perruthenate (tetrabutylammonium) ), Tetraoxoruthenium (VI) dipotassium, tetraoxoruthenium (VI) disodium, tantalum pentachloride, potassium tantalate, rhenium trichloride, rhenium pentachloride, ammonium perrhenate, potassium perrhenate, Sodium rhenate, dirhenium heptoxide, palladium dichloride, palladium diacetate, palladium dinitrate, palladium hydroxide, lanthanum trichloride, lanthanum trinitrate, lanthanum phosphate, dilanthanum tricarbonate, lanthanum formate, cerium chloride, Cerium trinitrate, cerium tetrahydroxide, cerium tricarbonate, cerium phosphate, samarium trichloride, samarium triacetate, samarium trinitrate, ytterbium trichloride, ytterbium trinitrate, ytterbium triacetate, ytterbium phosphate, lutetium trichloride, Luteti triacetate Lutetium trinitrate, zirconium tetrachloride, zirconium tetranitrate, hafnium tetrachloride, hafnium tetranitrate, niobium pentachloride, niobium trioxide, molybdenum trichloride, molybdenum pentachloride, ammonium tetracosaoxoheptamolybdate (VI), Potassium tetraoxomolybdate (VI), sodium tetraoxomolybdate (VI), tungsten tetrachloride, tungsten hexachloride, silicotungstic acid, potassium silicotungstate, sodium paratungstate, ammonium paratungstate, potassium tungstate, di Cobalt chloride, cobalt dinitrate, cobalt phosphate, cobalt diacetate, nickel dichloride, nickel dinitrate, nickel dihydroxide, copper monochloride, copper dichloride, copper nitrate, copper phosphate, copper acetate, gold monochloride, Gold trichloride , Tetrachloroauric acid, gold hydroxide, and potassium tetrachloride. More preferably,
Rhodium trichloride, rhodium trinitrate, iridium trichloride, iridium tetrachloride, iridium chloride, platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, platinum hydroxide, ruthenium trichloride, potassium perruthenate, perruthenic acid ( Tetrapropylammonium), tantalum pentachloride, potassium tantalate, rhenium trichloride, rhenium pentachloride, ammonium perrhenate, potassium perrhenate, dirhenium heptoxide, palladium dichloride, palladium diacetate, palladium dinitrate, trichloride Lanthanum, lanthanum trinitrate, cerium chloride, cerium trinitrate, samarium trichloride, samarium triacetate, samarium trinitrate, ytterbium trichloride, ytterbium trinitrate, ytterbium triacetate, lutetium trichloride, lutetium triacetate, lutetium trinitrate , Zirconium tetrachloride Zirconium tetranitrate, hafnium tetrachloride, hafnium tetranitrate, niobium pentachloride, niobium trioxide, molybdenum trichloride, molybdenum pentachloride, ammonium tetracosaoxoheptamolybdate (VI), potassium tetraoxomolybdate (VI) , Sodium tetraoxomolybdate (VI), tungsten tetrachloride, tungsten hexachloride, silicotungstic acid, potassium silicotungstate, sodium silicotungstate, ammonium paratungstate, cobalt dichloride, cobalt dinitrate, cobalt diacetate, two Nickel chloride, nickel dinitrate, nickel dihydroxide, copper monochloride, copper dichloride, copper nitrate, copper acetate, gold monochloride, gold trichloride, tetrachloroauric acid, and potassium tetrachloride are used.
なお、本発明においては、金属化合物(A)は、上記以外にもスカンジウム、イットリウム、チタン、バナジウム、チタン、マンガン、鉄などの金属化合物の使用も可能である。 In the present invention, the metal compound (A) may be a metal compound such as scandium, yttrium, titanium, vanadium, titanium, manganese, and iron in addition to the above.
(周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2))
周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)の金属としては、例えば、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、レニウムなどが挙げられるが、好ましくはバナジウム、モリブデン、タングステン、レニウムである。
(Metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table)
Examples of the metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium. Of these, vanadium, molybdenum, tungsten, and rhenium are preferable.
金属酸化物(B1)の形態は、ひとつの金属−酸素結合を有する化合物であれば特に限定されず、例えば、水和物や有機化合物の付加体であってもよく、過酸化金属酸、過酸化金属酸塩の形態をとっていても良い。更に、金属酸化物(B1)は、担体に担持されていてもよい。なお、これらの金属酸化物は、一種を単独で又は二種以上を混合して使用してもよい。 The form of the metal oxide (B1) is not particularly limited as long as it is a compound having one metal-oxygen bond, and may be, for example, a hydrate or an adduct of an organic compound. It may be in the form of a metal oxide salt. Furthermore, the metal oxide (B1) may be supported on a carrier. In addition, you may use these metal oxides individually by 1 type or in mixture of 2 or more types.
金属酸化物(B1)としては、酸化金属、過酸化金属酸及び過酸化金属酸塩からなる群より選択される少なくとも1種の金属酸化物が好適に使用される。その具体的な例としては、例えば、酸化バナジウム、三酸化二バナジウム、二酸化バナジウム、五酸化二バナジウム、三臭化バナジウム、ピロバナジン酸カリウム、テトラオキソバナジン(V)酸カリウム、トリオキソバナジン(V)酸カリウム、トリオキソバナジン(V)酸ナトリウム、ピロバナジン酸ナトリウム、トリオキソバナジン(V)酸リチウム等のバナジウム酸化物;ケイモリブデン酸、テトラコサオキソヘプタモリブデン(VI)酸アンモニウム、テトラオキソモリブデン(VI)酸カリウム、テトラオキソモリブデン酸カルシウム、テトラオキソモリブデン(VI)酸ナトリウム、テトラオキソモリブデン(VI)酸マグネシウム、テトラオキソモリブデン(VI)酸リチウム、二酸化モリブデン、三酸化モリブデン等のモリブデン酸化物;テトラオキソタングステン(VI)酸ナトリウム、テトラオキソタングステン(VI)酸カドミウム(II)、テトラオキソタングステン(VI)酸カリウム、テトラオキソタングステン(VI)酸カルシウム等のタングステン酸化物;テトラオキソレニウム(VII)酸アンモニウム、テトラオキソレニウム(VII)酸カリウム、テトラオキソレニウム(VII)酸ナトリウム、二酸化レニウム、三酸化レニウム、七酸化二レニウム等のレニウム酸化物が挙げられる。好ましくは、五酸化二バナジウム、トリオキソバナジン(V)酸カリウム、トリオキソバナジン(V)酸ナトリウム、ピロバナジン酸ナトリウム、テトラオキソタングステン(VI)酸ナトリウム、ケイモリブデン酸、テトラコサオキソヘプタモリブデン(VI)酸アンモニウム、テトラオキソモリブデン(VI)酸ナトリウムテトラオキソレニウム(VII)酸アンモニウム、テトラオキソレニウム(VII)酸カリウム、七酸化二レニウムが使用される。 As the metal oxide (B1), at least one metal oxide selected from the group consisting of metal oxides, metal peroxide acids and metal peroxide salts is preferably used. Specific examples thereof include, for example, vanadium oxide, divanadium trioxide, vanadium dioxide, divanadium pentoxide, vanadium tribromide, potassium pyrovanadate, potassium tetraoxovanadate (V), trioxovanadium (V). Potassium oxide, vanadium oxides such as sodium trioxovanadate (V), sodium pyrovanadate, lithium trioxovanadate (V); silicomolybdic acid, ammonium tetracosaoxoheptamolybdate (VI), tetraoxomolybdenum (VI ) Potassium oxide, calcium tetraoxomolybdate, sodium tetraoxomolybdate (VI), magnesium tetraoxomolybdenum (VI), lithium tetraoxomolybdate (VI), molybdenum dioxide, molybdenum trioxide, etc. Buden oxide; Tungsten oxide such as sodium tetraoxotungsten (VI), cadmium (II) tetraoxotungsten (VI), potassium tetraoxotungsten (VI), calcium tetraoxotungsten (VI); tetraoxo Examples include rhenium oxides such as ammonium rhenium (VII), potassium tetraoxorhenium (VII), sodium tetraoxorhenium (VII), rhenium dioxide, rhenium trioxide, and dirhenium heptoxide. Preferably, divanadium pentoxide, potassium trioxovanadate (V), sodium trioxovanadate (V), sodium pyrovanadate, sodium tetraoxotungstate (VI), silicomolybdic acid, tetracosaoxoheptamolybdenum (VI Ammonium acid, sodium tetraoxomolybdate (VI), ammonium tetraoxorhenium (VII), potassium tetraoxorhenium (VII), dirhenium heptoxide.
金属カルボニル化合物(B2)の形態は、ひとつの金属とカルボニル炭素結合(M−CO;Mは金属)を有する化合物であれば特に限定されず、例えば、水和物や有機化合物の付加体であってもよく、過酸化金属酸、過酸化金属酸塩の形態をとっていても良い。更に、金属カルボニル化合物(B2)は、担体に担持されていてもよい。なお、これらの金属酸化物は、一種を単独で又は二種以上を混合して使用してもよい。 The form of the metal carbonyl compound (B2) is not particularly limited as long as it is a compound having one metal and a carbonyl carbon bond (M-CO; M is a metal). For example, it is a hydrate or an adduct of an organic compound. It may be in the form of a metal peroxide acid or metal peroxide salt. Furthermore, the metal carbonyl compound (B2) may be supported on a carrier. In addition, you may use these metal oxides individually by 1 type or in mixture of 2 or more types.
金属カルボニル化合物(B2)としては、例えば、ヘキサカルボニルバナジウム、ヘキサカルボニルクロム、ヘキサカルボニルモリブデン、トリカルボニルシクロペンタジエニルモリブデンダイマー、ヘキサカルボニルタングステン、デカカルボニル二マンガン、トリカルボニルシクロペンタジエニルマンガン、ペンタカルボニルヒドリドマンガン、デカカルボニル二レニウム、ペンタカルボニルクロロレニウム、ペンタカルボニルブロモレニウム、ペンタカルボニルヒドリドレニウムが使用される。 Examples of the metal carbonyl compound (B2) include hexacarbonyl vanadium, hexacarbonyl chromium, hexacarbonyl molybdenum, tricarbonylcyclopentadienyl molybdenum dimer, hexacarbonyl tungsten, decacarbonyl dimanganese, tricarbonylcyclopentadienyl manganese, penta Carbonyl hydride manganese, decacarbonyl dirhenium, pentacarbonyl chlororhenium, pentacarbonyl bromorhenium, pentacarbonyl hydrido rhenium are used.
