KR101736180B1 - Method for purifying anhydrosugar alcohols to improve storage stability thereof - Google Patents
Method for purifying anhydrosugar alcohols to improve storage stability thereof Download PDFInfo
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- KR101736180B1 KR101736180B1 KR1020150168762A KR20150168762A KR101736180B1 KR 101736180 B1 KR101736180 B1 KR 101736180B1 KR 1020150168762 A KR1020150168762 A KR 1020150168762A KR 20150168762 A KR20150168762 A KR 20150168762A KR 101736180 B1 KR101736180 B1 KR 101736180B1
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 150000001298 alcohols Chemical class 0.000 title description 2
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 23
- 238000000746 purification Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 85
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 60
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 30
- 235000019253 formic acid Nutrition 0.000 claims description 30
- 235000000346 sugar Nutrition 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000003729 cation exchange resin Substances 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004042 decolorization Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 2
- 150000005846 sugar alcohols Chemical class 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 10
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 10
- 229960002920 sorbitol Drugs 0.000 description 10
- 239000000600 sorbitol Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 5
- 229930195725 Mannitol Natural products 0.000 description 5
- 239000000594 mannitol Substances 0.000 description 5
- 235000010355 mannitol Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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 description 4
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229960002479 isosorbide Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- FBPFZTCFMRRESA-ZXXMMSQZSA-N D-iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- OXQKEKGBFMQTML-UHFFFAOYSA-N alpha-Glucoheptitol Chemical compound OCC(O)C(O)C(O)C(O)C(O)CO OXQKEKGBFMQTML-UHFFFAOYSA-N 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N butane-1,2,3,4-tetrol Chemical compound OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- KLDXJTOLSGUMSJ-BXKVDMCESA-N (3s,3as,6s,6as)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@H]2[C@@H](O)CO[C@H]21 KLDXJTOLSGUMSJ-BXKVDMCESA-N 0.000 description 1
- KLDXJTOLSGUMSJ-UHFFFAOYSA-N 2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound OC1COC2C(O)COC21 KLDXJTOLSGUMSJ-UHFFFAOYSA-N 0.000 description 1
- -1 And more preferably Chemical compound 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
- A61K31/34—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having five-membered rings with one oxygen as the only ring hetero atom, e.g. isosorbide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Birds (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
본 발명은 무수당 알코올의 정제 방법에 관한 것으로, 보다 상세하게는, 무수당 알코올을 정제함에 있어서 강염기성 음이온 교환 수지를 사용하여 정제를 수행함으로써 무수당 알코올의 저장 안정성을 획기적으로 향상시켜, 우수한 품질의 무수당 알코올을 제공할 수 있는 방법에 관한 것이다.More particularly, the present invention relates to a method for purifying an alcohol-free alcohol, and more particularly, to a method for purifying an alcohol-free alcohol by significantly improving the storage stability of alcohol-free alcohol by performing purification using a strongly basic anion- And to provide a method for providing high-purity alcohol.
수소화 당(“당 알코올”이라고도 함)은 당류가 갖는 환원성 말단기에 수소를 부가하여 얻어지는 화합물을 의미하는 것으로, 일반적으로 HOCH2(CHOH)nCH2OH (여기서, n은 2 내지 5의 정수)의 화학식을 가지며, 탄소수에 따라 테트리톨, 펜티톨, 헥시톨 및 헵티톨(각각, 탄소수 4, 5, 6 및 7)로 분류된다. 그 중에서 탄소수가 6개인 헥시톨에는 소르비톨, 만니톨, 이디톨, 갈락티톨 등이 포함되며, 소르비톨과 만니톨은 특히 효용성이 큰 물질이다.Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH 2 (CHOH) n CH 2 OH (where n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.
무수당 알코올은 분자 내 하이드록시기가 두 개인 디올(diol) 형태를 가지며, 전분에서 유래하는 헥시톨을 활용하여 제조할 수 있다(예컨대, 한국등록특허 제10-1079518호, 한국공개특허공보 제10-2012-0066904호). 무수당 알코올은 재생 가능한 천연자원으로부터 유래한 친환경 물질이라는 점에서 오래 전부터 많은 관심과 함께 그 제조방법에 관한 연구가 진행되어 오고 있다. 이러한 무수당 알코올 중에서 솔비톨로부터 제조된 이소소르비드가 현재 산업적 응용범위가 가장 넓다. Anhydrosugar alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared by utilizing hexitol derived from starch (for example, Korean Patent No. 10-1079518, Korean Patent Laid- -2012-0066904). Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.
무수당 알코올의 용도는 심장 및 혈관 질환 치료, 패치의 접착제, 구강 청정제 등의 약제, 화장품 산업에서 조성물의 용매, 식품산업에서는 유화제 등 매우 다양하다. 또한, 폴리에스테르, PET, 폴리카보네이트, 폴리우레탄, 에폭시 수지 등 고분자 물질의 유리전이온도를 올릴 수 있고, 이들 물질의 강도 개선효과가 있으며, 천연물 유래의 친환경소재이기 때문에 바이오 플라스틱 등 플라스틱 산업에서도 매우 유용하다. 또한, 접착제, 친환경 가소제, 생분해성 고분자, 수용성 락카의 친환경 용매로도 사용될 수 있는 것으로 알려져 있다. 이렇듯 무수당 알코올은 그 다양한 활용가능성으로 인해 많은 관심을 받고 있으며, 실제 산업에의 이용도도 점차 증가하고 있다.The use of anhydrous alcohol is widely used in the treatment of cardiovascular diseases, patches, adhesives, oral cleansers and the like, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. In addition, it is possible to increase the glass transition temperature of a polymer substance such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, to improve the strength of these materials, and to be an environmentally friendly material derived from natural materials. useful. It is also known to be used as an environmentally friendly solvent for adhesives, environmentally friendly plasticizers, biodegradable polymers, and water-soluble lacquers. As such, alcohol-free alcohol has attracted a great deal of attention due to its versatility and its use in real industry is increasing.
