JPH04247095A - Production of sucrose fatty acid ester - Google Patents
Production of sucrose fatty acid esterInfo
- Publication number
- JPH04247095A JPH04247095A JP3012289A JP1228991A JPH04247095A JP H04247095 A JPH04247095 A JP H04247095A JP 3012289 A JP3012289 A JP 3012289A JP 1228991 A JP1228991 A JP 1228991A JP H04247095 A JPH04247095 A JP H04247095A
- Authority
- JP
- Japan
- Prior art keywords
- sucrose
- fatty acid
- alcohol
- organic solvent
- reaction
- 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
- 229930006000 Sucrose Natural products 0.000 title claims abstract description 101
- 239000005720 sucrose Substances 0.000 title claims abstract description 101
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 36
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 36
- 239000000194 fatty acid Substances 0.000 title claims abstract description 36
- -1 sucrose fatty acid ester Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 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 claims abstract description 85
- 150000003839 salts Chemical class 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000011541 reaction mixture Substances 0.000 claims abstract description 20
- 239000012071 phase Substances 0.000 claims abstract description 19
- 239000008346 aqueous phase Substances 0.000 claims abstract description 17
- 239000007790 solid phase Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- 239000003957 anion exchange resin Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 4
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 239000012044 organic layer Substances 0.000 abstract 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 16
- 238000000622 liquid--liquid extraction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000000638 solvent extraction Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 239000004310 lactic acid Substances 0.000 description 8
- 235000014655 lactic acid Nutrition 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000005185 salting out Methods 0.000 description 4
- BYPIKLIXBPMDBY-UHFFFAOYSA-N 2-hydroxypropanoic acid;potassium Chemical compound [K].CC(O)C(O)=O BYPIKLIXBPMDBY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 1
- 239000001521 potassium lactate Substances 0.000 description 1
- 235000011085 potassium lactate Nutrition 0.000 description 1
- 229960001304 potassium lactate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ショ糖脂肪酸エステル
（以下、ＳＥと略記する。）の製造方法に係わる。さら
に詳しくは、本発明は溶媒法によって製造された反応混
合物から、ＳＥと未反応ショ糖、溶媒、無機塩および／
または有機酸塩（以下、これらを合わせて塩と略すこと
がある。）を効率よく分離する方法に係わるものである
。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing sucrose fatty acid ester (hereinafter abbreviated as SE). More specifically, the present invention combines SE, unreacted sucrose, solvent, inorganic salts and/or
Alternatively, it relates to a method for efficiently separating organic acid salts (hereinafter, these may be collectively abbreviated as salts).
【０００２】0002
【従来の技術】ＳＥは可食性の分散剤、乳化剤或は洗浄
剤等として有用な非イオン性界面活性剤である。従来そ
の製造方法としてＮ，Ｎ−ジメチルホルムアミド、ジメ
チルスルホキシド（以下、ＤＭＳＯと略記する。）等の
溶媒中で、アルカリ触媒の存在下、ショ糖と脂肪酸メチ
ルのような脂肪酸エステルとのエステル交換反応による
方法（特公昭３５−１３１０２）等が知られている。BACKGROUND OF THE INVENTION SE is a nonionic surfactant useful as an edible dispersant, emulsifier, detergent, etc. Conventionally, its production method involves a transesterification reaction between sucrose and a fatty acid ester such as fatty acid methyl in a solvent such as N,N-dimethylformamide or dimethyl sulfoxide (hereinafter abbreviated as DMSO) in the presence of an alkali catalyst. (Japanese Patent Publication No. 35-13102) and the like are known.
【０００３】上記方法によって得られた反応混合物は、
ＳＥの他に溶媒、未反応ショ糖およびアルカリ触媒など
を含有している。この混合物からＳＥを分離するには、
通常、反応混合物に酸を添加して触媒を中和失活させた
後、溶媒を部分的に蒸留し、次いでヘキサン、ブチルア
ルコール、メチルエチルケトン、メチルイソブチルケト
ンのような有機溶媒および水を用いて抽出処理し、主と
してＳＥを有機溶媒相中に、また主として未反応ショ糖
、反応溶媒および塩を水相中にそれぞれ移行させて分液
し、主としてＳＥを含有する有機溶媒相から有機溶媒を
蒸留除去しＳＥを回収する方法が提案されている。
（例えば特公昭４８−２１９２７、特公昭４８−３５０
４９、特開昭５０−２９４１７、特開昭５０−１３０７
１２）水相中に回収した未反応ショ糖および反応溶媒は
、水を蒸留除去した後、再びＳＥ製造原料として使用す
ることが工業的製造方法および経済的操業方法として重
要である。しかしながら有機溶媒および水を用いて行な
う抽出処理操作工程において、良好な分液性を得る為に
は有機酸塩等の塩析剤添加が必要であるので（特開昭５
０−１３０７１２）、結果として水相中に回収したショ
糖には塩の蓄積がある。水を蒸留除去して回収ショ糖を
そのまま再びＳＥ製造原料として使用した場合、蓄積し
た塩の影響でエステル交換反応速度が遅延する等、当該
方法は経済的操業のための問題点となっている。The reaction mixture obtained by the above method is
In addition to SE, it contains a solvent, unreacted sucrose, and an alkali catalyst. To separate SE from this mixture,
Typically, an acid is added to the reaction mixture to neutralize and deactivate the catalyst, followed by partial distillation of the solvent, followed by extraction with an organic solvent such as hexane, butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, and water. The organic solvent is removed by distillation from the organic solvent phase containing mainly SE. A method for recovering SE has been proposed. (For example, Special Publication No. 48-21927, Special Publication No. 48-350
49, JP-A-50-29417, JP-A-50-1307
12) It is important as an industrial production method and an economical operation method that the unreacted sucrose and reaction solvent recovered in the aqueous phase are used again as SE production raw materials after removing water by distillation. However, in the extraction process using an organic solvent and water, it is necessary to add a salting-out agent such as an organic acid salt in order to obtain good liquid separation properties (JP-A-5
0-130712), as a result there is salt accumulation in the sucrose recovered in the aqueous phase. If water is removed by distillation and the recovered sucrose is directly used as a raw material for SE production, the rate of transesterification reaction is delayed due to the influence of accumulated salts, which poses problems for economical operation. .
【０００４】0004
【発明が解決しようとする課題】本発明は、ＳＥ製造反
応混合物から塩の蓄積のないショ糖を回収し、再びＳＥ
製造原料として使用する工業的製造方法および経済的操
業方法を提供するものである。Problems to be Solved by the Invention The present invention aims to recover sucrose without salt accumulation from the SE production reaction mixture and to recover it from the SE production reaction mixture.