前記周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)の使用量は、金属化合物(A)の合計量1モルに対して、好ましくは0.1〜30モル、更に好ましくは0.5〜20モルである。金属酸化物(B1)或いは金属カルボニル化合物(B2)の使用量が多すぎると、反応における活性が低下し、少なすぎると反応における選択率が低下する。 The amount of the metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, Group 6 or Group 7 of the periodic table is preferably based on 1 mol of the total amount of the metal compound (A). It is 0.1-30 mol, More preferably, it is 0.5-20 mol. When the amount of the metal oxide (B1) or the metal carbonyl compound (B2) used is too large, the activity in the reaction is lowered, and when too small, the selectivity in the reaction is lowered.
(担体)
本発明の触媒は担体に担持された触媒(担持触媒)であってもよい。使用される担体は、多孔質の担体が好適に用いられる。具体的には、例えば、シリカ、アルミナ、シリカアルミナ(アルミノシリケート)、セリア、マグネシア、カルシア、チタニア、シリカチタニア(チタノシリケート)、ジルコニア及び活性炭、グラフェン、カーボンナノチューブ、ゼオライト、メソ孔体(メソポーラス−アルミナ、メソポーラス−シリカ、メソポーラス−カーボン)などであり、好ましくは、シリカ、アルミナ、シリカアルミナ(アルミノシリケート)、チタニア、ジルコニア及び活性炭、グラフェン、カーボンナノチューブ、ゼオライト等が使用され、更に好ましくはシリカ、アルミナ、及び活性炭が使用される。これらの担体は、一種を単独で又は二種以上を混合して使用してもよい。
(Carrier)
The catalyst of the present invention may be a catalyst supported on a carrier (supported catalyst). As the carrier used, a porous carrier is preferably used. Specifically, for example, silica, alumina, silica alumina (aluminosilicate), ceria, magnesia, calcia, titania, silica titania (titanosilicate), zirconia and activated carbon, graphene, carbon nanotube, zeolite, mesoporous material (mesoporous) -Alumina, mesoporous-silica, mesoporous-carbon), preferably silica, alumina, silica alumina (aluminosilicate), titania, zirconia and activated carbon, graphene, carbon nanotubes, zeolite, etc. are used, more preferably silica. , Alumina, and activated carbon are used. These carriers may be used alone or in combination of two or more.
本発明の触媒が担持触媒である場合には、前記混合物と担体とを含む組成物を焼成してもよい。焼成温度は、好ましくは50〜800℃、より好ましくは100〜600℃である。焼成時間は適宜調整することが可能であり、好ましくは0.1〜20時間、より好ましくは0.25〜15時間である。 When the catalyst of the present invention is a supported catalyst, the composition containing the mixture and the support may be calcined. The firing temperature is preferably 50 to 800 ° C, more preferably 100 to 600 ° C. The firing time can be appropriately adjusted, and is preferably 0.1 to 20 hours, more preferably 0.25 to 15 hours.
(多価酸塩)
本発明の触媒では、前記混合物に多価酸塩を共存させてもよく、このような多価酸塩としては、炭酸や硫酸、リン酸等のような2価以上の酸に由来する塩のことをいう。そのような多価酸塩としては、多価無機酸塩であれば、例えば、リン酸三カリウム、リン酸一水素二カリウム、リン酸三ナトリウム、リン酸一水素二ナトリウム、リン酸三アンモニウム、リン酸一水素二アンモニウム等のリン酸塩;炭酸アンモニウム、炭酸水素アンモニウム、炭酸カリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸水素ナトリウム等の炭酸塩(炭酸水素塩も含む広い意味として);硫酸カリウム、硫酸ナトリウム、硫酸アンモニウム等の硫酸塩等が挙げられる。又、多価有機酸塩であれば、例えば、シュウ酸カリウム、シュウ酸ナトリウム等の多価カルボン酸塩が挙げられる。これらの多価酸塩は、水和物や有機化合物の付加体であっても良く、又、担体に担持されていても良い。
(Polyvalent acid salt)
In the catalyst of the present invention, a polyvalent acid salt may coexist in the mixture, and as such a polyvalent acid salt, a salt derived from a divalent or higher acid such as carbonic acid, sulfuric acid, phosphoric acid or the like is used. That means. As such polyvalent acid salt, if it is a polyvalent inorganic acid salt, for example, tripotassium phosphate, dipotassium monohydrogen phosphate, trisodium phosphate, disodium monohydrogen phosphate, triammonium phosphate, Phosphates such as diammonium phosphate monobasic; carbonates such as ammonium carbonate, ammonium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate (as a broad meaning including hydrogen carbonate); potassium sulfate, Examples thereof include sulfates such as sodium sulfate and ammonium sulfate. Examples of the polyvalent organic acid salt include polyvalent carboxylates such as potassium oxalate and sodium oxalate. These polyvalent acid salts may be hydrates or adducts of organic compounds, or may be supported on a carrier.
なお、好適には多価無機酸塩であり、リン酸三カリウム、リン酸三ナトリウム、リン酸三アンモニウム、リン酸一水素二アンモニウム、炭酸アンモニウム、炭酸カリウム、炭酸ナトリウム、硫酸カリウム、硫酸ナトリウム、硫酸アンモニウム、更に好ましくはリン酸三カリウム、リン酸三アンモニウム、炭酸アンモニウム、リン酸一水素二アンモニウム、炭酸カリウム、硫酸カリウムが使用される。 The polyvalent inorganic acid salt is preferably tripotassium phosphate, trisodium phosphate, triammonium phosphate, diammonium monohydrogen phosphate, ammonium carbonate, potassium carbonate, sodium carbonate, potassium sulfate, sodium sulfate, Ammonium sulfate, more preferably tripotassium phosphate, triammonium phosphate, ammonium carbonate, diammonium monohydrogen phosphate, potassium carbonate, potassium sulfate is used.
前記多価無機酸塩を用いる際の使用量は、金属化合物(A)の合計量1モルに対して、好ましくは0.1〜30モル、更に好ましくは0.5〜10モルである。なお、これらの値は、金属原子換算である。 The amount of the polyvalent inorganic acid salt used is preferably 0.1 to 30 mol, more preferably 0.5 to 10 mol, per 1 mol of the total amount of the metal compound (A). These values are in terms of metal atoms.
(触媒の製造)
本発明の触媒の製造においては、まず、ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の金属化合物(A)と、
周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)と、
を混合するが、その混合形態は特に制限されない(このとき混合物が生成)。
(Manufacture of catalyst)
In the production of the catalyst of the present invention, first, rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper And at least two metal compounds (A) selected from the group consisting of gold and
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
However, the mixing form is not particularly limited (at this time, a mixture is formed).
前記混合物の還元処理は、水素を発生させることが可能な通常の還元剤を用いて行うことができる。例えば、当該混合物と水素ガスとを接触させる方法が好適に採用される。当該混合物と水素ガスとを接触させる際の接触温度は、好ましくは40〜300℃、より好ましくは50〜200℃であり、接触圧力は、好ましくは常圧〜20MPa、より好ましくは0.2〜15MPaである。 The reduction treatment of the mixture can be performed using a normal reducing agent capable of generating hydrogen. For example, a method of bringing the mixture into contact with hydrogen gas is suitably employed. The contact temperature when contacting the mixture with hydrogen gas is preferably 40 to 300 ° C., more preferably 50 to 200 ° C., and the contact pressure is preferably atmospheric pressure to 20 MPa, more preferably 0.2 to 15 MPa.
本発明の触媒の好ましい態様としては、
ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の貴金属化合物(A)と、
周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)と、
担体と、
必要に応じて多価無機酸塩と、
を混合し、還元処理して得られるものである。
As a preferred embodiment of the catalyst of the present invention,
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold Noble metal compound (A) of
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
A carrier;
If necessary, with polyvalent inorganic acid salt,
Are mixed and reduced.
なお、本発明の触媒は、例えば、濾過、洗浄する等して一旦単離してもよく、懸濁液の状態でそのままアルコール化合物の製造に使用してもよい。 The catalyst of the present invention may be isolated once by, for example, filtration and washing, or may be used in the production of an alcohol compound as it is in a suspension state.
以上の方法によって得られた触媒は、カルボン酸化合物からアルコール化合物を製造する触媒として用いることができる。次に、上述の触媒を用いたアルコール化合物の製造方法の好適な実施形態を説明する。 The catalyst obtained by the above method can be used as a catalyst for producing an alcohol compound from a carboxylic acid compound. Next, a preferred embodiment of a method for producing an alcohol compound using the above-described catalyst will be described.
(アルコール化合物の製造)
本発明の反応は、水素源の存在下、カルボン酸化合物と、前記触媒とを接触させることによって、対応するアルコール化合物を製造するものである。
(Production of alcohol compounds)
The reaction of the present invention is to produce a corresponding alcohol compound by bringing a carboxylic acid compound into contact with the catalyst in the presence of a hydrogen source.
前記カルボン酸化合物は、少なくとも1つのカルボキシル基を有する化合物であるが、カルボキシル基の数に特に限定はない。また、前記化合物は、例えば、ヒドロキシル基、アシル基、アルコキシル基、ハロゲン基などの置換基や、多重結合を有していても良い。 The carboxylic acid compound is a compound having at least one carboxyl group, but the number of carboxyl groups is not particularly limited. Moreover, the said compound may have substituents, such as a hydroxyl group, an acyl group, an alkoxyl group, a halogen group, and a multiple bond, for example.
そのような化合物の具体例としては、例えば、以下のようなモノカルボン酸やポリカルボン酸(複数のカルボキシル基を有する化合物)が挙げられる。
モノカルボン酸としては、例えば、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、イソ吉草酸、ピバル酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸、ノナデカン酸、エイコサン酸、アクリル酸、プロピオール酸、メタクリル酸、クロトン酸、イソクロトン酸、オレイン酸、9−ヘキサデセン酸、11−オクタデセン酸、リノール酸、シクロプロパンカルボン酸、シクロブタンカルボン酸、シクロペンタンカルボン酸、シクロヘキサンカルボン酸、テトラヒドロフラン−2−カルボン酸、
ポリカルボン酸としては、例えば、シュウ酸、フマル酸、マレイン酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スペリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、イタコン酸アコニット酸、フランジカルボン酸、リンゴ酸、クエン酸、グルカル酸、酒石酸、タルトロン酸、シトラマル酸
芳香族カルボン酸としては、安息香酸、フタル酸、イソフタル酸、テレフタル酸、サリチル酸、3−ヒドロキシ安息香酸、4−ヒドロキシ安息香酸、2−フランカルボン酸、没食子酸、フランジカルボン酸、トルイル酸(位置異性体を含む)、キシリル酸(位置異性体を含む)、α−トルイル酸、ケイ皮酸、
その他のカルボン酸としては、グリコール酸、乳酸、3−ヒドロキシプロピオン酸、グリセリン酸、2−ヒドロキシ酪酸、3−ヒドロキシ酪酸、4−ヒドロキシ酪酸、ロイシン酸、メバロン酸、バントイン酸、リシノール酸、リシネライジン酸、セレブロン酸、ピルビン酸、オキサロ酢酸、α−ケトグルタル酸、アセト酢酸、オキサロ酢酸、アセトンジカルボン酸、レブリン酸、
などが使用される。これらのカルボン酸は複数の混合物であっても良い。
Specific examples of such compounds include the following monocarboxylic acids and polycarboxylic acids (compounds having a plurality of carboxyl groups).
