JP5267964B2 - Method for producing anhydrosugar - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for safely and easily producing an anhyrosugar in high yield from e.g. monosaccharide, oligosaccharide or their glycoside, polysaccharide or their mixture. <P>SOLUTION: The method for producing the anhyrosugar(s) of the general formula(1), the general formula(2) and/or the general formula(3) comprises using, as feedstock, at least one water-soluble saccharide compound selected from monosaccharide, oligosaccharide or their glycoside, polysaccharide and their mixture, and heating the aqueous solution of the saccharide compound(s) solely without addition of additive(s) such as a catalyst at all. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention provides a raw material containing at least one water-soluble sugar compound selected from monosaccharides, oligosaccharides or glycosides thereof, polysaccharides and mixtures thereof without adding any additive such as a catalyst, The present invention relates to a method for producing an anhydrosugar characterized in that only an aqueous solution containing a sugar compound is heated and reacted in a water vapor state.

Examples of anhydrosaccharide derived from 6 monosaccharides include 1,6-anhydrohexopyranose represented by the general formula (1) such as levoglucosan, mannosan, galactosan, etc., which are anhydrides such as glucose, mannose, galactose, and the general formula (2). 1,6-anhydrohexofuranose and the like.
Examples of the anhydrosugar derived from pentose such as ribose and xylose include 1,4-anhydropentopyranose represented by the general formula (3).

  Anhydro sugars are biodegradable bioplastics, chemical raw materials such as bioadhesives, raw materials for anticancer and anti-HIV agents, optical isomer resolution agents, and sugar-based safe medicines based on multi-branched polysaccharides. It is known to be useful as various functional polymer materials such as materials, and has attracted attention in various fields.

  Conventionally, as a method for producing levoglucosan, (1) a pyrolysis method in which a raw material containing a cellulose component is placed in a pressure vessel together with an organic solvent and heated to 250 to 350 ° C. (Japanese Patent Laid-Open No. 2-101093; Patent Document 1), ( 2) Pyrolysis method in which cellulose is stirred at 250 to 340 ° C. for 10 hours while pumping supercritical acetone into a pressure vessel (J. Anal. Appl. Pyrolysis (1991), 19, 119 to 129; Non-Patent Document 1), ( 3) A method in which a raw material mainly containing a polysaccharide consisting of hexose is placed in a pressure vessel together with sulfolane and thermally decomposed at a temperature of 300 ° C. or higher (Japanese Patent Laid-Open No. 2003-342289; Patent Document 2, J. Anal. Appl. Pyrolysis ( 2003), 70, 303-313; Non-Patent Document 2), and (4) Microwave pyrolysis method in which microwave is applied to the cellulose component (J. Wood Sci. (2001), 47, 502-506; Non-patent) Document 3) is known.

  However, these conventional methods for producing anhydrosugar have many problems to be solved such as a low yield or no established purification method, and are not yet put into practical use. Therefore, it is desired to establish a production method capable of obtaining anhydrosugar in a high yield with safety and simplicity.

Japanese Patent Laid-Open No. 2-101093 JP 2003-342289 A J. et al. Anal. Appl. Pyrolysis (1991), 19, 119-129 J. et al. Anal. Appl. Pyrolysis (2003), 70, 303-313 J. et al. Wood Sci. (2001), 47, 502-506.

    An object of the present invention is to produce an anhydro sugar in a safe, simple and high yield under milder conditions from a raw material compound such as a monosaccharide, a oligosaccharide containing a monosaccharide as a constituent component, or a glycoside or polysaccharide thereof. It is to provide a method.

  As a result of intensive studies to solve the above problems, the present inventors have found that at least one water-soluble sugar compound selected from monosaccharides, oligosaccharides or glycosides thereof, polysaccharides and mixtures thereof. As a raw material, it was found that anhydrosugar is produced in a good yield by reacting only an aqueous solution of the raw material in a water vapor state without adding any additives such as a catalyst.

