JP2022161913A - Catalyst for hydrogenation reaction used in hydrogenation of amide compound, and manufacturing method of amine compound using the same - Google Patents
Catalyst for hydrogenation reaction used in hydrogenation of amide compound, and manufacturing method of amine compound using the same Download PDFInfo
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- JP2022161913A JP2022161913A JP2022119654A JP2022119654A JP2022161913A JP 2022161913 A JP2022161913 A JP 2022161913A JP 2022119654 A JP2022119654 A JP 2022119654A JP 2022119654 A JP2022119654 A JP 2022119654A JP 2022161913 A JP2022161913 A JP 2022161913A
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- Prior art keywords
- platinum
- compound
- catalyst
- vanadium
- solvent
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- -1 amide compound Chemical class 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title abstract description 84
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 203
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 86
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 38
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 47
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 47
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 26
- 229910052707 ruthenium Inorganic materials 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000007809 chemical reaction catalyst Substances 0.000 claims 3
- 238000006722 reduction reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 description 68
- 238000000034 method Methods 0.000 description 49
- 229910052751 metal Inorganic materials 0.000 description 45
- 239000002184 metal Substances 0.000 description 45
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 42
- 150000003058 platinum compounds Chemical class 0.000 description 28
- 150000003682 vanadium compounds Chemical class 0.000 description 27
- 239000011877 solvent mixture Substances 0.000 description 25
- 239000007788 liquid Substances 0.000 description 24
- 239000002245 particle Substances 0.000 description 20
- 230000009467 reduction Effects 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 150000003304 ruthenium compounds Chemical class 0.000 description 14
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000013507 mapping Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 7
- FSJSYDFBTIVUFD-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O FSJSYDFBTIVUFD-XHTSQIMGSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910003446 platinum oxide Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- ICTAZHZJEOVXOW-UHFFFAOYSA-N platinum vanadium Chemical compound [V].[Pt].[Pt].[Pt] ICTAZHZJEOVXOW-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- DBDVAKGHPZJLTH-UHFFFAOYSA-N 1-(2-phenylethyl)piperidine Chemical compound C1CCCCN1CCC1=CC=CC=C1 DBDVAKGHPZJLTH-UHFFFAOYSA-N 0.000 description 1
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 1
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KFBXVBQQAUQWAY-UHFFFAOYSA-N 4-(cyclohexylmethyl)morpholine Chemical compound C1COCCN1CC1CCCCC1 KFBXVBQQAUQWAY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910002839 Pt-Mo Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- ORENQBLTKHJNGZ-UHFFFAOYSA-N [V].[Ru].[Pt] Chemical compound [V].[Ru].[Pt] ORENQBLTKHJNGZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical group N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ISTDKKXGLPXJHF-UHFFFAOYSA-N calcium oxygen(2-) phosphoric acid Chemical class [O--].[Ca++].OP(O)(O)=O ISTDKKXGLPXJHF-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CVGBLJMVPLUNMI-UHFFFAOYSA-N nitroso nitrate;ruthenium(2+) Chemical compound [Ru+2].[O-][N+](=O)ON=O CVGBLJMVPLUNMI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- MHHDXUNFNAZUGB-UHFFFAOYSA-N oxidovanadium(2+) Chemical compound [V+2]=O MHHDXUNFNAZUGB-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical group [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003511 tertiary amides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
新規性喪失の例外適用申請有り There is an application for exception to loss of novelty
本発明は、アミド化合物をアミン化合物にする水素添加反応に用いる、白金とバナジウムを含み、担体に担持された触媒およびこれを用いたアミン化合物の製造方法に関するものである。 TECHNICAL FIELD The present invention relates to a catalyst containing platinum and vanadium and supported on a carrier, which is used in the hydrogenation reaction of an amide compound to an amine compound, and a method for producing an amine compound using the catalyst.
アミド化合物をアミン化合物にする還元反応は、アミドが難還元性であるため、カルボン酸誘導体の還元の中で最も難しい反応の一つである。 A reduction reaction of an amide compound to an amine compound is one of the most difficult reactions among reductions of carboxylic acid derivatives because amides are difficult to reduce.
アミド化合物をアミン化合物にする還元反応は研究等の少量試験では水素化アルミニウムリチウム（ＬｉＡｌＨ４）、水素化ホウ素ナトリウム（ＮａＢＨ４）等の強力な還元剤を化学量論的に用いる方法が一般だが、工業規模の合成に使用するには大量の金属廃棄物の発生や反応性が高いために大量に用いると水素等が発生し危険であり、後処理等の操作が煩雑であること等が問題となっていた。 The reduction reaction of an amide compound to an amine compound is generally performed by using a stoichiometrically strong reducing agent such as lithium aluminum hydride (LiAlH 4 ), sodium borohydride (NaBH 4 ), etc. in small-quantity tests such as research. However, when used in industrial-scale synthesis, it generates a large amount of metal waste and is highly reactive, so if used in large amounts, hydrogen and other substances are generated, which is dangerous, and operations such as post-treatment are complicated. It was.
一方、分子状水素を還元剤とするアミドからアミンへの還元反応は、無害な水のみを副生するため環境調和型のアミンの合成方法である。このアミドの触媒的水素還元反応は古くから研究されており、銅－クロム、レニウムまたはニッケル触媒を用いて行われてきたが、水素圧２００気圧、反応温度２００℃以上等の高温高圧な反応条件を必要とする。 On the other hand, the reduction reaction from amides to amines using molecular hydrogen as a reducing agent is an environmentally friendly method for synthesizing amines because it produces only harmless water as a by-product. The catalytic hydrogen reduction reaction of this amide has been studied for a long time, and has been carried out using a copper-chromium, rhenium or nickel catalyst. need.
近年、非特許文献１や２ではモレキュラーシーブスを反応系内に添加することで１２０℃、１０ａｔｍまたは１６０℃、５ａｔｍという低温低圧条件下でのアミドの水素化が報告されている。しかし、基質適用性に乏しく、Ｃ－Ｎ開裂によるアルコールが副生してしまうという問題点があった。また、これらの触媒は再使用できない。
In recent years,
また、非特許文献３で報告されている均一系触媒を用いた反応もあるが、Ｃ－Ｎ開裂によるアルコールが副生してしまうという問題点があった。また、均一系触媒を用いた反応では高価な触媒を繰り返し使用することが難しい。
There is also a reaction using a homogeneous catalyst reported in
そのため、工業的に使用するためには、温和な条件下でも使用でき、高い活性を維持したまま、繰り返し使用できるような耐久性が高い触媒が求められる。 Therefore, for industrial use, there is a demand for a highly durable catalyst that can be used under mild conditions and that can be used repeatedly while maintaining high activity.
従って、本発明の課題は、アミド化合物をアミン化合物にする還元反応を行える触媒であって、温和な条件下でも使用でき、高い活性を維持したまま、繰り返し使用できるような耐久性も備えた触媒を提供することである。 Accordingly, an object of the present invention is to provide a catalyst capable of reducing an amide compound to an amine compound, which can be used under mild conditions, and which is durable enough to be used repeatedly while maintaining high activity. is to provide
本発明者らは、上記課題を解決するために鋭意研究した結果、白金とバナジウムを含み、担体に担持された触媒が、アミド化合物に対する高い水素化活性、選択性、耐久性、反応性を有することを見出し、本発明を完成させた。 As a result of intensive research by the present inventors to solve the above problems, a catalyst containing platinum and vanadium and supported on a carrier has high hydrogenation activity, selectivity, durability, and reactivity for amide compounds. We found that and completed the present invention.
すなわち、本発明は、白金とバナジウムが担体に担持されたことを特徴とするアミド化合物の水素添加反応用触媒である。 That is, the present invention is a catalyst for the hydrogenation reaction of an amide compound, characterized in that platinum and vanadium are supported on a carrier.
また、本発明は、溶媒中で、白金とバナジウムを担体に担持させた後、これを乾燥することを特徴とする上記アミド化合物の水素添加反応用触媒の製造方法である。 The present invention also provides a method for producing a catalyst for a hydrogenation reaction of an amide compound, characterized by carrying platinum and vanadium on a carrier in a solvent and then drying the carrier.
更に、本発明は、白金とバナジウムとルテニウムが担体に担持されたことを特徴とするアミド化合物の水素添加反応用触媒である。 Further, the present invention is a catalyst for hydrogenation reaction of an amide compound, characterized in that platinum, vanadium and ruthenium are supported on a carrier.
また更に、本発明は、溶媒中で、白金とバナジウムとルテニウムを担体に担持させた後、これを乾燥することを特徴とする上記アミド化合物の水素添加反応用触媒の製造方法である。 Further, the present invention is a method for producing a catalyst for hydrogenation reaction of an amide compound, characterized in that platinum, vanadium and ruthenium are supported on a carrier in a solvent and then dried.
更にまた、本発明は、アミド化合物を、上記アミド化合物の水素添加反応用触媒に接触させて水素添加し、アミン化合物を得ることを特徴とするアミン化合物の製造方法である。 Furthermore, the present invention is a method for producing an amine compound, which comprises bringing an amide compound into contact with the above catalyst for hydrogenation reaction of the amide compound and hydrogenating the amide compound to obtain the amine compound.
また、本発明は、上記アミン化合物の製造方法で製造されたアミン化合物である。 The present invention also provides an amine compound produced by the method for producing an amine compound described above.
本発明の触媒は、温和な条件下で使用できるため、アミド化合物からアミン化合物への合成が安全で容易になる。 Since the catalyst of the present invention can be used under mild conditions, the synthesis of amine compounds from amide compounds is safe and easy.
また、本発明の触媒は、製造の際に、特別な操作を必須としないため、安価で安全に製造できる。 In addition, the catalyst of the present invention does not require any special operation during its production, so that it can be produced inexpensively and safely.
そのため、本発明の触媒は、アミド化合物からアミン化合物への工業的な合成に利用できる。 Therefore, the catalyst of the present invention can be used for industrial synthesis from amide compounds to amine compounds.