Examples of monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecane Acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, oleic acid, 9-hexadecenoic acid, 11-octadecenoic acid, linoleic acid , Cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, tetrahydrofuran-2-carboxylic acid,
Examples of the polycarboxylic acid include oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, itacone Acid aconitic acid, furandicarboxylic acid, malic acid, citric acid, glucaric acid, tartaric acid, tartronic acid, citramalic acid As aromatic carboxylic acids, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, 3-hydroxybenzoic acid 4-hydroxybenzoic acid, 2-furancarboxylic acid, gallic acid, furandicarboxylic acid, toluic acid (including positional isomer), xylyl acid (including positional isomer), α-toluic acid, cinnamic acid,
Other carboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, leucine acid, mevalonic acid, bantoic acid, ricinoleic acid, ricinaleic acid , Cerebronic acid, pyruvic acid, oxaloacetic acid, α-ketoglutaric acid, acetoacetic acid, oxaloacetic acid, acetone dicarboxylic acid, levulinic acid,
Etc. are used. These carboxylic acids may be a plurality of mixtures.
本実施形態における反応において使用する触媒の量は、金属化合物(A)の合計量の金属原子換算で、カルボン酸1モルに対して、好ましくは0.0005〜0.1モル、より好ましくは0.001〜0.075モルである。この使用量とすることで、十分な反応速度を得つつ、高収率且つ高選択的にアルコール化合物を得ることができる。なお、触媒は、複数種の触媒を別々に調製して使用してもよい。 The amount of the catalyst used in the reaction in the present embodiment is preferably 0.0005 to 0.1 mol, more preferably 0 with respect to 1 mol of the carboxylic acid, in terms of metal atoms of the total amount of the metal compound (A). 0.001 to 0.075 mol. By using this amount, an alcohol compound can be obtained with high yield and high selectivity while obtaining a sufficient reaction rate. In addition, a catalyst may prepare and use several types of catalysts separately.
本実施形態における反応において使用する水素源とは、水素を提供する化合物ならば特に限定されず、例えば、水素ガス、アンモニアガス等の還元性ガス(窒素、ヘリウム、アルゴン等の不活性ガスで希釈されていてもよい);水;メタノール、エタノール、イソプロピルアルコール等のアルコール類;ギ酸、酢酸、クロロギ酸等の有機酸類;塩酸、硫酸等の無機酸類であり、好ましくは還元性ガス、より好ましくは水素ガスが使用される。 The hydrogen source used in the reaction in the present embodiment is not particularly limited as long as it is a compound that provides hydrogen. For example, it is diluted with a reducing gas such as hydrogen gas or ammonia gas (inert gas such as nitrogen, helium, or argon). Water; alcohols such as methanol, ethanol and isopropyl alcohol; organic acids such as formic acid, acetic acid and chloroformic acid; inorganic acids such as hydrochloric acid and sulfuric acid, preferably reducing gas, more preferably Hydrogen gas is used.
上述の水素源の量は、カルボン酸化合物1モルに対して、好ましくは5〜200モル、より好ましくは10〜160モルである。この使用量とすることで、十分な反応速度を得つつ、高収率且つ高選択的にアルコール化合物を得ることができる。なお、触媒は、複数種の触媒を別々に調製して使用してもよい。 The amount of the hydrogen source is preferably 5 to 200 mol, more preferably 10 to 160 mol, per 1 mol of the carboxylic acid compound. By using this amount, an alcohol compound can be obtained with high yield and high selectivity while obtaining a sufficient reaction rate. In addition, a catalyst may prepare and use several types of catalysts separately.
本実施形態における反応は溶媒中で行うことが好ましい。使用する溶媒としては反応を阻害しないものであれば特に限定されず、例えば、水;メタノール、エタノール、n−プロピルアルコール、イソプロピルアルコール、n−ブチルアルコール、t−ブチルアルコール、エチレングリコール等のアルコール類;ヘプタン、ヘキサン、シクロヘキサン、トルエン等の炭化水素類;N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン等のアミド類;ジエチルエーテル、ジイソプロピルエーテル、1,2−ジメトキシメタン、1,2−ジエトキシエタン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン、1,4−ジオキサン等のエーテル類;塩化メチレン、ジクロロエタン、クロロシクロヘキサン等のハロゲン化炭化水素類が挙げられる。これらのうち、好ましくは水、炭化水素類、エーテル類であり、より好ましくは水、エーテル類、特に好ましくは水、1,2−ジエトキシメタン、1,4−ジオキサン、ジエチレングリコールジメチルエーテルである。なお、これらの溶媒は、単独又は二種以上を混合して使用してもよい。 The reaction in this embodiment is preferably performed in a solvent. The solvent used is not particularly limited as long as it does not inhibit the reaction. For example, water; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, and ethylene glycol Hydrocarbons such as heptane, hexane, cyclohexane and toluene; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; diethyl ether, diisopropyl ether, 1,2- Ethers such as dimethoxymethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane; methylene chloride, dichloroethane, chlorocyclohexane, etc. Halogenated hydrocarbons. Of these, water, hydrocarbons, and ethers are preferable, and water, ethers, more preferably water, 1,2-diethoxymethane, 1,4-dioxane, and diethylene glycol dimethyl ether are more preferable. In addition, you may use these solvents individually or in mixture of 2 or more types.
上記溶媒の使用量は、カルボン酸化合物1gに対して、好ましくは0.05〜100g、より好ましくは0.1〜20gである。この使用量とすることで、攪拌が速やかに行われ、反応をスムーズに進行させることができる。 The amount of the solvent used is preferably 0.05 to 100 g, more preferably 0.1 to 20 g, relative to 1 g of the carboxylic acid compound. By setting it as this usage-amount, stirring can be performed rapidly and reaction can be advanced smoothly.
本実施形態における反応形態は、触媒の形態により回分式(バッチ式)又は連続式のいずれの方法も選択することができる。また、触媒の性質により均一系、及び不均一系(懸濁反応)のどちらの反応系でも実施できる。担体に担持させた触媒であれば、固定床で連続的に反応を行うこともできる。 As the reaction form in the present embodiment, either a batch type or a continuous type can be selected depending on the form of the catalyst. Depending on the nature of the catalyst, the reaction can be carried out in either a homogeneous system or a heterogeneous system (suspension reaction). If the catalyst is supported on a carrier, the reaction can be carried out continuously in a fixed bed.
本実施形態における反応は、例えば、カルボン酸化合物、触媒及び溶媒を混合し、水素源の存在下にて、攪拌しながら反応させる等の方法によって行われる。その際の反応温度は、好ましくは25〜300℃、より好ましくは50〜200℃であり、反応圧力は、水素分圧として、好ましくは常圧〜20MPa、より好ましくは0.2〜15MPaである。この反応温度、及び反応圧力とすることで、副生成物の生成を抑制しつつ、高い反応速度で、高収率且つ高選択的に目的物であるアルコール化合物を得ることができる。なお、反応を促進させるために、必要に応じて、塩酸、硫酸、リン酸、酢酸等の酸又は水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム等の塩基を存在させてもよい。このような酸又は塩基の量は、カルボン酸化合物1モルに対して、好ましくは0.001〜0.1モル、より好ましくは0.005〜0.05モルである。 The reaction in the present embodiment is performed by, for example, a method of mixing a carboxylic acid compound, a catalyst, and a solvent and reacting with stirring in the presence of a hydrogen source. The reaction temperature at that time is preferably 25 to 300 ° C., more preferably 50 to 200 ° C., and the reaction pressure is preferably a normal pressure to 20 MPa, more preferably 0.2 to 15 MPa as a hydrogen partial pressure. . By setting the reaction temperature and the reaction pressure, it is possible to obtain an alcohol compound as a target product with high yield and high selectivity at a high reaction rate while suppressing the formation of by-products. In order to accelerate the reaction, an acid such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid or a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate is used as necessary. May be present. The amount of such an acid or base is preferably 0.001 to 0.1 mol, more preferably 0.005 to 0.05 mol, per 1 mol of the carboxylic acid compound.
本実施形態における反応により、目的とするアルコール化合物が得られる。このアルコール化合物は、反応終了後、得られた反応液から、例えば、濾過、濃縮、抽出、蒸留、昇華、再結晶、カラムクロマトグラフィー等の一般的な操作によって単離・精製することができる。 The target alcohol compound is obtained by the reaction in the present embodiment. After completion of the reaction, the alcohol compound can be isolated and purified from the resulting reaction solution by general operations such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography and the like.
以上、本発明の好適な実施形態を説明したが、本発明は、上記実施形態に限定されるものではない。 The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.
次に、実施例を挙げて本発明を具体的に説明するが、本発明はこれら実施例に制限されるものではない。なお、本発明の触媒の略語は以下の構成からなる。
(金属化合物(A)の1つ目の金属)−(金属化合物(A)の2つ目の金属)−(周期表第5族〜7族の金属)/(担体)触媒
EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples. In addition, the abbreviation of the catalyst of this invention consists of the following structures.