It provides an industrial manufacturing method and an economical operating method for use as a manufacturing raw material.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上述の問題
点を解決するための鋭意検討した結果、有機溶媒および
水を用いた従来の方法で分離した水相から、水及び反応
溶媒を濃縮除去し、得られた回収混合物をアルコールと
混合し、塩の混入のない未反応ショ糖を固体として分離
回収して再使用することによって、その目的を達成した
。すなわち、本発明は、アルカリの存在下、ジメチルス
ルホキシドを反応溶媒として、ショ糖と脂肪酸低級アル
コールエステルを反応させてショ糖脂肪酸エステルを製
造する方法において、■ 反応混合物を有機溶媒およ
び水と混合し、次いでショ糖脂肪酸エステルを含む有機
溶媒相と、未反応ショ糖、塩およびジメチルスルホキシ
ドを含む水相とに分離し、■ ■で得た有機溶媒相か
ら有機溶媒を除去してショ糖脂肪酸エステルを回収し、
■ ■で得た水相から水およびジメチルスルホキシド
を濃縮除去した回収混合物を、アルコールと混合し、次
いで塩とジメチルスルホキシドを含むアルコール相と、
未反応ショ糖を含む固相とに分離し、■ ■で得た固
相を次の反応系に再使用することを特徴とするショ糖脂
肪酸エステルの製造方法である。[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventors have devised a method for removing water and a reaction solvent from an aqueous phase separated by a conventional method using an organic solvent and water. This objective was achieved by concentrating and removing the sucrose, mixing the resulting recovered mixture with alcohol, and separating and recovering unreacted sucrose without salt contamination as a solid for reuse. That is, the present invention provides a method for producing sucrose fatty acid ester by reacting sucrose and fatty acid lower alcohol ester in the presence of an alkali using dimethyl sulfoxide as a reaction solvent, which comprises: (1) mixing the reaction mixture with an organic solvent and water; Next, the organic solvent phase containing the sucrose fatty acid ester and the aqueous phase containing unreacted sucrose, salt, and dimethyl sulfoxide are separated, and the organic solvent is removed from the organic solvent phase obtained in step 2 to obtain the sucrose fatty acid ester. Collect the
■ The recovered mixture obtained by concentrating and removing water and dimethyl sulfoxide from the aqueous phase obtained in (■) is mixed with alcohol, and then an alcohol phase containing salt and dimethyl sulfoxide is mixed.
This is a method for producing sucrose fatty acid ester, which is characterized in that it is separated into a solid phase containing unreacted sucrose, and the solid phase obtained in step (1) and (2) is reused in the next reaction system.
【０００６】本発明における脂肪酸低級アルコールエス
テルとしては、炭素数６〜３０、好ましくは１２〜２２
の飽和または不飽和脂肪酸（例えばカプロン酸、カプリ
ン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステ
アリン酸、ベヘニン酸などの飽和脂肪酸；リノール酸、
オレイン酸、リノレイン酸、エルカ酸、リシノール酸な
どの不飽和脂肪酸など）と炭素数１〜６の低級アルコー
ル（例えばメタノール、エタノール、プロパノール、ブ
タノールなど）とのエステルが挙げられる。かかる低級
アルコールエステルは、２種以上の混合物として用いて
もよい。脂肪酸低級アルコールエステルは、ショ糖１モ
ルに対して通常０．１〜２０モル、好ましくは０．２〜
８モル使用する。The fatty acid lower alcohol ester in the present invention has 6 to 30 carbon atoms, preferably 12 to 22 carbon atoms.
saturated or unsaturated fatty acids such as caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid; linoleic acid,
Examples include esters of unsaturated fatty acids such as oleic acid, linoleic acid, erucic acid, and ricinoleic acid) and lower alcohols having 1 to 6 carbon atoms (for example, methanol, ethanol, propanol, butanol, etc.). Such lower alcohol esters may be used as a mixture of two or more. The fatty acid lower alcohol ester is usually 0.1 to 20 mol, preferably 0.2 to 20 mol, per 1 mol of sucrose.
Use 8 moles.
【０００７】本発明における反応溶媒としては、熱的安
定性、ショ糖に対する溶解性および安全性の点からして
、ＤＭＳＯが用いられる。溶媒の使用量は、ショ糖と脂
肪酸低級アルコールエステルとの合計仕込量に対して、
通常２０〜１５０重量％、好ましくは５０〜８０重量％
である。本発明におけるアルカリ触媒としては、アルカ
リ金属水素化物、アルカリ金属水酸化物、弱酸のアルカ
リ金属塩等が有効であり、特に炭酸アルカリ金属塩（例
えば炭酸カリウムなど）が好ましい。[0007] DMSO is used as the reaction solvent in the present invention from the viewpoints of thermal stability, solubility in sucrose, and safety. The amount of solvent used is based on the total amount of sucrose and fatty acid lower alcohol ester.
Usually 20-150% by weight, preferably 50-80% by weight
It is. As the alkali catalyst in the present invention, alkali metal hydrides, alkali metal hydroxides, alkali metal salts of weak acids, and the like are effective, and alkali metal carbonates (eg, potassium carbonate) are particularly preferred.
【０００８】本発明における触媒の中和失活に用いられ
る酸としては、硝酸、硫酸、塩酸、リン酸などの無機酸
、ギ酸、酢酸、プロピオン酸、シュウ酸、コハク酸、安
息香酸、クエン酸、乳酸、さらに炭素数８〜２２の高級
脂肪酸などの有機酸などがあげられる。これらの中、装
置材質への腐食性、水への溶解性、食品用添加物として
の安全性の点から、クエン酸または乳酸が特に好ましい
。[0008] Acids used to neutralize and deactivate the catalyst in the present invention include inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, benzoic acid, and citric acid. , lactic acid, and organic acids such as higher fatty acids having 8 to 22 carbon atoms. Among these, citric acid or lactic acid is particularly preferred from the viewpoint of corrosivity to equipment materials, solubility in water, and safety as a food additive.
【０００９】本発明においては、エステル交換反応後の
反応混合物に有機溶媒と水を混合して、液−液抽出を行
う。ここで、必ずしも必須ではないが、液−液抽出前に
反応混合物からＤＭＳＯを濃縮除去しておくことが、抽
出に要する有機溶媒と水の使用量削減の点から好ましい
。ＤＭＳＯの除去は、通常は反応混合物中のＤＭＳＯ濃
度として５〜６０重量％、好ましくは１０〜５０重量％
まで濃縮除去すればよい。ＤＭＳＯを除去しすぎると濃
縮混合物の粘度が大きくなり、以後の取扱いに不都合と
なる。In the present invention, an organic solvent and water are mixed with the reaction mixture after the transesterification reaction to perform liquid-liquid extraction. Here, although not necessarily essential, it is preferable to concentrate and remove DMSO from the reaction mixture before liquid-liquid extraction from the viewpoint of reducing the amount of organic solvent and water required for extraction. The removal of DMSO is usually carried out at a concentration of DMSO in the reaction mixture of 5 to 60% by weight, preferably 10 to 50% by weight.
All you have to do is concentrate and remove it. If too much DMSO is removed, the viscosity of the concentrated mixture increases, making it inconvenient for subsequent handling.