また、本発明の触媒は担体に担持されているため使用後に、ろ過によって容易に高価な白金を回収可能であり、更にこの回収された触媒は当初の活性・選択性を維持できる。 In addition, since the catalyst of the present invention is supported on a carrier, expensive platinum can be easily recovered by filtration after use, and the recovered catalyst can maintain its initial activity and selectivity.
そのため、本発明の触媒は、再利用も容易である。 Therefore, the catalyst of the present invention can be easily reused.
本発明のアミド化合物の水素添加反応用触媒（以下、「本発明の触媒」という）は、白金とバナジウムが、担体に担持されたものである。なお、本明細書においては、本発明の触媒は、「Ｘ－Ｙ／Ｚ」（Ｘ、Ｙは白金、バナジウム等の金属名、Ｚは担体名）等と記載することがある。 The catalyst for hydrogenation of an amide compound of the present invention (hereinafter referred to as "catalyst of the present invention") comprises platinum and vanadium supported on a carrier. In this specification, the catalyst of the present invention may be described as "XY/Z" (where X and Y are the names of metals such as platinum and vanadium, and Z is the name of the carrier).
（白金）
本発明の触媒を構成する白金は、特に限定されないが、例えば、白金粒子が好ましい。ここで白金粒子とは、金属白金または酸化白金の少なくとも１種から選ばれる白金の粒子であり、好ましくは金属白金の粒子である。
(platinum)
Although the platinum constituting the catalyst of the present invention is not particularly limited, for example, platinum particles are preferable. Here, the platinum particles are particles of platinum selected from at least one of platinum metal and platinum oxide, preferably particles of platinum metal.
ここで、白金粒子は、白金を含有していれば特に制限されるものではなく、ルテニウム（Ｒｕ）やロジウム（Ｒｈ）やパラジウム（Ｐｄ）等の貴金属を少量含んでいてもよいが、好ましくは金属白金である。白金粒子は一次粒子でもよく、二次粒子であってもよい。白金粒子の平均粒子径は１～３０ｎｍが好ましく、１～１０ｎｍがより好ましい。なお、本明細書において「平均粒子径」とは、電子顕微鏡で任意の数の粒子の直径を観察し、それらの直径の平均値のことをいう。 Here, the platinum particles are not particularly limited as long as they contain platinum, and may contain a small amount of precious metals such as ruthenium (Ru), rhodium (Rh) and palladium (Pd), but preferably It is metal platinum. The platinum particles may be primary particles or secondary particles. The average particle size of platinum particles is preferably 1 to 30 nm, more preferably 1 to 10 nm. As used herein, the term "average particle size" refers to the average value of the diameters of an arbitrary number of particles observed with an electron microscope.
（バナジウム）
本発明の触媒を構成するバナジウムは、特に限定されないが、例えば、バナジウム酸化物が好ましい。バナジウム酸化物としては、例えば、バナジン酸イオン（ＶＯ４
３-、ＶＯ３
３-）、五酸化バナジウム、酸化バナジウム（II）または酸化バナジウム（IV）等のうち少なくとも１種から選ばれるものであり、好ましくはＶ２Ｏ５である。
(vanadium)
Although the vanadium constituting the catalyst of the present invention is not particularly limited, vanadium oxide is preferable, for example. The vanadium oxide is selected from, for example, at least one of vanadate ions (VO 4 3- , VO 3 3- ), vanadium pentoxide, vanadium (II) oxide, vanadium (IV) oxide, and the like. , preferably V 2 O 5 .
（白金－バナジウム［Ｐｔ－Ｖ］のモル比）
本発明の触媒における、白金とバナジウムの組成比は、金属としての白金（Ｐｔ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｔ：Ｖ］＝１：０．１～１０、好ましくは１：０．５～５、更に好ましくは１：０．８～１．２である。
(Platinum-vanadium [Pt-V] molar ratio)
The composition ratio of platinum and vanadium in the catalyst of the present invention is a molar ratio [Pt:V]=1:0. 1 to 10, preferably 1:0.5 to 5, more preferably 1:0.8 to 1.2.
（ルテニウム）
本発明の触媒には、更にルテニウムを含有させることができる。このルテニウムは、特に限定されないが、例えば、酸化ルテニウム、金属ルテニウム等である。また、金属ルテニウムは白金と合金化していてもよく、酸化ルテニウムが酸化バナジウムと複合酸化物を形成していてもよい。なお、前記合金化や複合酸化物の形成は常法に従ってすることができる。
(ruthenium)
The catalyst of the invention can further contain ruthenium. The ruthenium is not particularly limited, but includes, for example, ruthenium oxide, metallic ruthenium, and the like. Moreover, metallic ruthenium may be alloyed with platinum, and ruthenium oxide may form a composite oxide with vanadium oxide. The alloying and formation of the composite oxide can be carried out according to conventional methods.
本発明の触媒に、ルテニウムを含有させる場合、上記した白金またはバナジウムの一部をルテニウムに置き換えればよい。 When ruthenium is contained in the catalyst of the present invention, part of platinum or vanadium described above may be replaced with ruthenium.
（白金－ルテニウム－バナジウム［Ｐｔ－Ｒｕ－Ｖ］のモル比）
本発明の触媒における、白金とルテニウムとバナジウムの組成比は、白金とバナジウムの組成比に関しては前述の通りであり、金属としての白金（Ｐｔ）：金属としてのルテニウム（Ｒｕ）のモル数のモル数換算で、モル比［Ｐｔ：Ｒｕ］＝１：０．１～１０、好ましくは１：０．５～５、更に好ましくは１：０．８～１．２である。
(Platinum-ruthenium-vanadium [Pt-Ru-V] molar ratio)
The composition ratio of platinum, ruthenium, and vanadium in the catalyst of the present invention is as described above for the composition ratio of platinum and vanadium, and the number of moles of platinum (Pt) as metal: ruthenium (Ru) as metal In numerical terms, the molar ratio [Pt:Ru]=1:0.1-10, preferably 1:0.5-5, more preferably 1:0.8-1.2.
（担体）
本発明の触媒の担体（母材）は、特に限定されるものではない。担体の吸着能等の諸物性も、特に限定されるものではないが、例えば、その吸着能は、いわゆるＢＥＴ値として０.１～３００ｍ２／ｇであってもよく、平均粒径としては０.０２～１００μｍであってもよい。本発明においては、担体の吸着能は、０.５～１８０ｍ２／ｇであることが好ましい。
(Carrier)
The carrier (base material) of the catalyst of the present invention is not particularly limited. Various physical properties such as the adsorption capacity of the carrier are not particularly limited. It may be from 0.02 to 100 μm. In the present invention, the carrier preferably has an adsorption capacity of 0.5 to 180 m 2 /g.
また、担体の形態は、特に限定されず、例えば、粉末状、球形粒状、不定形顆粒状、円柱形ペレット状、押し出し形状、リング形状等が挙げられる。 The shape of the carrier is not particularly limited, and examples thereof include powder, spherical granules, irregular granules, cylindrical pellets, extruded shapes, and ring shapes.
上記のような担体としては、例えば、ハイドロキシアパタイト（ＨＡＰ）、チタニア、アルミナ、シリカ等の無機酸化物やカーボン粉末等を用いることができ、好ましくはハイドロキシアパタイトである。 Examples of the above carrier include inorganic oxides such as hydroxyapatite (HAP), titania, alumina and silica, carbon powder, and the like, preferably hydroxyapatite.
上記ハイドロキシアパタイトとしては、特に制限されることはなく、一般的なＣａ１０（ＰＯ４）６（ＯＨ）２の化学量論的組成の水酸化リン酸カルシウムのみならず、この組成に類似した組成の水酸化リン酸カルシウム化合物やリン酸三カルシウム等を含む。 The hydroxyapatite is not particularly limited, and includes not only calcium hydroxide phosphate having a general stoichiometric composition of Ca 10 (PO 4 ) 6 (OH) 2 , but also water having a composition similar to this composition. Including calcium oxide phosphate compounds and tricalcium phosphate.
本発明の触媒において、白金とバナジウムが担体に担持される態様は、特に制限されるものではなく、担体の形態により、種々の態様を採ることができ、担持される位置も単純に制御されていなくてもよいし、細孔や層の内側であったり、表面のみであってもよいが、粒子径の小さな白金が分散して担持され、バナジウムは、白金の近傍または白金上に存在する方が好ましい。なお、本発明の触媒における白金とバナジウム酸化物の担体への担持量は、特に限定されないが、例えば、金属換算の白金の量で０.１～１０ｗｔ％であることが好ましい。 In the catalyst of the present invention, the mode in which platinum and vanadium are supported on the carrier is not particularly limited, and various modes can be adopted depending on the form of the carrier, and the positions at which they are supported are simply controlled. It may be absent, inside the pores or layers, or only on the surface, but platinum with a small particle size is dispersed and supported, and vanadium is present near or on platinum. is preferred. The amount of platinum and vanadium oxide supported on the carrier in the catalyst of the present invention is not particularly limited, but is preferably, for example, 0.1 to 10 wt % in terms of platinum as metal.
本発明の触媒は、上記したような担体を用いているため、反応に使用した後に分離も容易になり、触媒の再使用においても有利であることは言うまでもない。 Since the catalyst of the present invention uses the carrier as described above, it is easy to separate after being used in the reaction, and it is needless to say that it is advantageous in reuse of the catalyst.
（触媒に追加できる成分）
本発明の触媒は、上記した白金とバナジウム（必要によりルテニウム）が担体に担持されていればよく、効果を損なわない範囲で、遷移金属やアルカリ金属やアルカリ土類金属などを触媒成分や担体成分として常法に従って含有させてもよい。
(Ingredients that can be added to the catalyst)
In the catalyst of the present invention, the above-described platinum and vanadium (ruthenium if necessary) may be supported on a carrier, and transition metals, alkali metals, alkaline earth metals, etc. may be added as catalyst components and carrier components within a range that does not impair the effect. may be contained according to a conventional method.
