JPS58116689A - Ester-exchange of oil and fat using lipase - Google Patents
Ester-exchange of oil and fat using lipaseInfo
- Publication number
- JPS58116689A JPS58116689A JP56210264A JP21026481A JPS58116689A JP S58116689 A JPS58116689 A JP S58116689A JP 56210264 A JP56210264 A JP 56210264A JP 21026481 A JP21026481 A JP 21026481A JP S58116689 A JPS58116689 A JP S58116689A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- lipase
- water
- amount
- oils
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 102000004882 Lipase Human genes 0.000 title claims abstract description 54
- 108090001060 Lipase Proteins 0.000 title claims abstract description 54
- 239000004367 Lipase Substances 0.000 title claims abstract description 48
- 235000019421 lipase Nutrition 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 28
- 238000005809 transesterification reaction Methods 0.000 claims description 19
- 239000003925 fat Substances 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 17
- 239000002250 absorbent Substances 0.000 claims description 12
- 235000014593 oils and fats Nutrition 0.000 claims description 12
- 230000002745 absorbent Effects 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 34
- 229940040461 lipase Drugs 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 25
- 239000002253 acid Substances 0.000 description 16
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 235000019197 fats Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- -1 alcohol ester Chemical class 0.000 description 13
- 102000004190 Enzymes Human genes 0.000 description 12
- 108090000790 Enzymes Proteins 0.000 description 12
- 229940088598 enzyme Drugs 0.000 description 12
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 11
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 9
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 9
- 229940117972 triolein Drugs 0.000 description 9
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- 235000000346 sugar Nutrition 0.000 description 7
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- 239000008101 lactose Substances 0.000 description 6
- 235000021314 Palmitic acid Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 5
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- NPERTKSDHFSDLC-UHFFFAOYSA-N ethenol;prop-2-enoic acid Chemical compound OC=C.OC(=O)C=C NPERTKSDHFSDLC-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
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- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 3
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
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- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 3
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- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 235000019626 lipase activity Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000004006 olive oil Substances 0.000 description 3
- 235000008390 olive oil Nutrition 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- JFISYPWOVQNHLS-LBXGSASVSA-N 1,2-dioleoyl-3-palmitoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(COC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC JFISYPWOVQNHLS-LBXGSASVSA-N 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose 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)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002527 Glycogen Polymers 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
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- 240000005384 Rhizopus oryzae Species 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- DLRVVLDZNNYCBX-ZZFZYMBESA-N beta-melibiose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)O1 DLRVVLDZNNYCBX-ZZFZYMBESA-N 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 235000001046 cacaotero Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 229940067592 ethyl palmitate Drugs 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- MNQZXJOMYWMBOU-UHFFFAOYSA-N glyceraldehyde Chemical compound OCC(O)C=O MNQZXJOMYWMBOU-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 description 1
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- AIHDCSAXVMAMJH-GFBKWZILSA-N levan Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(CO[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 AIHDCSAXVMAMJH-GFBKWZILSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 229940116369 pancreatic lipase Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 229940057910 shea butter Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- UQZIYBXSHAGNOE-XNSRJBNMSA-N stachyose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO[C@@H]3[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O3)O)O2)O)O1 UQZIYBXSHAGNOE-XNSRJBNMSA-N 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、油脂類のリパーゼによるエステル基交換反応
方法、詳しくは、リパーゼ、水および高吸水性樹脂の存
在下に反応を行なうことを特徴とする油脂類のリパーゼ
によるエステル基交換反応方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for transesterification of fats and oils using lipase, specifically, a method for transesterification of fats and oils using lipase, which is characterized in that the reaction is carried out in the presence of lipase, water and a super absorbent resin. This invention relates to a transesterification reaction method.
酵素を触媒とする反応系の場合、系内に存在する酵素の
活性を充分に発揮させるために、多量の水の存在下で反
応を行なうことが一般的である。ところが、油脂類のリ
パーゼによるエステル基交換反応の場合、水の比較的多
い反応系では、望ましくない副反応である加水分解が助
長され、望ましい反応組成物を得ることが非常に困難で
あった。このような理由により、従来公知のリパーゼに
よる油脂類のエステル基交換反応は、極度に水分を低下
させた反応系で行なわれている。たとえは、特開昭55
−71797号公報(不二製油)には、反応系に存在す
る水分が基質に対して0.188重量以下の方法が記載
されている。また、特開昭52−104506号公報(
ユニリーバ−、ナームローセ、ペンノートシャープ)に
は、少量の水の存在下、あるいは基質に対して0.2〜
1重lチの水の存在下で行なう方法が記載されている。In the case of a reaction system using an enzyme as a catalyst, the reaction is generally carried out in the presence of a large amount of water in order to fully demonstrate the activity of the enzyme present in the system. However, in the case of the transesterification reaction of fats and oils using lipase, in a reaction system containing a relatively large amount of water, hydrolysis, which is an undesirable side reaction, is promoted, making it extremely difficult to obtain a desired reaction composition. For these reasons, the transesterification reaction of oils and fats using conventionally known lipases is carried out in a reaction system in which the water content is extremely reduced. The analogy is JP-A-55
Publication No. 71797 (Fuji Oil Co., Ltd.) describes a method in which the amount of water present in the reaction system is 0.188 weight or less relative to the substrate. In addition, Japanese Patent Application Laid-Open No. 52-104506 (
(Unilever, Nahmrose, Pen Note Sharp) in the presence of a small amount of water or 0.2~
A method is described which is carried out in the presence of 1 part water.
しかし、なから、公知の方法のように極度に水分の少な
い反応系では、酵素は死んだ状態あるいは睡眠状態にあ
り、生きた状態では存在しえなく、シたがって、酵素リ
パーゼが充分に活性化されず、充分な反応速度を得るこ
とができないかあるいは全く反応が進まない。またさら
に、極度に水分の少ない反応系で、充分な反応速度を得
るべく酵素使用量を増加させても、さらに反応速度を増
加することができないばかりか、添加された酵素の不活
性化が犬となり工業的にはなりたたない。However, in a reaction system with extremely low water content, as in the known method, the enzyme is in a dead or sleeping state and cannot exist in a living state. Therefore, the enzyme lipase is not sufficiently active. , and the reaction cannot reach a sufficient reaction rate or the reaction does not proceed at all. Furthermore, even if the amount of enzyme used is increased to obtain a sufficient reaction rate in a reaction system with extremely low water content, not only will the reaction rate not be increased further, but the added enzyme will be inactivated. Therefore, it is not suitable for industrial use.