【００１０】本発明における液−液抽出は二相の比重差
を利用する搭式向流接触装置、あるいはこれに機械的攪
拌とか脈動を与える方式などのほかに、遠心力を利用し
て混合と分離を行うポトビルニヤク遠心式抽出機などの
向流方式、オリフィス搭、エゼクターなどの並流方式か
ら選択される。通常、向流方式が採用され、分配効率お
よび水の使用量の点からして向流多段抽出法が工業的方
法として好ましい。本発明における反応混合物の液−液
抽出に用いられる有機溶媒としては、通常、ヘキサン、
ｎ−ブタノール、イソブタノール、メチルエチルケトン
、メチルイソブチルケトン等であり、好ましくはｎ−ブ
タノール、イソブタノール等が挙げられる。液−液抽出
は塩析剤を添加しなくてもよいが、安定操業上添加する
ことが好ましい。添加する塩析剤は触媒の中和失活時に
生成するものと同種が好ましく、食品添加物としての安
定性および抽出時の界面形成の点からクエン酸塩または
乳酸塩が好ましい。[0010] The liquid-liquid extraction in the present invention can be carried out by using a tower-type countercurrent contact device that utilizes the difference in specific gravity between two phases, or by applying mechanical stirring or pulsation to this device, as well as by using centrifugal force for mixing. The choice is between a countercurrent method such as the Potvilnyak centrifugal extractor that performs separation, and a cocurrent method such as an orifice tower or ejector. Usually, a countercurrent method is employed, and a countercurrent multistage extraction method is preferred as an industrial method in terms of distribution efficiency and water usage. The organic solvent used for liquid-liquid extraction of the reaction mixture in the present invention is usually hexane,
Examples include n-butanol, isobutanol, methyl ethyl ketone, methyl isobutyl ketone, and preferred examples include n-butanol and isobutanol. Although it is not necessary to add a salting-out agent in liquid-liquid extraction, it is preferable to add it for stable operation. The salting-out agent to be added is preferably the same type as that produced when the catalyst is neutralized and deactivated, and citrate or lactate is preferred from the viewpoint of stability as a food additive and interface formation during extraction.
【００１１】本発明における液−液抽出操作温度は通常
、大気圧下における有機溶媒の沸点以下で行われ、好ま
しくは４０〜８０℃である。有機溶媒の使用量は、反応
混合物中のＳＥ１重量部に対して、通常０．５〜２０重
量部、好ましくは１〜１０重量部である。有機溶媒と水
との使用割合は、通常有機溶媒１重量部に対して、水０
．０５〜１０重量部、好ましくは０．２〜２重量部であ
る。本発明における液−液抽出で得た有機溶媒相からは
、有機溶媒を除去してＳＥを回収する。かくして得られ
たＳＥはそのまま一般的使用に供することができるが、
食品添加物としての用途向けには更に高度に精製するこ
とが好ましい。すなわち、水蒸気処理することにより微
量の有機溶媒を除去することが好ましい。水蒸気処理後
の水を含む粗ＳＥは濃縮・乾固することにより、精製さ
れたＳＥが製造できる。[0011] The liquid-liquid extraction operation temperature in the present invention is usually carried out below the boiling point of the organic solvent under atmospheric pressure, preferably 40 to 80°C. The amount of the organic solvent used is usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 1 part by weight of SE in the reaction mixture. The ratio of organic solvent and water used is usually 1 part by weight of organic solvent to 0 part by weight of water.
．． 05 to 10 parts by weight, preferably 0.2 to 2 parts by weight. From the organic solvent phase obtained by liquid-liquid extraction in the present invention, the organic solvent is removed to recover SE. The SE thus obtained can be put to general use as is, but
For use as a food additive, it is preferable to purify it to a higher degree. That is, it is preferable to remove trace amounts of organic solvents by steam treatment. Purified SE can be produced by concentrating and drying the water-containing crude SE after steam treatment.
【００１２】本発明における液−液抽出後の水相は、未
反応ショ糖、ＤＭＳＯおよび塩を含んでいる。この水相
から水とＤＭＳＯを濃縮除去後、さらに塩を除去して未
反応ショ糖のみを分離回収する工程へと移行する。まず
、上記水相から水を蒸留除去し、更に、要すればＤＭＳ
Ｏ濃縮除去を行う。未反応ショ糖の安定性の点から、減
圧下で蒸留することが好ましく、先に水、次いでＤＭＳ
Ｏが留去される。水は、アルコールを加えてショ糖を析
出させる次工程において不都合であるので、できるだけ
除去することが必要である。水の留去に引続いてＤＭＳ
Ｏを濃縮除去する場合、沸点の関係から、水の濃度は回
収混合物中、通常、約１重量％以下となる。ＤＭＳＯ濃
縮除去することが不要である場合も同様に、水の濃度は
回収混合物中、通常１重量％以下、好ましくは０．１重
量％以下となるように調節する。ＤＭＳＯの濃縮除去も
、水の場合と同様に、できるだけ除去することが好まし
いが、全量を除去してしまうと回収混合物の粘度が上昇
するなど、取扱いに不便をきたすので、通常は回収混合
物中のＤＭＳＯ濃度として５〜５０重量％、好ましくは
１０〜３０重量％とする。但し、反応混合物からのＤＭ
ＳＯ除去量が充分多い場合には、回収混合物中のＤＭＳ
Ｏ濃度が初めから適当であることがあり、かかる場合に
は、あえてＤＭＳＯの濃縮除去を要さない。[0012] The aqueous phase after liquid-liquid extraction in the present invention contains unreacted sucrose, DMSO and salt. After concentrating and removing water and DMSO from this aqueous phase, the process moves on to a step in which salts are further removed and only unreacted sucrose is separated and recovered. First, water is distilled off from the aqueous phase, and if necessary, DMS is added.
Perform O concentration removal. From the viewpoint of stability of unreacted sucrose, it is preferable to distill it under reduced pressure, first adding water and then DMS.
O is distilled off. Water is inconvenient in the next step of adding alcohol to precipitate sucrose, so it is necessary to remove it as much as possible. Distillation of water followed by DMS
When O is concentrated and removed, the concentration of water in the recovered mixture is usually about 1% by weight or less due to its boiling point. Similarly, when it is not necessary to concentrate and remove DMSO, the concentration of water in the recovered mixture is generally adjusted to 1% by weight or less, preferably 0.1% by weight or less. As with water, it is preferable to concentrate and remove DMSO as much as possible, but if the entire amount is removed, the viscosity of the recovered mixture will increase, making it inconvenient to handle. The DMSO concentration is 5 to 50% by weight, preferably 10 to 30% by weight. However, DM from the reaction mixture
If the amount of SO removed is sufficiently large, the DMS in the recovered mixture
The O concentration may be appropriate from the beginning, and in such cases it is not necessary to concentrate and remove DMSO.