무수당 알코올에 포름산이 포함되어 있는데, 포름산은 무수당 알코올의 pH를 떨어뜨리는 역할을 하기 때문에 정제 공정에서 제거가 필수적이다.Formic acid is contained in anhydrous alcohol, and formic acid is required to be removed in the purification process because it acts to lower the pH of anhydrous alcohol.
무수당 알코올 제품은, 특히 기온이 올라가는 여름철의 경우, 장기간 저장 시 pH가 낮아지는 문제가 있다. 특히, 무수당 알코올 제품에 포름산이 포함되어 있는 경우에는, 포름산이 급격히 증가하면서 무수당 알코올의 pH를 떨어뜨리는 역할을 한다.Free alcohol product has a problem that pH is lowered during long-term storage, particularly in the summer when the temperature rises. In particular, when formic acid is contained in an alcohol-free alcoholic beverage, the formic acid is rapidly increased to lower the pH of the alcohol-free alcohol.
따라서, 무수당 알코올로부터 포름산을 효과적으로 제거하여, 고온에서 장기간 저장 시에도 pH를 적정 수준으로 안정하게 유지할 수 있는 무수당 알코올의 정제 기술이 요구되고 있다.Accordingly, there is a demand for a technique for purifying alcohol without sugar, which effectively removes formic acid from alcohol without sugar, and can stably maintain pH at an appropriate level even at a high temperature for a long period of storage.
본 발명의 목적은, 고온에서 장기 저장 시에도 pH를 적정 수준으로 안정하게 유지할 수 있도록 무수당 알코올의 저장 안정성을 획기적으로 향상시킬 수 있는 무수당 알코올의 정제 방법을 제공하는 것이다.It is an object of the present invention to provide a method for purifying an alcohol without sugar, which can remarkably improve the storage stability of alcohol-free alcohol so that the pH can be stably maintained at an appropriate level even during long-term storage at a high temperature.
본 발명의 일 측면에 따르면, 무수당 알코올을 정제하는 방법으로서, 강염기성 음이온 교환 수지를 사용하여 정제를 수행하는 단계를 포함하며, 정제된 무수당 알코올이 포름산을 함유하지 않거나 포름산 함량이 1ppm 이하인, 방법이 제공된다.According to one aspect of the present invention, there is provided a method for purifying an alcohol-free alcohol, comprising the step of performing purification using a strongly basic anion exchange resin, wherein the purified alcohol-free alcohol contains no formic acid or has a formic acid content of 1 ppm or less , A method is provided.
본 발명의 다른 측면에 따르면, 상기 방법에 따라 정제된 것으로서, 포름산을 함유하지 않거나 포름산 함량이 1ppm 이하인, 무수당 알코올이 제공된다.According to another aspect of the present invention, there is provided an alcohol-free alcohol which is purified according to the above method and which contains no formic acid or a formic acid content of 1 ppm or less.
본 발명의 또 다른 측면에 따르면, 수소화 당을 탈수반응시켜 무수당 알코올을 제조하는 단계; 및 제조된 무수당 알코올에 대하여 강염기성 음이온 교환 수지를 사용한 정제를 수행하는 단계를 포함하며, 정제된 무수당 알코올이 포름산을 함유하지 않거나 포름산 함량이 1ppm 이하인, 무수당 알코올의 제조 방법이 제공된다.According to still another aspect of the present invention, there is provided a process for producing a nonaqueous alcohol, comprising the steps of: And performing purification using the strongly basic anion exchange resin for the produced anhydrosugar alcohol, wherein the purified anhydrosugar alcohol does not contain formic acid or the formic acid content is 1 ppm or less .
본 발명에 따라 무수당 알코올을 정제하면, 고온에서 장기 저장 시에도, 적정 수준의 pH(예컨대, 20 중량% 농도의 수용액으로 희석시 5.0~7.0의 pH)를 나타내고, 또한 포름산을 함유하지 않거나 포름산 함량이 1ppm 이하(예컨대, 0.0001~1ppm)로 낮은, 저장 안정성이 획기적으로 개선된 무수당 알코올을 얻을 수 있다.According to the present invention, it is possible to purify an alcohol without sugar, which exhibits an appropriate level of pH (for example, a pH of 5.0 to 7.0 when diluted with an aqueous solution having a concentration of 20% by weight) Free alcohol having a low content of 1 ppm or less (for example, 0.0001 to 1 ppm) and having a remarkably improved storage stability can be obtained.
