JP5783548B2 - Method for producing lactic acid using tin-containing compound - Google Patents
Method for producing lactic acid using tin-containing compound Download PDFInfo
- Publication number
- JP5783548B2 JP5783548B2 JP2010244406A JP2010244406A JP5783548B2 JP 5783548 B2 JP5783548 B2 JP 5783548B2 JP 2010244406 A JP2010244406 A JP 2010244406A JP 2010244406 A JP2010244406 A JP 2010244406A JP 5783548 B2 JP5783548 B2 JP 5783548B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- lactic acid
- reaction
- catalyst
- chloride
- 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.)
- Expired - Fee Related
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- 150000001875 compounds Chemical class 0.000 title claims description 38
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title description 116
- 235000014655 lactic acid Nutrition 0.000 title description 79
- 239000004310 lactic acid Substances 0.000 title description 37
- 238000000034 method Methods 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 39
- -1 lithium halides Chemical class 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 150000004820 halides Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000003903 lactic acid esters Chemical class 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001805 chlorine compounds Chemical group 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 5
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000002994 raw material Substances 0.000 description 34
- 229910052718 tin Inorganic materials 0.000 description 34
- 235000014633 carbohydrates Nutrition 0.000 description 32
- 239000000047 product Substances 0.000 description 32
- 238000004811 liquid chromatography Methods 0.000 description 31
- 238000004458 analytical method Methods 0.000 description 30
- 229920002678 cellulose Polymers 0.000 description 22
- 239000001913 cellulose Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 12
- 229940091250 magnesium supplement Drugs 0.000 description 12
- 235000011150 stannous chloride Nutrition 0.000 description 12
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 12
- 230000007704 transition Effects 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 235000000346 sugar Nutrition 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003426 co-catalyst Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000002772 monosaccharides Chemical class 0.000 description 8
- 238000000855 fermentation Methods 0.000 description 7
- 230000004151 fermentation Effects 0.000 description 7
- 238000006317 isomerization reaction Methods 0.000 description 7
- 229910001507 metal halide Inorganic materials 0.000 description 7
- 150000005309 metal halides Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 6
- 229930091371 Fructose Natural products 0.000 description 5
- 239000005715 Fructose Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 5
- 229920001542 oligosaccharide Polymers 0.000 description 5
- 150000002482 oligosaccharides Chemical class 0.000 description 5
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 5
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- RBGLVWCAGPITBS-UHFFFAOYSA-L bis(trifluoromethylsulfonyloxy)tin Chemical compound [Sn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F RBGLVWCAGPITBS-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- UBOGEXSQACVGEC-UHFFFAOYSA-K phenyltin(3+);trichloride Chemical compound Cl[Sn](Cl)(Cl)C1=CC=CC=C1 UBOGEXSQACVGEC-UHFFFAOYSA-K 0.000 description 3
- ASHVULSQMDWKFO-UHFFFAOYSA-N 5-(methoxymethyl)furan-2-carbaldehyde Chemical compound COCC1=CC=C(C=O)O1 ASHVULSQMDWKFO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NVLRFXKSQQPKAD-UHFFFAOYSA-N tricarbon Chemical compound [C]=C=[C] NVLRFXKSQQPKAD-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 1
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- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
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- 102000004190 Enzymes Human genes 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- LVRCYPYRKNAAMX-UHFFFAOYSA-M bis(triphenylphosphine)iminium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)N=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LVRCYPYRKNAAMX-UHFFFAOYSA-M 0.000 description 1
- AAZXYDTXKRXEHM-UHFFFAOYSA-M butyltin(1+);chloride Chemical compound CCCC[Sn]Cl AAZXYDTXKRXEHM-UHFFFAOYSA-M 0.000 description 1
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- DNMAATNKUOPVBT-UHFFFAOYSA-N dibutyltin;trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.CCCC[Sn]CCCC DNMAATNKUOPVBT-UHFFFAOYSA-N 0.000 description 1
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- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical group C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
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- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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)
Description
本発明は、炭水化物含有原料から、触媒としてスズ含有化合物、並びに助触媒としてリチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩からなる群から選択される少なくとも1種の化合物を用いて乳酸類を製造する方法に関する。 The present invention comprises at least selected from the group consisting of carbohydrate-containing raw materials, tin-containing compounds as catalysts, and lithium halides, magnesium halides, first transition series metal halides and quaternary ammonium salts as promoters. The present invention relates to a method for producing lactic acids using one kind of compound.
現在、工業的に実施されている乳酸の製造法は糖類の乳酸発酵によるものである（特許文献１参照）。しかしながらこの方法でセルロースを乳酸発酵の原料とするには、酸又は酵素などを用いた糖化工程を経る必要がある。また一般に発酵による乳酸製造法は反応速度が遅く、巨大な発酵槽が必要となり、生成する乳酸の濃度が低いため、精製のためのエネルギー消費量が大きくなる問題がある。加えて、乳酸発酵は発酵の進行とともに溶液のｐＨが低下することにより、乳酸菌の発酵効率が低下してしまうため、塩基で中和させながら発酵が行われる。従って、この乳酸発酵法により生成するのは乳酸塩であり、乳酸塩より乳酸を遊離させるために酸で処理することが行われ、そこから生じる中和塩の処理もプロセス上大きな問題となっている。 At present, a method for producing lactic acid that is industrially used is based on lactic acid fermentation of saccharides (see Patent Document 1). However, in order to use cellulose as a raw material for lactic acid fermentation by this method, it is necessary to go through a saccharification step using an acid or an enzyme. In general, the lactic acid production method by fermentation has a slow reaction rate, requires a huge fermenter, and has a problem that the energy consumption for purification becomes large because the concentration of lactic acid produced is low. In addition, lactic acid fermentation is performed while neutralizing with a base because the fermentation efficiency of lactic acid bacteria decreases as the pH of the solution decreases as the fermentation progresses. Accordingly, lactate is produced by this lactic acid fermentation method, and treatment with acid is performed to liberate lactic acid from lactate, and treatment of neutralized salt resulting therefrom is a major problem in the process. Yes.
生物学的な方法によらない乳酸の製造法としては、炭水化物をアルカリ存在下で水熱処理する化学的な方法が知られている。例えば糖類（非特許文献１、２参照）、セルロース（特許文献２、非特許文献３参照）、又は有機性廃棄物（非特許文献４参照）をこの方法で処理すると、高温高圧の反応条件下で分解した炭水化物の一部が異性化して乳酸が生成する。しかし、この方法では乳酸は触媒として加えられたアルカリと反応し、乳酸塩となっているため、乳酸を酸として分離するためには反応液になんらかの無機酸を添加して酸性にしなければならず、アルカリと無機酸が量論的に消費されるという問題がある。 As a method for producing lactic acid that does not depend on a biological method, a chemical method in which a carbohydrate is hydrothermally treated in the presence of an alkali is known. For example, when saccharides (see Non-Patent Documents 1 and 2), cellulose (see Patent Documents 2 and 3), or organic waste (see Non-Patent Document 4) are treated by this method, reaction conditions of high temperature and high pressure are performed. Lactic acid is produced by isomerization of some of the carbohydrates decomposed in However, in this method, lactic acid reacts with the alkali added as a catalyst to form a lactate, so that in order to separate lactic acid as an acid, it is necessary to add some inorganic acid to the reaction solution to make it acidic. There is a problem that the alkali and the inorganic acid are consumed stoichiometrically.