リパーゼを用いる油脂類のエステル基交換反応の工業的
利用のためには、これらの難点を技術的に解決する必要
がある。In order to industrially utilize the transesterification reaction of fats and oils using lipase, it is necessary to technically solve these difficulties.
本発明の目的は、リパーゼによる油脂類のエステル基交
換反応の工業的利用を達成すべく、望ましくない副反応
である加水分解を併発させることなく、反応系内のリパ
ーゼを充分活性化し、工業化可能な程度にまで反応速度
を高めることにある。さらに、系内におけるリパーゼの
の不活性化を防止し、リパーゼの効果的な再使用を可能
にし、該工程の経済性を高めることにある。The purpose of the present invention is to fully activate the lipase in the reaction system without causing hydrolysis, which is an undesirable side reaction, in order to achieve industrial utilization of the transesterification reaction of oils and fats using lipase, thereby making it possible to industrialize the reaction. The goal is to increase the reaction rate to a certain degree. Furthermore, the present invention aims to prevent inactivation of lipase within the system, enable effective reuse of lipase, and improve the economic efficiency of the process.
本発明者らは、リパーゼによる油脂類のエステル基交換
反応において、リパーゼ活性を有効に発揮させる該酵素
反応条件を種々検討した結果、リパーゼ、水および高吸
水性樹脂の存在下に反応を行なうことにより、副反応の
程度を抑え、かつ速かに反応を進行させうることを見い
出し、さらに、系内におけるリパーゼの不活性化を防止
し、リパーゼの効果的な再使用を可能にし本発明の目的
を達成することができた。The present inventors investigated various enzyme reaction conditions for effectively exerting lipase activity in the transesterification reaction of oils and fats by lipase, and as a result, the present inventors found that the reaction was carried out in the presence of lipase, water, and a super absorbent resin. It has been found that the degree of side reactions can be suppressed and the reaction can proceed rapidly, and furthermore, the inactivation of lipase in the system can be prevented and the lipase can be effectively reused.Objectives of the present invention was able to achieve this.
本発明は、リパーゼ、水および高吸水性粒1脂の存在下
に反応を行なうことを特徴とするリパーゼによる油脂類
のエステル基交換反応方法である。好ましくはさらに糖
類が添加された、リパーゼ、水および高吸水性樹脂″の
存在下に反応を行うリパーゼによる油脂類のエステル基
交換反応方法である。望ましい反応系中の水分量は、基
質に対して3〜30重fJ’ % 、より望ましくは1
0〜15重量%である。また、望ましい高吸水性樹脂の
iIkは、系中の水分11(単位f)に対して0.00
5〜s t/l、よシ望ましくは0.02〜1?/lで
ある。さらに、望まI−い糖類の量は、系中の水分量(
単位量)に対して0.005〜2 t / t、より望
まし7〈は0.02〜1f/lである。壕だ該反応原条
件に加え、望ましいリパーゼ酵素量(活性単位U)に、
基質(単位量)に対し、て20〜500 U/f、
よシ望まし、くけ50〜20 oU/fである。また、
より有効な本発明の特徴は、該諸条件に加え反応系内の
基質に対し、て0.05〜5.0重量−の界面活性剤の
存在下で反応を行なうことである。The present invention is a method for transesterifying fats and oils using lipase, which is characterized in that the reaction is carried out in the presence of lipase, water, and highly water-absorbing granules. Preferably, this is a method for transesterification of oils and fats using lipase, in which the reaction is carried out in the presence of lipase, water, and a super absorbent resin to which sugars have been added.The desired amount of water in the reaction system is 3 to 30 fJ'%, more preferably 1
It is 0 to 15% by weight. In addition, iIk of a desirable superabsorbent resin is 0.00 relative to water 11 (unit: f) in the system.
5~s t/l, preferably 0.02~1? /l. Furthermore, the amount of desired sugars is determined by the amount of water in the system (
unit amount) is 0.005 to 2 t/t, more preferably 7< is 0.02 to 1 f/l. In addition to the reaction conditions, the desired amount of lipase enzyme (activity unit U),
20-500 U/f for the substrate (unit amount),
The preferred range is 50 to 20 oU/f. Also,
A more effective feature of the present invention is that, in addition to the above conditions, the reaction is carried out in the presence of a surfactant in an amount of 0.05 to 5.0% by weight relative to the substrate in the reaction system.
なお、上記基質とは油脂又は油脂及び脂肪酸をいい、グ
リセリン、モノグリセリド、ジグリセリドあるいは、脂
肪酸のアルコールエステル等が系中に存在する場合には
これらの物質も含まれる。The above-mentioned substrate refers to fats and oils or fats and oils and fatty acids, and includes glycerin, monoglyceride, diglyceride, alcohol ester of fatty acid, etc. when these substances are present in the system.
本発明で用いられるリパーゼとし7てハ、リゾプス系、
アスイルギルス系、カンデイダ系、ムコール系、すい臓
リパーゼ等が使用でき、これらのIJ ハーゼの多くは
市販品として入手できる。Lipases used in the present invention include 7) Rhizopus type lipases,
Asyrugillus type, Candida type, Mucor type, pancreatic lipase, etc. can be used, and many of these IJ hases are available as commercial products.
またグリセリドの1.3位の脂肪酸基を特異的にエステ
ル交換を行なう場合には、該目的に合致し、た特性を有
するリパーゼ、例えばリゾプステレマー、リソフスヤボ
ニカス、ムコールヤボニカス等を用いればよい。In addition, when specifically transesterifying the fatty acid group at the 1.3-position of glyceride, a lipase that meets the purpose and has the desired characteristics, such as Rhizopstolemer, Lisophusiabonicas, Mucorjavonicas, etc., may be used. Bye.