이하, 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 있어서, '수소화 당(hydrogenated sugar)'은 일반적으로 당 알코올(sugar alcohol)로도 불리우며, 당류가 갖는 환원성 말단기에 수소를 부가하여 얻어지는 화합물을 의미한다. 수소화 당은 탄소수에 따라 테트리톨, 펜티톨, 헥시톨 및 헵티톨(각각, 탄소수 4, 5, 6 및 7)로 분류된다. 그 중에서 탄소수가 6개인 헥시톨에는 소르비톨, 만니톨, 이디톨, 갈락티톨 등이 포함되며, 소르비톨과 만니톨은 특히 효용성이 큰 물질이다. In the present invention, 'hydrogenated sugar' is also generally referred to as sugar alcohol, which means a compound obtained by adding hydrogen to a reducing end group of a saccharide. Hydrogenated sugars are classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively) depending on the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.
본 발명에 있어서, '무수당 알코올'은 임의의 방식으로 하나 이상의 단계에서 상기 수소화 당의 원래 내부 구조로부터 하나 이상의 물 분자를 제거하여 얻은 임의의 물질을 의미한다. In the present invention, 'anhydrous alcohol' means any material obtained by removing one or more water molecules from the original internal structure of the hydrogenated sugar in one or more steps in any manner.
본 발명에 있어서, 수소화 당으로는 헥시톨이 바람직하게 사용되고, 보다 바람직하게는 소르비톨, 만니톨, 이디톨 및 이들의 혼합물로부터 선택된 수소화 당이 사용되며, 보다 더 바람직하게는 전분에서 유래하는 글루코오스에 수첨 반응을 통해 쉽게 제조될 수 있는 소르비톨이 사용된다.In the present invention, as the hydrogenated sugar, hexitol is preferably used, more preferably hydrogenated sugar selected from sorbitol, mannitol, editol and a mixture thereof is used, and more preferably, glucose derived from starch is hydrolyzed Sorbitol, which can be easily prepared through the reaction, is used.
본 발명에 있어서, 무수당 알코올은 바람직하게는 헥시톨의 탈수물인 디안하이드로헥시톨이고, 보다 바람직하게는 이소소르비드(1,4-3,6-디안하이드로소르비톨), 이소만니드(1,4-3,6-디안하이드로만니톨), 이소이디드(1,4-3,6-디안하이드로이디톨) 및 이들의 혼합물로부터 선택된 무수당 알코올이다. 그 중에서 이소소르비드는 산업적 활용도가 특히 높다. In the present invention, the alcohol without sugar is preferably dianhydrohexitol, which is a dehydrate of hexitol, more preferably isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1 , 4-3,6-dianhydro mannitol), isoided (1,4-3,6-dianhydroiditol), and mixtures thereof. Among them, isosorbide is particularly high in industrial utilization.
본 발명의 무수당 알코올 정제 방법은, 무수당 알코올을 정제함에 있어서, 강염기성 음이온 교환 수지를 사용하여 정제를 수행하는 단계를 포함하는 것을 특징으로 한다.The method for purifying alcohol-free alcohol according to the present invention is characterized by comprising the step of purifying the alcohol-free alcohol using a strongly basic anion exchange resin.
일 구체예에서, 상기 강염기성 음이온 교환 수지로는 암모늄기를, 보다 구체적으로는 4급 암모늄기를 관능기로 가지고 있는 강염기성 음이온 교환 수지를 사용할 수 있다.In one embodiment, a strongly basic anion exchange resin having an ammonium group, more specifically a quaternary ammonium group as a functional group, may be used as the strongly basic anion exchange resin.
상기 강염기성 음이온 교환 수지로는, 예컨대, 전 pH 영역(예컨대, pH 1~14)에서 이온 교환능을 가지고, 평균 입도 범위가 0.3~1.2mm이며, 겉보기밀도가 650~700g/L인 강염기성 음이온 교환 수지를 사용할 수 있으며, 보다 구체적으로는, 관능기가 트리메틸암모늄, 다이메틸에탄올암모늄 및 이들의 조합으로부터 선택된 것을 사용할 수 있다.Examples of the strongly basic anion exchange resin include strongly basic anions having an ion exchange capacity in the entire pH range (for example, pH 1 to 14), an average particle size range of 0.3 to 1.2 mm and an apparent density of 650 to 700 g / L Exchange resin can be used. More specifically, a functional group selected from trimethylammonium, dimethylethanolammonium, and combinations thereof can be used.
일 구체예에서, 무수당 알코올의 정제는, 정제될 무수당 알코올의 수용액을 강염기성 음이온 교환 수지로 충전된 컬럼에 통과시키는 방식으로 수행될 수도 있고, 다르게는 정제될 무수당 알코올의 수용액과 강염기성 음이온 교환 수지를 반응기 내에서 교반하여 혼합하는 방식으로 수행될 수도 있다. In one embodiment, the purification of the anhydrosugar alcohol may be carried out by passing an aqueous solution of anhydrosugar alcohol to be purified through a column packed with a strongly basic anion exchange resin, or alternatively, by passing an aqueous solution of anhydrosugar alcohol And mixing the basic anion exchange resin in the reactor by stirring.
상기 컬럼 방식으로 무수당 알코올을 정제하는 경우, 무수당 알코올 수용액의 컬럼 통과 속도(통액 속도)는 공간속도(space velocity, SV)로 0.2 내지 6.0일 수 있고, 보다 바람직하게는 0.2 내지 5.0일 수 있으나, 이에 한정되는 것은 아니다.When the anhydrous alcohol is purified by the above-mentioned column method, the column passing rate (passing velocity) of the aqueous alcohol-free alcohol solution may be 0.2 to 6.0, more preferably 0.2 to 5.0 days at a space velocity (SV) However, the present invention is not limited thereto.