（本発明の触媒の製造方法）
本発明の触媒のうち、白金とバナジウムが担体に担持されたことを特徴とするアミド化合物の水素添加反応用触媒は、溶媒中で、白金とバナジウムを担体に担持させた後、これを乾燥することにより製造できる（以下、「本発明方法Ａ」という）。
(Method for producing the catalyst of the present invention)
Among the catalysts of the present invention, the catalyst for the hydrogenation reaction of an amide compound, which is characterized in that platinum and vanadium are supported on a carrier, is obtained by supporting platinum and vanadium on the carrier in a solvent and then drying it. (hereinafter referred to as "method A of the present invention").
具体的に本発明方法Ａにおいて、白金とバナジウムを溶媒中で担体に担持させる方法は特に限定されないが、例えば、担体と、白金化合物およびバナジウム化合物を含有する溶媒混合液とを混合して、白金とバナジウムを溶媒中で担体に担持させる方法や、担体と、白金化合物を含有する溶媒液と、バナジウム化合物を含有する溶媒液とを何れかの順序で混合して、白金とバナジウムを溶媒中で担体に担持させる方法が挙げられる。 Specifically, in method A of the present invention, the method of supporting platinum and vanadium on a carrier in a solvent is not particularly limited. and a method of supporting vanadium on a carrier in a solvent, or by mixing a carrier, a solvent liquid containing a platinum compound, and a solvent liquid containing a vanadium compound in any order, and platinum and vanadium in a solvent A method of supporting on a carrier can be mentioned.
本発明方法Ａに用いられる白金化合物は、特に限定されないが、好ましくは乾燥した際に担体上で白金粒子となるものである。このような白金化合物としては、例えば、白金アセチルアセトナト（Ｐｔ（ａｃａｃ）２）、テトラアンミン白金（II）酢酸塩、ジニトロジアンミン白金（II）、ヘキサアンミン白金（IV）炭酸塩、ビス（ジベンザルアセトン）白金（0）等の白金錯体塩、塩化白金、硝酸白金、テトラクロロ白金酸カリウム等の塩が挙げられ、特にＰｔ（ａｃａｃ）２が好ましい。 The platinum compound used in method A of the present invention is not particularly limited, but is preferably one that forms platinum particles on the carrier when dried. Examples of such platinum compounds include platinum acetylacetonato (Pt(acac) 2 ), tetraammineplatinum(II) acetate, dinitrodiammineplatinum(II), hexaammineplatinum(IV) carbonate, bis(dibene Examples thereof include platinum complex salts such as saracetone)platinum(0), and salts such as platinum chloride, platinum nitrate and potassium tetrachloroplatinate, with Pt(acac) 2 being particularly preferred.
また、本発明方法Ａに用いられるバナジウム化合物は、特に限定されないが、好ましくは乾燥した際に担体上でバナジウム酸化物を生じるものである。このようなバナジウム化合物としては、例えば、バナジルアセチルアセトナト（ＶＯ（ａｃａｃ）２）、ビス（タルトラト）ビス［オキソバナジウム（IV）］酸テトラメチルアンモニウム等のバナジウム錯体塩、バナジン（Ｖ）酸アンモニウム、ナフテン酸バナジウム等の塩が挙げられ、特にＶＯ（ａｃａｃ）２が好ましい。 The vanadium compound used in the method A of the present invention is not particularly limited, but is preferably one that forms vanadium oxide on the carrier when dried. Examples of such vanadium compounds include vanadyl acetylacetonate (VO(acac) 2 ), vanadium complex salts such as tetramethylammonium bis(tartrate)bis[oxovanadium(IV)]ate, and ammonium vanadate(V). , and vanadium naphthenate, and VO(acac) 2 is particularly preferred.
本発明方法Ａに用いられる白金化合物およびバナジウム化合物を含有する溶媒混合液は、上記白金化合物およびバナジウム化合物を、溶媒に懸濁させたものである。この溶媒混合液における白金化合物とバナジウム化合物はモル比で１：０．１～１０、好ましくは１：０．５～５、更に好ましくは１：１である。また、溶媒としては、例えば、水や、アルコール、アセトン等の有機溶媒が挙げられ、水であればコスト、安全性共に優れているため好ましい。これらの溶媒は１種または２種以上を組み合わせてもよい。なお、溶媒の温度は特に限定されないが、例えば、０～１００℃、好ましくは１０～５０℃である。 The solvent mixture containing the platinum compound and the vanadium compound used in the method A of the present invention is obtained by suspending the platinum compound and the vanadium compound in a solvent. The molar ratio of the platinum compound and the vanadium compound in this solvent mixture is 1:0.1-10, preferably 1:0.5-5, more preferably 1:1. Examples of the solvent include water and organic solvents such as alcohol and acetone. Water is preferable because it is excellent in both cost and safety. These solvents may be used singly or in combination of two or more. Although the temperature of the solvent is not particularly limited, it is, for example, 0 to 100°C, preferably 10 to 50°C.
上記のようにして調製した溶媒混合液は、次に、担体と混合すればよい。上記溶媒混合液と、担体を混合する方法は特に限定されないが、各成分が十分に分散する量があればよく、金属換算の白金０．１ｍｍｏｌに対して担体０．１～１００ｇ、好ましくは１～１０ｇの量で撹拌しながら行う。混合後は０．５～１２時間、好ましくは１～６時間撹拌を続ける。 The solvent mixture prepared as described above may then be mixed with the carrier. The method of mixing the solvent mixture and the carrier is not particularly limited, but it is sufficient that each component is sufficiently dispersed, and 0.1 to 100 g, preferably 1 Amounts of ˜10 g are carried out with stirring. After mixing, stirring is continued for 0.5 to 12 hours, preferably 1 to 6 hours.
また、本発明方法Ａに用いられる白金化合物を含有する溶媒液と、バナジウム化合物を含有する溶媒液は、上記白金化合物およびバナジウム化合物を、それぞれ溶媒に懸濁させたものである。これらの溶媒液における各化合物の含有量は、これら溶媒液を混合した際に上記白金化合物およびバナジウム化合物を含有する溶媒混合液と同じになる量にすればよい。また、これらに使用する溶媒や溶媒の温度は上記溶媒混合液と同様にすればよい。 The platinum compound-containing solvent solution and the vanadium compound-containing solvent solution used in the method A of the present invention are obtained by suspending the above-mentioned platinum compound and vanadium compound in a solvent, respectively. The content of each compound in these solvent solutions should be the same as the solvent mixture containing the above platinum compound and vanadium compound when these solvent solutions are mixed. Moreover, the solvent and the temperature of the solvent used for these may be the same as those for the solvent mixture.
上記のようにして調製された白金化合物を含有する溶媒液と、バナジウム化合物を含有する溶媒液は、次に、担体と、白金化合物を含有する溶媒液と、バナジウム化合物を含有する溶媒液とを何れかの順序で混合すればよい。担体と白金化合物を含有する溶媒液を混合した後にバナジウム化合物を含有する溶媒液の順序で混合すると白金化合物の上に遷移金属が担持される傾向があるためよく、白金化合物を後に混合すると高価な白金のロスが少なくなる場合があるためよい。また、上記溶媒液と、担体を混合する方法は、上記混合溶液を用いる場合と同様にすればよい。 The solvent liquid containing the platinum compound and the solvent liquid containing the vanadium compound prepared as described above are then combined with the carrier, the solvent liquid containing the platinum compound, and the solvent liquid containing the vanadium compound. They may be mixed in any order. If the solvent solution containing the vanadium compound is mixed in that order after the carrier and the solvent solution containing the platinum compound are mixed, the transition metal tends to be supported on the platinum compound. This is good because loss of platinum may be reduced. The method of mixing the solvent liquid and the carrier may be the same as in the case of using the mixed solution.
以上のようにして溶媒混合液と担体を混合あるいは各溶媒液と担体を混合して、溶媒中で、白金とバナジウムを担体に担持させた後は乾燥させればよい。乾燥の前には、洗浄、ろ過、濃縮等の前処理をして溶媒を除去させることが好ましい。乾燥の条件は特に限定されないが、例えば、８０～２００℃で１～５６時間乾燥させる。乾燥後は、例えば、マッフル炉等を使用して２５０～７００℃で１～１２時間焼成等することが好ましく、更に、粉砕等を行ってもよい。 As described above, the solvent mixture and the carrier may be mixed, or each solvent liquid and the carrier may be mixed, platinum and vanadium may be supported on the carrier in the solvent, and then dried. Before drying, it is preferable to remove the solvent by pretreatment such as washing, filtration, and concentration. Although the drying conditions are not particularly limited, for example, drying is performed at 80 to 200° C. for 1 to 56 hours. After drying, for example, it is preferably calcined at 250 to 700° C. for 1 to 12 hours using a muffle furnace or the like, and may be further pulverized.
なお、本発明方法Ａにおいて溶媒として水を使用する場合、白金化合物としては、例えば、ヘキサクロロ白金（IV）酸塩（Ｈ２ＰｔＣｌ６）、テトラクロロ白金（II）酸塩（Ｋ２ＰｔＣｌ４等）等の白金塩が挙げられる。これらの中でもテトラクロロ白金（II）酸カリウム（Ｋ２ＰｔＣｌ４）が好ましい。また、バナジウム化合物としては、例えば、塩化バナジウム（ＶＣｌ３）等のバナジウム塩や、メタバナジン酸ナトリウム（ＮａＶＯ３）、オルトバナジン（Ｖ）酸ナトリウム（Ｎａ３ＶＯ４）、メタバナジン酸カリウム（ＫＶＯ３）、メタバナジン酸アンモウム（ＮＨ４ＶＯ３）等のバナジン酸塩が挙げられる。これらの中でも塩化バナジウムが好ましい。 When water is used as a solvent in the method A of the present invention, examples of platinum compounds include hexachloroplatinate (IV) (H 2 PtCl 6 ), tetrachloroplatinate (II) (K 2 PtCl 4 , etc.). ) and other platinum salts. Among these, potassium tetrachloroplatinate (II) (K 2 PtCl 4 ) is preferred. Examples of vanadium compounds include vanadium salts such as vanadium chloride (VCl 3 ), sodium metavanadate (NaVO 3 ), sodium orthovanadate (V) (Na 3 VO 4 ), and potassium metavanadate (KVO 3 ). and vanadates such as ammonium metavanadate (NH 4 VO 3 ). Among these, vanadium chloride is preferred.