本発明に用いられる上記油脂としては一般の植物性、動
物性の油脂もしくは加工油脂あるいは、これらの混合油
脂があけられ、例えば、大豆油、綿実油、ナタネ油、オ
リーブ油、コーン油、ヤシ油、ザフラワー油、牛脂、ラ
ード、魚油等である。さらrカカオバター代用脂の原料
となる特定組成のグリセリド、すなわち、1,3−ジス
テアロー2−オレオクリセリド、1−パルミト−2オレ
オ−3−ステアログリセリド、1.5−ジバルミトー2
−オレオグリセリドをエステル交換反応の目的物とする
場合には、グリセリドの2位にオレイン酸を多n:Ic
含有する油脂、例えばオリーブ油、椿油、山茶花油、パ
ーム油、サル脂、イリツベ脂、コクム脂、シア脂、マウ
ア脂、フルワラ脂、ポルネオタロー脂又はこれらの分別
油脂を使用するととができる。The above-mentioned oils and fats used in the present invention include general vegetable oils, animal oils, processed oils and fats, or mixtures thereof, such as soybean oil, cottonseed oil, rapeseed oil, olive oil, corn oil, coconut oil, and coconut oil. These include flower oil, beef tallow, lard, and fish oil. Furthermore, glycerides with a specific composition are used as raw materials for cocoa butter substitutes, namely, 1,3-distearo-2-oleocryceride, 1-palmito-2-oleo-3-stearoglyceride, and 1,5-divalmito-2.
- When using oleoglyceride as the target product of the transesterification reaction, oleic acid is added to the 2-position of the glyceride in a polyn:Ic
It can be obtained by using oils and fats contained therein, such as olive oil, camellia oil, sasanqua oil, palm oil, monkey fat, iris fat, kokum butter, shea butter, maua butter, furwara butter, porneotallow fat, or fractionated oils and fats thereof.
また、脂肪酸としては、炭素数2〜22の直鎖の飽和又
は不飽和の脂肪酸が利用できる。例えば、パルミチン酸
、ステアリン酸、オレイン酸等を利用することができる
〜
また、脂肪酸のアルコールエステルとしては上記脂肪酸
と炭素数1〜6のiM鎖飽和−価アルコールのエステル
化物があり、例えば、パルミチン酸メチル、パルミチン
酸エチル、ステアリン酸メチル、ステアリン酸エチルe
6けることができる。Further, as the fatty acid, a linear saturated or unsaturated fatty acid having 2 to 22 carbon atoms can be used. For example, palmitic acid, stearic acid, oleic acid, etc. can be used. Also, as alcohol esters of fatty acids, there are esterification products of the above fatty acids and iM chain saturated alcohols having 1 to 6 carbon atoms, such as palmitic acid. Methyl acid, ethyl palmitate, methyl stearate, ethyl stearate e
I can put 6.
本発明で用いる高吸水性樹脂とは、水、あるいは緩衝液
あるいは糖水溶液を自重の数十〜数千倍程度吸収、吸着
する能力をもち、かつ圧力をかけても離水しすらいもの
である。The superabsorbent resin used in the present invention has the ability to absorb and adsorb water, a buffer solution, or an aqueous sugar solution to the extent of tens to thousands of times its own weight, and is capable of releasing water even when pressure is applied.
本発明で用いる高吸水性樹脂としては、吸水性ポリウレ
タン樹脂、ポリヒドロギシエチルメタクリレート、ポリ
アクリル酸系和1脂、澱粉−アクリル酸グラフト重合物
(澱粉にアクリル酸をグラフト重合させ、中和し、少量
の架橋剤で架橋したもの)、澱粉−アクリルニトリルグ
ラフト重合物(第二セリウム塩や放射線により澱粉にア
クリルニトリルをグラフト重合させ、加水分解し、精製
、乾燥したもの)、澱粉をモノクロル酢酸でカルボキシ
メチル化し、ホルマリンで架橋したもの、あるいはセル
ロース−アクリルニトリルグラフト重合物、セルロース
をモノクロル酢酸でカルボキシメチル化し、ホルマリン
で架橋したもの、あるいは、ビニルアルコールとアクリ
ル酸共重合物あるいは酢酸ビニルとメタクリル酸メチル
の共重合物を加水分解して自己架橋させたもの、ジアル
デヒドあるいは放射線によ多分子間架橋したポリビニル
アルコール、架橋ポリエチレンオキサイド等々が挙げら
れる。これらの高吸水性樹脂は単独に用いてもよいし、
二種以上併用してもよい。これらの高吸水性樹脂のなか
で澱粉−アクリル酸クラフト重合物およびビニルアルコ
ールとアクリル酸共重合物あるいは酢酸ビニルとメタク
リル酸メチルの共重合物を加水分解して自己架橋させた
ものが好擾しく使用しつる。前者としては、三洋化成工
業株式会社製商品名、サンウェット■M−300、後者
としては、住友化学工業株式会社製、商品名スミカゲル
5−50が市販品として入手できる。The super-absorbent resin used in the present invention includes water-absorbing polyurethane resin, polyhydroxyethyl methacrylate, polyacrylic acid-based Wa 1 fat, starch-acrylic acid graft polymer (starch is graft-polymerized with acrylic acid and neutralized). , cross-linked with a small amount of cross-linking agent), starch-acrylonitrile graft polymer (product in which acrylonitrile is graft-polymerized onto starch using ceric salt or radiation, hydrolyzed, purified, and dried), starch with monochloroacetic acid or cellulose-acrylonitrile graft polymer, cellulose carboxymethylated with monochloroacetic acid and cross-linked with formalin, or vinyl alcohol and acrylic acid copolymer, or vinyl acetate and methacrylate. Examples include those obtained by hydrolyzing and self-crosslinking a copolymer of acid methyl, polyvinyl alcohol intermolecularly crosslinked with dialdehyde or radiation, and crosslinked polyethylene oxide. These super absorbent resins may be used alone or
Two or more types may be used in combination. Among these superabsorbent resins, self-crosslinked ones obtained by hydrolyzing starch-acrylic acid kraft polymers, vinyl alcohol and acrylic acid copolymers, or vinyl acetate and methyl methacrylate copolymers are preferred. Use vine. The former is commercially available under the trade name Sanwet ■M-300 manufactured by Sanyo Chemical Industries, Ltd., and the latter is available as a commercial product under the trade name Sumikagel 5-50 manufactured by Sumitomo Chemical Industries, Ltd.