일 구체예에서, 무수당 알코올의 정제는, 10 내지 80℃의 온도조건에서 수행될 수 있으나, 이에 한정되는 것은 아니다.In one embodiment, the purification of the anhydrosugar alcohol can be carried out at a temperature of 10 to 80 占 폚, but is not limited thereto.
본 발명의 방법에 의하여 정제되는 무수당 알코올에는 특별한 제한이 없다. 일 구체예에 따르면, 본 발명에 의하여 정제되는 무수당 알코올은 수소화 당을 탈수 반응시켜 제조된 것일 수 있다.There is no particular limitation on the free sugar alcohol which is purified by the method of the present invention. According to one embodiment, the anhydrosugar alcohol which is purified by the present invention may be one prepared by dehydrogenating a hydrogenated sugar.
수소화 당을 탈수하는 방법에는 특별한 제한이 없으며, 당 분야에 알려진 공지의 방법을 그대로 또는 적절히 변형하여 활용할 수 있다. There is no particular limitation on the method of dehydrogenating the hydrogenated sugar, and known methods known in the art can be used as it is or modified appropriately.
수소화 당을 탈수시켜 무수당 알코올로 전환하는 데에는 산 촉매가 사용되는 것이 바람직하다. It is preferable that an acid catalyst is used to convert the hydrogenated sugar to dehydrated and converted to anhydrated alcohol.
일 구체예에 따르면, 상기 산 촉매로서 황산, 질산, 염산, 인산, p-톨루엔 설폰산, 메탄 설폰산, 에탄 설폰산, 벤젠 설폰산, 나프탈렌 설폰산 및 황산 알루미늄으로 구성되는 군으로부터 선택되는 1종 이상을 사용할 수 있으며, 바람직하게는 황산과 다른 산(예컨대, p-톨루엔 설폰산, 메탄 설폰산, 에탄 설폰산, 벤젠 설폰산, 나프탈렌 설폰산 또는 황산 알루미늄)을 혼합하여 사용할 수 있다. 산 촉매의 사용량은 수소화 당(예컨대, 헥시톨) 100중량부당 0.5 내지 10중량부인 것이 바람직하다. According to one embodiment, the acid catalyst is selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, And more preferably, sulfuric acid and another acid (for example, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or aluminum sulfate) may be mixed and used. The amount of the acid catalyst to be used is preferably 0.5 to 10 parts by weight per 100 parts by weight of hydrogenated sugar (e.g., hexitol).
수소화 당의 탈수 반응은 상기한 바와 같은 산 촉매의 존재하에 105 ~ 190℃의 온도조건 및 1 내지 100mmHg의 압력조건에서 1 ~ 10시간 동안 수행될 수 있으나, 이에 반드시 제한되는 것은 아니다. The dehydrogenation reaction of the hydrogenated saccharide can be carried out in the presence of an acid catalyst as described above at a temperature of 105 to 190 DEG C and a pressure of 1 to 100 mmHg for 1 to 10 hours, but is not limited thereto.
수소화 당의 탈수 반응시 산 촉매를 사용하는 경우, 반응 결과액은 수산화나트륨과 같은 공지의 알칼리로 중화되는 것이 바람직하다. 중화된 반응 결과액의 pH는 6~8인 것이 바람직하다. 또한, 수소화 당의 탈수 반응 결과액은 후속 처리 단계(예컨대, 증류 단계)에 투입하기 전에, 탈수 반응 결과액 내에 잔류하는 수분 및 비점이 낮은 물질을 제거하기 위하여 가열/감압 하에 전처리될 수 있다.When an acid catalyst is used in the dehydration reaction of the hydrogenated sugar, the reaction liquid is preferably neutralized with a known alkali such as sodium hydroxide. The pH of the solution is preferably 6 to 8 as a result of the neutralization reaction. Further, the dehydration reaction liquid of the hydrogenated sugar can be pre-treated under heating / decompression to remove moisture and low boiling substances remaining in the liquid as a result of the dehydration reaction, before being put into a subsequent treatment step (for example, distillation step).
본 발명의 방법에 의하여 정제되는 무수당 알코올은, 바람직하게는, 상기와 같이 수소화 당을 탈수 반응시켜 얻어진 탈수 반응 결과액을 증류한 뒤, 증류 결과물을 예비 정제하여 얻어진 것이다. The alcohol-free alcohol to be purified by the method of the present invention is preferably obtained by subjecting the resulting product to distillation after distillation of the dehydration reaction obtained by dehydration reaction of the hydrogenated sugar as described above.
