WO2012081785A1 - Methods for distilling and manufacturing anhydrosugar alcohols - Google Patents

Methods for distilling and manufacturing anhydrosugar alcohols Download PDF

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Publication number
WO2012081785A1
WO2012081785A1 PCT/KR2011/005222 KR2011005222W WO2012081785A1 WO 2012081785 A1 WO2012081785 A1 WO 2012081785A1 KR 2011005222 W KR2011005222 W KR 2011005222W WO 2012081785 A1 WO2012081785 A1 WO 2012081785A1
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anhydrosugar alcohol
acid
manufacturing
alcohol
saccharide
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PCT/KR2011/005222
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French (fr)
Inventor
Young Jae Jung
Hoon Ryu
Young Seok Kim
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Samyang Genex Corporation
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Publication of WO2012081785A1 publication Critical patent/WO2012081785A1/en

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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

Definitions

  • the present invention relates to methods for distilling and manufacturing anhydrosugar alcohol, more specifically, to a method for distilling anhydrosugar alcohol using saccharide in the distillation of anhydrosugar alcohol, and a method for manufacturing anhydrosugar alcohol by using the same.
  • Sugar alcohol is a compound obtained by adding hydrogen to the reductive terminal group of saccharide and can be classified into tetritol, pentitol, hexitol and heptitol according to carbon number.
  • hexitol having carbon number of 6 includes sorbitol, mannitol and iditol, and sorbitol and mannitol are particularly useful.
  • Anhydrosugar alcohol derived from starch can be manufactured from aforesaid sugar alcohols in diol form having two hydroxy groups in a molecule. Since anhydrosugar alcohol is an environment-friendly resource derived from renewable natural resources, it has attracted a lot of attention for a long time and its production method has been a subject of research.
  • Such an anhydrosugar alcohol is useful as a medicament such as a therapeutic agent to cardiac and vascular diseases, an adhesive for patch, a mouthwash, etc. and can be used as a solvent for composition in the cosmetics industry, an emulsifier in the food industry and the like.
  • it is very useful in the plastics industry such as polyester. It can elevate a glass transition temperature of polyester, polyethylene terephthalate, polycarbonate, polyurethane, etc. and it shows an effect of improving strength, and thus has a high value of application as a biodegradable environment-friendly material. It is also known that it can be used as an adhesive, an environment-friendly plasticizer, a biodegradable polymer and an environment-friendly solvent for a water-soluble lacquer.
  • Anhydrosugar alcohols are produced by dehydration of the corresponding sugar alcohols (or monoanhydrosugar alcohols) by the action of various dehydration catalysts, typically strong acid catalysts. Following the dehydration procedure, the dehydrated anhydrosugar alcohol mixture is purified by vacuum distillation, filtration, and/or addition of activated charcoal with subsequent crystallization. In a preferred embodiment, vacuum distillation is used. In order to further purify and isolate the anhydrosugar alcohol, the anhydrosugar alcohol distillate is subjected to melt crystallization.
  • US Patent No. 4408061 discloses a method of dehydration of a sugar or sugar alcohol.
  • US Patent No. 6670033 discloses a process for the formation of a purified anhydrosugar alcohol.
  • the anhydrosugar alcohol is purified by distillation, recrystallization from methanol, ethanol or ethylene glycol, melt recrystallization, or a combination thereof.
  • Such conventional separations by distillation (or evaporation) as disclosed in the prior arts are difficult to achieve because of the low vapor pressure of isosorbide. For example, it has been found that at 140°C, the vapor pressure is only 1.75 mmHg.
  • Anhydrosugar alcohol can be applied in various industries as above.
  • conventional methods for manufacturing anhydrosugar alcohol have a problem of low distillation yield or the like, and thus it is underutilized.
  • the present invention provides a method for distilling anhydrosugar alcohol with high distillation yield.
  • the present invention provides a method for manufacturing anhydrosugar alcohol by using the distillation method.
  • the method for distilling anhydrosugar alcohol according to the examples of the present invention comprises a step of adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture.
  • the saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol.