本発明で高吸水性樹脂と併用(2うる糖類としては、単
糖類、少糖類および多糖類を挙げることができる。In the present invention, the saccharides used in combination with the superabsorbent resin include monosaccharides, oligosaccharides, and polysaccharides.
単糖類としては、グリセロース、トレオロース、エリト
ロース、リボース、キシロース、アラビノース、リキソ
ース、グルコース、マンノース、アロース、アルドロー
ス、キュロース、インドース、ガラクトース、タロース
、ジオキシアセトン、ケトトレオース、エリスロケトペ
ントース、フラクトース、タガトース、プシコース、ソ
ルボース、ビシコース等が絡げラレるが、このなかで特
に、アラビノース、リボース、ガラクトース、グルコー
スが有効であった。少糖類トしては、マルトース、セロ
ビオース、トレハロース、ケンチオビオース、イソマル
トース、ラクトース、シュークロース、メリビオース、
ラフィノース、ケンチアノース、スタキオース等が挙け
られるが、このなかで特に、トレハロース、ラフィノー
ス、ラクトース、シュークロースが有効であった。多糖
類としては、キシラン、アラパン、デンプン、デキスト
リン、セルロース、グリコーゲン、テキストラン、イヌ
リン、レバン、ガラクタン、サイクロデキストリンが挙
けられるが、このなかで特に、テキストリン、セルロー
ス、グリコーゲン、テキストラン、サイクロテキストリ
ンが有効であった。Monosaccharides include glycerose, threolose, erythrose, ribose, xylose, arabinose, lyxose, glucose, mannose, allose, aldulose, culose, indose, galactose, talose, dioxyacetone, ketothreose, erythroketopentose, fructose, tagatose, psicose. Among them, arabinose, ribose, galactose, and glucose were particularly effective. Examples of oligosaccharides include maltose, cellobiose, trehalose, kenthiobiose, isomaltose, lactose, sucrose, melibiose,
Examples include raffinose, kenthianose, and stachyose, among which trehalose, raffinose, lactose, and sucrose were particularly effective. Examples of polysaccharides include xylan, arapan, starch, dextrin, cellulose, glycogen, textolan, inulin, levan, galactan, and cyclodextrin. Text link was effective.
これらの糖類は単独に用いてもよいし、二種以上併用し
てもよい。These saccharides may be used alone or in combination of two or more.
本発明において、系中に高吸水性(61脂を存在せしめ
るには抽々の方法がとられるが好ましい方法としては、
先ずリパーゼと水を充分接触させておき、そのなかに尚
吸水性樹脂を添加し、よく混合して充分接触させること
により調製する方法、または、リパーゼと水および糖類
な充分接触させておき、そのなかに高吸水性樹脂を添加
し、よく混合して充分接触させることにより調製する方
法である。In the present invention, in order to make the highly water-absorbent (61 fat) exist in the system, a drastic method is taken, but as a preferable method,
First, lipase and water are brought into sufficient contact with each other, then a water-absorbing resin is added thereto, and the water-absorbent resin is added thereto, mixed well and brought into contact. This is a method of preparation by adding a super absorbent resin to the mixture, mixing well, and bringing them into sufficient contact.
このように調製されたリパーゼと高吸水性樹脂と水もし
くは、これと糖類を含む組成物は、基質溶液に分散添加
し、て反応を行なうことができる。さらに、該組成物を
カラムに充填し、該カラムに基質溶液を通過させること
により連続的な流通反応を行なうことができる。The composition containing the lipase, the superabsorbent resin, and water, or the lipase and the saccharide prepared in this manner can be dispersed and added to a substrate solution to carry out the reaction. Furthermore, a continuous flow reaction can be performed by filling a column with the composition and passing a substrate solution through the column.
該組成物の一部として反応系に添加される水の望ましい
添加′に1′は、基質に対して3〜30重量%である。The preferred amount of water added to the reaction system as part of the composition is 3 to 30% by weight, based on the substrate.
基質に対する水分量が3重量%未満では、充分な反応速
度を得ることができす、また基質に対して30重量%以
上の水分量では、さらに水分を増加しても、より速かな
反応速度を得ることができない。まだ、該反応系のより
望ましい水分量は、基質に対して10〜15重1m%で
ある。該組成物の一部である高吸水性樹脂の望ましい世
は、水分量(部位置)に対して、11−
0、005〜sr/rである。o、oosr/r未満で
は加水分解反応を抑えることが困難となシ、また5f/
を以上では反応速度がおそくなる。より望ましい高吸水
性樹脂の量は、0.02〜1t/Vである。まだ該組成
物の一部である糖類の望ましい量は、水分量(単位量)
に対して、0.005〜2f/f1より望ましく n
o、 05〜1 y/Vである。糖類の添加は、反応速
度をよシ速かにする効果がある。When the water content is less than 3% by weight relative to the substrate, a sufficient reaction rate can be obtained, and when the water content is 30% by weight or more relative to the substrate, even if the water content is further increased, a faster reaction rate can be obtained. can't get it. However, a more desirable water content of the reaction system is 10 to 15 1 m% by weight based on the substrate. The desirable value of the superabsorbent resin which is a part of the composition is 11-0.005 to sr/r based on the water content (part position). o, less than oosr/r, it is difficult to suppress the hydrolysis reaction;
Above , the reaction speed becomes slow. A more desirable amount of super absorbent resin is 0.02 to 1 t/V. The desired amount of sugar that is still part of the composition is the amount of water (unit amount)
For n
o, 05-1 y/V. Addition of sugar has the effect of increasing the reaction rate.
該組成物の一部として反応系に添加されるリパーゼ酵素
量(活性単位U)は、基質(単位量)に対して2O−s
oou/rである。20U/V未満では充分な反応速度
を得ることが困難であり、まだ5oou/r以上では、
さらに酵素量を増加させても反応速度の増加が少なく不
経済となる。さらに、より望ましい酵素の添加量は、基
質(単位量)に対して50〜200 U/7である。た
だし、酵素の活性単位Uは、オリーブ油乳化液5−と0
.1 M IJン酸塩緩衝液4−に酵素を加え、37℃
で30分間反応したときに、12−
0.05N水酸化す) l)ラム水溶液0.061R1
に和尚する脂肪酸を生成する毎に1活性率位(U)とし
た。The amount of lipase enzyme (activity unit U) added to the reaction system as part of the composition is 2O-s relative to the substrate (unit amount).
oou/r. If it is less than 20 U/V, it is difficult to obtain a sufficient reaction rate, and if it is still more than 5 oou/r,
Furthermore, even if the amount of enzyme is increased, the reaction rate will not increase much and it will be uneconomical. Furthermore, a more desirable amount of enzyme to be added is 50 to 200 U/7 relative to the substrate (unit amount). However, the activity unit U of the enzyme is olive oil emulsion 5- and 0
.. Add enzyme to 1M IJ phosphate buffer 4- and incubate at 37°C.