(First metal of metal compound (A))-(Second metal of metal compound (A))-(Metal of Group 5 to Group 7 of the periodic table) / (Support) catalyst
実施例1(触媒の製造)
50mlのガラス製内筒管を備えたオートクレーブに、三塩化ロジウム・3水和物13.3mg(ロジウムが0.050mmol)、四塩化白金16.9mg(白金が0.050mmol)、リン酸三カリウム24.8mg(0.12mmol)及び水3mlを加え、100℃で60分間加熱攪拌した。これを一旦室温まで冷却した溶液に、七酸化二レニウム18.2mg(レニウムが0.075mmol)と活性炭(AC、カルゴンカーボンジャパン製、MH4−8A)200mgを加え、室温で5分攪拌した。次いで、室温にて水素雰囲気にて8MPaまで加圧し、120℃で1時間加熱攪拌して混合物を還元処理した。得られた溶液を室温まで冷却し、遠心分離により水層を除き、残渣として活性炭にロジウムが2.1質量%、白金が4.3質量%、レニウムが6.1質量%担持された触媒(以下、「Rh−Pt−Re/AC触媒(1)」と称することもある)を得た。
Example 1 (Production of catalyst)
In an autoclave equipped with a 50 ml glass inner tube, 13.3 mg rhodium trichloride trihydrate (0.050 mmol rhodium), 16.9 mg platinum tetrachloride (0.050 mmol platinum), tripotassium phosphate 24.8 mg (0.12 mmol) and 3 ml of water were added, and the mixture was heated and stirred at 100 ° C. for 60 minutes. To the solution once cooled to room temperature, 18.2 mg of dirhenium heptoxide (0.075 mmol of rhenium) and 200 mg of activated carbon (AC, manufactured by Calgon Carbon Japan, MH4-8A) were added and stirred at room temperature for 5 minutes. Next, the mixture was pressurized to 8 MPa in a hydrogen atmosphere at room temperature, and heated and stirred at 120 ° C. for 1 hour to reduce the mixture. The obtained solution was cooled to room temperature, the aqueous layer was removed by centrifugation, and a catalyst in which rhodium was supported by 2.1% by mass, platinum by 4.3% by mass, and rhenium by 6.1% by mass was retained as activated carbon ( Hereinafter, “Rh—Pt—Re / AC catalyst (1)” may be obtained.
実施例2(触媒の製造)
三塩化ロジウム・3水和物13.3mg(ロジウムが0.050mmol)、四塩化白金16.9mg(白金が0.050mmol)、リン酸三カリウム24.8mg(0.12mmol)及び水3mlを混合し、均一水溶液を調製した。調製した水溶液を活性炭(AC:カルゴンカーボンジャパン製、商品名:MH4−8A)に加え、80℃で減圧濃縮し、溶媒を留去した。次いで、水2mlに七酸化二レニウム18.2mg(レニウムが0.075mmol)を溶解させた水溶液を加え、再び80℃で減圧濃縮し、溶媒を留去した。得られた残渣を更に60℃で8時間減圧乾燥して、活性炭にロジウムが2.2質量%、白金が4.1質量%、レニウムが5.5質量%担持された固体(以下、「Rh−Pt−Re/AC(2)」と称することもある)260mgを得た。
Example 2 (Production of catalyst)
Rhodium trichloride trihydrate (13.3 mg, rhodium is 0.050 mmol), platinum tetrachloride (16.9 mg, platinum is 0.050 mmol), tripotassium phosphate (24.8 mg, 0.12 mmol) and water (3 ml) are mixed. A homogeneous aqueous solution was prepared. The prepared aqueous solution was added to activated carbon (AC: Calgon Carbon Japan, trade name: MH4-8A) and concentrated under reduced pressure at 80 ° C., and the solvent was distilled off. Subsequently, an aqueous solution in which 18.2 mg of dirhenium heptoxide (0.075 mmol of rhenium) was dissolved in 2 ml of water was added, and the mixture was again concentrated under reduced pressure at 80 ° C., and the solvent was distilled off. The obtained residue was further dried under reduced pressure at 60 ° C. for 8 hours, and a solid in which activated carbon supported 2.2% by mass of rhodium, 4.1% by mass of platinum, and 5.5% by mass of rhenium (hereinafter referred to as “Rh”). 260 mg (sometimes referred to as -Pt-Re / AC (2) ").
実施例3(触媒の製造)
実施例2において、活性炭をシリカ(SiO2;富士シリシア化学株式会社製、商品名:CARiACT G−6)に変えた以外は、実施例2と同様にしてシリカにロジウムが1.8質量%、白金が3.8質量%、レニウムが4.9質量%担持された固体(以下、「Rh−Pt−Re/SiO2(1)」と称することもある)260mgを得た。
Example 3 (Production of catalyst)
In Example 2, rhodium was 1.8% by mass in silica in the same manner as in Example 2 except that the activated carbon was changed to silica (SiO 2 ; manufactured by Fuji Silysia Chemical Ltd., trade name: CARiACT G-6). 260 mg of a solid (hereinafter also referred to as “Rh—Pt—Re / SiO 2 (1)”) on which 3.8% by mass of platinum and 4.9% by mass of rhenium were supported was obtained.
実施例4(触媒の製造)
実施例1において、七酸化レニウムをナトリウムテトラオキソモリブデン(VI)酸ナトリウム(モリブデンが0.075mmol)に、活性炭の使用量を450mgに変えた以外は、実施例1と同様にして活性炭にロジウムが1.2質量%、白金が2.2質量%、モリブデンが1.6質量%担持された触媒(以下、「Rh−Pt−Mo/AC触媒(1)」と称することもある)を得た。
Example 4 (Production of catalyst)
In Example 1, rhodium was added to the activated carbon in the same manner as in Example 1 except that rhenium heptoxide was changed to sodium tetraoxomolybdate (VI) sodium (0.075 mmol of molybdenum) and the amount of activated carbon used was changed to 450 mg. A catalyst carrying 1.2% by mass, 2.2% by mass of platinum, and 1.6% by mass of molybdenum (hereinafter sometimes referred to as “Rh—Pt—Mo / AC catalyst (1)”) was obtained. .
実施例5(触媒の製造)
実施例2において、七酸化二レニウムをナトリウムテトラオキソモリブデン(VI)酸ナトリウム(モリブデンが0.075mmol)に変えた以外は、実施例2と同様にして活性炭にロジウムが1.9質量%、白金が3.8質量%、モリブデンが2.7質量%担持された固体(以下、「Rh−Pt−Mo/AC触媒(2)」と称することもある)を得た。
Example 5 (Production of catalyst)
In Example 2, except that the dirhenium heptoxide was changed to sodium tetraoxomolybdate (VI) sodium (molybdenum was 0.075 mmol), rhodium was 1.9% by mass in activated carbon in the same manner as in Example 2, platinum Was 3.8% by mass and molybdenum was supported by 2.7% by mass (hereinafter, also referred to as “Rh—Pt—Mo / AC catalyst (2)”).
実施例6(触媒の製造)
実施例1において、四塩化白金を二塩化パラジウム9.0mg(0.050mmol)に変更した以外は、実施例1と同様にして活性炭にロジウムが2.1質量%、パラジウムが2.1質量%、レニウムが6.1質量%担持された触媒(以下、「Rh−Pd−Re/AC触媒(1)」と称することもある)を得た。
Example 6 (Production of catalyst)
In Example 1, except that platinum tetrachloride was changed to 9.0 mg (0.050 mmol) of palladium dichloride, rhodium was 2.1% by mass and palladium was 2.1% by mass in the same manner as in Example 1. Thus, a catalyst carrying 6.1% by mass of rhenium (hereinafter sometimes referred to as “Rh—Pd—Re / AC catalyst (1)”) was obtained.
実施例7(触媒の製造)
実施例1において、四塩化白金を三塩化ルテニウム・n水和物(0.050mmol)に変更した以外は、実施例1と同様にして活性炭にルテニウムが2.0質量%、ロジウムが2.1質量%、レニウムが6.1質量%担持された触媒(以下、「Ru−Rh−Re/AC触媒(1)」と称することもある)を得た。
Example 7 (Production of catalyst)
In Example 1, except that the platinum tetrachloride was changed to ruthenium trichloride n-hydrate (0.050 mmol), the activated carbon was 2.0% by mass of ruthenium and the rhodium was 2.1% in the same manner as in Example 1. A catalyst (hereinafter, also referred to as “Ru—Rh—Re / AC catalyst (1)”) on which mass% and rhenium were supported by 6.1 mass% was obtained.
実施例8(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化イリジウム・n水和物(0.050mmol)に、活性炭の使用量を450mgに変えた以外は、実施例1と同様にして活性炭にイリジウムが2.2質量%、白金が2.2質量%、レニウムが3.1質量%担持された触媒(以下、「Ir−Pt−Re/AC触媒(1)」と称することもある)を得た。
Example 8 (Production of catalyst)
In Example 1, rhodium trichloride trihydrate was converted to iridium trichloride n hydrate (0.050 mmol), and the activated carbon was changed to activated carbon in the same manner as in Example 1 except that the amount of activated carbon used was changed to 450 mg. A catalyst carrying 2.2% by mass of iridium, 2.2% by mass of platinum and 3.1% by mass of rhenium (hereinafter sometimes referred to as “Ir-Pt-Re / AC catalyst (1)”) Obtained.
実施例9(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化イリジウム・n水和物(0.050mmol)に、七酸化二レニウムをナトリウムテトラオキソモリブデン(VI)酸ナトリウム(0.075mmol)に、活性炭の使用量を450mgに変えた以外は、実施例1と同様にして活性炭にイリジウムが2.2質量%、白金が2.2質量%、モリブデンが1.5質量%担持された触媒(以下、「Ir−Pt−Mo/AC触媒(1)」と称することもある)を得た。
Example 9 (Production of catalyst)
In Example 1, rhodium trichloride trihydrate was converted to iridium trichloride n hydrate (0.050 mmol), dirhenium heptoxide was added to sodium tetraoxomolybdate (VI) sodium (0.075 mmol), Except that the amount of the activated carbon used was changed to 450 mg, a catalyst having 2.2% by mass of iridium, 2.2% by mass of platinum and 1.5% by mass of molybdenum supported on the activated carbon in the same manner as in Example 1 And “Ir—Pt—Mo / AC catalyst (1)”).
実施例10(触媒の製造)
50mlのガラス製内筒管を備えたオートクレーブに、塩化ルテニウム・3水和物6.5mg(ルテニウムが0.025mmol)、三塩化ロジウム・3水和物6.6mg(ロジウムが0.025mmol)、リン酸三カリウム13.3mg(0.063mmol)及び水4mlを加え、100℃で60分間加熱攪拌した。これを一旦室温まで冷却した溶液に、七酸化二レニウム9.1mg(レニウムが0.038mmol)と活性炭(AC、カルゴンカーボンジャパン製、MH4−8A)96.1mgを加え、室温で5分攪拌した。次いで、室温にて水素雰囲気にて8MPaまで加圧し、120℃で1時間加熱攪拌して混合物を還元処理した。得られた溶液を室温まで冷却し、遠心分離により水層を除き、残渣として活性炭にロジウムが2.7質量%、ルテニウムが2.6質量%、レニウムが7.3質量%担持された触媒(以下、「Ru−Rh−Re/AC触媒(2)」と称することもある)を得た。
Example 10 (Production of catalyst)
In an autoclave equipped with a 50 ml glass inner tube, ruthenium chloride trihydrate 6.5 mg (ruthenium 0.025 mmol), rhodium trichloride trihydrate 6.6 mg (rhodium 0.025 mmol), 13.3 mg (0.063 mmol) of tripotassium phosphate and 4 ml of water were added, and the mixture was heated and stirred at 100 ° C. for 60 minutes. To this solution, which was once cooled to room temperature, 9.1 mg of dirhenium heptoxide (rhenium was 0.038 mmol) and 96.1 mg of activated carbon (AC, MH4-8A manufactured by Calgon Carbon Japan) were added and stirred at room temperature for 5 minutes. . Next, the mixture was pressurized to 8 MPa in a hydrogen atmosphere at room temperature, and heated and stirred at 120 ° C. for 1 hour to reduce the mixture. The resulting solution was cooled to room temperature, the aqueous layer was removed by centrifugation, and a catalyst in which rhodium 2.7% by mass, ruthenium 2.6% by mass, and rhenium 7.3% by mass were supported on activated carbon as a residue ( Hereinafter, “Ru—Rh—Re / AC catalyst (2)” may be obtained.