アルカリを使わない乳酸の化学的製造法としては、金属ハロゲン化物を触媒として、デンプン、オリゴ糖又は単糖を、アルコールと反応させることにより、乳酸エステルに変換する方法が報告されている（特許文献３参照）。しかし、本発明者らが検討したところ、この方法は２００℃未満ではセルロース系の原料を分解できず、乳酸や乳酸エステルの生成が認められなかった。 As a chemical production method of lactic acid without using an alkali, there has been reported a method of converting starch, oligosaccharide or monosaccharide into a lactic acid ester by reacting with alcohol using a metal halide as a catalyst (Patent Literature). 3). However, as a result of investigations by the present inventors, the cellulose-based raw material could not be decomposed at a temperature lower than 200 ° C., and formation of lactic acid or lactic acid ester was not recognized.
またアルカリを使用せず、セルロース系の原料を化学的な反応により直接、乳酸へ変換した例も報告されているが、これは非常に高温高圧（温度３５０℃以上４００℃未満、圧力２０ＭＰａ以上３５ＭＰａ）の反応条件を必要としておりエネルギー消費量が大きい上、乳酸の収率も不十分である（特許文献４参照）。 In addition, an example in which a cellulose-based raw material is directly converted to lactic acid by a chemical reaction without using an alkali has been reported, but this is very high temperature and high pressure (temperature 350 ° C. or more and less than 400 ° C., pressure 20 MPa or more and 35 MPa). ), The energy consumption is large, and the yield of lactic acid is insufficient (see Patent Document 4).
またセルロース系の原料より一段階で乳酸を製造した報告として、第３族金属塩を触媒として用いた例（特許文献５、６参照）及び希土類金属酸化物を触媒として用いた例（特許文献７参照）が報告されている。これらは比較的高価な第３族金属や希土類金属を使用するため、乳酸製造時のコスト増加につながると考えられる。 In addition, as a report of producing lactic acid from cellulose-based raw materials in one step, examples using Group 3 metal salts as catalysts (see Patent Documents 5 and 6) and examples using rare earth metal oxides as catalysts (Patent Document 7). Have been reported). Since these use relatively expensive Group 3 metals or rare earth metals, it is thought that this leads to an increase in costs during the production of lactic acid.
本発明は、炭水化物含有原料から乳酸類を効率的に製造するための代替法を提供することを課題とする。 An object of the present invention is to provide an alternative method for efficiently producing lactic acids from a carbohydrate-containing raw material.
本発明者らは、上記課題を解決するため鋭意検討を重ねた結果、触媒としてスズ含有化合物、並びに助触媒としてリチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩からなる群から選択される少なくとも1種の化合物を用いることにより、比較的低温の反応温度にて、炭水化物含有原料から乳酸類を効率的に製造できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a tin-containing compound as a catalyst, a lithium halide, a magnesium halide, a first transition series metal halide and a quaternary as a promoter. It has been found that by using at least one compound selected from the group consisting of ammonium salts, lactic acids can be efficiently produced from carbohydrate-containing raw materials at a relatively low reaction temperature, and the present invention has been completed. It was.
すなわち、本発明は以下を包含する。
［１］ 触媒としてスズ又は有機スズのハロゲン化物及びスズ又は有機スズのパーフルオロアルキルスルホン酸塩からなる群より選択される一種以上のスズ含有化合物を含み、かつ助触媒としてリチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩からなる群より選択される少なくとも１種の化合物を含む、水及び／又はアルコールを含有する溶媒中で、炭水化物含有原料を加熱処理することを特徴とする、乳酸類の製造方法。
［２］ 触媒として用いるスズ又は有機スズのハロゲン化物が塩化物である、［１］の方法。
［３］ 触媒として用いるパーフルオロアルキルスルホン酸塩が、トリフルオロメタンスルホン酸塩である、［１］又は［２］の方法。
That is, the present invention includes the following.
[1] Tin or organotin halide as a catalyst and one or more tin-containing compounds selected from the group consisting of tin or organotin perfluoroalkylsulfonates, and lithium halide as a cocatalyst, magnesium The carbohydrate-containing raw material is heat-treated in a solvent containing water and / or alcohol containing at least one compound selected from the group consisting of halides of the above, halides of first transition series metals and quaternary ammonium salts A process for producing lactic acid, characterized in that
[2] The method according to [1], wherein the tin or organotin halide used as the catalyst is a chloride.
[3] The method of [1] or [2], wherein the perfluoroalkyl sulfonate used as a catalyst is trifluoromethane sulfonate.
［４］ 助触媒として用いるリチウムのハロゲン化物、マグネシウムのハロゲン化物及び第一遷移系列金属のハロゲン化物が塩化物である、［１］〜［３］のいずれかの方法。
［５］ 助触媒として用いる四級アンモニウム塩がハロゲン化物である、［１］〜［３］のいずれかの方法。
［６］ 加熱処理が、１００℃〜３００℃で加熱することによるものである、［１］〜［５］のいずれかの方法。
[4] The method according to any one of [1] to [3], wherein the halide of lithium, the halide of magnesium and the halide of the first transition series metal used as a promoter are chlorides.
[5] The method according to any one of [1] to [3], wherein the quaternary ammonium salt used as a cocatalyst is a halide.
[6] The method according to any one of [1] to [5], wherein the heat treatment is performed by heating at 100 ° C to 300 ° C.
本発明の方法では、セルロースやフルクトース等の炭水化物含有原料から、比較的低温の反応温度を用いて、乳酸類を効率的に製造することができる。 In the method of the present invention, lactic acids can be efficiently produced from carbohydrate-containing raw materials such as cellulose and fructose using a relatively low reaction temperature.
以下、本発明を詳細に説明する。
本発明では、触媒として機能する少なくとも１種のスズ含有化合物並びに助触媒として機能する、リチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩からなる群より選択される少なくとも１種の化合物を含めた、水及び／又はアルコールを含有する溶媒中で、炭水化物含有原料を加熱処理することにより、乳酸類を反応生成物として取得することができる。
Hereinafter, the present invention will be described in detail.
In the present invention, at least one tin-containing compound that functions as a catalyst, and a lithium halide, a magnesium halide, a first transition series metal halide, and a quaternary ammonium salt that function as a cocatalyst are selected. By subjecting the carbohydrate-containing raw material to a heat treatment in a solvent containing water and / or alcohol including at least one kind of compound, lactic acids can be obtained as a reaction product.
本発明の方法を用いれば、炭水化物含有原料中の炭水化物、例えば、セルロースなどの多糖、フルクトースなどの単糖、オリゴ糖から、比較的低温の反応温度を用いても、乳酸類を簡便かつ高効率に製造することができる。 By using the method of the present invention, lactic acids can be easily and efficiently produced from carbohydrates in carbohydrate-containing raw materials, for example, polysaccharides such as cellulose, monosaccharides such as fructose, and oligosaccharides even at relatively low reaction temperatures. Can be manufactured.
本発明において「乳酸類」とは、乳酸及び／又は乳酸エステルを意味する。乳酸エステルは特に限定されないが、好ましくは乳酸メチルである。 In the present invention, “lactic acid” means lactic acid and / or lactic acid ester. The lactic acid ester is not particularly limited, but is preferably methyl lactate.