  • the monosaccharide may comprise one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose;
  • the disaccharide may comprise one or more selected from sucrose, maltose and lactose;
  • the sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
  • the method for manufacturing anhydrosugar alcohol according to the examples of the present invention comprises a step of dehydrating sugar alcohol to form anhydrosugar alcohol; and a step of adding saccharide to a mixture solution containing the anhydrosugar alcohol and distilling the resulting mixture.
  • the sugar alcohol may comprise hexitol.
  • the hexitol may comprise one or more selected from sorbitol, mannitol, iditol and galactitol.
  • the saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol.
  • the monosaccharide may comprise one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose;
  • the disaccharide may comprise one or more selected from sucrose, maltose and lactose;
  • the sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
  • the anhydrosugar alcohol may be 1,4-3,6-dianhydrohexitol such as isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dianhydromannitol) or isoidide (1,4-3,6-dianhydroiditol).
  • the dehydration reaction may be conducted in the presence of an acid catalyst.
  • the acid catalyst may be a single acid selected from sulfuric acid, hydrochloric acid and phosphoric acid, or it may be a mixed acid comprising sulfuric acid and one or more selected from p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and aluminum sulfate.
  • the saccharide may be added in an amount of 1 to 20 parts by weight based on 100 parts by weight of said sugar alcohol.
  • the distillation may be performed at 150 to 250°C under vacuum.
  • the method for manufacturing anhydrosugar alcohol may further comprise a step of neutralizing the mixture solution by adding alkali thereto, before the distillation is performed.
  • the method for manufacturing anhydrosugar alcohol may further comprise a step of performing one or more of activated carbon treatment, activated clay treatment and ion-purification treatment, in order to decolorize the distilled liquid obtained by the distillation.
  • the distillation efficiency can be improved by using saccharide in the distillation of anhydrosugar alcohol.
  • the distillation yield can be improved even without the addition of facilities or processes.
  • the flowability of anhydrosugar alcohol is remarkably improved and thus the process can proceed easily, and the distillation yield can be improved.
  • the saccharide, as a biomass, used in the manufacturing method according to the examples of the present invention is an environment-friendly material which is a major raw material in an environment-friendly green industry, and is industrially very useful since the application scope of starch, etc. can be expanded.
  • the anhydrosugar alcohol may mean a material obtained by eliminating one or more water molecules from the inner structure of a sugar alcohol.
  • the distillation method of anhydrosugar alcohol according to the examples of the present invention may comprise a step of adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture.
  • the saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol.
  • the monosaccharide may comprise one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose;
  • the disaccharide may comprise one or more selected from sucrose, maltose and lactose;
  • the sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
  • the distillation yield may increase by adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture as above because of the improvement in the flowability of anhydrosugar alcohol.
  • the method for manufacturing anhydrosugar alcohol uses the distillation method of anhydrosugar alcohol and may comprise a step of dehydrating sugar alcohol to form anhydrosugar alcohol and a step of adding saccharide to a mixture solution containing the anhydrosugar alcohol and distilling the resulting mixture.
  • the sugar alcohol may comprise hexitol.
  • the hexitol may comprise one or more selected from sorbitol, mannitol, iditol and galactitol.
  • the saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol, and may improve the distillation efficiency of the anhydrosugar alcohol.
  • the monosaccharide may comprise one or more selected from hexoses such as glucose, fructose, mannose, galactose and the like, and pentoses such as ribose, arabinose, xylose and the like.
  • the disaccharide may comprise one or more selected from sucrose, maltose and lactose.
  • the sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
  • glucose derived from starch sucrose derived from sugar cane, or sorbitol which can be manufactured easily through hydrogenation reaction to glucose.
  • the anhydrosugar alcohol may be 1,4-3,6-dianhydrohexitol such as isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dianhydromannitol) or isoidide (1,4-3,6-dianhydroiditol).
  • the dehydration reaction may be conducted in the presence of an acid catalyst.
  • the acid catalyst may be a single acid selected from sulfuric acid, hydrochloric acid and phosphoric acid, or it may be a mixed acid comprising sulfuric acid and one or more selected from p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and aluminum sulfate.