【００１３】このようにして、水、更に要すればＤＭＳ
Ｏを除去して得られた回収混合物を、次いでアルコール
と混合する。アルコールの使用量は、この回収混合物１
重量部に対し、通常１〜１０重量部、好ましくは２〜７
重量部である。アルコールは未反応ショ糖を含む回収混
合物中に添加しても良いが、逆にアルコール中に回収混
合物を添加する方が未反応ショ糖の回収率及び未反応シ
ョ糖と塩の分離の点から好ましい。回収混合物のアルコ
ール中への添加方法は一括、間欠および連続添加から任
意に選択されるが、未反応ショ糖の回収率および未反応
ショ糖と塩の分離の点から連続添加が好ましい。アルコ
ールとの混合温度は通常、大気圧下でアルコールの沸点
以下の温度から選択され、たとえば回収混合物の粘度、
未反応ショ糖の回収率、未反応ショ糖と塩の分離および
ショ糖の安定性等の点から、通常、３０〜１００℃、好
ましくは４０〜８０℃の範囲から選ばれる。本発明にお
けるショ糖析出用のアルコールとしては、通常低級アル
コールを使用する。好ましい低級アルコールの例として
はメタノール、エタノール、ｎ−プロパノール、イソプ
ロパノール、ｎ−ブタノール、イソブタノール等が挙げ
られる。ＳＥの生成反応中に、原料である脂肪酸低級ア
ルコールエステル由来の低級アルコールが反応副生物と
して生成するので、該低級アルコールを、本発明のショ
糖析出用アルコールとして使用する方法は特に工業的に
有利である。[0013] In this way, water and, if necessary, DMS
The recovered mixture obtained after O removal is then mixed with alcohol. The amount of alcohol used is
Usually 1 to 10 parts by weight, preferably 2 to 7 parts by weight
Parts by weight. Alcohol may be added to the recovered mixture containing unreacted sucrose, but conversely, it is better to add the recovered mixture to alcohol in terms of recovery rate of unreacted sucrose and separation of unreacted sucrose and salt. preferable. The method of adding the recovered mixture to the alcohol can be arbitrarily selected from batch, intermittent, and continuous addition, but continuous addition is preferable from the viewpoint of recovery rate of unreacted sucrose and separation of unreacted sucrose and salt. The temperature of mixing with the alcohol is typically chosen to be below the boiling point of the alcohol at atmospheric pressure and depends on, for example, the viscosity of the recovered mixture;
The temperature is usually selected from the range of 30 to 100°C, preferably 40 to 80°C, from the viewpoint of recovery rate of unreacted sucrose, separation of unreacted sucrose and salt, stability of sucrose, etc. As the alcohol for sucrose precipitation in the present invention, a lower alcohol is usually used. Examples of preferred lower alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and the like. During the SE production reaction, a lower alcohol derived from fatty acid lower alcohol ester, which is a raw material, is produced as a reaction byproduct, so the method of using this lower alcohol as the alcohol for sucrose precipitation of the present invention is particularly industrially advantageous. It is.
【００１４】本発明における固液分離、すなわち未反応
ショ糖を含む固相と塩を含むアルコール相の分離は、濾
過器、ストレナーなどを用いて行う濾過、プレスを利用
する圧搾および遠心分離などから任意に選択される。当
該工程で回収した固相はその主成分が未反応ショ糖であ
るので、これは、ＳＥ製造原料として再利用される。か
くして回収した未反応ショ糖は、塩をほとんど含まない
ものであり、次の反応系に繰り返し再使用してもエステ
ル交換反応が遅延することがないものである。Solid-liquid separation in the present invention, that is, separation of the solid phase containing unreacted sucrose and the alcohol phase containing salt, can be performed by filtration using a filter, strainer, etc., squeezing using a press, centrifugation, etc. arbitrarily selected. Since the main component of the solid phase recovered in this step is unreacted sucrose, it is reused as a raw material for SE production. The unreacted sucrose thus recovered contains almost no salt, and the transesterification reaction will not be delayed even if it is repeatedly reused in the next reaction system.
【００１５】一方、アルコール相は、アルコールを主成
分とし、ＤＭＳＯおよび塩を含む混合液である。該アル
コール相からアルコールとＤＭＳＯを除いて塩を回収し
、この塩から相当する酸を回収することが出来る。まず
、アルコールは蒸留処理して回収するが、これを未反応
ショ糖析出用に再使用することが工業上有利であり好ま
しい。次いで、ＤＭＳＯを回収するが、これも反応溶媒
として再使用することが好ましい。ＤＭＳＯの回収は通
常の蒸留処理により行われるが、処理温度が高いと微量
混入しているショ糖が分解しやすく、回収したＤＭＳＯ
がショ糖分解生成物により汚染されるので、減圧下で行
うことが好ましい。例えば特開昭５８−４０３８で開示
された横形薄膜蒸発器などを使用するとＤＭＳＯ回収率
の点でより好ましく、横形薄膜蒸発器から排出する濃縮
物へ塩は回収される。On the other hand, the alcohol phase is a liquid mixture containing alcohol as a main component, DMSO and salt. The alcohol and DMSO are removed from the alcohol phase to recover the salt, from which the corresponding acid can be recovered. First, alcohol is recovered by distillation, but it is industrially advantageous and preferable to reuse it for precipitation of unreacted sucrose. The DMSO is then recovered, preferably also reused as a reaction solvent. DMSO is recovered by normal distillation treatment, but if the treatment temperature is high, the trace amount of sucrose that is mixed in will be easily decomposed, and the recovered DMSO
It is preferable to carry out under reduced pressure since the sucrose is contaminated with sucrose degradation products. For example, it is more preferable to use a horizontal thin film evaporator disclosed in Japanese Patent Application Laid-Open No. 58-4038 from the viewpoint of DMSO recovery rate, and the salt is recovered as a concentrate discharged from the horizontal thin film evaporator.
【００１６】本発明における上記の回収塩は、さらにイ
オン交換樹脂で処理して塩に相当する酸として回収する
ことが経済的製造方法として特に好ましい。ＤＭＳＯ除
去後の濃縮された回収塩は、水で希釈してイオン交換樹
脂処理することが好ましい。水溶液中の塩濃度は通常０
．１〜５０重量％、好ましくは１〜３０重量％である。
本発明におけるイオン交換樹脂処理温度としては、通常
５〜１００℃、好ましくは２０〜７０℃である。[0016] It is particularly preferable as an economical production method that the above-mentioned recovered salt in the present invention is further treated with an ion exchange resin and recovered as an acid corresponding to the salt. The concentrated recovered salt after DMSO removal is preferably diluted with water and treated with an ion exchange resin. Salt concentration in aqueous solution is usually 0
．． It is 1 to 50% by weight, preferably 1 to 30% by weight. The ion exchange resin treatment temperature in the present invention is usually 5 to 100°C, preferably 20 to 70°C.