また、本発明方法Ａにおいて溶媒として水を使用する際、上記化合物が溶媒に溶解しにくい場合は、触媒性能に問題がない範囲で、ｐＨ調整剤やバインダー等を用いたり、超音波をかけたり温度を調整してもよい。ｐＨ調整剤としては水酸化ナトリウムや炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、アンモニア、酢酸、クエン酸、炭酸、乳酸等が挙げられる。また、バインダーとしてはポリエチレングリコールやポリビニルアルコール等の有機化合物やシリカ等の無機化合物等が挙げられる。 In addition, when water is used as a solvent in the method A of the present invention, if the above compound is difficult to dissolve in the solvent, a pH adjuster, a binder, etc. may be used, or ultrasonic waves may be applied within a range where there is no problem with the catalytic performance. Temperature may be adjusted. Examples of pH adjusters include sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, ammonia, acetic acid, citric acid, carbonic acid, and lactic acid. Examples of the binder include organic compounds such as polyethylene glycol and polyvinyl alcohol, and inorganic compounds such as silica.
本発明の触媒のうち、白金とバナジウムとルテニウムが担体に担持されたことを特徴とするアミド化合物の水素添加反応用触媒は、溶媒中で、白金とバナジウムとルテニウムを担体に担持させた後、これを乾燥することにより製造できる（以下、「本発明方法Ｂ」という）。 Among the catalysts of the present invention, the catalyst for the hydrogenation reaction of an amide compound is characterized in that platinum, vanadium and ruthenium are supported on a carrier. It can be produced by drying this (hereinafter referred to as "method B of the present invention").
具体的に本発明方法Ｂにおいて、白金とバナジウムとルテニウムを溶媒中で担体に担持させる方法は特に限定されないが、例えば、担体と、白金化合物、バナジウム化合物およびルテニウム化合物を含有する溶媒混合液とを混合して、白金とバナジウムとルテニウムを溶媒中で担体に担持させる方法や、担体と、白金化合物を含有する溶媒混合液と、バナジウム化合物を含有する溶媒混合液と、ルテニウム化合物を含有する溶媒混合液を何れかの順序で混合して、白金とバナジウムとルテニウムを溶媒中で担体に担持させる方法が挙げられる。 Specifically, in method B of the present invention, the method of supporting platinum, vanadium and ruthenium on a carrier in a solvent is not particularly limited. A method of mixing and supporting platinum, vanadium and ruthenium on a carrier in a solvent, a carrier, a solvent mixture containing a platinum compound, a solvent mixture containing a vanadium compound, and a solvent mixture containing a ruthenium compound. A method of mixing liquids in any order to support platinum, vanadium and ruthenium on a carrier in a solvent can be mentioned.
本発明方法Ｂに用いられる白金化合物、バナジウム化合物は、本発明方法Ａで用いられるものと同じである。また、本発明方法Ｂに用いられるルテニウム化合物は、特に限定されないが、例えば、塩化ルテニウム、酢酸ルテニウム等の塩やルテニウムアセチルアセトナト、ドデカカルボニル三ルテニウム（０）、ホルマトジカルボニルルテニウム（I）、硝酸ルテニウム（II）ニトロシル、ヘキサアンミンルテニウム酢酸塩等の錯体塩等が挙げられる。これらの中でも塩化ルテニウム、Ｒｕ（ａｃａｃ）３が好ましい。 The platinum compound and vanadium compound used in the method B of the present invention are the same as those used in the method A of the present invention. In addition, the ruthenium compound used in the method B of the present invention is not particularly limited. Complex salts such as ruthenium (II) nitrosyl nitrate and hexaammineruthenium acetate are included. Among these, ruthenium chloride and Ru(acac) 3 are preferred.
本発明方法Ｂに用いられる白金化合物、バナジウム化合物およびルテニウム化合物を含有する溶媒混合液は、上記白金化合物、バナジウム化合物およびルテニウム化合物を、溶媒に懸濁させたものである。この溶媒混合液における白金化合物とバナジウム化合物はモル比で１：０．１～１０、好ましくは１：０．５～５、更に好ましくは１：１である。そして、ルテニウム化合物は、上記した白金化合物またはバナジウム化合物の一部をルテニウムに置き換えればよい。また、これらに使用する溶媒や溶媒の温度は本発明方法Ａと同様にすればよい。 The solvent mixture containing the platinum compound, vanadium compound and ruthenium compound used in method B of the present invention is obtained by suspending the above platinum compound, vanadium compound and ruthenium compound in a solvent. The molar ratio of the platinum compound and the vanadium compound in this solvent mixture is 1:0.1-10, preferably 1:0.5-5, more preferably 1:1. As for the ruthenium compound, part of the platinum compound or vanadium compound described above may be replaced with ruthenium. Moreover, the solvent and the temperature of the solvent used for these may be the same as those of the method A of the present invention.
上記のようにして調製した溶媒混合液は、次に、担体と混合すればよい。上記溶媒混合液と、担体を混合する方法は、上記溶媒混合液を用いる以外は本発明方法Ａと同様にすればよい。 The solvent mixture prepared as described above may then be mixed with the carrier. The method of mixing the solvent mixture and the carrier may be the same as the method A of the present invention except that the solvent mixture is used.
また、本発明方法Ｂに用いられる白金化合物を含有する溶媒液と、バナジウム化合物を含有する溶媒液と、ルテニウム化合物を含有する溶媒液は、上記白金化合物、バナジウム化合物およびルテニウム化合物を、それぞれ溶媒に懸濁させたものである。これらの溶媒混合液における各化合物の含有量は、これら溶媒液を混合した際に上記白金化合物、バナジウム化合物およびルテニウム化合物を含有する溶媒混合液と同じになる量にすればよい。また、これらに使用する溶媒や溶媒の温度は本発明方法Ａと同様にすればよい。 Further, the solvent solution containing a platinum compound, the solvent solution containing a vanadium compound, and the solvent solution containing a ruthenium compound used in the method B of the present invention are the above-mentioned platinum compound, vanadium compound and ruthenium compound as solvents, respectively. It is suspended. The content of each compound in these solvent mixtures should be the same as the solvent mixture containing the platinum compound, vanadium compound and ruthenium compound when these solvent solutions are mixed. Moreover, the solvent and the temperature of the solvent used for these may be the same as those of the method A of the present invention.
上記のようにして調製された白金化合物を含有する溶媒液と、バナジウム化合物を含有する溶媒液と、ルテニウム化合物を含有する溶媒液は、次に、担体と、白金化合物を含有する溶媒液と、バナジウム化合物を含有する溶媒液と、ルテニウム化合物を含有する溶媒液とを何れかの順序で混合すればよい。また、上記溶媒液と、担体を混合する方法は、上記溶媒液を用いる以外は本発明方法Ａと同様にすればよい。 The solvent liquid containing the platinum compound, the solvent liquid containing the vanadium compound, and the solvent liquid containing the ruthenium compound prepared as described above are then combined with a carrier, the solvent liquid containing the platinum compound, The solvent liquid containing the vanadium compound and the solvent liquid containing the ruthenium compound may be mixed in any order. Moreover, the method of mixing the solvent liquid and the carrier may be the same as the method A of the present invention except that the solvent liquid is used.
以上のようにして溶媒混合液と担体を混合あるいは各溶媒液と担体を混合して、溶媒中で、白金とバナジウムとルテニウムを担体に担持させた後は、本発明方法Ａと同様に乾燥をさせればよい。また、乾燥後は、本発明方法Ａと同様に焼成、粉砕等を行ってもよい。 After mixing the solvent mixture and the carrier or mixing each solvent liquid and the carrier as described above and supporting platinum, vanadium and ruthenium on the carrier in the solvent, drying is carried out in the same manner as the method A of the present invention. Let it be. After drying, firing, pulverization, etc. may be performed in the same manner as in method A of the present invention.
なお、本発明方法Ｂにおいて溶媒として水を使用する場合、ルテニウム化合物としては、塩化ルテニウム（III）（ＲｕＣｌ３）、ルテニウム酸ナトリウム（Ｋ２ＲｕＯ４）、ニトロシル硝酸ルテニウム（Ｒｕ（ＮＯ）（ＮＯ３）３）等のルテニウム塩等が挙げられる。これらの中でも塩化ルテニウムが好ましい。これ以外の条件については全て本発明方法Ａと同様にすればよい。 When water is used as the solvent in method B of the present invention, ruthenium compounds include ruthenium chloride (III) (RuCl 3 ), sodium ruthenate (K 2 RuO 4 ), ruthenium nitrosylnitrate (Ru(NO) (NO 3 ) and ruthenium salts such as 3 ). Among these, ruthenium chloride is preferred. All other conditions may be the same as those of the method A of the present invention.
本発明の触媒は、白金とバナジウム（必要によりルテニウム）（以下、単に「白金等」という）が担体粒子中に均一に担持されていてもよく、担体の表面側に偏在して担持していてもよい。このような白金等の担持位置については、特に白金等のように高価な成分を有効に利用しようとする場合には担体の表面側に偏在担持させることが望ましい。担体表面に偏在担持させることで、反応基質と白金等とが接触する機会が増し、触媒の活性向上が期待できる。 In the catalyst of the present invention, platinum and vanadium (ruthenium if necessary) (hereinafter simply referred to as "platinum etc.") may be uniformly supported on the carrier particles, or may be unevenly distributed on the surface side of the carrier. good too. As for the supporting position of such platinum or the like, it is desirable that it is unevenly distributed and supported on the surface side of the carrier, especially when an expensive component such as platinum is to be effectively used. By unevenly distributing and supporting it on the surface of the carrier, the chances of contact between the reaction substrate and platinum or the like increase, and an improvement in the activity of the catalyst can be expected.