12-0.05N hydroxide) l) Rum aqueous solution 0.061R1
Each time a fatty acid was produced, it was defined as 1 activity rate (U).
また、基質に対して0.05〜5.0チの界面活性剤の
存在により反応速度を速かにすることができる。界面活
性剤とし、ては、ショ糖脂肪酸エステル、ソルビタン脂
肪酸エステル、プロピレングリコール脂肪酸エステル、
ポリグリセリン脂肪酸エステル、レシチン、モノグリセ
リドよりなる群から選ばれる単独あるいは二種以上が有
効に使用し得る。特にHLB1〜8程度のショ糖脂肪酸
エステルが効果的であることを見い出した。In addition, the reaction rate can be increased by the presence of 0.05 to 5.0 h of surfactant relative to the substrate. Examples of surfactants include sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester,
One or more selected from the group consisting of polyglycerol fatty acid ester, lecithin, and monoglyceride can be effectively used. It has been found that sucrose fatty acid esters having an HLB of about 1 to 8 are particularly effective.
エステル交換反応は反応温度20〜50℃で行なわれる
のがよく、反応時間は系によって異なるが8〜30時間
程度で目的の組成物を得ることができる。The transesterification reaction is preferably carried out at a reaction temperature of 20 to 50°C, and the desired composition can be obtained in about 8 to 30 hours, although the reaction time varies depending on the system.
反応基質の中で、例えば高融点の油脂と脂肪酸の混合物
等を用いた場合、反応温度で不均一な系とな、ることか
あるが、そのような場合にはリパーゼに対して不活性な
有機溶剤に反応基質を溶解し均一系として反応を行なう
ことができる。この種の有機溶剤としては、n−ヘキサ
ン、工業用へキサン、石油エーテルなどがあり、基質に
対して0.1〜5倍量(重量)で用いることができる。For example, when using a mixture of oils and fats with high melting points and fatty acids as reaction substrates, the reaction temperature may result in a non-uniform system. The reaction can be carried out in a homogeneous system by dissolving the reaction substrate in an organic solvent. Examples of this type of organic solvent include n-hexane, industrial hexane, and petroleum ether, which can be used in an amount of 0.1 to 5 times the amount (by weight) of the substrate.
エステル交換反応の終了後、有機溶剤を使用した場合は
蒸留により有機溶剤の除去を行ない反応油を得る。反応
油中の脂肪酸、モノグリセリド、ジグリセリドまた添加
された界面活性剤等は、通常のアルカリ中和等の化学的
精製方法、水蒸気蒸留、真空蒸留およびクロマトグラフ
ィー等の物理的精製方法によシ除去することができる。After completion of the transesterification reaction, if an organic solvent is used, the organic solvent is removed by distillation to obtain a reaction oil. Fatty acids, monoglycerides, diglycerides, and added surfactants in the reaction oil are removed by conventional chemical purification methods such as alkali neutralization, and physical purification methods such as steam distillation, vacuum distillation, and chromatography. be able to.
本発明の効果は、系内に多量の水が存在するためリパー
ゼ酵素のエステル交換活性が促進され、一方では多量の
水の存在にもかかわらず望ましくない副反応であるエス
テルの加水分解反応を抑制できるために従来公知の方法
に比較して約10〜20倍程度の反応速度を得ることの
できる極めて効率的で、生産性の高い油脂類のエステル
交換方法を提供したことにある。The effect of the present invention is that the presence of a large amount of water in the system promotes the transesterification activity of the lipase enzyme, while suppressing the ester hydrolysis reaction, which is an undesirable side reaction, despite the presence of a large amount of water. The object of the present invention is to provide an extremely efficient and highly productive method for transesterifying fats and oils, which is capable of achieving a reaction rate approximately 10 to 20 times faster than conventionally known methods.
また本発明の他の効果は、反応における酵素の失活が少
なくかつ反応時間も短かいエステル交換反応方法が採ら
れることによって、反応後回収されたリパーゼ酵素の効
果的な再使用を可能VCし、工程の経済性を向上させた
ことである。Another advantage of the present invention is that by employing a transesterification method that causes less deactivation of the enzyme in the reaction and a shorter reaction time, it is possible to effectively reuse the lipase enzyme recovered after the reaction. , which improved the economic efficiency of the process.
本発明による油脂類のエステル基交換反応方法によれば
、位置選択的リパーゼを用いることにより廉価原料から
効率的にカカオバター代用脂を製造することができる。According to the transesterification method for fats and oils according to the present invention, a cocoa butter substitute can be efficiently produced from inexpensive raw materials by using a regioselective lipase.
さらに特定条件下ではカカオ脂に類似のトリグリセリド
組成物を得ることができ工業的に非常に有用な方法とな
る。Furthermore, under specific conditions, a triglyceride composition similar to cacao butter can be obtained, making this a very useful method industrially.