【００１７】本発明における上記の酸の回収方法として
、塩を含む水溶液を塩基性陰イオン交換樹脂で処理し、
塩を相当する酸に変換して交換樹脂に保持させ、微量に
残存するショ糖及びＤＭＳＯを含む水溶液と分離する。
次いで該陰イオン交換樹脂に保持した酸はアルカリ水溶
液を通液すると、酸は再び塩の水溶液として交換樹脂か
ら分離する。ただしこの水溶液は、再生用のアルカリが
塩と同伴して排出してくるので、次に酸性陽イオン交換
樹脂で処理してアルカリを吸着させて除去することによ
り相当する酸が精製された形で回収される。[0017] As a method for recovering the above acid in the present invention, an aqueous solution containing a salt is treated with a basic anion exchange resin,
The salt is converted to the corresponding acid and retained on the exchange resin, and separated from the aqueous solution containing traces of remaining sucrose and DMSO. Next, the acid retained in the anion exchange resin is passed through an alkaline aqueous solution, and the acid is again separated from the exchange resin as an aqueous salt solution. However, since this aqueous solution is discharged with the alkali for regeneration along with the salt, it is then treated with an acidic cation exchange resin to adsorb and remove the alkali, resulting in the corresponding acid in a purified form. It will be collected.
【００１８】本発明において使用するイオン交換樹脂と
しては、種々の化学構造および物理構造を有するものが
挙げられる。その物理構造はゲル型またはポーラス型の
いずれの樹脂も使用することが出来る。また、その架橋
度は幅広いものが適用される。好ましいイオン交換樹脂
の代表的な例として以下に示すものが挙げられるが、本
発明で使用される樹脂はこれらに限定されるものではな
い。陰イオン交換樹脂；三次元に重縮合した高分子基体
に、交換基として４級アンモニウム基または１〜３級ア
ミンを結合させた樹脂であり、具体的な商品として、例
えば、三菱化成（株）製のダイヤイオンＳＡ、ＰＡ、Ｗ
Ａシリーズ等が挙げられる。本発明においてはポーラス
型のスチレン系強塩基性陰イオン交換樹脂であるＰＡシ
リーズが交換速度、脱色性、再生効率などの点で好まし
い。陽イオン交換樹脂；三次元に重縮合した高分子基体
に、交換基としてスルホン酸基やカルボン酸基などを結
合させた樹脂であり、具体的な商品として、例えば、三
菱化成（株）製のダイヤイオンＳＫ、ＰＫ、ＷＫシリー
ズ等が挙げられる。本発明においてはスチレン系強酸性
陽イオン交換樹脂であるＳＫシリーズが交換速度、再生
効率などの点で好ましい。Ion exchange resins used in the present invention include those having various chemical and physical structures. As for its physical structure, either gel type or porous type resin can be used. Further, a wide range of degrees of crosslinking can be applied. Representative examples of preferred ion exchange resins include those shown below, but the resins used in the present invention are not limited to these. Anion exchange resin: A resin in which a quaternary ammonium group or a primary to tertiary amine is bonded as an exchange group to a three-dimensionally polycondensed polymer base. Specific products include, for example, Mitsubishi Kasei Co., Ltd. Diamond Aeon SA, PA, W
Examples include the A series. In the present invention, the PA series, which is a porous styrene-based strongly basic anion exchange resin, is preferable in terms of exchange rate, decolorization property, regeneration efficiency, etc. Cation exchange resin: A resin in which sulfonic acid groups, carboxylic acid groups, etc. are bonded as exchange groups to a three-dimensionally polycondensed polymer base. Specific products include, for example, Mitsubishi Kasei Co., Ltd.'s Examples include the Diaion SK, PK, and WK series. In the present invention, the SK series, which is a styrene-based strongly acidic cation exchange resin, is preferable in terms of exchange rate, regeneration efficiency, etc.
【００１９】[0019]
【実施例】以下に実施例を挙げて詳述するが、本発明は
その要旨を超えない限りこれらの実施例によって限定さ
れるものではない。
参考例（従来法・新ショ糖使用）
反応・濃縮工程
充分に乾燥させた攪拌機付きの３０リットル容量の反応
器に、ショ糖３７４３ｇ、および溶媒としてＤＭＳＯ１
１．５ｋｇを仕込み、２０ｍｍＨｇの圧力下で溶媒を沸
騰させ、その溶媒蒸気を冷却して凝縮・還流させ、かつ
２０分後から溶媒の一部を留去し系内を脱水した。ＤＭ
ＳＯの留出量が１ｋｇに達した点でその留去を止め、系
内液の水分量を測定したところ、その含水量は０．０６
重量％であった。次いで、これに無水炭酸カリウム１２
ｇ、パルミチン酸メチル５２９．９ｇ、ステアリン酸メ
チル２２７．１ｇを添加し、２０ｍｍＨｇでＤＭＳＯを
沸騰させながら、その蒸気を冷却し、濃縮させて還流す
るとともに、生成するメタノールを反応系外に留出させ
ながら反応させた。反応温度は平均９０℃で、脂肪酸メ
チル９９％転換率の到達時間は２．８時間であった。反
応は３時間行った。反応終了後乳酸の５０％水溶液３２
ｇを添加し、触媒を失活させた。反応混合物をゲルパー
ミエーションクロマトグラフィーで分析したところ、Ｓ
Ｅ組成は、モノエステル８０．７％、ジエステル１７．
０％、トリエステル２．３％（面積百分率）であり、ガ
スクロマトグラフィーで分析したパルミチン酸メチルお
よびステアリン酸メチルの残存量から算出した脂肪酸メ
チルの転換率は９９．６％であることが認められた。反
応器からとりだした反応混合物の組成は、未反応ショ糖
１９．９重量％、ＳＥ９．７重量％、塩０．１５重量％
、ＤＭＳＯ７０．２重量％であった。反応器からとりだ
した反応混合物１５ｋｇは横形薄膜蒸発器（伝熱面積０
．１ｍ２ 、株式会社日立製作所製）を使用し、加熱部
スチーム温度１１０℃、圧力１０ｍｍＨｇの条件下、７
ｋｇ／Ｈｒの供給速度で通液したところ、排出液量は５
．４ｋｇであった。濃縮反応混合物の組成分析の結果、
ショ糖４９．５重量％、ＳＥ２４．１重量％、塩０．４
重量％、ＤＭＳＯ２６．０重量％であった。
液−液抽出工程
上記の濃縮反応混合物を１０％含水イソブタノール１５
．５ｋｇに溶解させた。次に、純水１５．５ｋｇを加え
てＳＥ−イソブタノール溶液中の未反応ショ糖とＤＭＳ
Ｏを２リットル分液ロートを繰り返し使用して水相側に
抽出した。更に、ＳＥ−イソブタノール溶液に乳酸カリ
１５００ｐｐｍ を含む純水を加え微量残存する未反応
ショ糖とＤＭＳＯを回収した。水相側はフラッシュエバ
ポレーターを使用して水を除去した後、未反応ショ糖−
ＤＭＳＯ溶液を回収した。回収した未反応ショ糖中の塩
濃度は１．８重量％であった。[Examples] The present invention will be described in detail below with reference to Examples, but the present invention is not limited by these Examples unless the gist thereof is exceeded. Reference example (conventional method/using new sucrose) Reaction/concentration process 3743 g of sucrose and 1 DMSO as a solvent were placed in a sufficiently dried 30 liter reactor equipped with a stirrer.
1.5 kg was charged, the solvent was boiled under a pressure of 20 mmHg, the solvent vapor was cooled, condensed and refluxed, and after 20 minutes, part of the solvent was distilled off to dehydrate the system. DM
When the amount of SO distilled reached 1 kg, the distillation was stopped and the water content of the system liquid was measured, and the water content was 0.06.