このような担体表面に白金等を偏在担持させる方法は特に限定されるものではなく、使用する触媒材料に応じて公知の手法の中から適宜選択することができる。具体的な例としては、上記白金化合物やバナジウム化合物（必要によりルテニウム化合物）を含有する溶媒混合液、あるいは、白金化合物を含有する溶媒液、バナジウム化合物を含有する溶媒液（必要によりルテニウム化合物を含有する溶媒液）のｐＨを調整する手法、担体上で白金等を非水溶化（沈殿）させるために、担体と上記溶媒混合液や上記溶媒液を混合する前または後に、アルカリ水溶液等の非水溶化に使用する水溶液で処理して白金等を固定化する手法、上記担体と上記溶媒混合液や上記溶媒液を混合した後、温度や静置時間を管理し、熟成をさせる手法、本発明の触媒製造後に、更に焼成工程を追加する手法等が挙げられる。なお、上記手法においては、適宜、洗浄、乾燥等を行ってもよい。 The method for unevenly distributing and supporting platinum or the like on the carrier surface is not particularly limited, and can be appropriately selected from known methods according to the catalyst material to be used. Specific examples include a solvent mixture containing the above platinum compound or vanadium compound (ruthenium compound if necessary), a solvent solution containing a platinum compound, or a solvent solution containing a vanadium compound (ruthenium compound if necessary). Before or after mixing the carrier with the above-mentioned solvent mixture or the above-mentioned solvent liquid, a non-aqueous solution such as an alkaline aqueous solution is added to the carrier in order to make the platinum or the like non-aqueous (precipitate) on the carrier. A technique of treating with an aqueous solution used for curing to immobilize platinum or the like, a technique of mixing the carrier with the solvent mixture or the solvent liquid, then managing the temperature and standing time to age, the method of the present invention. For example, a method of adding a calcination step after the catalyst is manufactured. In addition, in the above method, washing, drying, and the like may be performed as appropriate.
上記溶媒混合液や溶媒液のｐＨを調整する手法においては、上記したｐＨ調整剤を用いることができ、これらを用いて溶媒混合液や溶媒液のｐＨを担体への担持がしやすいように調整すればよく、酸性よりにしても良いし、アルカリ性よりにしても良いし、中性よりにしてもよい。 In the method of adjusting the pH of the solvent mixture or solvent liquid, the pH adjuster described above can be used, and the pH of the solvent mixture or solvent liquid is adjusted so that it can be easily supported on the carrier. It may be more acidic, more alkaline, or more neutral.
上記担体と溶媒混合液や溶媒液を混合する前または後に、アルカリ水溶液等の非水溶化に使用する水溶液で処理する手法においては、アルカリ性化合物を水等に溶解させたアルカリ水溶液が用いられる。アルカリ性化合物としては、例えば、アルカリ金属やアルカリ土類金属の水酸化物、アルカリ金属やアルカリ土類金属の重炭酸塩、アルカリ金属やアルカリ土類金属の炭酸塩、アルカリ金属やアルカリ土類金属のケイ酸塩、アンモニア等が挙げられる。また、この際のｐＨは特に限定されないが、７～１４、好ましくは８～１３である。 In the technique of treating with an aqueous solution used for desolubilization such as an alkaline aqueous solution before or after mixing the carrier and the solvent mixture or solvent solution, an alkaline aqueous solution in which an alkaline compound is dissolved in water or the like is used. Examples of alkaline compounds include hydroxides of alkali metals and alkaline earth metals, bicarbonates of alkali metals and alkaline earth metals, carbonates of alkali metals and alkaline earth metals, and alkali metals and alkaline earth metals. silicates, ammonia and the like. The pH at this time is not particularly limited, but is 7-14, preferably 8-13.
上記非水溶化の処理に用いるアルカリ水溶液の使用量は、白金化合物やバナジウム化合物（必要によりルテニウム化合物）を固定化することを目的とすることから、被還元対象に対してやや過剰なアルカリ量、例えば、１．０５～１．２倍になるように濃度を調整して使用することが好ましい。 The amount of the alkaline aqueous solution used in the above water-insolubilization treatment is for the purpose of immobilizing the platinum compound or vanadium compound (or the ruthenium compound if necessary). For example, it is preferable to adjust the concentration to 1.05 to 1.2 times.
上記熟成をさせる手法において、上記担体と溶媒混合液や溶媒液を混合した後の温度や静置時間は適宜設定すればよく、特に限定されないが、例えば、１０～１００℃で１～７２時間、好ましくは３０～７０℃で２～２４時間熟成させればよい。 In the aging method, the temperature and standing time after mixing the carrier and solvent mixture or solvent liquid may be appropriately set, and are not particularly limited. It is preferably aged at 30 to 70°C for 2 to 24 hours.
上記本発明の触媒製造後に、更に焼成工程を追加する手法においては、製造された本発明の触媒を、水素を含むガス雰囲気中で加熱還元処理を施しながら焼成すればよい。このような焼成を気相還元や水素還元ともいう。気相還元であれば還元時に介在する溶媒がなく被還元成分の移動が困難であり、白金等の粒子が凝集しづらく、白金等を小さな粒子の状態で担持させることができる。 In the method of adding a calcination step after manufacturing the catalyst of the present invention, the manufactured catalyst of the present invention may be calcined while being subjected to heat reduction treatment in a hydrogen-containing gas atmosphere. Such firing is also called vapor phase reduction or hydrogen reduction. In the case of gas phase reduction, there is no solvent intervening during the reduction, making it difficult for the components to be reduced to migrate. Particles of platinum and the like are less likely to aggregate, and platinum and the like can be supported in the form of small particles.
この焼成工程がある場合、焼成後に白金等が酸化されてしまうことがある。このような場合は還元処理を施すことが好ましい。このような還元処理には気相還元と液相還元が採用できる。気相還元は１００～５００℃に加熱した触媒に還元性の気体を供給して還元処理を施すものである。このような還元性の気体としては前述のような水素の他、一酸化炭素や低分子の炭化水素を使用してもよい。低分子の炭化水素としてはメタン、エタン、プロパン、ブタン、エチレン等も使用できる。また、気相還元の場合、気体の組成は還元成分のみからなるガスを使用してもよいが、窒素等、還元時に不活性なガスと混合して使用してもよい。 If there is this firing step, platinum or the like may be oxidized after firing. In such a case, it is preferable to apply a reduction treatment. Gas phase reduction and liquid phase reduction can be employed for such a reduction treatment. In the gas phase reduction, a reducing gas is supplied to a catalyst heated to 100 to 500° C. to perform a reduction treatment. As such a reducing gas, in addition to hydrogen as described above, carbon monoxide and low-molecular-weight hydrocarbons may be used. Methane, ethane, propane, butane, ethylene and the like can also be used as low-molecular-weight hydrocarbons. In the case of gas phase reduction, the gas composition may be a gas consisting only of reducing components, or may be mixed with a gas such as nitrogen that is inert during reduction.
また、液相還元は還元性の液体と触媒を混合し、８０～１５０℃で加熱することで酸化された触媒成分を還元するものである。使用される還元成分は特に限定されるものではなく、還元条件に応じて適宜選択すればよく、例えばギ酸、ギ酸ナトリウム、ヒドラジン等が挙げられる。 Liquid-phase reduction involves mixing a reducing liquid with a catalyst and heating the mixture at 80 to 150° C. to reduce the oxidized catalyst components. The reducing component to be used is not particularly limited, and may be appropriately selected depending on the reducing conditions. Examples thereof include formic acid, sodium formate, hydrazine and the like.
斯くして得られる本発明の触媒は、白金とバナジウム（必要によりルテニウム）が担体に担持されたものとなる。 In the catalyst of the present invention thus obtained, platinum and vanadium (or ruthenium if necessary) are supported on a carrier.
なお、本発明の触媒が製造できたことは、例えば、ＴＥＭ（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ；透過型電子顕微鏡）、ＦＥ－ＳＥＭ（Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ－Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ；電界放射型走査電子顕微鏡）、ＥＤＸ（Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ Ｘ－ｒａｙ Ｓｐｅｃｔｒｏｓｃｏｐｙ；エネルギー分散型Ｘ線分光法）等で確認することができる。 The fact that the catalyst of the present invention was able to be produced can be confirmed by, for example, TEM (Transmission Electron Microscope; transmission electron microscope), FE-SEM (Field Emission-Scanning Electron Microscope; field emission scanning electron microscope), EDX (Energy Dispersive It can be confirmed by X-ray Spectroscopy (energy dispersive X-ray spectroscopy) or the like.
（アミド化合物の水素化）
本発明の触媒は、アミド化合物の水素添加反応用である。そのため、本発明の触媒は、アミド化合物に接触させれば、水素添加（還元）してアミン化合物を製造することができる。
(Hydrogenation of amide compound)
The catalyst of the present invention is for the hydrogenation reaction of amide compounds. Therefore, when the catalyst of the present invention is brought into contact with an amide compound, it can be hydrogenated (reduced) to produce an amine compound.
アミド化合物としては、アミド結合を有する化合物であれば特に限定されないが、例えば、２級以上のアミド化合物または芳香族置換基を含むアミド化合物、ラクタムまたは３級アミドにおいてＮ原子に結合しているカルボニルを含まない置換基の２つがお互いに連結していて環状構造を取るアミド化合物等が好ましく、２級以上のアミド化合物または芳香族置換基を含むアミド化合物がより好ましい。 The amide compound is not particularly limited as long as it is a compound having an amide bond. An amide compound or the like having a cyclic structure in which two substituents not containing are linked to each other is preferable, and a secondary or higher amide compound or an amide compound containing an aromatic substituent is more preferable.