実施例11(触媒の製造)
シリカ(富士シリシア化学株式会社製、商品名:CARiACT G−6)0.50gを、テトラオキソルテニウム(VI)酸二カリウム水溶液(株式会社フルヤ金属製、ルテニウム濃度4.3質量%)0.244g(ルテニウム換算で0.104mmol)に水0.2gを加えた水溶液中に含浸させ、110℃で7時間乾燥した。次に、得られた粉末を、六塩化イリジウム酸(和光純薬製、イリジウム濃度37.7質量%)53.0mg(イリジウム換算で0.104mmol)を水0.4gに溶解させた水溶液中に含浸させ、110℃で7時間乾燥した。さらに、得られた粉末を、テトラオキソレニウム(VII)酸アンモニウム27.9mg(レニウム換算で0.104mmol)を水0.4gに溶解させた溶液中に含浸させ、110℃で7時間乾燥させた。この粉末を250℃で4時間乾燥して、シリカにルテニウムが2.1質量%、イリジウムが4.0質量%、レニウムが3.9質量%担持された固体触媒(以下、「Ru−Ir−Re/SiO2触媒(1)」と称することもある)588mgを得た。
Example 11 (Production of catalyst)
Silica (Fuji Silysia Chemical Co., Ltd., trade name: CARiACT G-6) 0.50 g, tetraoxoruthenium (VI) dipotassium aqueous solution (Fluya Metal Co., Ltd., ruthenium concentration 4.3 mass%) 0.244 g It was impregnated in an aqueous solution obtained by adding 0.2 g of water (0.104 mmol in terms of ruthenium) and dried at 110 ° C. for 7 hours. Next, the obtained powder was placed in an aqueous solution in which 53.0 mg (0.104 mmol in terms of iridium) of hexachloroiridium acid (manufactured by Wako Pure Chemical Industries, Ltd., iridium concentration: 37.7 mass%) was dissolved in 0.4 g of water. Impregnation and drying at 110 ° C. for 7 hours. Furthermore, the obtained powder was impregnated in a solution in which 27.9 mg of ammonium tetraoxorhenate (VII) (0.104 mmol in terms of rhenium) was dissolved in 0.4 g of water, and dried at 110 ° C. for 7 hours. . This powder was dried at 250 ° C. for 4 hours, and a solid catalyst (hereinafter referred to as “Ru—Ir—” in which 2.1% by mass of ruthenium, 4.0% by mass of iridium and 3.9% by mass of rhenium were supported on silica. 588 mg (sometimes referred to as “Re / SiO 2 catalyst (1)”) was obtained.
実施例12(触媒の製造)
実施例1において、七酸化レニウムをドデカカルボニル二レニウム(レニウムが0.075mmol)に変えた以外は、実施例1と同様にして活性炭にロジウムが2.2質量%、白金が4.1質量%、レニウムが5.5質量%担持された触媒(以下、「Rh−Pt−Re/AC触媒(3)」と称することもある)を得た。
Example 12 (Production of catalyst)
In Example 1, rhodium is 2.2% by mass and platinum is 4.1% by mass in the same manner as in Example 1 except that rhenium heptoxide is changed to dodecacarbonyl dirhenium (rhenium is 0.075 mmol). Thus, a catalyst carrying 5.5% by mass of rhenium (hereinafter sometimes referred to as “Rh—Pt—Re / AC catalyst (3)”) was obtained.
実施例13(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化ルテニウム・n水和物(0.050mmol)に、四塩化白金を五塩化タンタル(0.050mmol)に変えた以外は、実施例1と同様にして活性炭にタンタルが3.9質量%、ルテニウムが2.2質量%、レニウムが6.1質量%担持された触媒(以下、「Ta−Ru−Re/AC触媒(1)」と称することもある)を得た。
Example 13 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to tantalum pentachloride (0.050 mmol). In the same manner as above, a catalyst (hereinafter referred to as “Ta-Ru-Re / AC catalyst (1)”) in which activated carbon is supported by 3.9% by mass of tantalum, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium is supported. Sometimes called).
実施例14(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化ルテニウム・n水和物(0.050mmol)に、四塩化白金を五塩化レニウム(0.050mmol)に変えた以外は、実施例1と同様にして活性炭にレニウムが4.0質量%、ルテニウムが2.2質量%、レニウムが6.1質量%担持された触媒(以下、「Re−Ru−Re/AC触媒(1)」と称することもある)を得た。
Example 14 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to rhenium pentachloride (0.050 mmol). In the same manner as described above, a catalyst (hereinafter referred to as “Re-Ru-Re / AC catalyst (1)”) in which activated carbon is supported by 4.0% by mass of rhenium, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium. Sometimes called).
実施例15(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化ルテニウム・n水和物(0.050mmol)に、四塩化白金を四塩化金酸(0.050mmol)に変えた以外は、実施例1と同様にして活性炭にルテニウムが2.2質量%、金が4.3質量%、レニウムが6.1質量%担持された触媒(以下、「Ru−Au−Re/AC触媒(1)」と称することもある)を得た。
Example 15 (Production of catalyst)
In Example 1, except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to tetrachloroauric acid (0.050 mmol). In the same manner as in No. 1, a catalyst having 2.2% by mass of ruthenium, 4.3% by mass of gold, and 6.1% by mass of rhenium supported on activated carbon (hereinafter referred to as “Ru—Au—Re / AC catalyst (1)”). May also be called).
実施例16(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化ルテニウム・n水和物(0.050mmol)に、四塩化白金を二塩化パラジウム(0.050mmol)に変えた以外は、実施例1と同様にして活性炭にルテニウムが2.2質量%、パラジウムが2.2質量%、レニウムが6.1質量%担持された触媒(以下、「Ru−Pd−Re/AC触媒(1)」と称することもある)を得た。
Example 16 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to palladium dichloride (0.050 mmol). In the same manner as described above, a catalyst in which 2.2% by mass of ruthenium, 2.2% by mass of palladium and 6.1% by mass of rhenium are supported on activated carbon (hereinafter referred to as “Ru—Pd—Re / AC catalyst (1)”). Sometimes called).
実施例17(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化ルテニウム・n水和物(0.050mmol)に、四塩化白金を四塩化ジルコニウム(0.050mmol)に変えた以外は、実施例1と同様にして活性炭にジルコニウムが2.0質量%、ルテニウムが2.2質量%、レニウムが6.1質量%担持された触媒(以下、「Zr−Ru−Re/AC触媒(1)」と称することもある)を得た。
Example 17 (Production of catalyst)
Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to zirconium tetrachloride (0.050 mmol). In the same manner as above, a catalyst in which 2.0% by mass of zirconium, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium are supported on activated carbon (hereinafter referred to as “Zr-Ru—Re / AC catalyst (1)”). Sometimes called).
実施例18(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化ルテニウム・n水和物(0.050mmol)に、四塩化白金を四塩化ハフニウム(0.050mmol)に変えた以外は、実施例1と同様にして活性炭にハフニウムが3.9質量%、ルテニウムが2.2質量%、レニウムが6.1質量%担持された触媒(以下、「Hf−Ru−Re/AC触媒(1)」と称することもある)を得た。
Example 18 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to hafnium tetrachloride (0.050 mmol). In the same manner as above, a catalyst (hereinafter referred to as "Hf-Ru-Re / AC catalyst (1)") in which activated carbon is supported with 3.9% by mass of hafnium, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium. Sometimes called).
実施例19(触媒の製造)
実施例1において、担体を活性炭からグラフェン(STREM製)に変えた以外は、実施例1と同様にして活性炭にロジウムが2.1質量%、白金が4.3質量%、レニウムが6.1質量%担持された触媒(以下、「Rh−Pt−Re/グラフェン触媒(1)」と称することもある)を得た。
Example 19 (Production of catalyst)
In Example 1, except that the support was changed from activated carbon to graphene (manufactured by STREM), rhodium was 2.1% by mass, platinum was 4.3% by mass, rhenium was 6.1% by mass in the same manner as Example 1. A mass% supported catalyst (hereinafter sometimes referred to as “Rh—Pt—Re / graphene catalyst (1)”) was obtained.
実施例20(触媒の製造)
実施例1において、三塩化ロジウム・3水和物を三塩化ルテニウム・n水和物(0.050mmol)に、四塩化白金を二塩化パラジウム(0.050mmol)に担体を活性炭からグラフェン(STREM製)に変えた以外は、実施例1と同様にして活性炭にルテニウムが2.2質量%、パラジウムが2.2質量%、レニウムが6.1質量%担持された触媒(以下、「Ru−Pd−Re/グラフェン触媒(1)」と称することもある)を得た。
Example 20 (Production of catalyst)
In Example 1, rhodium trichloride trihydrate is converted to ruthenium trichloride n hydrate (0.050 mmol), platinum tetrachloride is converted to palladium dichloride (0.050 mmol), and the carrier is graphene (made by STREM). Except for the above, the catalyst in which ruthenium was supported by 2.2% by mass, palladium by 2.2% by mass, and rhenium by 6.1% by mass was supported in the same manner as in Example 1 (hereinafter referred to as “Ru—Pd”). -Re / graphene catalyst (1) ”).
実施例1A(コハク酸からの1,4−ブタンジオール合成) Example 1A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例1で得られた残渣(Rh−Pt−Re/AC触媒(1))、コハク酸0.600g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で12時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は69.8%、同選択率は69.8%、1−ブタノールの収率は9.7%、同選択率は9.7%、γ−ブチロラクトンの収率は2.1%、同選択率は2.1%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh-Pt-Re / AC catalyst (1)), succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 69.8%. The yield was 69.8%, the yield of 1-butanol was 9.7%, the selectivity was 9.7%, the yield of γ-butyrolactone was 2.1%, and the selectivity was 2.1%. It was.