炭水化物からの乳酸類の生成反応は、セルロースを出発原料とする場合には、例えば、以下のように進行する。 When the cellulose is used as a starting material, the production reaction of lactic acids from carbohydrate proceeds, for example, as follows.
セルロースはアルコール中又は水中、高温高圧下で加溶媒分解されて糖類を生成する。この反応条件下では、生成された糖類はさらに分解して低分子化合物に変化するか、逆に重合して炭素質の高分子化合物となる。その分解反応としては、脱水反応とレトロアルドリゼーションがある。脱水反応では５−メトキシメチルフルフラール、レトロアルドリゼーションでは、グリコールアルデヒド（二炭糖）、ジヒドロキシアセトン又はグリセルアルデヒド（三炭糖）、エリスリトール（四炭糖）が生成する。このうち三炭糖は、異性化により、乳酸に変換することができる。さらに乳酸は、アルコールとの脱水縮合反応により乳酸エステルへと変換される。 Cellulose is solvolyzed in alcohol or water under high temperature and pressure to produce saccharides. Under this reaction condition, the produced saccharide is further decomposed to be converted into a low molecular compound, or conversely polymerized into a carbonaceous polymer compound. The decomposition reaction includes dehydration reaction and retroaldolization. In the dehydration reaction, 5-methoxymethylfurfural is produced, and in retroaldolization, glycolaldehyde (dicarbon sugar), dihydroxyacetone or glyceraldehyde (tricarbon sugar), and erythritol (tetracarbon sugar) are produced. Among these, tricarbon sugar can be converted into lactic acid by isomerization. Furthermore, lactic acid is converted into a lactic acid ester by a dehydration condensation reaction with alcohol.
本発明の方法において原料として使用できる炭水化物含有原料は、炭水化物を含有する任意の原料であってよい。限定するものではないが、炭水化物含有原料は、単糖、オリゴ糖（単糖が２〜９個結合したもの）、若しくは多糖（単糖が１０個以上結合したもの）などの任意の炭水化物、又はそれを含む生物由来材料であってよい。多糖としては、限定するものではないが、セルロースが好ましい。炭水化物含有原料は、例えば、セルロース、ホロセルロース、セロビオース、デンプン（例えば、可溶性デンプン）、マルトース、グルコース、マンノース、フルクトース、ガラクトース、グロース等の六炭糖を含む炭水化物、ヘミセルロース、キシロース、アラビノース等の五炭糖を含むヘミセルロース系物質、又はそれらの少なくとも１つを含有する、例えばリグノセルロース系の原料であってもよい。炭水化物含有原料は、特に限定されないが、例えば、上記のような炭水化物（例えば、セルロース、単糖、オリゴ糖等）を含むバイオマス材料であってもよい。炭水化物含有原料の例としては、古紙、製材残材、麦藁、コーンストーバー、コーンコブ、トウモロコシの穂などの農産廃棄物をはじめとするリグノセルロース系バイオマス材料、デンプンやグルコース等の糖類を含む食品廃棄物等が挙げられる。本発明の方法において使用する炭水化物含有原料は上記のような炭水化物に加えて水を含んでいることも好ましい。 The carbohydrate-containing raw material that can be used as the raw material in the method of the present invention may be any raw material containing carbohydrate. Without limitation, the carbohydrate-containing material can be any carbohydrate such as a monosaccharide, oligosaccharide (2-9 linked monosaccharides), or polysaccharide (10 or more monosaccharides bonded), or It may be a biological material containing it. Although it does not limit as a polysaccharide, A cellulose is preferable. Carbohydrate-containing raw materials include, for example, carbohydrates containing hexoses such as cellulose, holocellulose, cellobiose, starch (for example, soluble starch), maltose, glucose, mannose, fructose, galactose, and growth, hemicellulose, xylose, arabinose, etc. It may be a hemicellulose-based material containing carbon sugar, or at least one of them, for example, a lignocellulosic material. Although a carbohydrate containing raw material is not specifically limited, For example, the biomass material containing the above carbohydrates (for example, a cellulose, a monosaccharide, an oligosaccharide etc.) may be sufficient. Examples of carbohydrate-containing raw materials include lignocellulosic biomass materials including agricultural waste such as waste paper, sawn timber, wheat straw, corn stover, corn cob, and corn ears, and food waste containing sugars such as starch and glucose Etc. The carbohydrate-containing raw material used in the method of the present invention preferably contains water in addition to the carbohydrate as described above.
本発明の方法では、少なくとも１種のスズ含有化合物を、セルロースの分解反応、及び糖の分解・異性化反応のための触媒として使用する。 In the method of the present invention, at least one tin-containing compound is used as a catalyst for cellulose decomposition reaction and sugar decomposition / isomerization reaction.
本発明において「スズ含有化合物」とは、スズ又は有機スズのハロゲン化物及びスズ又は有機スズのパーフルオロアルキルスルホン酸塩からなる群より選択される少なくとも一種の化合物を意味する。 In the present invention, the “tin-containing compound” means at least one compound selected from the group consisting of tin or organotin halides and tin or organotin perfluoroalkylsulfonates.
ここで「有機スズ」とは、１つ以上の有機置換基（炭化水素基）が結合したスズ（Ｓｎ）をいう。本発明で使用され得る有機スズのスズ原子上に結合する置換基としては、特に限定されないが例えば、ｎ−ブチル基、ｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基などが挙げられる。スズ又は有機スズのパーフルオロアルキルスルホン酸塩は、スズ（ＩＩ）塩であってもスズ（ＩＶ）塩であってもよい。 Here, “organotin” refers to tin (Sn) to which one or more organic substituents (hydrocarbon groups) are bonded. Although it does not specifically limit as a substituent couple | bonded on the tin atom of the organotin which can be used by this invention, For example, n-butyl group, t-butyl group, n-hexyl group, n-octyl group etc. are mentioned. The perfluoroalkyl sulfonate of tin or organotin may be a tin (II) salt or a tin (IV) salt.
「スズ又は有機スズのハロゲン化物」としては、スズ又は有機スズのフッ化物、塩化物、臭化物、及びヨウ化物が挙げられ、好ましくは塩化物である。特に限定されないが、例えば塩化スズ（ＩＩ）、塩化スズ（ＩＶ）五水和物、臭化スズ（ＩＩ）、ｎ−ブチルスズ（ＩＩ）塩化物、三塩化フェニルスズをとりわけ好適に使用することができる。 Examples of the “tin or organotin halide” include fluoride, chloride, bromide, and iodide of tin or organotin, with chloride being preferred. Although not particularly limited, for example, tin (II) chloride, tin (IV) chloride pentahydrate, tin (II) bromide, n-butyltin (II) chloride, and phenyltin trichloride can be particularly preferably used. .