  • the saccharide may be added, based on 100 parts by weight of said sugar alcohol, in an amount of 1 to 20 parts by weight, preferably 5 to 20 parts by weight, and more preferably 10 to 20parts by weight. If the addition amount of the saccharide is less than 1 part by weight, the flowability is not improved greatly and the distillation efficiency may not be improved greatly. If the amount is greater than 20 parts by weight, the distillation efficiency may not be improved greatly and the economy according to the addition amount increase of the saccharide may be lowered.
  • the distillation may be performed at a temperature of from 150 to 250°C, preferably 180 to 240°C under vacuum condition of 5mmHg or lower. If the distillation temperature is lower than 150°C, highly pure anhydrosugar alcohol may be obtained but the distillation of anhydrosugar alcohol may not be accomplished well. If the distillation temperature is higher than 250°C, it may be carbonized or high-molecular weight materials may be formed, and decolorization may become difficult if the color becomes dark due to the formation of coloring materials.
  • the distillation may be performed by using a conventional distillatory ⁇ for example, a thin film distillator and the like.
  • the mixture solution Before the distillation is performed, the mixture solution may be neutralized by adding alkali thereto.
  • one or more of activated carbon treatment, activated clay treatment and ion-purification treatment may be performed.
  • sorbitol powder (D-sorbitol, Samyang Genex Corporation), which is a sugar alcohol, was fed into a 4-necked glass reactor equipped with an agitator, and the temperature was elevated to 110°C to melt it.
  • 12g of concentrated sulfuric acid (95%, Duksan Chemical) and 7.2g of methane sulfonic acid (70%, Sigma) were added, respectively, and the reaction temperature was then elevated to 135°C.
  • the dehydration reaction was conducted for 4 hours under vacuum condition of 3mmHg to convert the sorbitol to isosorbide which is an anhydrosugar alcohol.
  • the conversion rate to the anhydrosugar alcohol was 89.5%.
  • Example 2 The same procedure as in Example 1 was carried out, except that 120.0g of sorbitol powder was used as the saccharide for improving flowability.
  • the distillation yield of the anhydrosugar alcohol was 69.6%, and its purity was 96.1%.
  • Example 2 The same procedure as in Example 1 was carried out, except that 180.0g of sorbitol powder was used as the saccharide for improving flowability.
  • the distillation yield of the anhydrosugar alcohol was 70.7%, and its purity was 96.0%.
  • Example 2 The same procedure as in Example 1 was carried out, except that 240.0g of sorbitol powder was used as the saccharide for improving flowability.
  • the distillation yield of the anhydrosugar alcohol was 71. 2%, and its purity was 96.0%.
  • Example 2 The same procedure as in Example 1 was carried out, except that 120.0g of glucose powder (anhydrous crystalline glucose, Samyang Genex Corporation), which is a monosaccharide, was used as the saccharide for improving flowability.
  • the distillation yield of the anhydrosugar alcohol was 65.2%, and its purity was 95.9%.
  • Example 2 The same procedure as in Example 1 was carried out, except that 120.0g of sucrose powder (white sugar, Samyang Corporation), which is a disaccharide, was used as the saccharide for improving flowability.
  • sucrose powder white sugar, Samyang Corporation
  • the distillation yield of the anhydrosugar alcohol was 64.6%, and its purity was 95.9%.
  • Example 2 The same procedure as in Example 1 was carried out, except that no saccharide for improving flowability was used.
  • the distillation yield of the anhydrosugar alcohol was 56.7%, and its purity was 96.2%.
  • Example 2 In addition, the same procedure as in Example 1 was carried out, except that 300.0 g of sorbitol powder was used as the saccharide for improving flowability.
  • the distillation yield of the anhydrosugar alcohol and its purity was the same as in Example 4, and there is no significant difference (data are not shown in the table).

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  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

A method for distilling anhydrosugar alcohol and a method for manufacturing anhydrosugar alcohol by using the same are provided. The distillation method comprises a step of adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture, and the manufacturing method comprises a step of dehydrating sugar alcohol to form anhydrosugar alcohol and a step of adding saccharide to a mixture solution containing the anhydrosugar alcohol and distilling the resulting mixture. The saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol.

Description

METHODS FOR DISTILLING AND MANUFACTURING ANHYDROSUGAR ALCOHOLS
The present invention relates to methods for distilling and manufacturing anhydrosugar alcohol, more specifically, to a method for distilling anhydrosugar alcohol using saccharide in the distillation of anhydrosugar alcohol, and a method for manufacturing anhydrosugar alcohol by using the same.
