WO2013169029A1 - 박막증류를 통한 고순도 무수당 알코올의 제조방법 - Google Patents
박막증류를 통한 고순도 무수당 알코올의 제조방법 Download PDFInfo
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- WO2013169029A1 WO2013169029A1 PCT/KR2013/004077 KR2013004077W WO2013169029A1 WO 2013169029 A1 WO2013169029 A1 WO 2013169029A1 KR 2013004077 W KR2013004077 W KR 2013004077W WO 2013169029 A1 WO2013169029 A1 WO 2013169029A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/06—Evaporators with vertical tubes
- B01D1/065—Evaporators with vertical tubes by film evaporating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
- B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
- B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
- B01D5/0063—Reflux condensation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/26—Hexahydroxylic alcohols
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
Definitions
- the present invention relates to a technique for producing anhydrosugar alcohol from the hydrogenated sugar as a raw material, and more specifically, after adding the acid to hexitol to convert to anhydrosugar alcohol, the conversion reaction solution is a condenser One-stage distillation using a built-in thin film evaporator (internal condenser type), high purity of 97.5% or more (more preferably 98.5% or more), distillate pH 3.7 or more (more preferably pH 4.0 or more)
- the present invention relates to a technique capable of producing anhydrosugar alcohols (particularly isosorbide, isomannide, isoidide, etc.) with a distillation yield of 87% or more (more preferably 90% or more).
- Anhydrous sugar alcohols can be prepared using hexitol derived from starch, and its utilization is very wide in the pharmaceutical and chemical industries.
- Anhydrous sugar-alcohol derivatives are useful for heart and vascular diseases, can be used in medicaments such as adhesives of patches, oral cleansers, and can also be applied to cosmetic compositions.
- anhydrosugar alcohols when using anhydrosugar alcohols to make polyester, polyurethane, epoxy resin, etc., various physical properties can be imparted to the resin.
- Anhydrosugar alcohols may also be used as raw materials for plastic plasticizers and organic solvents. When the anhydrosugar alcohol is utilized in the resin manufacturing field, heat-resistant PET, polyester fibers, high-strength sheets, films, polyurethane, etc. may be more environmentally friendly.
- hexitol is dehydrated under reduced pressure in a batch reactor using an acid catalyst (eg, an inorganic acid, cationic resin, zeolite, etc.), and then distilled and recrystallized from the reaction product (eg, acetone, alcohol, ethyl acetate). , Using water, etc.), melt crystallization (meltcrystallization), activated carbon purification, ionic purification and the like to apply one or two or more combinations of the production of anhydrosugar alcohols.
- an acid catalyst eg, an inorganic acid, cationic resin, zeolite, etc.
- Batch distillation or simple distillation has a disadvantage in that it is difficult to economically produce on a commercial scale due to a long distillation time.
- distillation of the conversion reaction liquid at a low temperature takes a long time distillation, when distilling at a relatively high temperature (for example 170 °C or more), distillation time is shortened, but anhydrous sugars
- the alcohol is pyrolyzed at a temperature of 170 ° C. or higher to generate by-products such as formic acid and furfural, resulting in lower purity and lower pH of the distillate.
- an anhydrosugar alcohol such as isosorbide is thermally decomposed at a distillation temperature of 170 ° C or higher, and as a result, distillation yield and distillation purity are lowered.
- the purity of the single-step distillation in the US patent was 97.1% and distillation yield was 80%, but this degree of purity and yield is still unsuitable for commercial scale large scale production processes.
- An object of the present invention is to solve the above-mentioned problems of the prior art, after converting the hydrogenated sugar to anhydrosugar alcohol, only one step of distillation to a high level of purity and high yield suitable for large scale production process It is a technical problem to provide a method for producing a sugar alcohol.
- the present invention includes the step of dehydrating the hydrogenated sugar to anhydrosugar alcohol and distilling the resultant of the conversion step, the distillation step is a built-in condenser, raw material input line, It provides a method for producing anhydrosugar alcohols, characterized in that it is carried out in a condenser built-in thin film distillator comprising a distillation residue discharge line, a vacuum line and a distillate discharge line.
- the inside of the distiller is further decompressed through a distillation residue discharge line together with the decompression through the vacuum line. do.
- the present invention includes a built-in condenser, raw material input line, distillation residue discharge line, vacuum line and distillate discharge line, characterized in that the distillation residue discharge line has a side line for forming vacuum A thin film distillator with a condenser is provided.