「パーフルオロアルキルスルホン酸塩」としては、特に限定されないが、例えばトリフルオロメタンスルホン酸塩、ペンタフルオロメタンスルホン酸塩、ヘプタフルオロプロパンスルホン酸塩、ノナフルオロブタンスルホン酸塩等が挙げられる。本発明において、より好ましいパーフルオロアルキルスルホン酸塩は、トリフルオロメタンスルホン酸塩（慣用名：トリフラート）である。スズのパーフルオロアルキルスルホン酸塩としては、例えば、トリフルオロメタンスルホン酸スズ（ＩＩ）（Ｓｎ（ＯＴｆ）２）（Ｔｆはトリフルオロメチルスルホニル基ＣＦ３ＳＯ２−を表す。以後同様。）をとりわけ好適に使用することができる。有機スズのパーフルオロアルキルスルホン酸塩としては、例えば、トリフルオロメタンスルホン酸ジブチルスズ（ＩＩ）（ｎＢｕ２Ｓｎ（ＯＴｆ）２）をとりわけ好適に使用することができる。 The “perfluoroalkyl sulfonate” is not particularly limited, and examples thereof include trifluoromethane sulfonate, pentafluoromethane sulfonate, heptafluoropropane sulfonate, and nonafluorobutane sulfonate. In the present invention, a more preferred perfluoroalkyl sulfonate is trifluoromethane sulfonate (common name: triflate). As the perfluoroalkyl sulfonate of tin, for example, tin (II) trifluoromethanesulfonate (Sn (OTf) 2 ) (Tf represents a trifluoromethylsulfonyl group CF 3 SO 2 —, the same applies hereinafter). It can be preferably used. The perfluoroalkyl sulfonates organotin, for example, it can be used trifluoromethanesulfonic acid dibutyltin (II) to (n Bu 2 Sn (OTf) 2) especially favorably.
１つの反応系において、スズ含有化合物の１種類を使用してもよいし、２種類以上を組み合わせて使用してもよい。 In one reaction system, one type of tin-containing compound may be used, or two or more types may be used in combination.
本発明の方法ではさらに、リチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩からなる群から選択される少なくとも1種の化合物を、セルロースの分解反応、及び糖の分解・異性化反応のための助触媒として使用する。 In the method of the present invention, at least one compound selected from the group consisting of a halide of lithium, a halide of magnesium, a halide of a first transition series metal, and a quaternary ammonium salt is further decomposed into a cellulose decomposition reaction, and Used as a co-catalyst for sugar decomposition and isomerization reactions.
本発明において「助触媒」とは、スズ含有化合物の存在下において、当該スズ含有化合物と共同して作用することによりセルロースの分解反応、及び糖の分解・異性化反応を促進・強化する化合物を意味する。助触媒自体は単独で、すなわち、スズ含有化合物の非存在下において、セルロースの分解反応、及び糖の分解・異性化反応を触媒しても良いし、しなくても良い。 In the present invention, the term “co-catalyst” refers to a compound that promotes and strengthens the decomposition reaction of cellulose and the decomposition / isomerization reaction of sugar by acting together with the tin-containing compound in the presence of the tin-containing compound. means. The cocatalyst itself may or may not catalyze the decomposition reaction of cellulose and the decomposition / isomerization reaction of sugar in the absence of a tin-containing compound.
「リチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物」としては、リチウム、マグネシウム及び第一遷移系列金属（すなわち、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛）のフッ化物、塩化物、臭化物、及びヨウ化物が挙げられ、好ましくは塩化物である。特に限定されないが、例えば、塩化リチウム、塩化マンガン四水和物、塩化コバルト六水和物、塩化コバルト六水和物、塩化ニッケル四水和物、塩化鉄（ＩＩ）六水和物などをとりわけ好適に使用することができる。 “Lithium halide, magnesium halide, halide of first transition series metal” includes lithium, magnesium and first transition series metals (ie, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel , Copper, zinc) fluoride, chloride, bromide, and iodide, with chloride being preferred. Although not particularly limited, for example, lithium chloride, manganese chloride tetrahydrate, cobalt chloride hexahydrate, cobalt chloride hexahydrate, nickel chloride tetrahydrate, iron (II) chloride hexahydrate, among others It can be preferably used.
「四級アンモニウム塩」としては、特に限定されないが、例えば四級アンモニウム塩のハロゲン化物（フッ化物、塩化物、臭化物、及びヨウ化物）が挙げられ、そのような四級アンモニウム塩のハロゲン化物としては、限定されるものではないが、例えば、ビス（トリフェニルホスフィン）イミニウムクロライド、テトラブチルアンモニウムブロミド、トリオクチルメチルアンモニウムクロリドなどをとりわけ好適に使用することができる。 The “quaternary ammonium salt” is not particularly limited, and examples thereof include quaternary ammonium salt halides (fluoride, chloride, bromide, and iodide). Although there is no limitation, for example, bis (triphenylphosphine) iminium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride and the like can be used particularly preferably.
１つの反応系において、助触媒の１種類を使用してもよいし、２種類以上を組み合わせて使用してもよい。 In one reaction system, one type of promoter may be used, or two or more types may be used in combination.
本発明の方法に用いる、水及び／又はアルコールを含有する溶媒は、水若しくはアルコール、又はその両方を含む溶液である。この溶媒は、水又はアルコール単独であってもよいし、水とアルコールの混合液であってもよいし、それらに他の成分、例えば他の有機溶媒が混合された溶液であってもよい。水としては、蒸留水、イオン交換水、工業用水等を使用することができる。アルコールとしては、特に限定されないが、炭素数１から８までの脂肪族アルコールが好ましい。例えばメタノール、エタノール、プロパノール、イソプロパノール、１−ブタノール、２−ブタノール、エチレングリコールなどを挙げることができる。含水アルコールも本発明において溶媒として好適に使用できる。１種又は２種以上のアルコールが溶媒に含まれていてもよい。また本発明の方法において、乳酸を製造する場合は水を溶媒として使用し、乳酸エステルを製造する場合は、アルコールを含有する溶媒を使用すればよい。 The solvent containing water and / or alcohol used in the method of the present invention is a solution containing water or alcohol, or both. This solvent may be water or alcohol alone, a mixed solution of water and alcohol, or a solution in which other components such as other organic solvents are mixed. As water, distilled water, ion exchange water, industrial water, or the like can be used. Although it does not specifically limit as alcohol, A C1-C8 aliphatic alcohol is preferable. For example, methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, ethylene glycol and the like can be mentioned. Hydrous alcohol can also be suitably used as a solvent in the present invention. One or two or more alcohols may be contained in the solvent. In the method of the present invention, when producing lactic acid, water is used as a solvent, and when producing a lactic acid ester, a solvent containing alcohol may be used.
炭水化物含有原料に対する、水及び／又はアルコールを含有する溶媒の使用量は、当業者が適宜選択することができ、特に限定されるものではないが、通常、重量比で原料：溶媒＝１：１〜１：１０００であり、好ましくは１：５〜１：１００である。 The amount of water and / or alcohol-containing solvent used for the carbohydrate-containing raw material can be appropriately selected by those skilled in the art and is not particularly limited, but is usually raw material: solvent = 1: 1 in weight ratio. ˜1: 1000, preferably 1: 5 to 1: 100.