% by weight. Next, 12% of anhydrous potassium carbonate was added to this.
g, 529.9 g of methyl palmitate, and 227.1 g of methyl stearate were added, and while boiling DMSO at 20 mmHg, the vapor was cooled, concentrated, and refluxed, and the methanol produced was distilled out of the reaction system. I reacted while doing so. The reaction temperature was an average of 90°C, and the time required to reach 99% conversion of fatty acid methyl was 2.8 hours. The reaction was carried out for 3 hours. After completion of the reaction, 50% aqueous solution of lactic acid 32
g was added to deactivate the catalyst. When the reaction mixture was analyzed by gel permeation chromatography, S
E composition is 80.7% monoester, 17% diester.
0%, triester 2.3% (area percentage), and the conversion rate of fatty acid methyl calculated from the residual amounts of methyl palmitate and methyl stearate analyzed by gas chromatography was found to be 99.6%. It was done. The composition of the reaction mixture taken out from the reactor was 19.9% by weight of unreacted sucrose, 9.7% by weight of SE, and 0.15% by weight of salt.
, DMSO was 70.2% by weight. 15 kg of the reaction mixture taken out from the reactor was transferred to a horizontal thin film evaporator (heat transfer area: 0).
．． 1 m2, manufactured by Hitachi, Ltd.) under the conditions of a heating section steam temperature of 110°C and a pressure of 10 mmHg.
When the liquid was passed at a supply rate of kg/Hr, the amount of liquid discharged was 5.
．． It weighed 4 kg. As a result of compositional analysis of the concentrated reaction mixture,
Sucrose 49.5% by weight, SE 24.1% by weight, salt 0.4
% by weight, DMSO was 26.0% by weight. Liquid-liquid extraction step The above concentrated reaction mixture was diluted with 10% aqueous isobutanol 15
．． It was dissolved in 5 kg. Next, 15.5 kg of pure water was added to mix the unreacted sucrose and DMS in the SE-isobutanol solution.
O was extracted into the aqueous phase using a 2 liter separatory funnel repeatedly. Further, pure water containing 1500 ppm of potassium lactate was added to the SE-isobutanol solution to recover trace amounts of unreacted sucrose and DMSO. After removing water from the aqueous phase using a flash evaporator, unreacted sucrose was removed.
The DMSO solution was collected. The salt concentration in the recovered unreacted sucrose was 1.8% by weight.
【００２０】比較例１〜４（従来法による繰り返し反応
）
参考例で水相側から回収した未反応ショ糖（２０００ｇ
）−ＤＭＳＯ溶液を再使用し、新ショ糖１７４３ｇを加
えてショ糖原料とし、参考例と同様の原料仕込み組成と
なるようにして、反応、濃縮、液−液抽出、ショ糖−Ｄ
ＭＳＯ溶液の回収、新ショ糖を加えての再使用を４回繰
り返し、ＳＥを製造し、脂肪酸メチル９９％転換率の到
達時間を測定した。その結果を後記の表１に示した。
実施例１（未反応ショ糖の回収、塩の除去）比較例の繰
り返し反応１回目（比較例１）後の未反応ショ糖−ＤＭ
ＳＯ溶液（ショ糖中の塩濃度３．０重量％）を使用して
未反応ショ糖と塩の分離を行った。未反応ショ糖−ＤＭ
ＳＯ溶液からＤＭＳＯを濃縮除去し、ＤＭＳＯ濃度を２
３重量％とした。メタノール３ｋｇをジャケット付きの
内容積５リットル卓上型ニーダー（株式会社入江商会製
ＰＮＶ−５型）へ仕込み４０℃に保持した後、６０
℃の回収ショ糖−ＤＭＳＯ溶液７５０ｇを３０分で滴下
し、滴下終了後６０分混合した。次に、保留粒子径１μ
ｍの濾紙を充填した内容積１リットルの加圧濾過器を使
用してニーダー内の液相と固相を分離した。その結果を
後記の表２に示した。回収した固相の未反応ショ糖中の
塩濃度は０．０３重量％であった。Comparative Examples 1 to 4 (repeated reactions by conventional method) Unreacted sucrose (2000 g) recovered from the aqueous phase in the reference example
)-DMSO solution was reused, 1743 g of new sucrose was added to make sucrose raw material, and the raw material preparation composition was the same as in the reference example, and the reaction, concentration, liquid-liquid extraction, and sucrose-D
Recovery of the MSO solution and reuse with addition of fresh sucrose were repeated four times to produce SE, and the time required to reach 99% fatty acid methyl conversion was measured. The results are shown in Table 1 below. Example 1 (Recovery of unreacted sucrose, removal of salt) Repeating comparative example Unreacted sucrose-DM after the first reaction (Comparative example 1)
Unreacted sucrose and salt were separated using SO solution (salt concentration in sucrose: 3.0% by weight). Unreacted sucrose-DM
DMSO is concentrated and removed from the SO solution, and the DMSO concentration is reduced to 2.
The content was 3% by weight. After charging 3 kg of methanol into a jacketed tabletop kneader with an inner volume of 5 liters (Model PNV-5, manufactured by Irie Shokai Co., Ltd.) and keeping it at 40°C,
C. 750 g of recovered sucrose-DMSO solution was added dropwise over 30 minutes, and mixed for 60 minutes after completion of the addition. Next, the retained particle size is 1μ
The liquid phase and solid phase in the kneader were separated using a pressurized filter with an internal volume of 1 liter filled with m filter paper. The results are shown in Table 2 below. The salt concentration in the recovered solid phase unreacted sucrose was 0.03% by weight.
【００２１】実施例２（未反応ショ糖の回収、塩の除去
）
比較例の繰り返し反応４回目（比較例４）後の未反応シ
ョ糖−ＤＭＳＯ溶液（ショ糖中の塩濃度５．８重量％）
を使用した以外は実施例１と同様の操作を行った。その
結果を後記の表３に示した。回収した固相の未反応ショ
糖中の塩濃度は０．５重量％であった。Example 2 (Recovery of unreacted sucrose, removal of salt) Unreacted sucrose-DMSO solution (salt concentration in sucrose 5.8 weight) after the fourth repeated reaction of the comparative example (comparative example 4) %)
The same operation as in Example 1 was performed except that . The results are shown in Table 3 below. The salt concentration in the recovered solid phase unreacted sucrose was 0.5% by weight.
【００２２】実施例３（本発明法の回収未反応ショ糖を
用いた反応）
実施例２の固相からメタノールを除去して、未反応ショ
糖（ショ糖９９．４重量％、塩０．５重量％）を回収し
、新ショ糖を補給せずにショ糖原料とした以外は参考例
と同様の仕込み組成でエステル交換反応を行った。その
結果、脂肪酸メチル９９％転換率の到達時間は２．８Ｈ
ｒであり、新ショ糖を使用した反応速度と同等であるこ
とが確認された。Example 3 (Reaction using recovered unreacted sucrose according to the method of the present invention) Methanol was removed from the solid phase of Example 2, and unreacted sucrose (sucrose 99.4% by weight, salt 0. 5% by weight) was collected, and a transesterification reaction was performed using the same charging composition as in the reference example, except that fresh sucrose was not supplemented and the sucrose raw material was used. As a result, the time required to reach 99% conversion rate of fatty acid methyl was 2.8 hours.
r, and it was confirmed that the reaction rate was equivalent to that using fresh sucrose.