Sugar alcohol is a compound obtained by adding hydrogen to the reductive terminal group of saccharide and can be classified into tetritol, pentitol, hexitol and heptitol according to carbon number. Among them, hexitol having carbon number of 6 includes sorbitol, mannitol and iditol, and sorbitol and mannitol are particularly useful.
Anhydrosugar alcohol derived from starch can be manufactured from aforesaid sugar alcohols in diol form having two hydroxy groups in a molecule. Since anhydrosugar alcohol is an environment-friendly resource derived from renewable natural resources, it has attracted a lot of attention for a long time and its production method has been a subject of research.
Such an anhydrosugar alcohol is useful as a medicament such as a therapeutic agent to cardiac and vascular diseases, an adhesive for patch, a mouthwash, etc. and can be used as a solvent for composition in the cosmetics industry, an emulsifier in the food industry and the like. In addition, it is very useful in the plastics industry such as polyester. It can elevate a glass transition temperature of polyester, polyethylene terephthalate, polycarbonate, polyurethane, etc. and it shows an effect of improving strength, and thus has a high value of application as a biodegradable environment-friendly material. It is also known that it can be used as an adhesive, an environment-friendly plasticizer, a biodegradable polymer and an environment-friendly solvent for a water-soluble lacquer.
Anhydrosugar alcohols are produced by dehydration of the corresponding sugar alcohols (or monoanhydrosugar alcohols) by the action of various dehydration catalysts, typically strong acid catalysts. Following the dehydration procedure, the dehydrated anhydrosugar alcohol mixture is purified by vacuum distillation, filtration, and/or addition of activated charcoal with subsequent crystallization. In a preferred embodiment, vacuum distillation is used. In order to further purify and isolate the anhydrosugar alcohol, the anhydrosugar alcohol distillate is subjected to melt crystallization.
US Patent No. 4408061 discloses a method of dehydration of a sugar or sugar alcohol. US Patent No. 6670033 discloses a process for the formation of a purified anhydrosugar alcohol. The anhydrosugar alcohol is purified by distillation, recrystallization from methanol, ethanol or ethylene glycol, melt recrystallization, or a combination thereof. However, such conventional separations by distillation (or evaporation) as disclosed in the prior arts are difficult to achieve because of the low vapor pressure of isosorbide. For example, it has been found that at 140°C, the vapor pressure is only 1.75 mmHg. If the evaporation or distillation is conducted at temperatures not much higher than about 140°C, product degradation can be minimized and highly pure isosorbide can be obtained, but the recovery is poor. If the evaporation or distillation is conducted at higher temperatures such as 170°C, more isosorbide is recovered, but the quality becomes poorer.
Anhydrosugar alcohol can be applied in various industries as above. However, conventional methods for manufacturing anhydrosugar alcohol have a problem of low distillation yield or the like, and thus it is underutilized.
To resolve the problems of prior arts as explained above, the present invention provides a method for distilling anhydrosugar alcohol with high distillation yield.
The present invention provides a method for manufacturing anhydrosugar alcohol by using the distillation method.
The method for distilling anhydrosugar alcohol according to the examples of the present invention comprises a step of adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture.
The saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol. The monosaccharide may comprise one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose; the disaccharide may comprise one or more selected from sucrose, maltose and lactose; and the sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
The method for manufacturing anhydrosugar alcohol according to the examples of the present invention comprises a step of dehydrating sugar alcohol to form anhydrosugar alcohol; and a step of adding saccharide to a mixture solution containing the anhydrosugar alcohol and distilling the resulting mixture.
The sugar alcohol may comprise hexitol. The hexitol may comprise one or more selected from sorbitol, mannitol, iditol and galactitol.
The saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol. The monosaccharide may comprise one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose; the disaccharide may comprise one or more selected from sucrose, maltose and lactose; and the sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
The anhydrosugar alcohol may be 1,4-3,6-dianhydrohexitol such as isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dianhydromannitol) or isoidide (1,4-3,6-dianhydroiditol).