水及び／又はアルコールを含有する溶媒に含有させる、触媒として用いるスズ含有化合物の合計量（使用量）としては、限定するものではないが、炭水化物含有原料中のグルコース残基又はフルクトース残基１ｍｏｌ当たり、質量比で０．００１〜１．０ｍｏｌ、好ましくは０．００５ｍｏｌ〜０．１ｍｏｌ、例えば０．０１〜０．０５ｍｏｌに相当する量を使用できる。使用量が少な過ぎるとセルロースの分解反応、及び糖の分解・異性化反応が進行しにくく、多過ぎると副反応のため目的とする乳酸類の収率が低下するため好ましくない。 The total amount (usage amount) of the tin-containing compound used as a catalyst to be contained in a solvent containing water and / or alcohol is not limited, but per 1 mol of glucose residue or fructose residue in the carbohydrate-containing raw material. An amount corresponding to 0.001 to 1.0 mol, preferably 0.005 mol to 0.1 mol, for example, 0.01 to 0.05 mol in terms of mass ratio can be used. If the amount used is too small, the decomposition reaction of cellulose and the decomposition / isomerization reaction of sugar are difficult to proceed, and if it is too large, the yield of the desired lactic acid is lowered due to side reactions, which is not preferable.
また、スズ含有化合物に対する助触媒として用いる、リチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩からなる群より選択される少なくとも1種の化合物の使用量は、当業者であれば適宜調節することができるが、触媒として用いるスズ含有化合物の使用量１．０ｍｏｌに対して０．１〜１０．０ｍｏｌであり、好ましくはスズ含有化合物の使用量と同等又はそれ以上の範囲であり、さらに好ましくは１．０ｍｏｌから４．０ｍｏｌの範囲である。 Further, the amount of at least one compound selected from the group consisting of lithium halides, magnesium halides, first transition series metal halides and quaternary ammonium salts used as a co-catalyst for tin-containing compounds is The amount of tin-containing compound used as a catalyst is 0.1 to 10.0 mol, preferably equivalent to the amount of tin-containing compound used, or can be adjusted as appropriate by those skilled in the art. The range is more than that, and more preferably in the range of 1.0 mol to 4.0 mol.
本発明の方法では、触媒としてスズ含有化合物並びに助触媒としてリチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウムより選択される少なくとも1種の化合物を含む、水及び／又はアルコールを含有する溶媒中で、炭水化物含有原料を加熱処理する。加熱処理の条件は、原料に含まれる糖類やアルコールの種類などによって当業者であれば適宜調節することができるが、１００℃〜３００℃が好ましく、１００℃〜２５０℃がより好ましく、例えば１５０℃〜１６０℃を好適に使用できる。本発明の方法ではこのように比較的低めの加熱温度で実施できる。 In the method of the present invention, a water containing a tin-containing compound as a catalyst and at least one compound selected from a lithium halide, a magnesium halide, a first transition series metal halide and a quaternary ammonium as a promoter. The carbohydrate-containing raw material is heat-treated in a solvent containing alcohol and / or alcohol. The conditions for the heat treatment can be appropriately adjusted by those skilled in the art depending on the type of saccharide or alcohol contained in the raw material, but are preferably 100 ° C to 300 ° C, more preferably 100 ° C to 250 ° C, for example, 150 ° C. -160 degreeC can be used conveniently. Thus, the method of the present invention can be carried out at a relatively low heating temperature.
本発明の方法では、加熱処理を、酸素の非存在下で行うことも好ましい。酸素の非存在条件にするためには、加熱処理前に不活性ガスを反応容器に充填して、空気をパージ（排除）することが好適である。不活性ガスの種類は特に限定されるものではないが、例えば、窒素ガス、アルゴンガス、炭酸ガスなどが例として挙げられる。 In the method of the present invention, the heat treatment is preferably performed in the absence of oxygen. In order to make the oxygen non-existing condition, it is preferable to fill the reaction vessel with an inert gas before the heat treatment and purge (exclude) the air. Although the kind of inert gas is not specifically limited, For example, nitrogen gas, argon gas, carbon dioxide gas etc. are mentioned as an example.
本発明の加熱処理は、加圧下で行うことも好ましい。反応圧力は大気圧以上であることが好ましく、０．３ＭＰａ〜２０ＭＰａが好ましく、０．４ＭＰａ〜１０ＭＰａがさらに好ましい。 The heat treatment of the present invention is also preferably performed under pressure. The reaction pressure is preferably at least atmospheric pressure, preferably 0.3 MPa to 20 MPa, and more preferably 0.4 MPa to 10 MPa.
本発明方法における水及び／又はアルコールを含有する溶媒中での反応は、限定するものではないが、例えばオートクレーブ中で行うことが好ましい。また他の好ましい反応形態として、連続流通系反応方法（連続法）が挙げられる。原料・溶媒・触媒を混合した反応液を、所定温度、圧力に制御された反応器に連続的に供給して、所定時間反応器内に滞留させて反応させることができる。 Although the reaction in the solvent containing water and / or alcohol in the method of the present invention is not limited, for example, it is preferably carried out in an autoclave. Another preferred reaction form is a continuous flow reaction method (continuous method). The reaction liquid in which the raw material / solvent / catalyst is mixed can be continuously supplied to a reactor controlled at a predetermined temperature and pressure, and allowed to stay in the reactor for a predetermined time for reaction.
本発明の方法では、例えば、電磁撹拌式オートクレーブに、触媒としてスズ含有化合物、助触媒としてリチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩より選択される少なくとも1種の化合物、炭水化物含有原料、並びに水及び／又はアルコールを含有する溶媒を仕込み、不活性ガスで空気をパージした後、上記加熱温度まで加熱して所定時間反応させればよい。加熱時間は、当業者であれば適宜調節でき、特に限定するものではないが、加熱温度に達してから３時間〜２４時間とすればよく、５時間〜１２時間が好ましい。所定の加熱時間経過後は、加熱を停止し、室温まで放冷させればよい。室温まで冷却した後、オートクレーブから反応生成物を取り出す。 In the method of the present invention, for example, an electromagnetic stirring autoclave is selected from a tin-containing compound as a catalyst, a lithium halide as a promoter, a magnesium halide, a first transition series metal halide and a quaternary ammonium salt. A solvent containing at least one compound, a carbohydrate-containing raw material, and water and / or alcohol may be charged, purged with air with an inert gas, heated to the above heating temperature, and allowed to react for a predetermined time. The heating time can be appropriately adjusted by those skilled in the art and is not particularly limited, but may be 3 to 24 hours after reaching the heating temperature, and preferably 5 to 12 hours. After a predetermined heating time has elapsed, heating may be stopped and allowed to cool to room temperature. After cooling to room temperature, the reaction product is removed from the autoclave.
また連続流通系反応方法を用いる本発明の方法では、炭水化物含有原料、水及び／又はアルコールを含有する溶媒、触媒としてスズ含有化合物、並びに助触媒としてリチウムのハロゲン化物、マグネシウムのハロゲン化物、第一遷移系列金属のハロゲン化物及び四級アンモニウム塩より選択される少なくとも1種の化合物を混合した反応液を、所定の加熱温度及び圧力に制御された反応器に連続的に供給し、所定の加熱時間にわたり反応器内に滞留させて反応させればよい。加熱時間経過後は、加熱を停止し、室温まで放冷させればよい。室温まで冷却した後、反応器から反応生成物を取り出す。 In the method of the present invention using a continuous flow reaction method, a carbohydrate-containing raw material, a solvent containing water and / or alcohol, a tin-containing compound as a catalyst, and a lithium halide, a magnesium halide as a cocatalyst, A reaction liquid in which at least one compound selected from a halide of a transition series metal and a quaternary ammonium salt is mixed is continuously supplied to a reactor controlled at a predetermined heating temperature and pressure, and a predetermined heating time is obtained. The reaction may be carried out by staying in the reactor. After the heating time has elapsed, heating may be stopped and allowed to cool to room temperature. After cooling to room temperature, the reaction product is removed from the reactor.