アミド化合物に、本発明の触媒を接触させて水素添加する方法は特に限定されず、適宜選択すればよい。具体的には、オートクレーブ等の耐圧性の容器中、液相で本発明の触媒と、アミド化合物と、水素ガスを接触させることによりアミド化合物の水素添加を行えばよい。また、水素添加の際には、水を除去して反応を進行させるために、モレキュラーシーブ等を容器中に入れておいてもよい。更に、本発明の触媒は、水素添加前に還元処理を予め行っておいてもよい。 The method of bringing the amide compound into contact with the catalyst of the present invention for hydrogenation is not particularly limited, and may be selected as appropriate. Specifically, hydrogenation of the amide compound may be carried out by bringing the catalyst of the present invention, the amide compound, and hydrogen gas into contact in a liquid phase in a pressure-resistant container such as an autoclave. Further, during the hydrogenation, a molecular sieve or the like may be placed in the vessel in order to remove water and advance the reaction. Furthermore, the catalyst of the present invention may be previously subjected to reduction treatment before hydrogenation.
液相は有機溶剤のみあるいは数種の有機溶剤の混液が好ましく、有機溶剤のみがより好ましい。上記で用いられる有機溶剤は、特に限定されないが、例えば、ドデカン、シクロヘキサン等の炭素原子数５～２０の脂肪族炭化水素、トルエン、キシレン等の炭素原子数７～９の芳香族炭化水素、ジメチルエーテル、ジメトキシエタン（ＤＭＥ）、オキセタン、テトラヒドロフラン（ＴＨＦ）、テトラヒロドピラン（ＴＨＰ）、フラン、ジベンゾフラン、フラン等の鎖状構造または環状構造を有するエーテル、ポリエチレングリコール、ポリプロピレングリコール等のポリエーテル等から選択される１種以上が挙げられ、これらの中でも特にＤＭＥが好ましい。 The liquid phase is preferably an organic solvent alone or a mixture of several organic solvents, more preferably an organic solvent alone. The organic solvent used above is not particularly limited, but examples include aliphatic hydrocarbons having 5 to 20 carbon atoms such as dodecane and cyclohexane, aromatic hydrocarbons having 7 to 9 carbon atoms such as toluene and xylene, and dimethyl ether. , dimethoxyethane (DME), oxetane, tetrahydrofuran (THF), tetrahydropyran (THP), ethers having a chain structure or a cyclic structure such as furan, dibenzofuran, furan, polyethers such as polyethylene glycol, polypropylene glycol, etc. One or more selected may be mentioned, and among these, DME is particularly preferred.
有機溶剤の使用量は、例えば、上記アミド化合物の濃度が０.５～２.０質量％程度となる範囲内が好ましい。また、本発明の触媒の使用量は、例えば、触媒中の白金の量を基準としてアミド化合物に対して０.０００１～５０モル％程度であり、０.０１～２０モル％程度が好ましく、０.１～５モル％程度がより好ましい。 The amount of the organic solvent used is preferably within a range in which the concentration of the amide compound is about 0.5 to 2.0 mass %. Further, the amount of the catalyst of the present invention used is, for example, about 0.0001 to 50 mol%, preferably about 0.01 to 20 mol%, relative to the amide compound based on the amount of platinum in the catalyst. About 1 to 5 mol % is more preferable.
本発明の触媒は、温和な条件でも、円滑に水素添加反応を進行させることができる。反応温度としては、基質の種類や目的生成物の種類等に応じて適宜調整することができ、例えば、１００℃以下、好ましくは１０～１００℃、より好ましくは２０～８０℃程度、特に好ましくは３０～７０℃程度である。反応時の圧力は、５ＭＰａ以下、好ましくは常圧～４ＭＰａ、より好ましくは２～３．５ＭＰａである。反応時間は、反応温度および圧力に応じて適宜調整することができ、例えば１０分～５６時間程度、好ましくは２０分～４８時間程度、特に好ましくは４０分～３０時間程度である。 The catalyst of the present invention allows the hydrogenation reaction to proceed smoothly even under mild conditions. The reaction temperature can be appropriately adjusted according to the type of substrate, the type of target product, and the like. It is about 30 to 70°C. The pressure during the reaction is 5 MPa or less, preferably atmospheric pressure to 4 MPa, more preferably 2 to 3.5 MPa. The reaction time can be appropriately adjusted according to the reaction temperature and pressure, and is, for example, about 10 minutes to 56 hours, preferably about 20 minutes to 48 hours, particularly preferably about 40 minutes to 30 hours.
上記した方法によりアミド化合物を水素添加してアミン化合物が得られるが、通常のクロスカップリング反応等で製造することが難しいようなアミン化合物でも本発明の方法では製造できる。具体的に、Ｃ－Ｎカップリングの代表例であるＢｕｃｈｗａｌｄ－Ｈａｒｔｗｉｇ反応では、ハロゲン化アリールと１・２級アミンをＰｄ触媒存在下で反応させて、当該アミンのＮ原子に直接アリール基を結合させることができるが、Ｎ原子と芳香環の間にひとつ以上の炭素原子またはメチレン鎖を介在させることはできない。しかしながら、上記した方法では、アミンのＮ原子をアシル化することによって得たアミド化合物を水素化することで、結果として元のアミンのＮ原子にひとつ以上の炭素原子またはメチレン鎖を介在させたＣ－Ｎ結合を生成させることができる。このような例としては、モルホリン→４－シクロヘキシルカルボニルモルホリン→４－シクロヘキシルメチルモルホリン、ピペリジン→１－フェニルアセチルピペリジン→１－フェネチルピペリジン、ベンジルメチルアミン→ベンジルメチルフェニルアセチルアミド→ベンジルメチルフェネチルアミン等が挙げられる。 Although an amine compound can be obtained by hydrogenating an amide compound by the above-described method, even an amine compound that is difficult to produce by a conventional cross-coupling reaction or the like can be produced by the method of the present invention. Specifically, in the Buchwald-Hartwig reaction, which is a representative example of C—N coupling, an aryl halide and a primary/secondary amine are reacted in the presence of a Pd catalyst to bond an aryl group directly to the N atom of the amine. but there cannot be more than one carbon atom or methylene chain between the N atom and the aromatic ring. However, in the methods described above, the amide compound obtained by acylating the N atom of the amine is hydrogenated, resulting in a C -N bonds can be generated. Such examples include morpholine→4-cyclohexylcarbonylmorpholine→4-cyclohexylmethylmorpholine, piperidine→1-phenylacetylpiperidine→1-phenethylpiperidine, benzylmethylamine→benzylmethylphenylacetylamide→benzylmethylphenethylamine, and the like. be done.
（触媒の再利用）
本発明の触媒は活性成分である白金が担体に担持されているため、反応中においても担持された白金が大きな粒子になりにくい。また、本発明の触媒は、例えば、水素添加後に反応液から濾過、遠心分離等の物理的な分離手法により容易に回収することができる。回収された本発明の触媒はそのまま、あるいは、必要により、洗浄、乾燥、焼成等を施した後、再利用することができる。洗浄、乾燥、焼成等は本発明の触媒の製造の際と同様に行えばよい。
(reuse of catalyst)
In the catalyst of the present invention, platinum, which is an active component, is supported on the carrier, so that the supported platinum is unlikely to form large particles even during the reaction. In addition, the catalyst of the present invention can be easily recovered from the reaction solution after hydrogenation by physical separation techniques such as filtration and centrifugation. The recovered catalyst of the present invention can be reused as it is, or after washing, drying, calcination, etc., if necessary. Washing, drying, calcination, etc. may be carried out in the same manner as in the production of the catalyst of the present invention.
回収された本発明の触媒は、未使用の本発明の触媒と比べ、ほぼ同等の触媒能を示すことができ、使用－再生を複数回繰り返しても、その触媒能の低下を著しく抑制することができる。そのため、本発明によれば、通常、水素添加の費用の多くの割合を占める触媒を回収し、繰り返し利用することができるため、アミド化合物の水素添加のコストを大幅に削減することができる。 The recovered catalyst of the present invention can exhibit substantially the same catalytic performance as the unused catalyst of the present invention, and can remarkably suppress deterioration of the catalytic performance even after repeated use-regeneration multiple times. can be done. Therefore, according to the present invention, the catalyst, which usually accounts for a large proportion of the cost of hydrogenation, can be recovered and reused repeatedly, so that the cost of hydrogenation of amide compounds can be greatly reduced.
以下、本発明の触媒、並びに本発明の実施例について具体的に説明するが、本発明は以下の実施例に限定されるものではなく、本発明の趣旨の範囲で広く応用が可能なものである。 The catalyst of the present invention and examples of the present invention will be specifically described below, but the present invention is not limited to the following examples, and can be widely applied within the scope of the present invention. be.
製 造 例 １
Ｐｔ－Ｖ／ＨＡＰの調製：
アセトン９０ｍＬにエヌ・イー ケムキャット社製Ｐｔ（ａｃａｃ）２ ０．４ｍｍｏｌとシグマアルドリッチ社のＶＯ（ａｃａｃ）２を０．４ｍｍｏｌ加え室温で３０分撹拌した。更に和光純薬社のＨＡＰ（商品名「リン酸三カルシウム」）１．０ｇを加えて室温で４時間撹拌した。得られた混合物から溶媒をロータリーエバポレータで除去し、淡緑色の粉末を得た。得られた粉末を１１０℃で終夜乾燥した。更に、乾燥した粉末をメノウ鉢で粉砕し、大気中で、２時間、３００℃で焼成し、濃灰色の粉末（Ｐｔ－Ｖ／ＨＡＰ）が得られた。
Manufacturing example 1
Preparation of Pt-V/HAP:
To 90 mL of acetone, 0.4 mmol of Pt(acac)2 from NE Chemcat and 0.4 mmol of VO(acac)2 from Sigma-Aldrich were added and stirred at room temperature for 30 minutes. Further, 1.0 g of HAP (trade name “tricalcium phosphate”) manufactured by Wako Pure Chemical Industries, Ltd. was added and stirred at room temperature for 4 hours. Solvent was removed from the resulting mixture on a rotary evaporator to give a pale green powder. The resulting powder was dried overnight at 110°C. Further, the dried powder was pulverized in an agate bowl and calcined at 300° C. for 2 hours in air to obtain a dark gray powder (Pt-V/HAP).