일 구체예에서, 상기 증류는 바람직하게는 100~250℃, 더 바람직하게는 100~200℃, 더욱 더 바람직하게는 120~190℃의 온도 조건 및 바람직하게는 20 mmHg 이하(예컨대, 0.0001~20 mmHg, 보다 구체적으로는 0.0001~16 mmHg), 더 바람직하게는 10 mmHg 이하(예컨대, 0.001~10 mmHg), 더욱 더 바람직하게는 5 mmHg 이하(예컨대, 0.01~5 mmHg, 보다 구체적으로는 0.01~4 mmHg)의 압력 조건 하에서 수행될 수 있다. 증류는 필요에 따라서 2회 이상의 단계를 거쳐 실시할 수 있다. 증류의 방법 및 장치에는 특별한 제한이 없으며, 당 분야에 알려진 공지의 방법 및 장치를 그대로 또는 적절히 변형하여 활용할 수 있다. 예컨대, 일반적인 컨덴서 타입 증류기 또는 증류탑 증류기를 사용할 수도 있고, 박막 증류기를 활용하여 실시할 수도 있다.In one embodiment, the distillation is preferably carried out at a temperature of 100 to 250 DEG C, more preferably 100 to 200 DEG C, even more preferably 120 to 190 DEG C, and preferably 20 mmHg or less (e.g., 0.0001 to 20 mmHg, more specifically 0.0001 to 16 mmHg), more preferably 10 mmHg or less (e.g., 0.001 to 10 mmHg), still more preferably 5 mmHg or less (e.g., 0.01 to 5 mmHg, 4 mmHg). ≪ / RTI > The distillation may be carried out in two or more stages as required. There is no particular limitation on the method and apparatus for distillation, and known methods and apparatuses known to those skilled in the art can be used as is or modified appropriately. For example, a general condenser type distiller or distillation tower still can be used, or a thin film still can be used.
일 구체예에서, 상기 예비 정제는 결정화, 탈색 및 양이온성 이온교환수지 처리 중에서 선택되는 하나 이상의 공정에 의하여 수행될 수 있다. 바람직한 일 구체예의 예비 정제 공정은, 증류 결과물의 결정화, 결정화 결과물의 탈색, 및 탈색 결과물의 양이온성 이온교환수지 처리를 순차적으로 수행하는 것일 수 있다.In one embodiment, the pre-purification may be performed by one or more processes selected from crystallization, decolorization, and cationic ion exchange resin treatment. The preliminary purification step of a preferred embodiment may be to sequentially perform the crystallization of the distillation result, the decolorization of the crystallization result, and the cationic ion exchange resin treatment of the decolorized product.
상기 결정화의 방법 및 장치에는 특별한 제한이 없으며, 당 분야에 오래 전부터 알려져 온 결정화 방법 및 장치를 그대로 또는 적절히 변형하여 활용할 수 있다. 구체적으로 예를 들면, 무수당 알코올을 물, 에틸아세테이트, 아세톤, 톨루엔, 벤젠, 자일렌, 알코올 등의 용매에 필요에 따라 승온 하에 용해시킨 후, 용액의 온도를 낮추어 무수당 알코올 결정을 석출시키는 방법을 사용할 수도 있고, 다르게는 용매를 사용하지 않는 용융 결정화 방법을 사용할 수도 있다. There is no particular limitation on the method and apparatus for the crystallization, and the crystallization method and apparatus that have been known in the art for a long time can be used as is or modified appropriately. Concretely, for example, an alcohol without anhydride is dissolved in a solvent such as water, ethyl acetate, acetone, toluene, benzene, xylene, alcohol or the like according to need, and then the temperature of the solution is lowered to precipitate an alcohol- Alternatively, a melt crystallization method which does not use a solvent may be used.
상기 탈색은 무수당 알코올의 결정화물을 물(예컨대, 증류수)에 녹인 수용액을 활성탄과 접촉시키는 것에 의해 수행될 수 있다. 활성탄으로는 목재, 야자 등의 식물계 원료나 갈탄, 유연탄, 역청탄, 무연탄 등의 광물계 원료를 활성화하여 얻어진 활성탄 군으로부터 선택되는 1종 이상을 사용할 수 있다. 활성탄의 평균 입도로는 0.25 내지 1.0mm가 바람직하고, 0.25 내지 0.70mm가 보다 바람직하다. 무수당 알코올 수용액과 활성탄의 접촉 방식에는 특별한 제한이 없다. 예컨대 활성탄으로 충전된 컬럼에 무수당 알코올 수용액을 통과시키는 방식으로 수행될 수도 있고, 다르게는 무수당 알코올 수용액과 활성탄을 반응기에 투입하고 일정 시간동안 교반하여 혼합하는 방식으로 수행될 수도 있다. The decolorization can be carried out by bringing an aqueous solution of the crystalline alcohol free of alcohol into water (for example, distilled water) in contact with the activated carbon. As the activated carbon, it is possible to use at least one selected from a plant raw material such as wood and coconut, and an activated carbon group obtained by activating a mineral raw material such as lignite, bituminous coal, bituminous coal and anthracite. The average particle size of the activated carbon is preferably 0.25 to 1.0 mm, more preferably 0.25 to 0.70 mm. There is no particular limitation on the method of contacting the aqueous solution of alcohol-free alcohol with the activated carbon. For example, a method in which an aqueous solution of an alcohol-free alcohol is passed through a column packed with activated carbon, or alternatively, an aqueous solution of an alcohol-free alcohol and an activated carbon may be fed into a reactor and stirred for a certain period of time.
상기 양이온성 이온교환수지 처리는, 탈색된 결과액과 양이온성 이온교환수지를 접촉시키는 것에 의해 이루어질 수 있으며, 이는 양이온성 이온교환수지로 충전된 컬럼에 탈색 결과액을 통과시키는 방식으로 수행될 수 있다. 양이온성 이온교환수지로는 강양이온성 이온교환수지( Sulfonate형), 약양이온성 이온교환수지(COOH형)가 모두 사용가능하다. The cationic ion exchange resin treatment can be carried out by contacting the decolorized resultant liquid with a cationic ion exchange resin which can be carried out in such a way that the solution is passed through a column filled with cationic ion exchange resin have. As the cationic ion exchange resin, a cation exchange resin (Sulfonate type) and a weak cationic ion exchange resin (COOH type) can be used.