- the level of high purity (purity of 97.5% or more, more preferably 98.5% or more; distillate pH) suitable for commercial scale large-scale production process
- Anhydrosugar alcohols can be produced in 3.7 or more, more preferably 4.0 or more) and in high yield (87% or more of distillation yield, more preferably 90% or more).
- FIG. 1 is a view schematically showing a preferred embodiment of the condenser built-in thin film distillation structure usable in the anhydrosugar alcohol production method of the present invention.
- the method for producing anhydrosugar alcohols of the present invention includes the step of converting the hydrogenated sugars to anhydrosugar alcohols.
- anhydrosugar alcohol means any substance obtained by removing one or more water molecules from the original internal structure of the hydrogenated sugar (or sugar alcohol) in one or more steps in any manner.
- hexitol is preferably used as the hydrogenated sugar, more preferably hydrogenated sugar selected from sorbitol, mannitol, iditol and mixtures thereof.
- dianhydrohexitol which is a dehydration product of hexitol is preferably obtained as the anhydrosugar alcohol, and more preferably isosorbide (1,4-3,6-dianhydrosorbitol), iso Anhydrosugar alcohols selected from mannide (1,4-3,6-dianhydromannitol), isoidide (1,4-3,6-dianhydroiditol) and mixtures thereof are obtained.
- isosorbide is particularly high in industrial and medical applications.
- the hydrogenated sugar is converted to anhydrosugar alcohol by dehydration reaction.
- dehydration reaction There is no particular limitation on the method of dehydrating hydrogenated sugars, and known methods known in the art may be used as they are or as appropriately modified.
- An acid catalyst is preferably used to dehydrate the hydrogenated sugar and convert it into anhydrosugar alcohol, more preferably a mixed acid of the first acid and the second acid can be used.
- the acid catalyst sulfuric acid, hydrochloric acid, phosphoric acid, etc. may be used in the case of a single acid catalyst, and sulfuric acid as the first acid in the case of mixed acid, p-toluene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, benzene as the second acid.
- One or more sulfur-containing acid salts selected from the group consisting of sulfonic acid, naphthalene sulfonic acid and aluminum sulfate can be used.
- the amount of acid catalyst used is preferably 0.5 to 10 parts by weight per 100 parts by weight of hydrogenated sugar (eg, hexitol). If the amount of the acid catalyst is too small in this range, the conversion time to anhydrosugar alcohol may be too long, while if the amount of the acid catalyst is too large in this range, there is a problem that the production of saccharide polymer is increased and the conversion rate is lowered. have.
- the step of converting the hydrogenated sugars to anhydrosugar alcohols may be performed for 1 to 10 hours at a temperature of 100 to 190 ° C. and a pressure of 20 mmHg or less in the presence of an acid catalyst as described above. Can be.
- the reaction resultant is preferably neutralized. Neutralization may be carried out after the dehydration reaction is completed by lowering the reaction resultant temperature (eg, 100 ° C. or lower) and adding a known alkali such as sodium hydroxide.
- the pH of the neutralized reaction resultant is preferably 6-8.
- the resultant step of converting the hydrogenated sugar to the anhydrosugar alcohol (preferably the resultant pretreated as above) is distilled in the condenser built-in thin film distiller.
- the thin film distillator 1 with the condenser according to FIG. 1 has a built-in condenser 5, a raw material input line 6, a distillation residue discharge line 7, a vacuum forming side line 7-1, and a vacuum line 8. And a distillate discharge line (9), in addition a heating jacket (2), a wiper (3), a condenser guard (4) and a coolant inlet / outlet line (10 and 11, respectively) for heating. Include.
- the condenser built-in thin film distillation apparatus that can be used in the present invention is not limited to the structure shown in FIG. 1, and may further include additional components as necessary in addition to the above components, and the shapes may be various.
- the distillation step can be effectively carried out under the temperature conditions of preferably 100 ⁇ 200 °C, more preferably 100 ⁇ 170 °C, even more preferably 110 ⁇ 160 °C. If the distillation temperature is less than 100 °C distillation of the anhydrosugar alcohol may not be effective.
- the pH of the distillate can be improved.
- Thermal decomposition of isosorbide, anhydrosugar alcohol produces by-products such as formic acid and perfural, and these by-products lower the pH of the distillate.
- the lower the pH of the distillate the lower the stability of the produced isosorbide. do. Therefore, it is necessary to maintain the pH of the final distillate above 6.0 through ion purification.