次に実施例により本発明をさらに具体的に説明するが本
発明はこれらの実施例に限定されるものではない。Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例1
リゾプスデレマ(Rh1zopua delemar
)リパーゼ(1り自りのリパーゼ活性3500U) 0
.57f15−
とイオン交換水1.2fを混合し、充分接触させた後ス
ミカゲル5−50 (住友化学工業株式会社製の高吸水
性樹脂)0.24fを添加混合し、密閉し、数時間冷暗
所に放置した後再びよく混合した。次に、トリオレイン
52、バルミチン酸5tおよびn−ヘキサン10fから
なる基質混合溶液を4つ目フラスコに仕込み、58℃の
湯浴に保持し、先に調製した、リパーゼ、水および高吸
水性樹脂からなる組成物をこの基質混合溶液によく分散
添加し、反応系をストッパーにより密閉し、反応温度3
8℃攪拌速度200rpmで反応を行なった。少量の反
応混合物を経時的に分取し、アセトンに溶解し、上澄液
部分を昇温ガスクロマトグラフィーにかけ、炭素数別の
トリグリセリド組成を測定した。また、反応停止後、反
応混合物をr過し、さらに溶剤を留去して油分を回収し
、酸価の測定を行ない、次表に示す結果を得た。Example 1 Rhizopus delemar
) Lipase (one-of-a-kind lipase activity 3500U) 0
.. 57f15- and 1.2f of ion-exchanged water, and after sufficient contact, 0.24f of Sumikagel 5-50 (super absorbent resin manufactured by Sumitomo Chemical Co., Ltd.) was added and mixed, sealed, and left in a cool, dark place for several hours. After being left to stand, the mixture was thoroughly mixed again. Next, a substrate mixed solution consisting of 52 triolein, 5 t of valmitic acid, and 10 f of n-hexane was charged into a fourth flask and kept in a water bath at 58°C. A composition consisting of was added to this substrate mixture solution in a well-dispersed manner, the reaction system was sealed with a stopper, and the reaction temperature was increased to 3.
The reaction was carried out at 8° C. and a stirring speed of 200 rpm. A small amount of the reaction mixture was separated over time, dissolved in acetone, and the supernatant portion was subjected to temperature-rising gas chromatography to measure the triglyceride composition by carbon number. Further, after the reaction was stopped, the reaction mixture was filtered, and the solvent was distilled off to recover the oil content, and the acid value was measured, and the results shown in the following table were obtained.
16−
この反応系の場合、C5oは、2−オレオ−1゜3−シ
バルミチンであり、C52ハ、1−パルミト−2,3−
ジオレインおよび3−パルミト−1,2−ジオレインで
あり、C51Iは、トリオレインである。なお、トリオ
レインは、先ず、つばき油脂肪酸よシ尿素付加法で高純
度オレイン酸を分取し、メチルエステル化によりオレイ
ン酸メチルにし、次に、トリアセチンとオレイン酸メチ
ルを常法のエステル交換反応により調製した。パルミチ
ン酸は市販の試薬一級品を用いた。16- In this reaction system, C5o is 2-oleo-1°3-cibalmitin and C52ha,1-palmito-2,3-
diolein and 3-palmito-1,2-diolein, and C51I is triolein. Note that triolein is produced by first separating high-purity oleic acid using a camellia oil fatty acid and shiurea addition method, converting it into methyl oleate through methyl esterification, and then transesterifying triacetin and methyl oleate using a conventional method. Prepared by As palmitic acid, a commercially available first grade reagent was used.
実施例2
リゾプスデレマリパーゼ0.57f、イオン交換水1.
2fおよびラクトース0.56?を充分混合接触させた
後、サンウエツ)IM−300(三洋化成工業株式会社
製の高吸水性樹脂)0.122を添加混合し、密閉し、
数時間冷暗所に放置した後再びよく混合し、トリオレイ
ン5f1パルミチン酸5f、シュガーエステル(第−工
業製薬株式会社製、DKエステルF−10、HLBl
〜2)0.05fおよびn−ヘキサン10Fからなる基
質混合溶液に分散添加して、反応温度68℃、攪拌速度
200 rpmで反応を行なった。反応時間6時間後の
トリグリセリド組成は、C3o10.0%、C5242
,1%、C544乙9%で酸価が125.4であった。Example 2 Rhizopus derema lipase 0.57f, ion exchange water 1.
2f and lactose 0.56? After sufficiently mixing and contacting, add 0.122 of Sanwetsu IM-300 (super absorbent resin manufactured by Sanyo Chemical Industries, Ltd.), mix, and seal.
After leaving it in a cool dark place for several hours, mix well again and add triolein 5f1 palmitic acid 5f, sugar ester (Dai Kogyo Seiyaku Co., Ltd., DK Ester F-10, HLBL).
~2) It was dispersed and added to a substrate mixed solution consisting of 0.05F and n-hexane 10F, and the reaction was carried out at a reaction temperature of 68° C. and a stirring speed of 200 rpm. The triglyceride composition after 6 hours of reaction time was C3o 10.0%, C5242
, 1% and C544 Otsu 9%, and the acid value was 125.4.
実施例8
リゾプスデレマリパーゼ0.286f、イオン交換水2
.5f、 ラクトース0.25f、セルロース0.75
FおよびスミカゲルS−500,75j’からなる組成
物を、トリオレイン5t、バルミチン酸5fおよびn−
ヘキサン10fからなる基質混合溶液に分散添加し、反
応温度37℃、攪拌速度20 Orpmで反応を行なっ
た。反応時間10時間後のトリグリセリド組成は、C3
o8.0チ、C5242,6チ、C5+449.4%で
酸価は127゜8であった。Example 8 Rhizopus derema lipase 0.286f, ion exchange water 2
.. 5f, lactose 0.25f, cellulose 0.75
A composition consisting of F and Sumikagel S-500,75j' was mixed with triolein 5t, valmitic acid 5f and n-
It was dispersed and added to a substrate mixed solution consisting of 10f hexane, and the reaction was carried out at a reaction temperature of 37° C. and a stirring speed of 20 Orpm. The triglyceride composition after 10 hours of reaction time is C3
The acid value was 127.8% with o8.0%, C5242.6%, and C5+449.4%.
実施例4
リゾプスデレマリパーゼ0.57f、イオン交換水1.
16f、ラクトースO,(15f、β−サイクロデキス
トリン’1.OrおよびサノウエットIM−3000,
07f’からなる組成物をトリオレイン5f1パルミチ
ン酸5f、 シュガーエステル(第−工業製薬株式会社
製、DKエステルF−10、HLB 1〜2 ) 0.
02 fおよびn−ヘキサン10fからなる基質混合溶
液に分散添加し、反応温度40℃、攪拌速度200 r
pmで反応を行なった。反応時間6時間後のトリグリセ
リド組成は、C5010,3%、C5245,6チ、C
5444,0優で酸価は1241でおった。Example 4 Rhizopus derema lipase 0.57f, ion exchange water 1.
16f, lactose O, (15f, β-cyclodextrin'1.Or and Sanowet IM-3000,
A composition consisting of triolein 5f, palmitic acid 5f, sugar ester (manufactured by Dai-Kogyo Seiyaku Co., Ltd., DK Ester F-10, HLB 1-2) 0.