以上のような方法により、乳酸類を高収率で生成させることができる。炭水化物含有原料がセルロースを含む場合、セルロースから効率よく加溶媒分解された糖類から乳酸類が多量に生成されることになる。本発明の方法によれば、乳酸類を、セルロースや単糖等を含む炭水化物含有原料中の１グルコース残基又は１フルクトース残基当たりの基準で、４５％〜６０％程度の収率で得ることができる。尚、収率は、原料のセルロースより理論上生成される、１グルコース残基当たりの乳酸類のモル数（乳酸類／グルコース残基＝２ｍｏｌ／１ｍｏｌ）に対する、乳酸及び／又は乳酸エステルのモル数（ｍｏｌ）の百分率（％）で表される。 By the above method, lactic acids can be produced in high yield. In the case where the carbohydrate-containing raw material contains cellulose, a large amount of lactic acid is produced from the saccharide efficiently solvolyzed from cellulose. According to the method of the present invention, lactic acids are obtained in a yield of about 45% to 60% on the basis of one glucose residue or one fructose residue in a carbohydrate-containing raw material containing cellulose, monosaccharides, and the like. Can do. The yield is the number of moles of lactic acid and / or lactic acid ester with respect to the number of moles of lactic acid per glucose residue that is theoretically produced from the raw material cellulose (lactic acid / glucose residue = 2 mol / 1 mol). It is expressed as a percentage (%) of (mol).
上記のようにして得られる反応液から、乳酸又は乳酸エステルを分離することも好ましい。この分離は、例えば液体クロマトグラフィー等の当業者に公知の有機酸分離方法によって行うことができる。 It is also preferable to separate lactic acid or lactic acid ester from the reaction solution obtained as described above. This separation can be performed by an organic acid separation method known to those skilled in the art, such as liquid chromatography.
本発明の方法では、触媒として使用する酸の使用量を少量に抑え、比較的低温の反応温度を用いながらも乳酸類の収率を向上させることができて有用である。 The method of the present invention is useful because the amount of the acid used as a catalyst is suppressed to a small amount, and the yield of lactic acid can be improved while using a relatively low reaction temperature.
以下、実施例を用いて本発明をさらに具体的に説明する。但し、本発明の技術的範囲はこれら実施例に限定されるものではない。
（実施例１）
５０ｍＬ容のステンレス製オートクレーブ（耐圧硝子工業製）に、原料としてＤ−フルクトース０．４５ｇ（２．５ｍｍｏｌ）、触媒として塩化スズ（ＩＩ）５ｍｇ（０．０２５ｍｍｏｌ）、助触媒として塩化マンガン四水和物２０ｍｇ（０．１ｍｍｏｌ）、溶媒としてメタノール１０ｍＬと、撹拌子を加え、蓋を閉めた。このオートクレーブ中の空気を窒素ガスでパージし、０．５ＭＰａまで加圧した後、マグネティックスターラーで混合物を撹拌しながら、電気炉を用いてオートクレーブを１５０℃になるまで加熱した。その後、１５０℃に保持しながら５時間撹拌を続けた後、オートクレーブを室温中で放冷した。冷却後、オートクレーブ中から反応溶液を取り出し、溶液中の生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。なお各収率は、原料のＤ−フルクトースより理論上生成される、乳酸類のモル数（乳酸類／フルクトース＝５ ｍｍｏｌ／２．５ ｍｍｏｌ）に対する、生成物のモル数（ｍｏｌ）の百分率（％）で表した。表中の「ｔｒａｃｅ」は０．５％未満であることを示す。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the technical scope of the present invention is not limited to these examples.
Example 1
In a 50 mL stainless steel autoclave (made by pressure-resistant glass industry), D-fructose 0.45 g (2.5 mmol) as a raw material, tin (II) chloride 5 mg (0.025 mmol) as a catalyst, manganese chloride tetrahydrate as a promoter 20 mg (0.1 mmol) of the product, 10 mL of methanol as a solvent, and a stirring bar were added, and the lid was closed. After the air in the autoclave was purged with nitrogen gas and pressurized to 0.5 MPa, the autoclave was heated to 150 ° C. using an electric furnace while stirring the mixture with a magnetic stirrer. Thereafter, stirring was continued for 5 hours while maintaining at 150 ° C., and then the autoclave was allowed to cool at room temperature. After cooling, the reaction solution was taken out from the autoclave, and the products in the solution were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below. Each yield is the percentage of the number of moles (mol) of the product with respect to the number of moles of lactic acid (lactic acid / fructose = 5 mmol / 2.5 mmol) theoretically generated from D-fructose as a raw material ( %). “Trace” in the table indicates less than 0.5%.
（実施例２）
塩化スズ（ＩＩ）に代えて臭化スズ（ＩＩ）７ｍｇ（０．０２５ｍｍｏｌ）を用いた点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 2)
The reaction was performed in the same manner as in Example 1 except that 7 mg (0.025 mmol) of tin (II) bromide was used instead of tin (II) chloride, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例３）
塩化スズ（ＩＩ）に代えてｎ−ブチルスズ三塩化物２８ｍｇ（０．１ｍｍｏｌ）を用いた点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 3)
The reaction was performed in the same manner as in Example 1 except that 28 mg (0.1 mmol) of n-butyltin trichloride was used in place of tin (II) chloride, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例４）
塩化スズ（ＩＩ）に代えて三塩化フェニルスズ３０ｍｇ（０．１ｍｍｏｌ）を使用し、１０時間の反応時間で加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
Example 4
In place of tin (II) chloride, 30 mg (0.1 mmol) of phenyltin trichloride was used and heat treatment was performed for a reaction time of 10 hours. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例５）
塩化スズ（ＩＩ）に代えてトリフルオロメタンスルホン酸スズ４２ｍｇ（０．１ｍｍｏｌ）を使用し、塩化マンガン四水和物に代えて塩化マグネシウム六水和物２０ｍｇ（０．１ｍｍｏｌ）を使用した。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 5)
In place of tin (II) chloride, 42 mg (0.1 mmol) of tin trifluoromethanesulfonate was used, and in place of manganese chloride tetrahydrate, 20 mg (0.1 mmol) of magnesium chloride hexahydrate was used. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例６）
塩化スズ（ＩＩ）に代えて、トリフルオロメタンスルホン酸スズ８ｍｇ（０．０２ｍｍｏｌ）及びｎ−ブチルスズ三塩化物２３ｍｇ（０．０８ｍｍｏｌ）を用いた点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 6)
In place of tin (II) chloride, the reaction was performed in the same manner as in Example 1 except that 8 mg (0.02 mmol) of tin trifluoromethanesulfonate and 23 mg (0.08 mmol) of n-butyltin trichloride were used. Various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例１）
触媒として塩化スズ（ＩＩ）２４ｍｇ（０．１２５ｍｍｏｌ）を使用し、助触媒を用いなかった点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 1)
A reaction was carried out in the same manner as in Example 1 except that 24 mg (0.125 mmol) of tin (II) chloride was used as a catalyst and no promoter was used, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例２）
触媒として臭化スズ（ＩＩ）３５ｍｇ（０．１２５ｍｍｏｌ）を使用し、助触媒を用いなかった点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 2)
A reaction was carried out in the same manner as in Example 1 except that 35 mg (0.125 mmol) of tin (II) bromide was used as a catalyst and no promoter was used, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例３）
触媒として塩化スズ(IV)五水和物３５ｍｇ（０．１ｍｍｏｌ）を使用し、助触媒を用いず、１０時間の反応時間で加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 3)
As a catalyst, 35 mg (0.1 mmol) of tin (IV) chloride pentahydrate was used, and a heat treatment was carried out with a reaction time of 10 hours without using a promoter. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例４）