実施例1B(アジピン酸からの1,6−ヘキサンジオールの合成) Example 1B (Synthesis of 1,6-hexanediol from adipic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例1で得られた残渣(Rh−Pt−Re/AC触媒(1))、アジピン酸1.460g(10.0mmol)を加え、アジピン酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で30時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、アジピン酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,6−ヘキサンジオールの収率は93.6%、同選択率は93.6%、1−ヘキサノールの収率は2.5%、同選択率は2.5%であった。
To the autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh—Pt—Re / AC catalyst (1)) and 1.460 g (10.0 mmol) of adipic acid were added, and adipic acid was added. The volume was adjusted to 15% with water. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 30 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
The obtained filtrate was analyzed by gas chromatography. The conversion of adipic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,6-hexanediol was 93.6%. The rate was 93.6%, the yield of 1-hexanol was 2.5%, and the selectivity was 2.5%.
実施例1C(レブリン酸からの1,4−ペンタンジオールの合成) Example 1C (Synthesis of 1,4-pentanediol from levulinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例1で得られた残渣(Rh−Pt−Re/AC触媒(1))、レブリン酸1.75g(15.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.30g(0.30mmol)を加え、レブリン酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で15時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、レブリン酸の転化率は100%であり、1,4−ペンタンジオールの収率は63.6%、同選択率は63.6%、γ−バレロラクトンの収率は1.7%、同選択率は1.7%、2−メチルテトラヒドロフランの収率は4.0%、同選択率は4.0%、2−ペンタノールの収率は4.3%、同選択率は4.3%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh—Pt—Re / AC catalyst (1)), levulinic acid 1.75 g (15.0 mmol), 1.0 mol / l 0.30 g (0.30 mmol) of an aqueous sodium hydroxide solution was added, and the volume was increased with water so that levulinic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 15 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
The obtained filtrate was analyzed by gas chromatography. The conversion of levulinic acid was 100%, the yield of 1,4-pentanediol was 63.6%, the selectivity was 63.6%, and γ- The yield of valerolactone is 1.7%, the selectivity is 1.7%, the yield of 2-methyltetrahydrofuran is 4.0%, the selectivity is 4.0%, and the yield of 2-pentanol is The selectivity was 4.3% and the selectivity was 4.3%.
実施例1D(ヘキサン酸からの1−ヘキサノールの合成) Example 1D (Synthesis of 1-hexanol from hexanoic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例1で得られた残渣(Rh−Pt−Re/AC触媒(1))、ヘキサン酸1.16g(10.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.20g(0.20mmol)を加え、ヘキサン酸が15%になるようにジエチレングリコールジメチルエーテルでメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら180℃で9時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、ヘキサン酸の転化率は97.3%であり、1−ヘキサノールの収率は58.6%、同選択率は57.0%、ヘキサン酸ヘキシルの収率は2.3%、同選択率は2.2%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh-Pt-Re / AC catalyst (1)), 1.16 g (10.0 mmol) of hexanoic acid, 1.0 mol / l 0.20 g (0.20 mmol) of an aqueous sodium hydroxide solution was added, and diluted with diethylene glycol dimethyl ether so that hexanoic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 180 ° C. for 9 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of hexanoic acid was 97.3%, the yield of 1-hexanol was 58.6%, the selectivity was 57.0%, and hexyl hexanoate. The yield was 2.3%, and the selectivity was 2.2%.
実施例2A(コハク酸からの1,4−ブタンジオールの合成) Example 2A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例2で得られた固体(Rh−Pt−Re/AC触媒(2))120mg、水2mlを加え、室温にて水素ガスで8MPaまで加圧し、120℃で1時間加熱攪拌して固体を還元処理した。得られた溶液を室温まで冷却し、遠心分離により水層を除いた。得られた残渣にコハク酸1.50g(12.7mmol)、1.0mol/l水酸化ナトリウム水溶液0.25g(0.25mmol)を加え、コハク酸が15%になるように水でメスアップした。水素ガスで8MPaまで加圧し、攪拌しながら120℃で36時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンによるエステル化で確認)、1,4−ブタンジオールの収率は82.3%、同選択率は82.3%、1−ブタノールの収率は11.5%、同選択率は11.5%、γ−ブチロラクトンの収率は0.16%、同選択率は0.16%であった。
To an autoclave equipped with a 50 ml glass inner tube, 120 mg of the solid obtained in Example 2 (Rh-Pt-Re / AC catalyst (2)) and 2 ml of water were added, and the pressure was increased to 8 MPa with hydrogen gas at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 1.50 g (12.7 mmol) of succinic acid and 0.25 g (0.25 mmol) of a 1.0 mol / l aqueous sodium hydroxide solution were added, and the volume of the succinic acid was increased to 15%. . The pressure was increased to 8 MPa with hydrogen gas, and the mixture was reacted at 120 ° C. for 36 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 82.3%, the same selection. The yield was 82.3%, the yield of 1-butanol was 11.5%, the selectivity was 11.5%, the yield of γ-butyrolactone was 0.16%, and the selectivity was 0.16%. It was.
実施例3A(コハク酸からの1,4−ブタンジオールの合成) Example 3A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例3で得られた固体(Rh−Pt−Re/SiO2(1))120mg、水2mlを加え、室温にて水素ガスで8MPaまで加圧し、120℃で1時間加熱攪拌して固体を還元処理した。得られた溶液を室温まで冷却し、遠心分離により水層を除いた。得られた残渣にコハク酸0.35g(3.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。水素ガスで8MPaまで加圧し、攪拌しながら120℃で18時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は82.9%、同選択率は82.9%、1−ブタノールの収率は15.5%、同選択率は15.5%、γ−ブチロラクトンの収率は3.9%、同選択率は3.9%であった。
To an autoclave equipped with a 50 ml glass inner tube, 120 mg of the solid (Rh—Pt—Re / SiO 2 (1)) obtained in Example 3 and 2 ml of water were added and heated to 8 MPa with hydrogen gas at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 0.35 g (3.0 mmol) of succinic acid and 0.10 g (0.10 mmol) of a 1.0 mol / l aqueous sodium hydroxide solution were added, and the volume was adjusted to 15% with succinic acid. . The pressure was increased to 8 MPa with hydrogen gas, and the reaction was performed at 120 ° C. for 18 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 82.9%. The yield was 12.9%, the yield of 1-butanol was 15.5%, the selectivity was 15.5%, the yield of γ-butyrolactone was 3.9%, and the selectivity was 3.9%. It was.
実施例3B(3−ヒドロキシプロピオン酸からの1,3−プロパンジオールの合成) Example 3B (Synthesis of 1,3-propanediol from 3-hydroxypropionic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例3で得られた固体(Rh−Pt−Re/SiO2(1))128mg、水2mlを加え、室温にて水素ガスで8MPaまで加圧し、120℃で1時間加熱攪拌して固体を還元処理した。得られた溶液を室温まで冷却し、遠心分離により水層を除いた。得られた残渣に3−ヒドロキシプロピオン酸の30%水溶液1.50g(5.0mmol)を加え、3−ヒドロキシプロピオン酸が10%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で4時間、更に140℃で14時間攪拌しながら反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、3−ヒドロキシプロピオン酸の転化率は77.6%であり、1,3−プロパンジオールの収率は65.1%、同選択率は83.9%、1−プロパノールの収率は12.2%、同選択率は15.7%であった。
To an autoclave equipped with a 50 ml glass inner tube, 128 mg of the solid (Rh—Pt—Re / SiO 2 (1)) obtained in Example 3 and 2 ml of water were added, and hydrogen gas was added up to 8 MPa at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 1.50 g (5.0 mmol) of a 30% aqueous solution of 3-hydroxypropionic acid was added, and the volume was increased with water so that 3-hydroxypropionic acid became 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out while stirring at 120 ° C. for 4 hours and further at 140 ° C. for 14 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of 3-hydroxypropionic acid was 77.6%, the yield of 1,3-propanediol was 65.1%, and the selectivity was 83. The yield of 9%, 1-propanol was 12.2%, and the selectivity was 15.7%.
実施例4A(コハク酸からの1,4−ブタンジオールの合成) Example 4A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例4で得られた残渣(Rh−Pt−Mo/AC触媒(1))、コハク酸0.600g(5.0mmol)、1.0mol/l NaOH水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で18時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は70.1%、同選択率は70.1%、1−ブタノールの収率は9.6%、同選択率は9.6%、γ−ブチロラクトンの収率は2.8%、同選択率は2.8%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue (Rh—Pt—Mo / AC catalyst (1)) obtained in Example 4, succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of NaOH aqueous solution was added, and the volume was increased with water so that succinic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 70.1%. The yield was 70.1%, the yield of 1-butanol was 9.6%, the selectivity was 9.6%, the yield of γ-butyrolactone was 2.8%, and the selectivity was 2.8%. It was.
実施例5A(コハク酸からの1,4−ブタンジオールの合成) Example 5A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例5で得られた固体(Rh−Pt−Mo/AC(2))120mg、水2mlを加え、室温にて水素ガスで8MPaまで加圧し、120℃で1時間加熱攪拌して固体を還元処理した。得られた溶液を室温まで冷却し、遠心分離により水層を除いた。得られた残渣にコハク酸0.35g(3.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。水素ガスで8MPaまで加圧し、攪拌しながら120℃で18時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンによるエステル化で確認)、1,4−ブタンジオールの収率は74.9%、同選択率は74.9%、1−ブタノールの収率は4.0%、同選択率は4.0、γ−ブチロラクトンの収率は3.7%、同選択率は3.7%であった。
To an autoclave equipped with a 50 ml glass inner tube, 120 mg of the solid (Rh—Pt—Mo / AC (2)) obtained in Example 5 and 2 ml of water were added, and the pressure was increased to 8 MPa with hydrogen gas at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 0.35 g (3.0 mmol) of succinic acid and 0.10 g (0.10 mmol) of a 1.0 mol / l aqueous sodium hydroxide solution were added, and the volume was adjusted to 15% with succinic acid. . The pressure was increased to 8 MPa with hydrogen gas, and the reaction was performed at 120 ° C. for 18 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 74.9%. The yield was 74.9%, the yield of 1-butanol was 4.0%, the selectivity was 4.0, the yield of γ-butyrolactone was 3.7%, and the selectivity was 3.7%. .