일 구체예에서, 본 발명에 따라 정제된 무수당 알코올은, 농축될 수 있다. 일 구체예에서, 상기 농축은 40℃~110℃의 온도 및 1 mmHg ~100 mmHg의 압력조건 하에서 30분 이상(예컨대, 30분~4시간) 수행될 수 있으나, 이에 한정되는 것은 아니다. 농축은 통상의 농축기(예컨대, 로타리 농축기, 강제순환농축기, 박막농축기) 내에서 수행될 수 있다. In one embodiment, the purified anhydrous alcohol according to the present invention can be concentrated. In one embodiment, the concentration can be performed for at least 30 minutes (e.g., 30 minutes to 4 hours) at a temperature of 40 ° C to 110 ° C and a pressure of 1 mmHg to 100 mmHg, but is not limited thereto. Concentration can be performed in conventional concentrators (e.g., a rotary condenser, forced circulation concentrator, thin film concentrator).
일 구체예에서, 본 발명에 따라 정제된 무수당 알코올은, 고온에서 장기 저장 후(예컨대, 60℃에서 5일), 20 중량% 농도의 수용액으로 희석시 5.0~ 7.0의 안정한 pH(예컨대, 상온(25±3℃)에서 측정시)를 나타낼 수 있다.In one embodiment, the purified anhydrosugar alcohol according to the present invention has a stable pH of 5.0 to 7.0 (for example, at room temperature (for example, at room temperature) when diluted with a 20 wt% (25 ± 3 ° C)).
또한, 본 발명에 따라 정제된 무수당 알코올은, 고온에서 장기 저장 후(예컨대, 60℃에서 10일), 포름산을 함유하지 않거나 1ppm 이하(예컨대, 0.0001~1ppm)의 낮은 포름산 함량을 나타낼 수 있다.In addition, the purified anhydrous alcohol according to the present invention may contain no formic acid or exhibit a low formic acid content of less than 1 ppm (e.g., 0.0001 to 1 ppm) after prolonged storage at high temperature (e.g., 10 days at 60 ° C) .
따라서, 본 발명의 또 다른 측면에 따르면, 수소화 당을 탈수반응시켜 무수당 알코올을 제조하는 단계; 및 제조된 무수당 알코올에 대하여 강염기성 음이온 교환 수지를 사용한 정제를 수행하는 단계를 포함하며, 정제된 무수당 알코올이 포름산을 함유하지 않거나 포름산 함량이 1ppm 이하인, 무수당 알코올의 제조 방법이 제공된다.Accordingly, in accordance with another aspect of the present invention, there is provided a process for producing an alcohol-free alcohol by dehydrogenating a hydrogenated sugar to produce an alcohol-free alcohol; And performing purification using the strongly basic anion exchange resin for the produced anhydrosugar alcohol, wherein the purified anhydrosugar alcohol does not contain formic acid or the formic acid content is 1 ppm or less .
이하, 실시예 및 비교예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐, 본 발명의 범위가 이로써 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples are intended to assist the understanding of the present invention, and the scope of the present invention is not limited thereto.
[실시예 및 비교예][Examples and Comparative Examples]
실시예 1Example 1
소르비톨 분말(D-소르비톨, ㈜삼양제넥스) 1,200g을 교반기가 부착된 4구 유리 반응기에 넣고 온도를 110℃로 승온하여 녹인 후, 여기에 진한 황산(덕산화공, 95%) 12g을 투입한 후에 반응 혼합물 온도를 135℃로 승온하였다. 이 온도를 유지하며 4시간 동안 40torr의 진공 조건 하에서 탈수 반응을 진행하여 출발물질인 소르비톨을 무수당 알코올인 이소소르비드로 전환시켰다. 이후, 반응물 온도를 110℃로 낮추고, 반응 결과액에 50% 수산화나트륨 용액(삼전순약) 31.2g을 첨가하여 중화시켰다. 1,200 g of sorbitol powder (D-sorbitol, manufactured by Samyang Genex Co., Ltd.) was placed in a four-necked glass reactor equipped with a stirrer, and the temperature was elevated to 110 ° C. to dissolve. Then, 12 g of concentrated sulfuric acid (Duksan Chemical Co., 95% The temperature of the reaction mixture was raised to 135 占 폚. The dehydration reaction was carried out under a vacuum of 40 torr for 4 hours while maintaining the temperature, and the starting material, sorbitol, was converted to isosorbide, a non-alcoholic alcohol. Thereafter, the temperature of the reactant was lowered to 110 캜, and 31.2 g of 50% sodium hydroxide solution (Samjeonpun) was added to the resultant solution to neutralize it.
중화된 무수당 알코올을 박막증류기를 이용하여 180℃, 5 mmHg 이하의 진공 하에서 증류하였다. The neutralized alcohol-free alcohol was distilled using a thin-film distillation apparatus at 180 ° C under a vacuum of 5 mmHg or less.