で示されるアンヒドロ糖の製造方法。
［２］水溶性糖化合物が、グルコース、マンノース、ガラクトース、グロース、アロース、アルトロース、イドース、タロース、リボース、キシロース、アラビノース、及びリキソースから選ばれる単糖、スクロース、マルトース、イソマルトース、セロビオース、トレハロース、トレハルロース、パラチノース、ニゲロース、ラクトース、ラクチュロース、グリコシルスクロース、ラクトスクロース、パノース、ラフィノース、シクロデキストリン類およびその誘導体、分岐シクロデキストリン類、シクロデキストラン、マルトオリゴ糖、イソマルトオリゴ糖、セロオリゴ糖、ガラクトオリゴ糖、マンノオリゴ糖、キシロオリゴ糖、フラクトオリゴ糖、パラチノースオリゴ糖、ニゲロオリゴ糖、ゲンチオオリゴ糖及び大豆オリゴ糖から選ばれる少糖、および可溶性デンプン、プルラン、アラビアガム、デキストラン、デキストリンおよびグルコマンナンから選ばれる多糖から選ばれる少なくとも１種類の水溶性糖化合物である前記１に記載のアンヒドロ糖の製造方法。
［３］水溶性糖化合物を含む原料が、蜂蜜、糖蜜、廃糖蜜、水飴、黒糖製品及びメープルシロップから選択される前記１に記載のアンヒドロ糖の製造方法。
［４］加熱温度が１００〜４６０℃の範囲である前記１に記載のアンヒドロ糖の製造方法。
［５］加熱した流通式反応器に水溶性糖化合物を含む原料の水溶液を連続的に供給して水蒸気状態で反応させ、反応混合物を冷却及び回収する前記１に記載のアンヒドロ糖を連続して製造する方法。
［６］予熱した原料水溶液を流通式反応器に供給する前記５に記載のアンヒドロ糖を連続して製造する方法。 That is, this invention provides the manufacturing method of the following anhydrosugar.
[1] A raw material aqueous solution containing at least one water-soluble sugar compound selected from monosaccharides, oligosaccharides or glycosides, polysaccharides and mixtures thereof is heated and reacted in a steam state. The following general formula (1), general formula (2) and / or general formula (3)

The manufacturing method of the anhydrosugar shown by these.
[2] Monosaccharide, sucrose, maltose, isomaltose, cellobiose, trehalose, wherein the water-soluble sugar compound is selected from glucose, mannose, galactose, growth, allose, altrose, idose, talose, ribose, xylose, arabinose, and lyxose , Trehalulose, palatinose, nigerose, lactose, lactulose, glycosyl sucrose, lactosucrose, panose, raffinose, cyclodextrins and derivatives thereof, branched cyclodextrins, cyclodextran, maltooligosaccharides, isomaltoligosaccharides, cellooligosaccharides, galactooligosaccharides, mannooligos Select from sugar, xylooligosaccharide, fructooligosaccharide, palatinose oligosaccharide, nigerooligosaccharide, gentiooligosaccharide and soybean oligosaccharide Oligosaccharides, and soluble starch, pullulan, gum arabic, dextran, dextrin and at least one method for producing anhydro sugars described in 1 a water-soluble sugar compound selected from a polysaccharide selected from glucomannan that.
[3] The process for producing an anhydrosugar as described in 1 above, wherein the raw material containing the water-soluble sugar compound is selected from honey, molasses, waste molasses, starch syrup, brown sugar product and maple syrup.
[4] The method for producing an anhydrosugar as described in 1 above, wherein the heating temperature is in the range of 100 to 460 ° C.
[5] An aqueous solution of a raw material containing a water-soluble saccharide compound is continuously supplied to a heated flow reactor and reacted in a steam state, and the reaction mixture is cooled and recovered. How to manufacture.
[6] The method for continuously producing the anhydrosugar as described in 5 above, wherein the preheated raw material aqueous solution is supplied to the flow reactor.

According to the present invention, the production of pyrolysis gases such as carbon dioxide and lower hydrocarbons, tars and carbides is extremely small, and anhydro sugar can be obtained easily and in high yield by dehydration reaction or depolymerization reaction of raw materials. . Since the present invention can be carried out from low pressure to light pressure reduction, not only the production apparatus can be simplified, but also it can be operated safely and easily.
Therefore, there are various chemical raw materials such as biodegradable bioplastics and bioadhesives, raw materials for anticancer agents and anti-HIV agents, optical isomer resolution agents, and safe medical materials derived from sugars based on multi-branched polysaccharides. Anhydro sugar useful as a functional polymer material can be supplied at low cost.

  In the present invention, only an aqueous solution containing a saccharide compound without adding any additive such as a catalyst to a raw material containing at least one water-soluble saccharide compound from monosaccharides, oligosaccharides or glycosides or polysaccharides thereof. Is heated and reacted in a steam state to produce anhydrosugar.

The anhydrosugar in the present invention refers to 1,6-anhydrohexopyranose such as levoglucosan, mannosan and galactosane represented by the following general formula (1), and 1,6-anhydrohexane represented by the following general formula (2). Sofuranose and / or anhydrosugar such as 1,4-anhydropentopyranose represented by the following general formula (3).