- the temperature is high during distillation, when a large amount of the by-product is generated, there is a problem that an overload occurs in the subsequent ion purification.
- the distillation temperature can be lowered to 145 ° C, resulting in a purity of 98.5% or more (eg, 98.5 to 100%), distillate pH 4.0 or more (eg, 4.0 to 7.0) Alcohol may be obtained in a distillation yield of 90% or more (eg, 90-100%).
- a vacuum pump connected to a vacuum line may also be connected to the vacuum forming side line of the residue discharge line so that the same degree of vacuum is applied to the distillation residue discharge line and the vacuum line, or alternatively to the vacuum formation of the distillation residue discharge line.
- a separate vacuum pump can be connected to the branch line to allow the degree of vacuum to be applied independently of the vacuum line.
- a specific example of distillation by connecting the same vacuum pump to the vacuum forming side line and the vacuum line of the distillation residue discharge line is as follows.
- the method for producing anhydrosugar alcohol of the present invention may further include, after the distillation step, performing a post-treatment selected from an adsorbent treatment, an ionic purifier, and a combination thereof with respect to the anhydrous sugar alcohol which is a distillation product.
- the adsorbent treatment is for decolorization, and may be performed according to a conventional adsorbent treatment method using a known adsorbent such as activated carbon.
- a known adsorbent such as activated carbon.
- the activated carbon one or more selected from the group of activated carbons obtained by activating plant-based raw materials such as wood and palm, and mineral-based raw materials such as lignite, bituminous coal, bituminous coal and anthracite coal can be used.
- the ion tablets are for removing ions that may be present in the anhydrosugar alcohol, and are selected from the group of strong cationic, weak cationic, strong anionic and weak anionic ion exchange resins according to the kind of ions that may be present. It may be carried out one or more times using one or more.
- high purity anhydrosugar alcohol having a purity of 98.5% or more and a distillate pH 4.0 or more to a distillation yield of 90% or more by only one step of distillation.
- further decolorization with an adsorbent and further purification of ions may yield white isosorbide.
- Distillation method is preferably used for the distillation of anhydrosugar alcohol, but may be applied to the distillation of other materials.
- distillation is performed in distilling a liquid material by using a condenser built-in thin film distiller having a built-in condenser, a raw material input line, a distillation residue discharge line, a vacuum line and a distillate discharge line.
- a distillation method is provided, characterized in that the inside of the municipal still is further depressurized through the distillation residue discharge line with the decompression through the vacuum line.
- the invention includes a built-in condenser, raw material input line, distillation residue discharge line, vacuum line and distillate discharge line, characterized in that the distillation residue discharge line has a side branch line for vacuum forming
- the thin film distillation machine with built-in condenser is provided.
- Specific examples of the condenser-embedded thin film distillation unit of the present invention and usage examples thereof are as described above, but are not limited thereto.
- the conversion resultant solution which completed neutralization and water removal was distilled using the condenser built-in thin film distiller under the conditions of the distillation temperature of 170 degreeC, and the internal pressure of 0.70 mmHg.
- the distillation was performed by additionally connecting the vacuum pump to the side line line for forming the vacuum of the distillation residue discharge line, and continuous distillation was possible even under the internal pressure of 1.40 mmHg.
- the purity of isosorbide in the obtained distillate was 97.5%, distillate pH was 3.70, the color of the distillate was yellow, the distillation yield was 92.0%, distillation time was less than 4 hours.
- the thin film was distilled from the conversion resultant obtained in Example 1 to which neutralization and water removal were completed. Distillation was carried out in the same manner using the same thin film distillator as in Example 1, except that the distillation temperature was 160 ° C. and the internal pressure of the distillator was 0.45 mmHg. The purity of isosorbide in the obtained distillate was 98.5%, the distillate pH was 4.00, the distillate color was yellow, the distillation yield was 92.0%, distillation time was less than 4 hours.
- the thin film was distilled from the conversion resultant obtained in Example 1 to which neutralization and water removal were completed. Distillation was carried out in the same manner using the same thin film distillator as in Example 1 except that the distillation temperature was set at 150 ° C. and the internal pressure of the distillator was 0.14 mmHg. The purity of isosorbide in the obtained distillate was 98.5%, distillate pH was 4.50, the color of the distillate was yellow, the distillation yield was 91.6%, distillation time was less than 4 hours.