02 f and n-hexane 10 f, and the reaction temperature was 40°C and the stirring speed was 200 r.
The reaction was carried out at pm. The triglyceride composition after 6 hours of reaction time was C5010.3%, C5245.6%, C
The acid value was 1241 with a score of 5444.0.
上記組成物を濾過により回収し、同様の基質混合溶液に
分散添加し、反応温度40℃、攪拌速度20 Orpm
で反応を行なった。反応時間6時間後のトリグリセリド
組成は、C504,3%、C5234,0%、C546
1,7チであった。The above composition was collected by filtration, dispersed and added to the same substrate mixed solution, and the reaction temperature was 40° C. and the stirring speed was 20 Orpm.
The reaction was carried out. The triglyceride composition after 6 hours of reaction time was C504.3%, C5234.0%, C546.
It was 1.7chi.
実施例5
リゾプスヤポニカス(Rh1zopus japoni
cus )リパーゼ(1g当りのリパーゼ活性4200
U)0.1:M’および0.1Mリン酸塩緩衝液(pH
6,0)1.2fをよく混合して、トレハロース0.0
2FおよびスミカゲルS−501rを添加してさらによ
く混合して密閉し、−晩冷暗所に放置した後、再度よく
混合し、トリオレイン52、バルミチン酸5tおよびn
−ヘキサン10fからなる基質混合溶液に分散添加し、
反応温度40℃、攪拌速度20 Orpmで反応を行な
った。反応時間30時間後のトリグリセリド組成は、C
3o6゜9%、C523B、0%、C5455,1%で
酸価は129.4であった。Example 5 Rhizopus japoni
cus) lipase (lipase activity per 1g 4200
U) 0.1:M' and 0.1M phosphate buffer (pH
6,0) Mix well 1.2f and add trehalose 0.0
Add 2F and Sumikagel S-501r, mix well, seal, and leave in a cool dark place overnight, mix well again, and add triolein 52, valmitic acid 5t, and n
- Dispersed and added to a substrate mixed solution consisting of 10f hexane,
The reaction was carried out at a reaction temperature of 40° C. and a stirring speed of 20 Orpm. The triglyceride composition after 30 hours of reaction time was C
The acid value was 129.4 with 3o6°9%, C523B, 0%, and C5455, 1%.
実施例6
リゾプスヤポニカスリパーゼ0.24f、イオン交換水
0.54 f、ラクトース0.02Fをよく混合し、さ
らにグリコーゲン0.02fおよびザンウエットIM−
!l OOG、25 fを添加混合し、数時間放置後、
基質混合溶液(トリオレイン5?、バルミチン酸51お
よびn−ヘキサン10F)に分散添加し、反応温度39
℃、攪拌速度200 rpmで反応を行なった。反応時
間12時間後のトリグリセリド組成は、C507−8’
l’ 、C5242,2q6、C5450,1チで酸価
は120.5であった。Example 6 Rhizopus japonicus lipase 0.24f, ion exchange water 0.54f, and lactose 0.02F were mixed well, and further glycogen 0.02f and Zanwet IM-
! l OOG, 25 f was added and mixed, and after standing for several hours,
Dispersed and added to the substrate mixed solution (triolein 5?, valmitic acid 51 and n-hexane 10F), and the reaction temperature was 39°C.
The reaction was carried out at a stirring speed of 200 rpm. The triglyceride composition after 12 hours of reaction time was C507-8'
l', C5242,2q6, and C5450,1chi, and the acid value was 120.5.
比較例1
リゾプスヤボニカスリバーゼ0.24fとイオン交換水
0.542をよく混合均一化した後、トリオレイン5f
、バルミチン酸52およびn−ヘキサン10fからなる
基質混合溶液に添加し、反応温度39℃、攪拌速度20
0 rpmで反応を行なった、反応時間12時間後のト
リグリセリド組成は、C3Q1.0%、C52j5.1
%、C5+183.9%であり、酸価は161.0であ
った。本比較例1は、酵素量および水分量が実施例6と
同一であるが、本比較例1においては加水分解反応が優
先的に進行I7ていることがわかる。Comparative Example 1 After thoroughly mixing and homogenizing 0.24f of Rhizopus abonicas rebarase and 0.542f of ion-exchanged water, 5f of triolein was added.
, added to a substrate mixed solution consisting of 52 f of valmitic acid and 10 f of n-hexane at a reaction temperature of 39°C and a stirring speed of 20
The triglyceride composition after 12 hours of reaction time at 0 rpm was C3Q 1.0%, C52j 5.1
%, C5+183.9%, and the acid value was 161.0. Comparative Example 1 has the same amount of enzyme and water as Example 6, but it can be seen that in Comparative Example 1, the hydrolysis reaction progresses preferentially.
比較例2
脱水処理したトリオレイン5f、バルミチン酸5fおよ
びn−ヘキサン10fからなる基質混合溶液(カールフ
ィッシャー水分計による水分io、07重量%)に、リ
ゾプスデレマリパーゼ0.286f、セライト0.32
およびセルロースパウダー0.6f混合物を徐々に真空
乾燥した後分散添加し、反応温度40℃、攪拌速度20
0rpmで反応を行ない、次表に示す結果を得た。Comparative Example 2 Rhizopus derema lipase 0.286f and Celite 0.32 were added to a substrate mixed solution (moisture io determined by Karl Fischer moisture meter, 07% by weight) consisting of dehydrated triolein 5f, valmitic acid 5f, and n-hexane 10f.
A mixture of 0.6f of cellulose powder and 0.6f of cellulose powder was gradually dried under vacuum and then dispersed and added at a reaction temperature of 40°C and a stirring speed of 20°C.
The reaction was carried out at 0 rpm and the results shown in the following table were obtained.
この反応系の基質当りの水分量ハ、約0.14重1′チ
程度であるが、このような微量の水分量では、大部分の
酵素が睡眠状態かあるいは死んだ状態であり、反応速度
が非常におそくなることが判明し、工業的条件とはなυ
得ないと判断される。The amount of water per substrate in this reaction system is about 0.14 x 1', but with such a small amount of water, most of the enzymes are in a sleeping or dead state, and the reaction rate is slow. was found to be very slow, and under industrial conditions υ
It is judged that it is not possible.