In the present invention, at least one water-soluble sugar compound is used as a raw material. The water-soluble sugar compound is not particularly limited as long as it is soluble in water and contains at least a monosaccharide unit in the molecule. Examples of water-soluble saccharide compounds include water-soluble monosaccharides, oligosaccharides, glycosides thereof, and polysaccharides.
Examples of monosaccharides include glucose, mannose, galactose, growth, allose, altrose, idose, talose, ribose, xylose, arabinose, lyxose and the like.
As oligosaccharides, those containing 10 or less monosaccharides as constituents, such as sucrose, maltose, isomaltose, cellobiose, trehalose, trehalulose, palatinose, nigerose, lactose, lactulose, glycosyl sucrose, lactosucrose, panose, raffinose, Cyclodextrins and their derivatives, branched cyclodextrins, cyclodextran, maltooligosaccharides (generic name for oligosaccharides with glucose α-1,4-linked), isomaltooligosaccharides (generic name for oligosaccharides with glucose α-1,6-linked) ), Cellooligosaccharide (generic name for oligosaccharides with β-1,4-linked glucose), galactooligosaccharide, manno-oligosaccharide, xylo-oligosaccharide, fructooligosaccharide, palatinose oligosaccharide, nigerooligosaccharide, gentio-oligosaccharide and soybean oligo Such as monosaccharide include 2-10 linked oligosaccharides.
Examples of monosaccharide or oligosaccharide glycosides include phenylglucopyranosides, arbutin, carminic acid, esculin, helicin, phlorizin, salicin, strophanthin, amygdalin, glycyrrhizin, hesperidin, rutin and the like.
Examples of the polysaccharide include soluble starch, pullulan, gum arabic, dextran, dextrin and glucomannan.
Among these, glucose, mannose, galactose, sucrose, maltose, isomaltose, cellobiose, trehalose, maltooligosaccharide, isomaltoligosaccharide, and soluble starch are particularly preferable.

  The raw material containing at least one water-soluble saccharide compound used in the present invention is not particularly limited as long as it contains water-soluble monosaccharides, oligosaccharides or glycosides or polysaccharides thereof, In addition, water-soluble polysaccharides that do not contain the above monosaccharides such as guar gum, locust bean gum, carrageenan, pectin, and alginic acid, proteins such as gelatin and collagen, semisynthetic polymers such as methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; Water-soluble synthetic polymers such as polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone and carboxyvinyl polymer may be mixed. Furthermore, the raw material may contain water or an acid or base that can be a catalyst.

  Raw materials containing water-soluble sugar compounds include honey, molasses, molasses, starch syrup, brown sugar products, various oligosaccharides such as maltooligosaccharides and isomaltooligosaccharides, syrups such as maple syrup, beet and sugarcane, cabbage and potatoes Examples include vegetables and root vegetables, fruits such as grapes and mandarin oranges, various cereals, corn, and bean juice. Furthermore, various foods and beverages composed of raw materials containing a water-soluble sugar compound such as various beverages such as alcoholic beverages and juices, bakery products, Western confectionery, Japanese confectionery, jams and desserts can also be applied.

  The method for producing an anhydrosugar of the present invention is characterized in that a water-soluble sugar compound is used as a raw material, and only an aqueous solution containing the sugar compound is heated and reacted in a water vapor state. Since it is not necessary to add any additive such as a catalyst, it is not necessary to consider removal of the catalyst from the reaction mixture or remaining catalyst.

  The concentration of the water-soluble sugar compound in the raw material aqueous solution in the present invention is not particularly limited, but is preferably in the range of 0.1 to 10% by mass.

  In the method for producing an anhydrosugar of the present invention, the reaction can be carried out preferably under a pressure range of 0.01 MPa or more and less than 5 MPa as a reaction condition in which an aqueous solution containing a water-soluble sugar compound is heated to a steam state. Preferably it is 0.05-2 MPa, Most preferably, it is the atmospheric pressure (about 0.1 MPa) vicinity.

  The reaction temperature and the heating time vary depending on the raw material containing water-soluble saccharides and the charged concentration, but the reaction temperature is preferably 100 ° C. or higher, more preferably 140 ° C. or higher, and further preferably 200 ° C. or higher. At a temperature lower than 100 ° C., the dehydration reaction or depolymerization reaction does not proceed sufficiently. The upper limit of the reaction temperature is not particularly limited, but if the temperature is increased, the production of tar and carbide is promoted, and separation and purification of the target product becomes difficult, and it is uneconomical. Is 400 ° C. or lower, more preferably 320 ° C. or lower.