実施例6A(コハク酸からの1,4−ブタンジオールの合成) Example 6A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例6で得られた残渣(Rh−Pd−Re/AC触媒(1))、コハク酸0.600g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で12時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は61.7%、同選択率は61.7%、1−ブタノールの収率は13.0%、同選択率は13.0%、γ−ブチロラクトンの収率は2.3%、同選択率は2.3%であった。であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 6 (Rh—Pd—Re / AC catalyst (1)), succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 61.7%. The yield was 61.7%, the yield of 1-butanol was 13.0%, the selectivity was 13.0%, the yield of γ-butyrolactone was 2.3%, and the selectivity was 2.3%. It was. Met.
実施例7A(コハク酸からの1,4−ブタンジオールの合成) Example 7A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例7で得られた残渣(Ru−Rh−Re/AC触媒(1))、コハク酸0.600g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で12時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は61.0%、同選択率は61.0%、1−ブタノールの収率は9.3%、同選択率は9.3%、γ−ブチロラクトンの収率は2.1%、同選択率は2.1%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 7 (Ru-Rh-Re / AC catalyst (1)), succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 61.0%. The yield was 61.0%, the yield of 1-butanol was 9.3%, the selectivity was 9.3%, the yield of γ-butyrolactone was 2.1%, and the selectivity was 2.1%. It was.
実施例8A(コハク酸からの1,4−ブタンジオールの合成) Example 8A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例8で得られた残渣(Ir−Pt−Re/AC触媒(1))、コハク酸1.20g(10mmol)、1.0mol/l水酸化ナトリウム水溶液0.20g(0.20mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら100℃で60時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は57.5%、同選択率は57.5%、1−ブタノールの収率は23.8%、同選択率は23.8%、γ−ブチロラクトンの収率は1.9%、同選択率は1.9%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue (Ir-Pt-Re / AC catalyst (1)) obtained in Example 8, succinic acid 1.20 g (10 mmol), 1.0 mol / l water Sodium oxide aqueous solution 0.20g (0.20mmol) was added, and it was made up with water so that succinic acid might be 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 100 ° C. for 60 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 57.5%. The yield was 57.5%, the yield of 1-butanol was 23.8%, the selectivity was 23.8%, the yield of γ-butyrolactone was 1.9%, and the selectivity was 1.9%. It was.
実施例9A(コハク酸からの1,4−ブタンジオールの合成) Example 9A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例9で得られた残渣(Ir−Pt−Mo/AC触媒(1))、コハク酸1.20g(10mmol)、1.0mol/l水酸化水溶液0.20g(0.20mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら100℃で60時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は60.8%、同選択率は60.8%、1−ブタノールの収率は10.8%、同選択率は10.8%、γ−ブチロラクトンの収率は6.9%、同選択率は6.9%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue (Ir-Pt-Mo / AC catalyst (1)) obtained in Example 9, succinic acid 1.20 g (10 mmol), 1.0 mol / l water 0.20 g (0.20 mmol) of an aqueous oxidation solution was added, and the volume was increased with water so that succinic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 100 ° C. for 60 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 60.8%. The yield was 60.8%, the yield of 1-butanol was 10.8%, the selectivity was 10.8%, the yield of γ-butyrolactone was 6.9%, and the selectivity was 6.9%. It was.
実施例10A(3−ヒドロキシプロピオン酸からの1,3−プロパンジオールの合成) Example 10A (Synthesis of 1,3-propanediol from 3-hydroxypropionic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例10で得られた残渣(Ru−Rh−Re/AC触媒(2))、3−ヒドロキシプロピオン酸の30%水溶液1.50g(5.0mmol)を加え、3−ヒドロキシプロピオン酸が10%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で4時間、更に140℃で14時間攪拌しながら反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、3−ヒドロキシプロピオン酸の転化率は88.0%であり、1,3−プロパンジオールの収率は76.3%、同選択率は86.7%、1−プロパノールの収率は8.8%、同選択率は10.0%であった。
In an autoclave equipped with a 50-ml glass inner tube, the residue obtained in Example 10 (Ru—Rh—Re / AC catalyst (2)), 1.50 g of a 30% aqueous solution of 3-hydroxypropionic acid (5. 0 mmol) was added, and the volume was made up with water so that 3-hydroxypropionic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out while stirring at 120 ° C. for 4 hours and further at 140 ° C. for 14 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of 3-hydroxypropionic acid was 88.0%, the yield of 1,3-propanediol was 76.3%, and the selectivity was 86. The yield of 7%, 1-propanol was 8.8%, and the selectivity was 10.0%.
実施例10B(乳酸からの1,2−プロパンジオールの合成) Example 10B (Synthesis of 1,2-propanediol from lactic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例10と同様の方法で得られた残渣(Rh−Ru−Re/AC触媒(2))、乳酸の90.3%水溶液0.50g(5.0mmol)を加え、乳酸が10%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら100℃で22時間攪拌しながら反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、乳酸の転化率は97.5%であり、1,2−プロパンジオールの収率は77.4%、同選択率は79.4%、1−プロパノールの収率は4.6%、同選択率は4.7%、2−プロパノールの収率は1.5%、同選択率は1.5%、であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue (Rh-Ru-Re / AC catalyst (2)) obtained in the same manner as in Example 10 and 0.50 g of a 90.3% aqueous solution of lactic acid ( 5.0 mmol) was added, and the volume was increased with water so that the amount of lactic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 22 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of lactic acid was 97.5%, the yield of 1,2-propanediol was 77.4%, the selectivity was 79.4%, The yield of -propanol was 4.6%, the selectivity was 4.7%, the yield of 2-propanol was 1.5%, and the selectivity was 1.5%.
実施例11A(3−ヒドロキシプロピオン酸からの1,3−プロパンジオールの合成) Example 11A (Synthesis of 1,3-propanediol from 3-hydroxypropionic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例11で得られた残渣(Ru−Ir−Re/SiO2触媒(1))60mg、3−ヒドロキシプロピオン酸の30%水溶液1.50g(5.0mmol)を加え、3−ヒドロキシプロピオン酸が10%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら100℃で4時間、更に140℃で11時間攪拌しながら反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、3−ヒドロキシプロピオン酸の転化率は87.0%であり、1,3−プロパンジオールの収率は65.8%、同選択率は75.6%、1−プロパノールの収率は18.9%、同選択率は2.2%であった。
In an autoclave equipped with a 50 ml glass inner tube, 60 mg of the residue obtained in Example 11 (Ru—Ir—Re / SiO 2 catalyst (1)), 1.50 g of a 30% aqueous solution of 3-hydroxypropionic acid ( 5.0 mmol) was added, and the volume was increased with water so that 3-hydroxypropionic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 4 hours and further at 140 ° C. for 11 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of 3-hydroxypropionic acid was 87.0%, the yield of 1,3-propanediol was 65.8%, and the selectivity was 75. The yield of 6%, 1-propanol was 18.9%, and the selectivity was 2.2%.
実施例11B(乳酸からの1,2−プロパンジオールの合成) Example 11B (Synthesis of 1,2-propanediol from lactic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例11で得られた残渣(Ru−Ir−Re/SiO2触媒(1))60mg、乳酸の90.3%水溶液0.50g(5.0mmol)を加え、乳酸が10%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら100℃で15時間攪拌しながら反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、乳酸の転化率は95.2%であり、1,2−プロパンジオールの収率は85.3%、同選択率は89.6%、1−プロパノールの収率は5.1%、同選択率は5.3%、2−プロパノールの収率は2.0%、同選択率は2.1%、であった。
In an autoclave equipped with a 50 ml glass inner tube, 60 mg of the residue (Ru—Ir—Re / SiO 2 catalyst (1)) obtained in Example 11 and 0.50 g of a 90.3% aqueous solution of lactic acid (5. 0 mmol) was added, and the volume of the lactic acid was increased to 10% with water. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 15 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of lactic acid was 95.2%, the yield of 1,2-propanediol was 85.3%, the selectivity was 89.6%, 1 The yield of -propanol was 5.1%, the selectivity was 5.3%, the yield of 2-propanol was 2.0%, and the selectivity was 2.1%.
実施例11C(プロピオン酸からの1−プロパノールの合成) Example 11C (Synthesis of 1-propanol from propionic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例11で得られた残渣(Ru−Ir−Re/SiO2触媒(1))60mg、プロピオン酸0.375g(5.0mmol)を加え、プロピオン酸が10%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら100℃で17時間攪拌しながら反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、プロピオン酸の転化率は98.9%であり、1−プロパノールの収率は93.2%、同選択率は94.2%であった。
To an autoclave equipped with a 50 ml glass inner tube, 60 mg of the residue (Ru—Ir—Re / SiO 2 catalyst (1)) obtained in Example 11 and 0.375 g (5.0 mmol) of propionic acid were added, The volume was increased with water so that the propionic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 17 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of propionic acid was 98.9%, the yield of 1-propanol was 93.2%, and the selectivity was 94.2%.
実施例12A(コハク酸からの1,4−ブタンジオールの合成) Example 12A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例12で得られた残渣(Rh−Pt−Re/AC触媒(3))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で36時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は64.6%、同選択率は64.6%、1−ブタノールの収率は11.6%、同選択率は11.6%、γ−ブチロラクトンの収率は5.9%、同選択率は5.9%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 12 (Rh—Pt—Re / AC catalyst (3)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 36 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 64.6%. The yield was 64.6%, the yield of 1-butanol was 11.6%, the selectivity was 11.6%, the yield of γ-butyrolactone was 5.9%, and the selectivity was 5.9%. It was.
実施例13A(コハク酸からの1,4−ブタンジオールの合成) Example 13A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例13で得られた残渣(Ta−Ru−Re/AC触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で36時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は87.2%、同選択率は87.2%、1−ブタノールの収率は7.8%、同選択率は7.8%、γ−ブチロラクトンの収率は4.7%、同選択率は4.7%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 13 (Ta-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 36 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 87.2%, the same selection. The yield was 87.2%, the yield of 1-butanol was 7.8%, the selectivity was 7.8%, the yield of γ-butyrolactone was 4.7%, and the selectivity was 4.7%. It was.
実施例14A(コハク酸からの1,4−ブタンジオールの合成) Example 14A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例13で得られた残渣(Re−Ru−Re/AC触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で18時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は80.9%、同選択率は80.9%、1−ブタノールの収率は4.9%、同選択率は4.9%、γ−ブチロラクトンの収率は2.2%、同選択率は2.2%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 13 (Re-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 80.9%. The yield was 80.9%, the yield of 1-butanol was 4.9%, the selectivity was 4.9%, the yield of γ-butyrolactone was 2.2%, and the selectivity was 2.2%. It was.