The dehydration reaction may be conducted in the presence of an acid catalyst. The acid catalyst may be a single acid selected from sulfuric acid, hydrochloric acid and phosphoric acid, or it may be a mixed acid comprising sulfuric acid and one or more selected from p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and aluminum sulfate.
The saccharide may be added in an amount of 1 to 20 parts by weight based on 100 parts by weight of said sugar alcohol.
The distillation may be performed at 150 to 250℃ under vacuum.
The method for manufacturing anhydrosugar alcohol may further comprise a step of neutralizing the mixture solution by adding alkali thereto, before the distillation is performed.
The method for manufacturing anhydrosugar alcohol may further comprise a step of performing one or more of activated carbon treatment, activated clay treatment and ion-purification treatment, in order to decolorize the distilled liquid obtained by the distillation.
According to the examples of the present invention, the distillation efficiency can be improved by using saccharide in the distillation of anhydrosugar alcohol. The distillation yield can be improved even without the addition of facilities or processes. In addition, the flowability of anhydrosugar alcohol is remarkably improved and thus the process can proceed easily, and the distillation yield can be improved. The saccharide, as a biomass, used in the manufacturing method according to the examples of the present invention is an environment-friendly material which is a major raw material in an environment-friendly green industry, and is industrially very useful since the application scope of starch, etc. can be expanded.
The present invention is explained in more detail through the examples below. The purpose, features and merits of the present invention will be easily understood through the examples below. The present invention is not limited to the examples explained herein and may be concretized in another form(s). The examples introduced herein are provided in order to make the disclosed contents thorough and perfect and to transfer the idea of the present invention sufficiently to a person having ordinary skill in the technical field of the present invention. Accordingly, the present invention must not be limited by the following examples.
In the present specification, the anhydrosugar alcohol may mean a material obtained by eliminating one or more water molecules from the inner structure of a sugar alcohol.
The distillation method of anhydrosugar alcohol according to the examples of the present invention may comprise a step of adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture.
The saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol. The monosaccharide may comprise one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose; the disaccharide may comprise one or more selected from sucrose, maltose and lactose; and the sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
The distillation yield may increase by adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture as above because of the improvement in the flowability of anhydrosugar alcohol.
The method for manufacturing anhydrosugar alcohol according to the examples of the present invention uses the distillation method of anhydrosugar alcohol and may comprise a step of dehydrating sugar alcohol to form anhydrosugar alcohol and a step of adding saccharide to a mixture solution containing the anhydrosugar alcohol and distilling the resulting mixture.
The sugar alcohol may comprise hexitol. The hexitol may comprise one or more selected from sorbitol, mannitol, iditol and galactitol.
The saccharide may comprise one or more selected from monosaccharide, disaccharide and sugar alcohol, and may improve the distillation efficiency of the anhydrosugar alcohol. The monosaccharide may comprise one or more selected from hexoses such as glucose, fructose, mannose, galactose and the like, and pentoses such as ribose, arabinose, xylose and the like. The disaccharide may comprise one or more selected from sucrose, maltose and lactose. The sugar alcohol may comprise one or more selected from sorbitol, mannitol and iditol.
As the saccharide, it is preferable to use glucose derived from starch, sucrose derived from sugar cane, or sorbitol which can be manufactured easily through hydrogenation reaction to glucose.
The anhydrosugar alcohol may be 1,4-3,6-dianhydrohexitol such as isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dianhydromannitol) or isoidide (1,4-3,6-dianhydroiditol).
The dehydration reaction may be conducted in the presence of an acid catalyst. The acid catalyst may be a single acid selected from sulfuric acid, hydrochloric acid and phosphoric acid, or it may be a mixed acid comprising sulfuric acid and one or more selected from p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and aluminum sulfate.
The saccharide may be added, based on 100 parts by weight of said sugar alcohol, in an amount of 1 to 20 parts by weight, preferably 5 to 20 parts by weight, and more preferably 10 to 20parts by weight. If the addition amount of the saccharide is less than 1 part by weight, the flowability is not improved greatly and the distillation efficiency may not be improved greatly. If the amount is greater than 20 parts by weight, the distillation efficiency may not be improved greatly and the economy according to the addition amount increase of the saccharide may be lowered.