比較例8
脱水処理したトリオレイン51、バルミチン酸5f、お
よびn−ヘキサン102からなる基質混合溶液(カール
フィッシャー水分計による水分量0.07重量%)に、
リゾプスデレマリパーゼ0.286fおよびセライト0
.32およびセルロースパウダー0.3f混合物を徐々
に真空乾燥し、た後分散添加し、さらに、イオン交換水
0゜[15m1を添加し、反応温度40℃、攪拌速度2
00 rpmで反応を行ない、次表に示す結果を得た。Comparative Example 8 To a substrate mixed solution (moisture content 0.07% by weight as measured by Karl Fischer moisture meter) consisting of dehydrated triolein 51, valmitic acid 5f, and n-hexane 102,
Rhizopus derema lipase 0.286f and Celite 0
.. A mixture of No. 32 and 0.3 f of cellulose powder was gradually dried in vacuum, then dispersed and added, and 0° [15 ml of ion-exchanged water was added, the reaction temperature was 40° C., and the stirring speed was 2.
The reaction was carried out at 0.00 rpm and the results shown in the following table were obtained.
この反応系の基質当りの水分量は、約0.64重it%
程度であるが、このような微量の水分量では、反応速度
が非常におそくなり、工業的条件とはなり得ないと判断
される。The water content per substrate in this reaction system is approximately 0.64 wt%
However, with such a small amount of water, the reaction rate becomes extremely slow, and it is judged that this cannot be achieved under industrial conditions.
523523
Claims (7)
を行なうことを特徴とするリパーゼによる油脂類のエス
テル基交換反応方法。(1) A method for transesterification of oils and fats using lipase, characterized in that the reaction is carried out in the presence of lipase, water, and a superabsorbent resin.
)に対して0.005〜51/vで反応を行なうことを
特徴とする特許請求の範囲第(1)項記載のリパーゼに
よる油脂類のエステル基交換反応方法。(2) Claim (1), characterized in that the superabsorbent resin in the reaction system reacts at a rate of 0.005 to 51/v with respect to water @ (unit amount) in the system. A method for transesterification of oils and fats using lipase.
吸水性樹脂の存在下に反応を行なうことを特徴とする特
許請求の範囲第(1)又は第(2)項記載のリパーゼに
よる油脂類のエステル基交換反応方法。(3) Fats and oils produced by lipase according to claim (1) or (2), characterized in that the reaction is carried out in the presence of lipase, water, and a super absorbent resin to which saccharide is further added. Transesterification reaction method.
、て0.005〜2v/2で反応を行なうことを特徴と
する特許請求の範囲第(3)項記載のリパーゼによる油
脂類のエステル基交換反応方法。(4) The lipase according to claim (3), wherein the saccharide in the reaction system reacts at a rate of 0.005 to 2 v/2 relative to the amount of water (unit amount) in the system. A method for transesterification of oils and fats.
で反応を行なうことを特徴とする特許請求の範囲第(1
)〜(4)頂側れかに記載のリパーゼによる油脂類のエ
ステル基交換反応方法。(5) Claim (1) characterized in that the reaction is carried out with the amount of water in the reaction system being 3 to 30% by weight relative to the substrate.
) to (4) A method for transesterifying fats and oils using the lipase described above.
0〜5ooU/fで反応を行なうことを特徴とする特許
請求の範囲第白)〜(5)m個れかに記載のリパーゼに
よる油脂類のエステル基交換反応方法。(6) The amount of lipase enzyme (activity unit U) is 2 relative to the substrate.
A method for transesterifying fats and oils using a lipase according to any one of claims 1) to (5)m, characterized in that the reaction is carried out at 0 to 5 ooU/f.
係の界面活性剤をさらに添加して、反応を行なうことを
特徴とする特許請求の範囲第(1)〜(6)項何れかに
記載のリパーゼによるエステル基交換反応方法。(7) Claims (1) to (6) characterized in that the reaction is carried out by further adding 0.05 to 5.0 weight ratio of surfactant to E7 to the substrate in the reaction system. ) The method for ester group exchange reaction using lipase according to any one of the above items.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56210264A JPS58116689A (en) | 1981-12-28 | 1981-12-28 | Ester-exchange of oil and fat using lipase |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56210264A JPS58116689A (en) | 1981-12-28 | 1981-12-28 | Ester-exchange of oil and fat using lipase |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58116689A true JPS58116689A (en) | 1983-07-11 |
JPH0357759B2 JPH0357759B2 (en) | 1991-09-03 |
Family
ID=16586501
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56210264A Granted JPS58116689A (en) | 1981-12-28 | 1981-12-28 | Ester-exchange of oil and fat using lipase |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58116689A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61149084A (en) * | 1984-12-21 | 1986-07-07 | Kao Corp | Method of activating enzyme |
JPH01309689A (en) * | 1988-06-07 | 1989-12-14 | Kanegafuchi Chem Ind Co Ltd | Process for ester interchange of oil and fat using microbial cell |
US5520933A (en) * | 1991-11-12 | 1996-05-28 | Kyowa Hakko Kogyo Co., Ltd. | Method for the production of foods and beverages |
US7626047B2 (en) * | 2002-02-20 | 2009-12-01 | Revo International Inc. | Method of producing fatty acid alkyl ester for diesel fuel oil |
-
1981
- 1981-12-28 JP JP56210264A patent/JPS58116689A/en active Granted
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61149084A (en) * | 1984-12-21 | 1986-07-07 | Kao Corp | Method of activating enzyme |
JPH0327199B2 (en) * | 1984-12-21 | 1991-04-15 | Kao Corp | |
JPH01309689A (en) * | 1988-06-07 | 1989-12-14 | Kanegafuchi Chem Ind Co Ltd | Process for ester interchange of oil and fat using microbial cell |
US5520933A (en) * | 1991-11-12 | 1996-05-28 | Kyowa Hakko Kogyo Co., Ltd. | Method for the production of foods and beverages |
US7626047B2 (en) * | 2002-02-20 | 2009-12-01 | Revo International Inc. | Method of producing fatty acid alkyl ester for diesel fuel oil |
Also Published As
Publication number | Publication date |
---|---|
JPH0357759B2 (en) | 1991-09-03 |
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