- the thin film was distilled from the conversion resultant obtained in Example 1 to which neutralization and water removal were completed. Distillation was carried out in the same manner using the same thin film distillator as in Example 1, except that the distillation temperature was set at 145 ° C. and the distillator internal pressure was set at 0.10 mmHg. The purity of isosorbide in the obtained distillate was 98.5%, distillate pH was 4.75, the color of the distillate was yellow, the distillation yield was 92.0%, distillation time was less than 4 hours.
- the thin film was distilled from the conversion resultant obtained in Example 1 to which neutralization and water removal were completed.
- the distillation was carried out in the same manner using the same thin film distillator as in Example 1, except that the distillation temperature was 170 ° C., the internal pressure of the distiller was 1.40 mmHg, and no vacuum pump was connected to the vacuum branch line. .
- the purity of isosorbide in the obtained distillate was 97.6%, the distillate pH was 3.70, the color of the distillate was yellow, the distillation yield was 87.0%, distillation time was less than 4 hours.
- the thin film was distilled from the conversion resultant obtained in Example 1 to which neutralization and water removal were completed. Condenser External Thin film distillers were used and there was no further decompression through the distillation residue discharge line.
- the distillation temperature was 180 ° C. and the distillator internal pressure was about 3.0 mmHg.
- the purity of isosorbide in the obtained distillate was 96.6%, the distillate pH was 3.50, the color of the distillate was yellow, the distillation yield was 78.0%, distillation time was less than 4 hours.
- the thin film was distilled from the conversion resultant obtained in Example 1 to which neutralization and water removal were completed. Distillation was carried out in the same manner using the same condenser external thin film distillator as in Comparative Example 1, except that the distillation temperature was 170 ° C and the internal pressure of the distillator was about 2.0 mmHg. The purity of isosorbide in the obtained distillate was 97.2%, distillate pH was 3.70, the color of the distillate was yellow, the distillation yield was 80.2%, distillation time was less than 4 hours.
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Abstract
Description
Claims (12)
- 수소화 당을 탈수 반응시켜 무수당 알코올로 전환시키는 단계, 및상기 전환 단계의 결과액을 증류하는 단계를 포함하며,상기 증류 단계가 내장형 응축기, 원료 투입라인, 증류 잔여물 배출 라인, 진공 라인 및 증류물 배출 라인을 포함하는 응축기 내장형 박막증류기 내에서 수행되는 것을 특징으로 하는,무수당 알코올의 제조방법.
- 제1항에 있어서, 증류 단계의 수행시 증류기 내부가 진공 라인을 통한 감압과 함께 증류 잔여물 배출 라인을 통하여 추가로 감압되는 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 수소화 당이 헥시톨이며, 무수당 알코올이 디언하이드로헥시톨인 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 수소화 당을 탈수시켜 무수당 알코올로 전환하는 단계에서 산 촉매가 사용되는 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 수소화 당의 무수당 알코올로의 전환 단계 결과액이, 증류 단계 투입 전에 수분 및 비점이 낮은 물질을 제거하기 위하여 전처리되는 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 증류 단계가 100~170℃의 온도 조건 하에서 수행되는 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 증류 단계가 1 mmHg 이하의 압력 조건 하에서 수행되는 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 증류 단계의 수행시 진공 라인의 진공도와 증류 잔여물 배출 라인의 진공도가 동일한 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 증류 단계후 증류액의 무수당 알코올 순도가 97.5% 이상이고, 증류액의 pH가 3.7 이상이며, 증류 수율이 87% 이상인 것을 특징으로 하는 무수당 알코올의 제조방법.
- 제1항 또는 제2항에 있어서, 증류 단계 이후에, 증류 결과물인 무수당 알코올에 대하여 흡착제 처리, 이온정제 및 이들의 조합으로부터 선택되는 후처리를 수행하는 단계를 추가로 포함하는 것을 특징으로 하는 무수당 알코올의 제조방법.
- 내장형 응축기, 원료 투입라인, 증류 잔여물 배출 라인, 진공 라인 및 증류물 배출 라인을 구비한 응축기 내장형 박막증류기를 사용하여 액상 물질을 증류함에 있어서, 증류 수행시 증류기 내부가 진공 라인을 통한 감압과 함께 증류 잔여물 배출 라인을 통하여 추가로 감압되는 것을 특징으로 하는 증류방법.