上記で得られたＰｔ－Ｖ／ＨＡＰについて種々の解析を行った。Ｐｔ－Ｖ／ＨＡＰのＴＥＭ像を図１に、ＡＤＦ－ＳＴＥＭ画像を図２に、Ｃａの元素マッピング画像を図３に、Ｖの元素マッピング画像を図４に、Ｐｔの元素マッピング画像を図５に、Ｃａ・Ｖ・Ｐｔの元素マッピング画像を重ねたものを図６に示した。これらの結果から、本発明の触媒は、白金粒子が担体に担持され、酸化バナジウム（Ｖ２Ｏ５）が白金粒子の近傍または上に存在し、金属としての白金（Ｐｔ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｔ：Ｖ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。また、Ｐｔ－Ｖ／ＨＡＰのＥＤＳライン分析の結果（図７）から、白金粒子の平均粒子径は２．２ｎｍであった。 Various analyzes were performed on the Pt-V/HAP obtained above. The TEM image of Pt-V/HAP is shown in FIG. 1, the ADF-STEM image is shown in FIG. 2, the elemental mapping image of Ca is shown in FIG. 3, the elemental mapping image of V is shown in FIG. 4, and the elemental mapping image of Pt is shown in FIG. FIG. 6 shows an elemental mapping image of Ca, V, and Pt superimposed on . From these results, the catalyst of the present invention has platinum particles supported on a carrier, vanadium oxide (V 2 O 5 ) is present near or on the platinum particles, and platinum (Pt) as metal: vanadium as metal It was found that the molar ratio [Pt:V] was 6:7 in terms of the number of moles of (V), and the amount of platinum as a metal was 5.8 wt%. Also, from the result of EDS line analysis of Pt-V/HAP (FIG. 7), the average particle size of the platinum particles was 2.2 nm.
製 造 例 ２
Ｐｔ－Ｖ／Ｃの調製：
製造例１のＨＡＰをシグマアルドリッチ社の多孔質カーボン（商品名：炭素、メソポーラス）に替えた以外は同様にしてＰｔ－Ｖ／Ｃが得られた。金属としての白金（Ｐｔ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｔ：Ｖ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 2
Preparation of Pt-V/C:
Pt-V/C was obtained in the same manner as in Production Example 1, except that HAP was replaced with porous carbon (trade name: carbon, mesoporous) available from Sigma-Aldrich. The molar ratio [Pt:V] = 6:7 in terms of the number of moles of platinum (Pt) as the metal and the number of moles of vanadium (V) as the metal, and the amount of platinum as the metal is 5.8 wt%. I found out.
製 造 例 ３
Ｐｔ－Ｖ／ＴｉＯ２の調製：
製造例１のＨＡＰを触媒学会の参照触媒であるチタニア（ＪＲＣ ＴＩＯ－４）に替えた以外は同様にしてＰｔ－Ｖ／ＴｉＯ２が得られた。金属としての白金（Ｐｔ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｔ：Ｖ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 3
Preparation of Pt-V/ TiO2 :
Pt-V/TiO 2 was obtained in the same manner as in Production Example 1, except that HAP was replaced with titania (JRC TIO-4), a reference catalyst of the Catalysis Society of Japan. The molar ratio [Pt:V] = 6:7 in terms of the number of moles of platinum (Pt) as the metal and the number of moles of vanadium (V) as the metal, and the amount of platinum as the metal is 5.8 wt%. I found out.
製 造 例 ４
Ｐｔ－Ｖ／Ａｌ２Ｏ３の調製：
製造例１のＨＡＰを住友化学社のアルミナ（ＡＫＰ－Ｇ０１５）に替えた以外は同様にしてＰｔ－Ｖ／Ａｌ２Ｏ３が得られた。金属としての白金（Ｐｔ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｔ：Ｖ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 4
Preparation of Pt-V/Al 2 O 3 :
Pt-V/Al 2 O 3 was obtained in the same manner as in Production Example 1, except that HAP was replaced with Sumitomo Chemical's alumina (AKP-G015). The molar ratio [Pt:V] = 6:7 in terms of the number of moles of platinum (Pt) as the metal and the number of moles of vanadium (V) as the metal, and the amount of platinum as the metal is 5.8 wt%. I found out.
製 造 例 ５
Ｐｔ－Ｖ／ＳｉＯ２の調製：
製造例１のＨＡＰを富士シリシア化学社のシリカ（Ｑ－３）に替えた以外は同様にしてＰｔ－Ｖ／ＳｉＯ２が得られた。金属としての白金（Ｐｔ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｔ：Ｖ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 5
Preparation of Pt-V/ SiO2 :
Pt-V/SiO 2 was obtained in the same manner as in Production Example 1, except that HAP was replaced with silica (Q-3) available from Fuji Silysia Chemical. The molar ratio [Pt:V] = 6:7 in terms of the number of moles of platinum (Pt) as the metal and the number of moles of vanadium (V) as the metal, and the amount of platinum as the metal is 5.8 wt%. I found out.
製 造 例 ６
Ｐｔ－Ｒｕ－Ｖ／ＴｉＯ２の調製：
水９０ｍＬにエヌ・イー ケムキャット社製４０ｍＭ ＲｕＣｌ３水溶液５．０ｍＬ（Ｒｕ：０．２ｍｍｏｌ）とＴｉＯ２ ０．５ｇ、Ｋ２（ＰｔＣｌ４）を０．０８５ｇ（Ｐｔ：０．２ｍｍｏｌ）加え、更に４０ｍＭ ＶＣｌ３水溶液 ５．０ｍＬ（Ｖ：０．２ｍｍｏｌ）加え室温で６時間撹拌した。得られた混合物に２８ｗｔ％アンモニア水１．０ｍＬを加え、９０℃で６時間加熱撹拌した。溶液を脱イオン水で濾過洗浄し、得られた粉末を１１０℃で終夜乾燥した。乾燥した粉末をメノウ鉢で粉砕し、灰色の粉末（Ｐｔ―Ｒｕ－Ｖ／ＨＡＰ）が得られた。得られた粉末中の金属比は金属としての白金（Ｐｔ）：金属としてのルテニウム（Ｒｕ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｔ：Ｒｕ：Ｖ］＝１：１：１、また金属としての白金量は７．８ｗｔ％であった。
Manufacturing example 6
Preparation of Pt-Ru-V/ TiO2 :
5.0 mL (Ru: 0.2 mmol) of 40 mM RuCl 3 aqueous solution (manufactured by NE Chemcat), 0.5 g of TiO 2 and 0.085 g (Pt: 0.2 mmol) of K 2 (PtCl 4 ) were added to 90 mL of water. 5.0 mL (V: 0.2 mmol) of 40 mM VCl 3 aqueous solution was added and stirred at room temperature for 6 hours. 1.0 mL of 28 wt % aqueous ammonia was added to the obtained mixture, and the mixture was heated and stirred at 90° C. for 6 hours. The solution was filtered washed with deionized water and the resulting powder was dried at 110° C. overnight. The dried powder was pulverized in an agate bowl to obtain a gray powder (Pt--Ru--V/HAP). The metal ratio in the obtained powder is platinum (Pt) as a metal: ruthenium (Ru) as a metal: vanadium (V) as a metal, in terms of the number of moles, and the molar ratio [Pt: Ru: V]. = 1:1:1, and the amount of platinum as a metal was 7.8 wt%.
製 造 例 ７
Ｐｔ－Ｒｅ／ＨＡＰの調製：
製造例１のＶＯ（ａｃａｃ）２をＳｔｒｅｍ Ｃｈｅｍｉｃａｌｓ社のＲｅ２（ＣＯ）１０に替えた以外は同様にしてＰｔ－Ｒｅ／ＨＡＰが得られた。金属としての白金（Ｐｔ）：金属としてのレニウム（Ｒｅ）のモル数のモル数換算で、モル比［Ｐｔ：Ｒｅ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 7
Preparation of Pt-Re/HAP:
Pt-Re/HAP was obtained in the same manner as in Production Example 1, except that VO(acac) 2 in Production Example 1 was replaced with Re 2 (CO) 10 from Strem Chemicals. The molar ratio [Pt:Re] = 6:7 in terms of the number of moles of platinum (Pt) as the metal: rhenium (Re) as the metal, and the amount of platinum as the metal is 5.8 wt%. I found out.
製 造 例 ８
Ｐｔ－Ｍｏ／ＨＡＰの調製：
製造例１のＶＯ（ａｃａｃ）２をナカライテスク社の（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏに替えた以外は同様にしてＰｔ－Ｍｏ／ＨＡＰが得られた。金属としての白金（Ｐｔ）：金属としてのモリブデン（Ｍｏ）のモル数のモル数換算で、モル比［Ｐｔ：Ｍｏ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 8
Preparation of Pt-Mo/HAP:
Pt--Mo/HAP was obtained in the same manner as in Production Example 1 except that VO(acac) 2 in Production Example 1 was replaced with (NH 4 ) 6 Mo 7 O 24.4H 2 O available from Nacalai Tesque. The molar ratio [Pt:Mo] = 6:7 in terms of the number of moles of platinum (Pt) as the metal: molybdenum (Mo) as the metal, and the amount of platinum as the metal is 5.8 wt%. I found out.