얻어진 증류액을 자켓이 달린 반응조에 넣고, 아세톤(삼전순약) 300g을 첨가하여 혼합물의 온도를 10℃로 낮추면서 결정화를 실시하였다. 결정화가 끝난 후에 탈수를 실시하고 모액과 분리하여 무수당 알코올 결정을 회수하였다. 얻어진 무수당 알코올 결정의 순도는 99.7%이었다.The obtained distillate was placed in a jacketed reactor, and 300 g of acetone (pure alkenes) was added to crystallize while lowering the temperature of the mixture to 10 캜. After the crystallization, dehydration was carried out and the mother liquor was separated to recover anhydrous alcohol crystals. The purity of the obtained alcohol-free alcohol crystals was 99.7%.
얻어진 결정 400g에 증류수 600g을 첨가하고 용해시켜 고형분 40%의 용액으로 제조하였다. 이 용액을 평균입도 0.25mm의 미세 입자상 활성탄으로 충전된 컬럼에 통과시켜 탈색시켰다. 탈색된 무수당 알코올의 포름산 함량은 4.3 ppm이었다. 포름산 함량은 HPLC(Agillent, 독일)를 사용하여 측정하였다.600 g of distilled water was added to 400 g of the obtained crystals and dissolved to prepare a solution having a solid content of 40%. This solution was decolorized by passing it through a column filled with fine particulate activated carbon having an average particle size of 0.25 mm. The formic acid content of decolorized anhydrous alcohol was 4.3 ppm. Formic acid content was determined using HPLC (Agillent, Germany).
탈색된 무수당 알코올을 이어서 약산성 양이온 교환 수지(WK60L, 삼양사)로 충전된 컬럼에 SV 1의 속도로 통과시킨 후, 그 결과액을 다시 4급 암모늄기를 관능기로 가지는 강염기성 음이온 교환 수지(UPRA 200, 삼양사)로 충전된 컬럼에 SV 1의 속도로 통과시켜, 최종 정제된 무수당 알코올을 얻었다. 상기 각각의 수지들은 재생과 세정 과정을 거친 후에 컬럼에 300mL씩 충진하여 사용하였다. The decolorized anhydrosugar alcohol was then passed through a column packed with a weakly acidic cation exchange resin (WK60L, Samyang Corp.) at a rate of SV 1, and the resultant solution was treated with a strong basic anion exchange resin (UPRA 200 , Samyang Corp.) at a rate of SV 1 to obtain a final purified free alcohol. Each of the above resins was used after being regenerated and washed, and then filled into the column with 300 mL each.
상기 정제된 무수당 알코올의 20 중량% 수용액의 상온(25±3℃)에서 측정한 pH는 5.8이었고, 포름산 함량은 0ppm이었다.The pH of the 20 wt% aqueous solution of the purified anhydrosugar alcohol measured at room temperature (25 3 C) was 5.8 and the formic acid content was 0 ppm.
상기 정제된 무수당 알코올을, 80℃로 셋팅된 로타리 농축기에서 20torr의 진공으로 2시간 동안 농축하였다. 농축이 완료된 무수당 알코올의 저장 안정성을 평가하기 위하여 20mL 바이알 병에 담은 후에 공기에 노출된 상태로 60℃ 건조기에서 5일 동안 보관한 후에 포름산 함량 및 20 중량% 수용액의 pH를 상온에서 측정한 결과, 무수당 알코올이 고온에서 5일 동안 대기 중에 노출되었음에도 불구하고, 포름산 함량은 0.8ppm으로 매우 낮았고, pH는 5.7로서 안정하게 유지되었다.The purified anhydrous alcohol was concentrated in a rotary evaporator set at 80 DEG C under a vacuum of 20 torr for 2 hours. In order to evaluate the storage stability of the concentrated alcohol-free alcohol, it was immersed in a 20 mL vial bottle and stored for 5 days in a drier at 60 ° C. in the state of being exposed to air. The pH of formic acid and 20 wt% aqueous solution were measured at room temperature , The formic acid content was very low at 0.8 ppm and the pH remained stable at 5.7, even though the free alcohol was exposed to the atmosphere for 5 days at high temperature.
실시예 2Example 2
양이온 교환 수지 및 음이온 교환 수지의 통액 속도를 각각 SV 0.2로 한 것을 제외하고는, 실시예 1과 동일하게 하여 정제된 무수당 알코올을 수득하였다. 정제된 무수당 알코올의 20 중량% 수용액의 상온에서 측정한 pH는 5.8이었고, 포름산 함량은 0ppm이었다.The purified anhydrosugar alcohol was obtained in the same manner as in Example 1, except that the passing speed of the cation exchange resin and the anion exchange resin was SV 0.2, respectively. The pH of the 20 wt% aqueous solution of the purified anhydrosugar alcohol measured at room temperature was 5.8 and the formic acid content was 0 ppm.
상기 정제된 무수당 알코올을 실시예 1과 동일하게 농축한 후, 60℃에서 5일 동안 보관한 후에 상온에서 측정한 무수당 알코올(20 중량% 수용액)의 pH는 5.7이었고, 포름산 함량은 0.9ppm으로, 저장 안정성이 매우 우수하였다.The purified anhydrosugar alcohol was concentrated in the same manner as in Example 1, and the pH of anhydrous alcohol (20 wt% aqueous solution) measured at room temperature after storage at 60 ° C for 5 days was 5.7, and the formic acid content was 0.9 ppm , And the storage stability was excellent.