- 내장형 응축기, 원료 투입라인, 증류 잔여물 배출 라인, 진공 라인 및 증류물 배출 라인을 포함하며, 상기 증류 잔여물 배출 라인이 진공형성용 곁가지 라인을 갖는 것을 특징으로 하는, 응축기 내장형 박막증류기.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2015511366A JP6034959B2 (ja) | 2012-05-11 | 2013-05-09 | 薄膜蒸留による高純度アンヒドロ糖アルコールの製造方法 |
EP13787187.7A EP2848603B1 (en) | 2012-05-11 | 2013-05-09 | Method for preparing high purity anhydrosugar alcohols by thin film distillation |
CN201380024324.2A CN104470880A (zh) | 2012-05-11 | 2013-05-09 | 通过薄膜蒸馏制备高纯度无水糖醇的方法 |
US14/399,031 US9290508B2 (en) | 2012-05-11 | 2013-05-09 | Method for preparing high purity anhydrosugar alcohols by thin film distillation |
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KR10-2012-0050316 | 2012-05-11 | ||
KR20120050316A KR101388676B1 (ko) | 2012-05-11 | 2012-05-11 | 박막증류를 통한 고순도 무수당 알코올의 제조방법 |
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US (1) | US9290508B2 (ko) |
EP (1) | EP2848603B1 (ko) |
JP (1) | JP6034959B2 (ko) |
KR (1) | KR101388676B1 (ko) |
CN (1) | CN104470880A (ko) |
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WO2017158303A1 (fr) | 2016-03-16 | 2017-09-21 | Roquette Freres | Procede de fabrication de dianhydrohexitol avec une etape de distillation sur un evaporateur a couche mince |
CN112933634A (zh) * | 2021-03-04 | 2021-06-11 | 安徽金禾实业股份有限公司 | 一种环列式的蔗糖-6-酯连续生产设备及生产工艺流程 |
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KR102262461B1 (ko) * | 2014-10-15 | 2021-06-08 | 에스케이이노베이션 주식회사 | 무수당 알코올의 연속 반응 및 증류 장치 |
WO2016105107A2 (ko) * | 2014-12-23 | 2016-06-30 | 에스케이이노베이션 주식회사 | 무수당 알코올의 효과적인 생산 및 정제 방법 |
KR20160076999A (ko) * | 2014-12-23 | 2016-07-01 | 에스케이이노베이션 주식회사 | 무수당 알코올의 연속적인 생산방법 |
CN109232676B (zh) * | 2018-11-16 | 2021-08-03 | 山东福田药业有限公司 | 一种l-核糖的分离方法 |
CN112999991B (zh) * | 2021-03-04 | 2022-09-02 | 安徽金禾实业股份有限公司 | 一种双刮板式的蔗糖-6-酯连续生产设备及生产工艺流程 |
CN112957760B (zh) * | 2021-03-04 | 2022-05-10 | 安徽金禾实业股份有限公司 | 一种蔗糖-6-酯不间断制备设备及生产工艺流程 |
CN112973164B (zh) * | 2021-03-04 | 2022-09-02 | 安徽金禾实业股份有限公司 | 一种高效率的蔗糖6酯连续生产设备及方法 |
CN114671884A (zh) * | 2022-05-13 | 2022-06-28 | 河南正通食品科技有限公司 | 一种聚合级糖类二醇的连续制备方法 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2017158303A1 (fr) | 2016-03-16 | 2017-09-21 | Roquette Freres | Procede de fabrication de dianhydrohexitol avec une etape de distillation sur un evaporateur a couche mince |
US10533017B2 (en) | 2016-03-16 | 2020-01-14 | Roquette Freres | Method for producing dianhydrohexitol with a step of distillation on a thin-film evaporator |
EP4219505A1 (fr) | 2016-03-16 | 2023-08-02 | Roquette Freres | Procede de fabrication de dianhydrohexitol avec une etape de distillation sur un evaporateur a couche mince |
CN112933634A (zh) * | 2021-03-04 | 2021-06-11 | 安徽金禾实业股份有限公司 | 一种环列式的蔗糖-6-酯连续生产设备及生产工艺流程 |
Also Published As
Publication number | Publication date |
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JP2015516413A (ja) | 2015-06-11 |
JP6034959B2 (ja) | 2016-11-30 |
KR20130126303A (ko) | 2013-11-20 |
EP2848603B1 (en) | 2017-11-08 |
US9290508B2 (en) | 2016-03-22 |
EP2848603A1 (en) | 2015-03-18 |
CN104470880A (zh) | 2015-03-25 |
US20150112088A1 (en) | 2015-04-23 |
KR101388676B1 (ko) | 2014-04-25 |
EP2848603A4 (en) | 2016-01-27 |
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