【００２３】実施例４〜７（本発明法の工程による繰り
返し反応）
実施例２でアルコール添加により析出させた固相から、
メタノールを除去して回収した未反応ショ糖２０００ｇ
を再使用し、新ショ糖１７４３ｇを加えてショ糖原料と
した。当該ショ糖原料を用い、参考例と同様の原料仕込
み組成となるようにして、反応、濃縮、液−液抽出、シ
ョ糖−ＤＭＳＯ溶液の回収およびアルコール添加による
塩の除去をおこなった。これに引き続き、新ショ糖を加
えての再使用を４回繰り返し、ＳＥを製造し、脂肪酸メ
チル９９％転換率の到達時間をそれぞれ測定した。その
結果を後記の表４に示した。実施例３〜７より判るよう
に、比較例１〜４と比として、本発明法は繰り返し未反
応回収ショ糖を再使用しても塩の蓄積は抑えられ、新シ
ョ糖を使用した場合とほぼ同等な脂肪酸メチル９９％転
換率の到達時間が得られる。Examples 4 to 7 (Repeated reactions according to the steps of the method of the present invention) From the solid phase precipitated by adding alcohol in Example 2,
2000g of unreacted sucrose recovered by removing methanol
was reused and 1,743 g of fresh sucrose was added to obtain a sucrose raw material. Using the sucrose raw material, reaction, concentration, liquid-liquid extraction, recovery of the sucrose-DMSO solution, and salt removal by addition of alcohol were carried out with the same raw material composition as in the reference example. Subsequently, fresh sucrose was added and reuse was repeated four times to produce SE, and the time required to reach 99% fatty acid methyl conversion was measured for each. The results are shown in Table 4 below. As can be seen from Examples 3 to 7, as compared to Comparative Examples 1 to 4, the method of the present invention suppresses salt accumulation even when unreacted recovered sucrose is repeatedly reused, and is more effective than when fresh sucrose is used. Approximately equivalent times to reach 99% conversion of fatty acid methyl are obtained.
【００２４】実施例８（酸の回収）
実施例２の液相からメタノールを除去して、微量のショ
糖、塩およびＤＭＳＯを回収した。更に、ロータリーエ
バポレーター（操作条件９０℃、１ｍｍＨｇ）を使用し
てＤＭＳＯを除去した後の組成は、ショ糖４７重量％、
塩（乳酸カリ）４８重量％、ＤＭＳＯ５重量％であった
。
これを純水で希釈して塩濃度１０重量％の水溶液とし、
イオン交換樹脂処理に供した。イオン交換樹脂は内径５
ｃｍ、高さ８０ｃｍのジャケット付きガラス製カラムに
三菱化成（株）製のＰＡ−３０８（強塩基性陰イオン交
換樹脂）を８００ｍｌ充填し、３０℃に保持した。次に
、３０℃の上記水溶液５００ｇを２４００ｍｌ／Ｈｒの
速度で通液した。全量通液後、５００ｍｌの純水を同様
に通液して洗浄した。上記操作で乳酸がＰＡ−３０８樹
脂に吸着し、ショ糖及びＤＭＳＯから乳酸が分離された
。乳酸を吸着したＰＡ−３０８に５重量％水酸化カリ水
溶液５００ｍｌを通液し、再生すると同時に、乳酸カリ
を排出した。排出した乳酸カリ水溶液は同時に水酸化カ
リを含むので、次に強酸性陽イオン交換樹脂（三菱化成
（株）製 ＳＫ−１Ｂ）を使用して処理した。操作条
件としては上述と同じガラスカラムに８００ｍｌのＳＫ
−１Ｂ樹脂を充填して使用し、３０℃で２４００ｍｌ／
Ｈｒで通液して、乳酸水溶液を得た。電位差中和滴定方
法で分析した乳酸の回収率は仕込み量（触媒中和用酸及
び塩析剤として添加された量の全量）の７０％であり、
高収率で回収されたことが認められた。Example 8 (Recovery of Acid) Methanol was removed from the liquid phase of Example 2 to recover trace amounts of sucrose, salt and DMSO. Furthermore, after removing DMSO using a rotary evaporator (operating conditions: 90°C, 1 mmHg), the composition was 47% by weight of sucrose,
The contents were 48% by weight of salt (potassium lactic acid) and 5% by weight of DMSO. This is diluted with pure water to make an aqueous solution with a salt concentration of 10% by weight,
It was subjected to ion exchange resin treatment. Ion exchange resin has an inner diameter of 5
800 ml of PA-308 (strongly basic anion exchange resin) manufactured by Mitsubishi Kasei Co., Ltd. was packed into a jacketed glass column with a height of 80 cm and a height of 80 cm, and maintained at 30°C. Next, 500 g of the above aqueous solution at 30° C. was passed through at a rate of 2400 ml/Hr. After passing the entire amount, 500 ml of pure water was passed in the same manner for washing. Through the above operation, lactic acid was adsorbed onto the PA-308 resin, and lactic acid was separated from sucrose and DMSO. 500 ml of a 5% by weight aqueous potassium hydroxide solution was passed through PA-308 that had adsorbed lactic acid, and at the same time as regeneration, potassium lactic acid was discharged. Since the discharged potassium lactic acid aqueous solution also contained potassium hydroxide, it was then treated using a strongly acidic cation exchange resin (SK-1B manufactured by Mitsubishi Kasei Corporation). As for the operating conditions, 800 ml of SK was added to the same glass column as above.
-1B resin is filled and used, 2400ml/at 30℃
A lactic acid aqueous solution was obtained by passing the solution under Hr. The recovery rate of lactic acid analyzed by potentiometric neutralization titration method was 70% of the amount charged (total amount of acid for neutralizing the catalyst and amount added as a salting-out agent),
It was observed that the product was recovered in high yield.
【００２５】[0025]
【表１】[Table 1]
【００２６】[0026]
【表２】[Table 2]
【００２７】[0027]
【表３】[Table 3]
【００２８】[0028]
【表４】[Table 4]
【００２９】[0029]
【発明の効果】本発明の方法によれば、反応混合物中か
ら高純度の未反応ショ糖を分離・回収して、反応に再使
用し、繰り返し使用することにより経済的に効率よくシ
ョ糖脂肪酸エステルを製造することができ、再使用して
もエステル交換反応を遅延させることがない。また、有
機酸／無機酸を経済的に分離・回収することが出来るの
で再使用することができる。[Effects of the Invention] According to the method of the present invention, highly pure unreacted sucrose is separated and recovered from the reaction mixture, reused in the reaction, and repeatedly used to economically and efficiently produce sucrose and fatty acids. Esters can be produced and reused without slowing the transesterification reaction. Furthermore, since organic acids/inorganic acids can be economically separated and recovered, they can be reused.