触媒としてトリフルオロメタンスルホン酸スズ２１ｍｇ（０．０５ｍｍｏｌ）を使用し、助触媒を用いず、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 4)
As a catalyst, 21 mg (0.05 mmol) of tin trifluoromethanesulfonate was used, and a heat treatment was performed at 160 ° C. without using a promoter. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例５）
助触媒として塩化マンガン四水和物２０ｍｇ（０．１ｍｍｏｌ）を使用し、触媒を用いなかった点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 5)
Manganese chloride tetrahydrate 20 mg (0.1 mmol) was used as a cocatalyst, and the reaction was carried out in the same manner as in Example 1 except that no catalyst was used, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例６）
助触媒として塩化マグネシウム六水和物２０ｍｇ（０．１ｍｍｏｌ）を使用し、触媒を用いなかった点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 6)
Magnesium chloride hexahydrate 20 mg (0.1 mmol) was used as a cocatalyst, and the reaction was carried out in the same manner as in Example 1 except that no catalyst was used, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例７）
塩化マンガン四水和物に代えて塩化コバルト六水和物６ｍｇ（０．０２５ｍｍｏｌ）を使用し、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 7)
Instead of manganese chloride tetrahydrate, 6 mg (0.025 mmol) of cobalt chloride hexahydrate was used, and heat treatment was performed at 160 ° C. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例８）
触媒として塩化スズ（ＩＩ）９ｍｇ（０．０５ｍｍｏｌ）を使用し、助触媒として塩化コバルト六水和物１２ｍｇ（０．０５ｍｍｏｌ）を使用し、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 8)
Heat treatment was performed at 160 ° C. using 9 mg (0.05 mmol) of tin (II) chloride as a catalyst and 12 mg (0.05 mmol) of cobalt chloride hexahydrate as a cocatalyst. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例９）
塩化マンガン四水和物に代えて塩化ニッケル六水和物６ｍｇ（０．０２５ｍｍｏｌ）を使用し、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
Example 9
Instead of manganese chloride tetrahydrate, 6 mg (0.025 mmol) of nickel chloride hexahydrate was used, and heat treatment was performed at 160 ° C. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例１０）
触媒として塩化スズ（ＩＩ）９ｍｇ（０．０５ｍｍｏｌ）を使用し、助触媒として塩化ニッケル六水和物１２ｍｇ（０．０５ｍｍｏｌ）を使用し、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 10)
Heat treatment was performed at 160 ° C. using 9 mg (0.05 mmol) of tin (II) chloride as a catalyst and 12 mg (0.05 mmol) of nickel chloride hexahydrate as a co-catalyst. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例７）
触媒として塩化スズ（ＩＩ）５ｍｇ（０．０２５ｍｍｏｌ）を使用し、助触媒を用いず、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 7)
As a catalyst, 5 mg (0.025 mmol) of tin (II) chloride was used, and a heat treatment was performed at 160 ° C. without using a promoter. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例８）
触媒として塩化スズ（ＩＩ）９ｍｇ（０．０５ｍｍｏｌ）を使用し、助触媒を用いず、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 8)
9 mg (0.05 mmol) of tin (II) chloride was used as a catalyst, and heat treatment was performed at 160 ° C. without using a promoter. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例９）
助触媒として塩化コバルト六水和物２４ｍｇ（０．１ｍｍｏｌ）を使用し、触媒を用いず、１６０℃にて加熱処理を行った。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 9)
24 mg (0.1 mmol) of cobalt chloride hexahydrate was used as a cocatalyst, and heat treatment was performed at 160 ° C. without using a catalyst. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例１０）
助触媒として塩化ニッケル六水和物２４ｍｇ（０．１ｍｍｏｌ）を使用し、触媒を用いなかった点以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 10)
Nickel chloride hexahydrate 24 mg (0.1 mmol) was used as a co-catalyst, and the reaction was performed in the same manner as in Example 1 except that the catalyst was not used, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例１１）
塩化マンガン四水和物に代えて塩化リチウム４ｍｇ（０．１ｍｍｏｌ）を使用した以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 11)
The reaction was performed in the same manner as in Example 1 except that 4 mg (0.1 mmol) of lithium chloride was used in place of manganese chloride tetrahydrate, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（実施例１２）
塩化マンガン四水和物に代えて塩化鉄（ＩＩ）四水和物２０ｍｇ（０．１ｍｍｏｌ）を使用した以外は、実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Example 12)
The reaction was conducted in the same manner as in Example 1 except that 20 mg (0.1 mmol) of iron (II) chloride tetrahydrate was used instead of manganese chloride tetrahydrate, and various products were quantitatively analyzed by liquid chromatography. did. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例１１）
助触媒として塩化リチウム４ｍｇ（０．１ｍｍｏｌ）を使用し、触媒を用いなかった。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 11)
4 mg (0.1 mmol) of lithium chloride was used as a cocatalyst, and no catalyst was used. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（比較例１２）
助触媒として塩化鉄（ＩＩ）四水和物２０ｍｇ（０．１ｍｍｏｌ）を使用し、触媒を用いなかった。その他の条件は実施例１と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表１に示す。
(Comparative Example 12)
As promoter, 20 mg (0.1 mmol) of iron (II) chloride tetrahydrate was used, and no catalyst was used. Other conditions were the same as in Example 1, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 1 below.
（結果）
表１に示すように、スズ含有化合物と助触媒を組み合わせて用いた場合（実施例１−１２）、スズ含有化合物又は助触媒のいずれかを用いなかった場合（比較例１−１２）と比べて、乳酸エステルを高い収率で得ることができた。助触媒として、塩化マンガン四水和物又は塩化マグネシウム六水和物を用いた場合（実施例１−６）に、乳酸エステルを高い収率で得られる傾向がみられた。また、２種のスズ含有化合物を助触媒と組み合わせて用いた場合（実施例６）、特に高い収率が得られた。さらに、二種類の触媒の使用量比率を変えた実施例７及び８並びに実施例９及び１０では、スズ含有化合物と助触媒の合計使用量がより多い方（実施例８及び１０）が、その使用量がより少ない場合（実施例７及び９）よりも乳酸エステルの収率は高かった。従って、スズ含有化合物と助触媒の合計使用量を比較的高くすることが、乳酸エステルを高い収率で得る上で有用であることが示された。
(result)
As shown in Table 1, when a tin-containing compound and a co-catalyst were used in combination (Example 1-12), compared with a case where either a tin-containing compound or a co-catalyst was not used (Comparative Example 1-12) Thus, a lactic acid ester could be obtained with a high yield. When manganese chloride tetrahydrate or magnesium chloride hexahydrate was used as a co-catalyst (Example 1-6), a tendency to obtain a lactic acid ester in a high yield was observed. In addition, when two tin-containing compounds were used in combination with a promoter (Example 6), a particularly high yield was obtained. Furthermore, in Examples 7 and 8 and Examples 9 and 10 in which the usage ratio of the two types of catalysts was changed, the one where the total usage amount of the tin-containing compound and the cocatalyst was larger (Examples 8 and 10) The yield of lactic acid ester was higher than when the amount used was smaller (Examples 7 and 9). Therefore, it was shown that a relatively high total amount of the tin-containing compound and the cocatalyst is useful for obtaining a lactic acid ester in a high yield.