実施例15A(コハク酸からの1,4−ブタンジオールの合成) Example 15A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例14で得られた残渣(Ru−Au−Re/AC触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら150℃で12時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は68.1%、同選択率は68.1%、1−ブタノールの収率は6.4%、同選択率は6.4%、γ−ブチロラクトンの収率は3.0%、同選択率は3.0%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue (Ru—Au—Re / AC catalyst (1)) obtained in Example 14, succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 150 ° C. for 12 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 68.1%. The yield was 68.1%, the yield of 1-butanol was 6.4%, the selectivity was 6.4%, the yield of γ-butyrolactone was 3.0%, and the selectivity was 3.0%. It was.
実施例16A(コハク酸からの1,4−ブタンジオールの合成) Example 16A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例15で得られた残渣(Ru−Pd−Re/AC触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で18時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は62.1%、同選択率は62.1%、1−ブタノールの収率は11.0%、同選択率は11.0%、γ−ブチロラクトンの収率は0.25%、同選択率は0.25%であった。
Into an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 15 (Ru—Pd—Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 62.1%. The yield was 62.1%, the yield of 1-butanol was 11.0%, the selectivity was 11.0%, the yield of γ-butyrolactone was 0.25%, and the selectivity was 0.25%. It was.
実施例17A(コハク酸からの1,4−ブタンジオールの合成) Example 17A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例17で得られた残渣(Zr−Ru−Re/AC触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で18時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は90.4%、同選択率は90.4%、1−ブタノールの収率は9.1%、同選択率は9.1%であり、γ−ブチロラクトンは観測されなかった。
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 17 (Zr-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 90.4%. The rate was 90.4%, the yield of 1-butanol was 9.1%, the selectivity was 9.1%, and γ-butyrolactone was not observed.
実施例18A(コハク酸からの1,4−ブタンジオールの合成) Example 18A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例18で得られた残渣(Hf−Ru−Re/AC触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で12時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は70.1%、同選択率は70.1%、1−ブタノールの収率は8.5%、同選択率は8.5%、γ−ブチロラクトンの収率は5.0%、同選択率は5.0%であった。
実施例19A(コハク酸からの1,4−ブタンジオールの合成)
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 18 (Hf-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 70.1%. The yield was 70.1%, the yield of 1-butanol was 8.5%, the selectivity was 8.5%, the yield of γ-butyrolactone was 5.0%, and the selectivity was 5.0%. It was.
Example 19A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例19で得られた残渣(Rh−Pt−Re/グラフェン触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で6時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は75.2%、同選択率は75.2%、1−ブタノールの収率は12.4%、同選択率は12.4%、γ−ブチロラクトンの収率は5.5%、同選択率は5.5%であった。
実施例20A(コハク酸からの1,4−ブタンジオールの合成)
In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 19 (Rh—Pt—Re / graphene catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 6 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 75.2%. The yield was 75.2%, the yield of 1-butanol was 12.4%, the selectivity was 12.4%, the yield of γ-butyrolactone was 5.5%, and the selectivity was 5.5%. It was.
Example 20A (Synthesis of 1,4-butanediol from succinic acid)
50mlのガラス製内筒管を備えたオートクレーブに、実施例20で得られた残渣(Ru−Pd−Re/グラフェン触媒(1))、コハク酸0.60g(5.0mmol)、1.0mol/l水酸化ナトリウム水溶液0.10g(0.10mmol)を加え、コハク酸が15%になるように水でメスアップした。室温にて水素ガスで8MPaまで加圧し、攪拌しながら120℃で15時間反応させた。反応終了後、得られた反応液を室温まで冷却し、次いでメンブランフィルター(0.45μm)を備えた注射器で濾過した。
得られた濾液をガスクロマトグラフィーで分析したところ、コハク酸の転化率は100%であり(トリメチルシリルジアゾメタンでエステル化して確認)、1,4−ブタンジオールの収率は80.8%、同選択率は80.8%、1−ブタノールの収率は11.0%、同選択率は11.0%、γ−ブチロラクトンの収率は2.4%、同選択率は2.4%であった。
In an autoclave equipped with a 50 ml glass inner tube, the residue (Ru—Pd—Re / graphene catalyst (1)) obtained in Example 20, succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 15 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 80.8%. The yield was 10.8%, the selectivity was 11.0%, the yield of γ-butyrolactone was 2.4%, and the selectivity was 2.4%. It was.
以上の結果から、
(1)ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の金属化合物(A)
(2)周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)
とを混合し、還元処理して得られる触媒(本発明の触媒)が、カルボン酸化合物と水素源の存在下にて接触することによって、高い反応速度で、高収率且つ高選択的に対応するアルコール化合物を与えることが分かった。
From the above results,
(1) selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold. At least two metal compounds (A)
(2) Metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table
The catalyst obtained by mixing and reducing the catalyst (the catalyst of the present invention) can be contacted in the presence of a carboxylic acid compound in the presence of a hydrogen source so that the reaction can be carried out at a high reaction rate with high yield and high selectivity. It was found to give an alcohol compound.
本発明により、カルボン酸化合物を還元して、高い反応速度で、高収率且つ高選択的に対応するアルコール化合物を与えうる触媒を提供することができる。上記カルボン酸化合物がジカルボン酸であれば、対応するジオール化合物を製造することができる。得られたジオール化合物は、例えば、ポリエステル、ポリカーボネート、ポリウレタン等のポリマー原料、樹脂添加剤、医農薬中間体原料、各種溶剤等として有用である。 According to the present invention, it is possible to provide a catalyst capable of reducing a carboxylic acid compound to give a corresponding alcohol compound with high reaction rate and high yield. If the carboxylic acid compound is a dicarboxylic acid, a corresponding diol compound can be produced. The obtained diol compound is useful as, for example, polymer raw materials such as polyester, polycarbonate, and polyurethane, resin additives, medical and agrochemical intermediate raw materials, various solvents, and the like.
Claims (8)
ロジウム、イリジウム、白金、ルテニウム、タンタル、レニウム、パラジウム、ランタン、セリウム、サマリウム、イッテルビウム、ルテチウム、ジルコニウム、ハフニウム、ニオブ、モリブデン、タングステン、コバルト、ニッケル、銅及び金からなる群より選ばれる少なくとも2種の金属化合物(A)と、
周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)と、
を混合し、還元処理して得られる触媒とを接触させることを特徴とする、アルコール化合物の製造方法。 A carboxylic acid compound in the presence of a hydrogen source;
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold A metal compound (A) of
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
A method for producing an alcohol compound, comprising mixing a catalyst and contacting with a catalyst obtained by reduction treatment.
周期表第5族、6族又は7族の金属を含む金属酸化物(B1)或いは金属カルボニル化合物(B2)と、
を混合し、還元処理して得られるアルコールを製造するための触媒。 At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold A metal compound (A) of
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
A catalyst for producing alcohol obtained by mixing and reducing.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2017039671A (en) * | 2015-08-20 | 2017-02-23 | 国立大学法人大阪大学 | Manufacturing method of 2-methyltetrahydrofuran |
WO2017085986A1 (en) * | 2015-11-16 | 2017-05-26 | 宇部興産株式会社 | Method for producing γ-valerolactone |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01503459A (en) * | 1987-03-31 | 1989-11-22 | ザ ブリテイッシュ ピトローリアム コンパニー ピー.エル.シー. | Catalytic hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters |
JPH09241192A (en) * | 1996-03-08 | 1997-09-16 | Sagami Chem Res Center | Production of alcohols |
JP2001046873A (en) * | 1999-08-17 | 2001-02-20 | Mitsubishi Chemicals Corp | Hydrogenating catalyst and production of alcohols from carboxylic acids using the same |
JP2001046871A (en) * | 1999-08-03 | 2001-02-20 | Standard Oil Co | Improved catalyst for hydrogenating maleic acid to produce 1,4-butane diol |
WO2013027766A1 (en) * | 2011-08-23 | 2013-02-28 | 宇部興産株式会社 | Hydrocracking catalyst, method for producing same, and method for producing hydroxy compound using said catalyst |
-
2013
- 2013-10-08 JP JP2013210728A patent/JP6268892B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01503459A (en) * | 1987-03-31 | 1989-11-22 | ザ ブリテイッシュ ピトローリアム コンパニー ピー.エル.シー. | Catalytic hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters |
JPH09241192A (en) * | 1996-03-08 | 1997-09-16 | Sagami Chem Res Center | Production of alcohols |
JP2001046871A (en) * | 1999-08-03 | 2001-02-20 | Standard Oil Co | Improved catalyst for hydrogenating maleic acid to produce 1,4-butane diol |
JP2001046873A (en) * | 1999-08-17 | 2001-02-20 | Mitsubishi Chemicals Corp | Hydrogenating catalyst and production of alcohols from carboxylic acids using the same |
WO2013027766A1 (en) * | 2011-08-23 | 2013-02-28 | 宇部興産株式会社 | Hydrocracking catalyst, method for producing same, and method for producing hydroxy compound using said catalyst |
Cited By (15)
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---|---|---|---|---|
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WO2017085986A1 (en) * | 2015-11-16 | 2017-05-26 | 宇部興産株式会社 | Method for producing γ-valerolactone |
JPWO2017085986A1 (en) * | 2015-11-16 | 2018-09-06 | 宇部興産株式会社 | Method for producing γ-valerolactone |
US10227318B2 (en) | 2015-11-16 | 2019-03-12 | Ube Industries, Ltd. | Method for producing gamma-valerolactone |
JPWO2020008617A1 (en) * | 2018-07-06 | 2021-06-10 | Toyo Tire株式会社 | Method for producing hydrogenation catalyst and diol |
WO2020008617A1 (en) * | 2018-07-06 | 2020-01-09 | Toyo Tire株式会社 | Catalyst for hydrogenation and production method for diol |
US11547984B2 (en) | 2018-07-06 | 2023-01-10 | Toyo Tire Corporation | Production methods of catalyst for hydrogenation and diol |
WO2020022256A1 (en) * | 2018-07-23 | 2020-01-30 | 三菱ケミカル株式会社 | Alcohol production method and catalyst |
JPWO2020022256A1 (en) * | 2018-07-23 | 2021-08-05 | 三菱ケミカル株式会社 | Alcohol production method and catalyst |
JP7342868B2 (en) | 2018-07-23 | 2023-09-12 | 三菱ケミカル株式会社 | Alcohol manufacturing method and catalyst |
WO2023041091A1 (en) * | 2022-02-09 | 2023-03-23 | 中国科学院广州能源研究所 | Method for preparing 2-butanol by means of catalytic hydrogenation of levulinic acid |
CN115536495A (en) * | 2022-10-12 | 2022-12-30 | 河北工业大学 | Method for preparing 1, 4-pentanediol |
CN115536495B (en) * | 2022-10-12 | 2023-12-15 | 河北工业大学 | Method for preparing 1, 4-pentanediol |
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