The distillation may be performed at a temperature of from 150 to 250℃, preferably 180 to 240℃ under vacuum condition of 5mmHg or lower. If the distillation temperature is lower than 150℃, highly pure anhydrosugar alcohol may be obtained but the distillation of anhydrosugar alcohol may not be accomplished well. If the distillation temperature is higher than 250℃, it may be carbonized or high-molecular weight materials may be formed, and decolorization may become difficult if the color becomes dark due to the formation of coloring materials. The distillation may be performed by using a conventional distillatory―for example, a thin film distillator and the like.
Before the distillation is performed, the mixture solution may be neutralized by adding alkali thereto. In order to decolorize the distilled liquid obtained by the distillation, one or more of activated carbon treatment, activated clay treatment and ion-purification treatment may be performed.
Examples and Comparative Examples
Example 1
1,200g of sorbitol powder (D-sorbitol, Samyang Genex Corporation), which is a sugar alcohol, was fed into a 4-necked glass reactor equipped with an agitator, and the temperature was elevated to 110℃ to melt it. To the reactor, 12g of concentrated sulfuric acid (95%, Duksan Chemical) and 7.2g of methane sulfonic acid (70%, Sigma) were added, respectively, and the reaction temperature was then elevated to 135℃. In maintaining the temperature, the dehydration reaction was conducted for 4 hours under vacuum condition of 3mmHg to convert the sorbitol to isosorbide which is an anhydrosugar alcohol. The conversion rate to the anhydrosugar alcohol was 89.5%.
After the temperature of the reactor was lowered to 110℃, 31.2g of 50% sodium hydroxide solution (Samchun Pure Chemical) was added to the mixture solution under the dehydration reaction to neutralize it. To the neutralized solution, 60g of sorbitol powder, which is a sugar alcohol, was added as a saccharide for improving flowability and agitated to melt it, and the resulting mixture was distilled under vacuum of 3mmHg while elevating the temperature to 220℃. The amount of the distilled liquid obtained as above was measured, and the purity of anhydrosugar alcohol was measured by high performance liquid chromatography (HPLC). The distillation yield of the anhydrosugar alcohol was 68.0%, and its purity was 96.2%.
Example 2
The same procedure as in Example 1 was carried out, except that 120.0g of sorbitol powder was used as the saccharide for improving flowability. The distillation yield of the anhydrosugar alcohol was 69.6%, and its purity was 96.1%.
Example 3
The same procedure as in Example 1 was carried out, except that 180.0g of sorbitol powder was used as the saccharide for improving flowability. The distillation yield of the anhydrosugar alcohol was 70.7%, and its purity was 96.0%.
Example 4
The same procedure as in Example 1 was carried out, except that 240.0g of sorbitol powder was used as the saccharide for improving flowability. The distillation yield of the anhydrosugar alcohol was 71. 2%, and its purity was 96.0%.
Example 5
The same procedure as in Example 1 was carried out, except that 120.0g of glucose powder (anhydrous crystalline glucose, Samyang Genex Corporation), which is a monosaccharide, was used as the saccharide for improving flowability. The distillation yield of the anhydrosugar alcohol was 65.2%, and its purity was 95.9%.
Example 6
The same procedure as in Example 1 was carried out, except that 120.0g of sucrose powder (white sugar, Samyang Corporation), which is a disaccharide, was used as the saccharide for improving flowability. The distillation yield of the anhydrosugar alcohol was 64.6%, and its purity was 95.9%.
Comparative Example 1
The same procedure as in Example 1 was carried out, except that no saccharide for improving flowability was used. The distillation yield of the anhydrosugar alcohol was 56.7%, and its purity was 96.2%.
The conversion rate analyses in the anhydrosugar alcohols manufactured in Examples 1 to 5 and Comparative Example 1 were performed by using a gas chromatography (GC，HP5890), and the purity analyses were performed by using a high-performance liquid chromatography (HPLC, HP1100). The measured purities and distillation yields of the anhydrosugar alcohols are shown in the following Table 1.