실시예 3Example 3
양이온 교환 수지 및 음이온 교환 수지의 통액 속도를 각각 SV 3.0로 한 것을 제외하고는, 실시예 1과 동일하게 하여 정제된 무수당 알코올을 수득하였다. 정제된 무수당 알코올의 20 중량% 수용액의 상온에서 측정한 pH는 5.8이었고, 포름산 함량은 0ppm이었다.A purified anhydrous alcohol was obtained in the same manner as in Example 1, except that the passing speed of the cation exchange resin and the anion exchange resin was SV 3.0, respectively. The pH of the 20 wt% aqueous solution of the purified anhydrosugar alcohol measured at room temperature was 5.8 and the formic acid content was 0 ppm.
상기 정제된 무수당 알코올을 실시예 1과 동일하게 농축한 후, 60℃에서 5일 동안 보관한 후에 상온에서 측정한 무수당 알코올(20 중량% 수용액)의 pH는 5.6이었고, 포름산 함량은 1.0ppm으로, 저장 안정성이 매우 우수하였다.The purified anhydrous alcohol was concentrated in the same manner as in Example 1, and the pH of anhydrous alcohol (20 wt% aqueous solution) measured at room temperature after storage at 60 ° C for 5 days was 5.6, and the formic acid content was 1.0 ppm , And the storage stability was excellent.
비교예 1Comparative Example 1
음이온 교환 수지로서 약염기성 음이온 교환 수지(DIAION WA20, 삼양사)를 사용한 것을 제외하고는, 실시예 1과 동일하게 하여 정제된 무수당 알코올을 수득하였다. 정제된 무수당 알코올의 20 중량% 수용액의 상온에서 측정한 pH는 5.2이었고, 포름산 함량은 1.3ppm이었다.A purified anhydrous alcohol was obtained in the same manner as in Example 1, except that a weakly basic anion exchange resin (DIAION WA20, Samyang Corp.) was used as the anion exchange resin. The pH of the 20 wt% aqueous solution of the purified anhydrosugar alcohol measured at room temperature was 5.2, and the formic acid content was 1.3 ppm.
상기 정제된 무수당 알코올을 실시예 1과 동일하게 농축한 후, 60℃에서 5일 동안 보관한 후에 상온에서 측정한 무수당 알코올(20 중량% 수용액)의 pH는 3.6으로 낮아졌고, 포름산 함량은 48ppm로 급격하게 증가하여, 저장 안정성이 매우 열악한 것으로 나타났다.The purified anhydrosugar alcohol was concentrated in the same manner as in Example 1, and after 5 days of storage at 60 ° C, the pH of anhydrous alcohol (20 wt% aqueous solution) measured at room temperature was lowered to 3.6 and the formic acid content 48ppm, indicating that the storage stability is very poor.
Claims (16)
암모늄기를 관능기로 갖는 강염기성 음이온 교환 수지를 사용하여 정제를 수행하는 단계를 포함하며,
정제된 무수당 알코올이 포름산을 함유하지 않거나 포름산 함량이 1ppm 이하이고,
상기 무수당 알코올이 디언하이드로헥시톨인, 방법.A method for purifying an alcohol-free alcohol,
And performing a purification using a strong basic anion exchange resin having an ammonium group as a functional group,
Wherein the purified anhydrosugar alcohol does not contain formic acid or has a formic acid content of 1 ppm or less,
Wherein said anhydrosugar alcohol is dianhydrohexitol.
수소화 당을 탈수반응시켜 무수당 알코올을 제조하는 단계; 및
제조된 무수당 알코올에 대하여 암모늄기를 관능기로 갖는 강염기성 음이온 교환 수지를 사용한 정제를 수행하는 단계를 포함하며,
정제된 무수당 알코올이 포름산을 함유하지 않거나 포름산 함량이 1ppm 이하이고,
상기 수소화 당이 헥시톨이고,
상기 무수당 알코올이 디언하이드로헥시톨인, 방법.A method for producing an alcohol-free alcohol,
Dehydrogenating the hydrogenated sugar to produce an anhydrous alcohol; And
And performing purification using a strongly basic anion exchange resin having an ammonium group as a functional group with respect to the produced anhydrosugar alcohol,
Wherein the purified anhydrosugar alcohol does not contain formic acid or has a formic acid content of 1 ppm or less,
Wherein the hydrogenated sugar is hexitol,
Wherein said anhydrosugar alcohol is dianhydrohexitol.
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| FR3116533A1 (en) | 2020-11-26 | 2022-05-27 | Roquette Freres | High Purity Sorbitol Internal Dehydration Product |
| KR20230089474A (en) * | 2021-12-13 | 2023-06-20 | 주식회사 켐스 엔바이오 | Dilution Steam System for Ethylene production process to reduce waste water |
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| FR3116533A1 (en) | 2020-11-26 | 2022-05-27 | Roquette Freres | High Purity Sorbitol Internal Dehydration Product |
| WO2022111849A1 (en) | 2020-11-26 | 2022-06-02 | Roquette Freres | Product of internal dehydration of high-purity sorbitol |
| KR20230089474A (en) * | 2021-12-13 | 2023-06-20 | 주식회사 켐스 엔바이오 | Dilution Steam System for Ethylene production process to reduce waste water |
| KR102688678B1 (en) | 2021-12-13 | 2024-07-26 | 주식회사 켐스 엔바이오 | Dilution Steam System for Ethylene production process to reduce waste water |
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