製 造 例 ９
Ｐｔ－Ｗ／ＨＡＰの調製：
製造例１のＶＯ（ａｃａｃ）２をシグマアルドリッチ社の（ＮＨ４）１０Ｈ２（Ｗ２Ｏ７）６・ｘＨ２Ｏに替えた以外は同様にしてＰｔ－Ｗ／ＨＡＰが得られた。金属としての白金（Ｐｔ）：金属としてのタングステン（Ｗ）のモル数のモル数換算で、モル比［Ｐｔ：Ｗ］＝６：７、また金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 9
Preparation of Pt-W/HAP:
Pt-W/HAP was obtained in the same manner as in Production Example 1, except that VO(acac) 2 in Production Example 1 was replaced with (NH 4 ) 10 H 2 (W 2 O 7 ) 6 ·xH 2 O available from Sigma-Aldrich. The molar ratio [Pt:W] = 6:7 in terms of the number of moles of platinum (Pt) as the metal and the number of moles of tungsten (W) as the metal, and the amount of platinum as the metal is 5.8 wt%. I found out.
製 造 例 １０
Ｐｄ－Ｖ／ＨＡＰの調製：
製造例１のエヌ・イー ケムキャット社製Ｐｔ（ａｃａｃ）２をシグマアルドリッチ社のＰｄ（ａｃａｃ）２に替えた以外は同様にしてＰｄ－Ｖ／ＨＡＰが得られた。金属としてのパラジウム（Ｐｄ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｐｄ：Ｖ］＝６：７、また金属としてのパラジウム量は３．２ｗｔ％であることが分かった。
Manufacturing example 10
Preparation of Pd-V/HAP:
Pd-V/HAP was obtained in the same manner as in Production Example 1 except that Pt(acac) 2 manufactured by NE Chemcat was replaced with Pd(acac) 2 manufactured by Sigma-Aldrich. Palladium (Pd) as the metal: The molar ratio [Pd:V] = 6:7 in terms of the number of moles of vanadium (V) as the metal, and the amount of palladium as the metal is 3.2 wt%. I found out.
製 造 例 １１
Ｒｕ－Ｖ／ＨＡＰの調製：
製造例１のエヌ・イー ケムキャット社製Ｐｔ（ａｃａｃ）２をエヌ・イー ケムキャット社製のＲｕ（ａｃａｃ）３に替えた以外は同様にしてＲｕ－Ｖ／ＨＡＰが得られた。金属としてのルテニウム（Ｒｕ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｒｕ：Ｖ］＝６：７、また金属としてのルテニウム量は３．０ｗｔ％であることが分かった。
Manufacturing example 11
Preparation of Ru-V/HAP:
Ru-V/HAP was obtained in the same manner as in Production Example 1 except that Pt(acac) 2 manufactured by NE Chemcat was replaced with Ru(acac) 3 manufactured by NE Chemcat. Ruthenium (Ru) as a metal: The molar ratio [Ru:V] = 6:7 in terms of the number of moles of vanadium (V) as a metal, and the amount of ruthenium as a metal is 3.0 wt%. I found out.
製 造 例 １２
Ｒｈ－Ｖ／ＨＡＰの調製：
製造例１のエヌ・イー ケムキャット社製Ｐｔ（ａｃａｃ）２を三津和化学薬品社のＲｈ（ａｃａｃ）３に替えた以外は同様にしてＲｈ－Ｖ／ＨＡＰが得られた。金属としてのロジウム（Ｒｈ）：金属としてのバナジウム（Ｖ）のモル数のモル数換算で、モル比［Ｒｈ：Ｖ］＝６：７、また金属としてのロジウム量は３．１ｗｔ％であることが分かった。
Manufacturing example 12
Preparation of Rh-V/HAP:
Rh-V/HAP was obtained in the same manner as in Production Example 1 except that Pt(acac) 2 manufactured by NE Chemcat was replaced with Rh(acac) 3 manufactured by Mitsuwa Chemicals. Rhodium (Rh) as a metal: The molar ratio [Rh:V] = 6:7 in terms of the number of moles of vanadium (V) as a metal, and the amount of rhodium as a metal is 3.1 wt%. I found out.
製 造 例 １３
Ｐｔ／ＨＡＰの調製：
製造例１のＶＯ（ａｃａｃ）２を除いた以外は同様にしてＰｔ／ＨＡＰが得られた。金属としての白金量は５．８ｗｔ％であることが分かった。
Manufacturing example 13
Preparation of Pt/HAP:
Pt/HAP was obtained in the same manner as in Production Example 1, except that VO(acac) 2 was omitted. The amount of platinum as metal was found to be 5.8 wt%.
製 造 例 １４
Ｖ／ＨＡＰの調製：
製造例１のエヌ・イー ケムキャット社製Ｐｔ（ａｃａｃ）２を除いた以外は同様にしてＶ／ＨＡＰが得られた。金属としてのバナジウム量は１．８ｗｔ％であることが分かった。
Manufacturing example 14
Preparation of V/HAP:
V/HAP was obtained in the same manner as in Production Example 1, except that Pt(acac) 2 manufactured by NE Chemcat was omitted. The amount of vanadium as metal was found to be 1.8 wt%.
実 施 例 １
製造例１～１４で得られた触媒を、それぞれ表１の触媒量と、溶媒である１，２－ジメトキシエタン（ＤＭＥ）５ｍＬ、そして基質であるＮ－アセチルモルホリン０.５ｍｍｏｌを５０ｍＬのステンレス製オートクレーブに加えて表１の条件で水素化反応を行った。反応後、ガスクロマトグラフを用いて２の収率を測定した。結果を表１に記した。
Example 1
The catalysts obtained in Production Examples 1 to 14 were prepared in 50 mL of stainless steel with the catalyst amount shown in Table 1, 5 mL of 1,2-dimethoxyethane (DME) as a solvent, and 0.5 mmol of N-acetylmorpholine as a substrate. A hydrogenation reaction was carried out under the conditions shown in Table 1 in addition to the autoclave. After the reaction, the yield of 2 was measured using a gas chromatograph. The results are shown in Table 1.
少なくとも白金とバナジウムの両方を担持した触媒は、アミド化合物の水素添加反応を温和な条件下で行えることが分かった。また、Ｐｔ－Ｖ／ＨＡＰは、アミド化合物の水素添加反応を温和な条件下で収率よく行えることが分かった。また、Ｐｔ－Ｒｕ－Ｖ／ＴｉＯ２も問題なく反応が進むことが分かった。 It was found that the catalyst carrying at least both platinum and vanadium can carry out the hydrogenation reaction of amide compounds under mild conditions. In addition, it was found that Pt-V/HAP allowed the hydrogenation reaction of amide compounds to be carried out in good yield under mild conditions. It was also found that Pt--Ru--V/TiO 2 proceeded without any problem.
実 施 例 ２
製造例１で得られたＰｔ－Ｖ／ＨＡＰを、それぞれ表２の触媒量と基質０．５ｍｍｏｌ、和光純薬社のモレキュラーシーブス４Å：０．１ｇを５０ｍＬのステンレス製オートクレーブに加え、溶媒である１，２－ジメトキシエタン（ＤＭＥ）５ｍＬを加えて、反応温度７０℃、水素圧３ＭＰａの下で水素化反応を行った。反応後、ガスクロマトグラフを用いて４の収率を測定した。結果を表２に記した。
Example 2
The Pt-V/HAP obtained in Production Example 1 is added to a 50 mL stainless steel autoclave with the catalyst amount and substrate 0.5 mmol shown in Table 2, and Wako Pure
Ｐｔ－Ｖ／ＨＡＰは、基質が変わってもアミド化合物の水素添加反応を温和な条件下で収率よく行えることが分かった。 It was found that Pt-V/HAP can carry out the hydrogenation reaction of amide compounds in good yield under mild conditions even if the substrate is changed.
実 施 例 ３
触媒の再利用：
実施例１の反応後、使用したＰｔ－Ｖ／ＨＡＰを遠心分離により分離し、溶媒である１，２－ジメトキシエタン（ＤＭＥ）で洗浄して反応系から回収した。この回収したＰｔ－Ｖ／ＨＡＰを、再度同じ反応に使用した。結果を表３に示した。
Example 3
Catalyst reuse:
After the reaction in Example 1, the Pt-V/HAP used was separated by centrifugation, washed with a solvent, 1,2-dimethoxyethane (DME), and recovered from the reaction system. This recovered Pt-V/HAP was used again in the same reaction. Table 3 shows the results.
Ｐｔ－Ｖ／ＨＡＰは、性能の劣化なく再利用できることがわかった。 It was found that Pt-V/HAP can be reused without deterioration in performance.
実 施 例 ４
製造例１で得られたＰｔ－Ｖ／ＨＡＰを、それぞれ触媒０．１ｇと基質０．５ｍｍｏｌ、和光純薬社のモレキュラーシーブス４Å：０．１ｇを５０ｍＬのステンレス製オートクレーブに加え、溶媒である１，２－ジメトキシエタン（ＤＭＥ）５ｍＬを加えて、表４に記載の反応温度および水素圧の下で水素化反応を行った。反応後、ガスクロマトグラフを用いて４の収率を測定した。結果を表４に記した。
Example 4
The Pt-V/HAP obtained in Production Example 1 was added to a 50 mL stainless steel autoclave with 0.1 g of the catalyst and 0.5 mmol of the substrate, and 0.1 g of Wako Pure Chemical's
Ｐｔ－Ｖ／ＨＡＰは、基質や水素圧や反応温度が変わってもアミド化合物の水素添加反応を温和な条件下で収率よく行えることが分かった。 It was found that Pt-V/HAP can carry out the hydrogenation reaction of amide compounds in good yield under mild conditions even if the substrate, hydrogen pressure and reaction temperature are changed.
本発明の触媒は、種々の医薬、農薬、その他種々の工業分野において有用なアミノ化合物を温和な条件で安全に製造するのに有用である。また、本発明の触媒は、安価で安全に製造できる。
以 上
INDUSTRIAL APPLICABILITY The catalyst of the present invention is useful for safely producing amino compounds useful in various pharmaceuticals, agricultural chemicals, and other industrial fields under mild conditions. Moreover, the catalyst of the present invention can be produced inexpensively and safely.
that's all
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| JP7185214B2 (en) | 2022-12-07 |
| JP7368813B2 (en) | 2023-10-25 |
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