Conversion rate (%):
Moles of anhydrosugar alcohol generated / Moles of hexitol added * 100
Purity (%):
Weight of anhydrosugar alcohol in distilled liquid / Weight of distilled liquid * 100
Distillation yield (%):
Moles of anhydrosugar alcohol in distilled liquid / Moles of hexitol added * 100
Table 1
Figure PCTKR2011005222-appb-T000001
As shown in the above Table 1, it can be known that the distillation yield increased by adding saccharide for improving flowability after the sugar alcohol was converted to anhydrosugar alcohol by dehydration reaction and performing the distillation.
In addition, the same procedure as in Example 1 was carried out, except that 300.0 g of sorbitol powder was used as the saccharide for improving flowability. The distillation yield of the anhydrosugar alcohol and its purity was the same as in Example 4, and there is no significant difference (data are not shown in the table).
The concrete examples of the present invention are explained as above. A person having ordinary skill in the technical field of the present invention could understand that the present invention may be embodied as a modified form within the scope of the nature of the present invention. Therefore, the disclosed examples should be considered from an explanatory viewpoint and not a limitative viewpoint. The scope of the present invention is shown in the claims and not in the aforesaid explanation. All differences within the scope equivalent thereto must be interpreted as being included in the present invention.

Claims (15)

  1. A method for distilling anhydrosugar alcohol comprising a step of adding saccharide to a mixture solution containing anhydrosugar alcohol and distilling the resulting mixture.
  2. The method for distilling anhydrosugar alcohol according to claim 1, wherein the saccharide comprises one or more selected from monosaccharide, disaccharide and sugar alcohol.
  3. The method for distilling anhydrosugar alcohol according to claim 2, wherein the monosaccharide comprises one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose; the disaccharide comprises one or more selected from sucrose, maltose and lactose; and the sugar alcohol comprises one or more selected from sorbitol, mannitol and iditol.
  4. A method for manufacturing anhydrosugar alcohol comprising:
    a step of dehydrating sugar alcohol to form anhydrosugar alcohol; and
    a step of adding saccharide to a mixture solution containing the anhydrosugar alcohol and distilling the resulting mixture.
  5. The method for manufacturing anhydrosugar alcohol according to claim 4, wherein the sugar alcohol comprises hexitol.
  6. The method for manufacturing anhydrosugar alcohol according to claim 5, wherein the hexitol comprises one or more selected from sorbitol, mannitol, iditol and galactitol.
  7. The method for manufacturing anhydrosugar alcohol according to claim 4, wherein the saccharide comprises one or more selected from monosaccharide, disaccharide and sugar alcohol.
  8. The method for manufacturing anhydrosugar alcohol according to claim 7, wherein the monosaccharide comprises one or more selected from glucose, fructose, mannose, galactose, ribose, arabinose and xylose; the disaccharide comprises one or more selected from sucrose, maltose and lactose; and the sugar alcohol comprises one or more selected from sorbitol, mannitol and iditol.
  9. The method for manufacturing anhydrosugar alcohol according to claim 4, wherein the anhydrosugar alcohol is isosorbide (1,4-3,6-dianhydrosorbitol), isomannide (1,4-3,6-dianhydromannitol) or isoidide (1,4-3,6-dianhydroiditol).
  10. The method for manufacturing anhydrosugar alcohol according to claim 4, wherein the dehydration reaction is conducted in the presence of an acid catalyst.
  11. The method for manufacturing anhydrosugar alcohol according to claim 10, wherein the acid catalyst is a single acid selected from sulfuric acid, hydrochloric acid and phosphoric acid; or a mixed acid comprising sulfuric acid and one or more selected from p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and aluminum sulfate.
  12. The method for manufacturing anhydrosugar alcohol according to claim 4, wherein the saccharide is added in an amount of 1 to 20 parts by weight based on 100 parts by weight of said sugar alcohol.
  13. The method for manufacturing anhydrosugar alcohol according to claim 4, wherein the distillation is performed at 150 to 250℃ under vacuum.
  14. The method for manufacturing anhydrosugar alcohol according to claim 4, further comprising a step of neutralizing the mixture solution by adding alkali thereto, before the distillation is performed.
  15. The method for manufacturing anhydrosugar alcohol according to claim 4, further comprising a step of performing one or more of activated carbon treatment, activated clay treatment and ion-purification treatment, in order to decolorize the distilled liquid obtained by the distillation.
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