（実施例１３）
５０ｍＬ容のステンレス製オートクレーブ（耐圧硝子工業製）に、原料としてＤ−フルクトース０．４５ｇ（２．５ｍｍｏｌ）、触媒として塩化スズ（ＩＶ）五水和物３５ｍｇ（０．１ｍｍｏｌ）、助触媒としてビストリフェニルホスフィンイミニウムクロリド５７ｍｇ（０．１ｍｍｏｌ）、溶媒としてメタノール２０ｍＬと、撹拌子を加え、蓋を閉めた。このオートクレーブ中の空気を窒素ガスでパージし、０．５ＭＰａまで加圧した後、マグネティックスターラーで混合物を撹拌しながら、電気炉を用いてオートクレーブを１５０℃になるまで加熱した。その後、１５０℃に保持しながら１０時間撹拌を続けた後、オートクレーブを室温中で放冷した。冷却後、オートクレーブ中から反応溶液を取り出し、溶液中の生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表２に示す。なお各収率は、実施例１と同様に、原料のＤ−フルクトースより理論上生成される、乳酸類のモル数（乳酸類／フルクトース＝５ ｍｍｏｌ／２．５ ｍｍｏｌ）に対する、生成物のモル数（ｍｏｌ）の百分率（％）で表した。
(Example 13)
In a 50 mL stainless steel autoclave (made by pressure-resistant glass industry), D-fructose 0.45 g (2.5 mmol) as a raw material, tin (IV) chloride pentahydrate 35 mg (0.1 mmol) as a catalyst, bistri as a promoter 57 mg (0.1 mmol) of phenylphosphine iminium chloride, 20 mL of methanol as a solvent, and a stir bar were added, and the lid was closed. After the air in the autoclave was purged with nitrogen gas and pressurized to 0.5 MPa, the autoclave was heated to 150 ° C. using an electric furnace while stirring the mixture with a magnetic stirrer. Thereafter, stirring was continued for 10 hours while maintaining at 150 ° C., and then the autoclave was allowed to cool at room temperature. After cooling, the reaction solution was taken out from the autoclave, and the products in the solution were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 2 below. Each yield is the same as in Example 1 with respect to the number of moles of lactic acid (lactic acid / fructose = 5 mmol / 2.5 mmol) theoretically generated from the raw material D-fructose. Expressed as a percentage (%) of a number (mol).
（実施例１４）
助触媒としてビストリフェニルホスフィンイミニウムクロリド１１５ｍｇ（０．２ｍｍｏｌ）を使用した以外は、実施例１３と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表２に示す。
(Example 14)
The reaction was conducted in the same manner as in Example 13 except that 115 mg (0.2 mmol) of bistriphenylphosphineiminium chloride was used as a cocatalyst, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 2 below.
（実施例１５）
塩化スズ（ＩＶ）五水和物に代えて、三塩化フェニルスズ３０ｍｇ（０．１ｍｍｏｌ）を使用した以外は、実施例１３と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表２に示す。
(Example 15)
The reaction was carried out in the same manner as in Example 13 except that 30 mg (0.1 mmol) of phenyltin trichloride was used instead of tin (IV) chloride pentahydrate, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 2 below.
（実施例１６）
助触媒としてトリオクチルメチルアンモニウムクロリド４０ｍｇ（０．１ｍｍｏｌ）を使用した以外は、実施例１３と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表２に示す。
(Example 16)
A reaction was carried out in the same manner as in Example 13 except that 40 mg (0.1 mmol) of trioctylmethylammonium chloride was used as a cocatalyst, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 2 below.
（実施例１７）
助触媒としてテトラブチルアンモニウムブロミド２８ｍｇ（０．１ｍｍｏｌ）を使用した以外は、実施例１３と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表２に示す。
(Example 17)
The reaction was conducted in the same manner as in Example 13 except that 28 mg (0.1 mmol) of tetrabutylammonium bromide was used as a cocatalyst, and various products were quantitatively analyzed by liquid chromatography. The yield of lactic acids in the analysis results is shown in Table 2 below.
（比較例１３）
触媒として塩化スズ（ＩＶ）五水和物３５ｍｇ（０．１ｍｍｏｌ）を使用し、助触媒を用いなかった点以外は、実施例１３と同様に反応を行い、各種生成物を液体クロマトグラフィーにより定量分析した。その分析結果における乳酸類の収率を後掲の表２に示す。
(Comparative Example 13)
The reaction was carried out in the same manner as in Example 13 except that 35 mg (0.1 mmol) of tin (IV) chloride pentahydrate was used as a catalyst and no promoter was used, and various products were quantified by liquid chromatography. analyzed. The yield of lactic acids in the analysis results is shown in Table 2 below.
（結果）
表２に示されるように、スズ／有機スズの塩化物を四級アンモニウム塩と共に使用した場合（実施例１３−１７）、四級アンモニウム塩を使用しなかった場合（比較例３）と比べて、乳酸類を高い収率で得ることができた。また、有機スズの塩化物を用いた場合（実施例１５）、スズの塩化物を用いた場合と比べて（実施例１３）、より高い収率が得られた。
(result)
As shown in Table 2, when tin / organotin chloride was used with a quaternary ammonium salt (Examples 13-17), compared to when no quaternary ammonium salt was used (Comparative Example 3). Lactic acids could be obtained in high yield. In addition, a higher yield was obtained when organotin chloride was used (Example 15) than when tin chloride was used (Example 13).
本発明の方法を用いれば、炭水化物含有原料、例えばセルロース、単糖、オリゴ糖資源を含むバイオマスを利用した、乳酸類の効率的な製造が可能となる。この方法によれば大量の強酸を用いることなく、副生成物の生成を抑制しつつ、乳酸類、とりわけ乳酸エステルを高収率で製造することができる。 By using the method of the present invention, it becomes possible to efficiently produce lactic acids using a biomass containing a carbohydrate-containing raw material, such as cellulose, monosaccharide, and oligosaccharide resources. According to this method, it is possible to produce lactic acids, particularly lactic acid esters, in high yield while suppressing the production of by-products without using a large amount of strong acid.
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| PCT/JP2011/058294 WO2011125882A1 (en) | 2010-03-31 | 2011-03-31 | Method for producing lactic acids from starting materials containing carbohydrates |
| MYPI2012004340A MY157001A (en) | 2010-03-31 | 2011-03-31 | Method for producing lactic acids from carbohydrate -containing raw material |
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