【図１】図１は、本発明の工程の一例を示す簡単なフロ
ー図である。FIG. 1 is a simple flow diagram illustrating an example of the process of the present invention.
Claims (6)
シドを反応溶媒として、ショ糖と脂肪酸低級アルコール
エステルを反応させてショ糖脂肪酸エステルを製造する
方法において、■ 反応混合物を有機溶媒および水と
混合し、次いでショ糖脂肪酸エステルを含む有機溶媒相
と、未反応ショ糖、塩およびジメチルスルホキシドを含
む水相とに分離し、■ ■で得た有機溶媒相から有機
溶媒を除去してショ糖脂肪酸エステルを回収し、■
■で得た水相から水およびジメチルスルホキシドを濃縮
除去した回収混合物を、アルコールと混合し、次いで塩
とジメチルスルホキシドを含むアルコール相と、未反応
ショ糖を含む固相とに分離し、■ ■で得た固相を次
の反応系に再使用することを特徴とするショ糖脂肪酸エ
ステルの製造方法。Claim 1. A method for producing sucrose fatty acid ester by reacting sucrose with fatty acid lower alcohol ester in the presence of an alkali using dimethyl sulfoxide as a reaction solvent, comprising: (1) mixing the reaction mixture with an organic solvent and water; Next, the organic solvent phase containing the sucrose fatty acid ester and the aqueous phase containing unreacted sucrose, salt, and dimethyl sulfoxide are separated, and the organic solvent is removed from the organic solvent phase obtained in step 2 to remove the sucrose fatty acid ester. Collect and ■
The recovered mixture obtained by concentrating and removing water and dimethyl sulfoxide from the aqueous phase obtained in step (2) is mixed with alcohol, and then separated into an alcohol phase containing salt and dimethyl sulfoxide and a solid phase containing unreacted sucrose. A method for producing sucrose fatty acid ester, characterized in that the solid phase obtained in step 1 is reused in the next reaction system.
ドを濃縮除去した回収混合物１重量部に対し、アルコー
ル１〜１０重量部を混合することを特徴とする請求項１
記載の製造方法。2. Claim 1, characterized in that 1 to 10 parts by weight of alcohol is mixed with 1 part by weight of the recovered mixture obtained by concentrating and removing water and dimethyl sulfoxide from the aqueous phase.
Manufacturing method described.
求項１ないし２記載の製造方法。3. The production method according to claim 1, wherein the alcohol is a lower alcohol.
、ｎ−プロパノール、イソプロパノール、ｎ−ブタノー
ル、イソブタノールから選ばれる請求項１ないし２記載
の製造方法。4. The method according to claim 1, wherein the alcohol is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.
シドを反応溶媒として、ショ糖と脂肪酸低級アルコール
エステルを反応させてショ糖脂肪酸エステルを製造する
方法において、■ 反応混合物を有機溶媒および水と
混合し、次いでショ糖脂肪酸エステルを含む有機溶媒相
と、未反応ショ糖、塩およびジメチルスルホキシドを含
む水相とに分離し、■ ■で得た有機溶媒相から有機
溶媒を除去してショ糖脂肪酸エステルを回収し、■
■で得た水相から水およびジメチルスルホキシドを濃縮
除去した回収混合物を、アルコールと混合し、次いで塩
とジメチルスルホキシドを含むアルコール相と、未反応
ショ糖を含む固相とに分離し、■ ■で得た固相を次
の反応系に再使用し、■ ■で得たアルコール相をイ
オン交換樹脂で処理することにより、塩に相当する酸を
回収することを特徴とするショ糖脂肪酸エステルの製造
方法。5. A method for producing a sucrose fatty acid ester by reacting sucrose with a fatty acid lower alcohol ester in the presence of an alkali using dimethyl sulfoxide as a reaction solvent, comprising: (1) mixing the reaction mixture with an organic solvent and water; Next, the organic solvent phase containing the sucrose fatty acid ester and the aqueous phase containing unreacted sucrose, salt, and dimethyl sulfoxide are separated, and the organic solvent is removed from the organic solvent phase obtained in step 2 to remove the sucrose fatty acid ester. Collect and ■
The recovered mixture obtained by concentrating and removing water and dimethyl sulfoxide from the aqueous phase obtained in step (2) is mixed with alcohol, and then separated into an alcohol phase containing salt and dimethyl sulfoxide and a solid phase containing unreacted sucrose. The solid phase obtained in step 1 is reused in the next reaction system, and the alcohol phase obtained in step 2 is treated with an ion exchange resin to recover the acid corresponding to the salt. Production method.
おいて、■ アルコール相からアルコールを除去した
のち水と混合して得られた水溶液を、陰イオン交換樹脂
で処理して塩に相当する酸を吸着させ、■ 該陰イオ
ン交換樹脂にアルカリ水溶液を通液して酸を脱着させ、
塩とアルカリ水溶液の混合物を得て、■ 該混合物を
陽イオン交換樹脂で処理することによりアルカリを吸着
させ、酸を回収することを特徴とする請求項５記載の製
造方法。[Claim 6] In the ion exchange resin treatment of the alcohol phase, (1) the aqueous solution obtained by removing alcohol from the alcohol phase and mixing it with water is treated with an anion exchange resin to adsorb acids corresponding to salts; , ■ Desorbing the acid by passing an alkaline aqueous solution through the anion exchange resin,
6. The production method according to claim 5, wherein a mixture of a salt and an aqueous alkali solution is obtained, and (1) the mixture is treated with a cation exchange resin to adsorb the alkali and recover the acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3012289A JP3013451B2 (en) | 1991-02-01 | 1991-02-01 | Method for producing sucrose fatty acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3012289A JP3013451B2 (en) | 1991-02-01 | 1991-02-01 | Method for producing sucrose fatty acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04247095A true JPH04247095A (en) | 1992-09-03 |
| JP3013451B2 JP3013451B2 (en) | 2000-02-28 |
Family
ID=11801191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3012289A Expired - Fee Related JP3013451B2 (en) | 1991-02-01 | 1991-02-01 | Method for producing sucrose fatty acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3013451B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0774469A2 (en) | 1995-11-14 | 1997-05-21 | Südzucker Aktiengesellschaft Mannheim/Ochsenfurt | Acylated saccharose monocarboxylic acids |
| JP2014091705A (en) * | 2012-11-02 | 2014-05-19 | Dai Ichi Kogyo Seiyaku Co Ltd | Solvent removal method |
-
1991
- 1991-02-01 JP JP3012289A patent/JP3013451B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0774469A2 (en) | 1995-11-14 | 1997-05-21 | Südzucker Aktiengesellschaft Mannheim/Ochsenfurt | Acylated saccharose monocarboxylic acids |
| JP2014091705A (en) * | 2012-11-02 | 2014-05-19 | Dai Ichi Kogyo Seiyaku Co Ltd | Solvent removal method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3013451B2 (en) | 2000-02-28 |
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