The reaction time is the time during which the water-soluble saccharide is exposed to water in a water vapor state, and varies depending on the reaction temperature, the raw material containing the water-soluble saccharide, the charged concentration, etc. Preferably, it is about 0.01 to 0.5 seconds. If the reaction time is too short, a large amount of unreacted raw material remains. If the reaction time is too long, the raw material and the produced anhydrosugar undergo a hyperdecomposition reaction or a polymerization reaction, and the yield of the target product decreases.
The reaction time can be adjusted, for example, by the amount of the aqueous solution fed into the reactor.

  The reaction apparatus used in the method of the present invention is not particularly limited as long as it can be reacted under the above-mentioned conditions, but a flow reactor is used, and the water-soluble saccharide is contained in the flow reactor. It is preferable to supply the raw material continuously. Since the reaction of the present invention can be carried out even under atmospheric pressure, there is no need for a pressure vessel, and any material that can withstand the reaction temperature may be used.

As a reaction apparatus including a flow reactor, for example, the one shown schematically in FIG. 1 can be used.
In the illustrated apparatus, a tank (1) containing a raw material aqueous solution, a reactor (3), a cooler (8) and a recovery device (10) are connected. A pump (2) is provided between the raw material tank (1) and the reactor (3), and a predetermined amount of raw material aqueous solution is continuously introduced into the reactor (3) by the pump (2). The reactor (3) is provided with thermocouples (6, 7) and heaters (4, 5), and the heater output is controlled based on the temperature information in the reactor obtained from the thermocouple, and the reactor interior is predetermined. Adjust to the temperature of. The reaction mixture that has passed through the reactor (3) is cooled by the cooler (8) and recovered by the recovery device (10). As the cooler (8), for example, a heat exchanger through which a coolant flows can be used. A preheater (11) for preheating the raw material aqueous solution may be provided in the flow path between the pump (2) and the reactor (3). By preheating the aqueous raw material solution to less than 100 ° C. with this preheater, temperature unevenness in the reactor (3) can be eliminated, and more uniform reaction conditions can be achieved. The preheating temperature is preferably 80 ° C. or higher, and more preferably 90 ° C. or higher. When the reaction is performed under pressure, a pressure regulating valve (9) can be provided between the cooler (8) and the recovery device (10). When the reaction is performed under reduced pressure, the recovery device ( A pump can be provided after 10) (not shown).

  According to the production method of the present invention, an anhydro sugar can be obtained in a high yield of 50% or more by appropriately selecting reaction conditions such as reaction temperature, reaction time, pressure, raw material, and charged concentration.

  The isolation / purification of the anhydrosugar produced by the production method of the present invention is not particularly limited. For example, after removing water from the reaction mixture, the reaction mixture is directly fractionated by silica gel column chromatography, The elution fraction can be purified by distilling off the elution solvent. In order to remove water from the reaction mixture, it can be easily carried out by freeze-drying or concentration under reduced pressure by an evaporator. As an elution solvent used for silica gel column chromatography, ethyl acetate, methanol, ethanol, isopropyl alcohol and the like are preferable. These are mixed as appropriate to adjust the polarity, and the target anhydrosugar is eluted and separated. For example, anhydrosugar is obtained by eluting the anhydrosugar with a mixed solvent of ethyl acetate / methanol (20/1 → 10/1) and distilling off the elution solvent from the eluted fraction.

  EXAMPLES Hereinafter, although an Example explains this invention in full detail, it is not limited to the following Example. In addition, the apparatus shown in FIG. 1 was used for the manufacturing apparatus of anhydro sugar.

Examples 1-11:
Glucose, sucrose and Fujioligo # 450P as raw materials (malto-oligosaccharide: glucose 1.0%, maltose 7.8%, maltotriose 10.2%, maltotetraose 50.5%, maltopentaose 2.5%, sugars with 6 or more glucose units 28.0%) The aqueous solution was reacted under the conditions shown in Table 1 under atmospheric pressure (0.1 MPa) and low pressure. The reaction time was 0.13 to 0.15 seconds for Examples 1 to 4 and Examples 8 to 11, and 0.27 to 0.30 seconds for Examples 5 to 7. The reaction product was analyzed by GPC analysis (column: Showa Denko KS-801, detector: differential refractometer).

From Table 1, by heating glucose, sucrose containing glucose as a component and maltooligosaccharide in water vapor, the glucose molecule undergoes a dehydration reaction in the molecule or the oligosaccharide undergoes a depolymerization reaction, and an anhydro sugar, It can be seen that levoglucosan and 1,6-anhydroglucofuranose can be produced in high yield.
In particular, 1,6-anhydroglucofuranose is hardly obtained by the conventional thermal decomposition method, but can be obtained in a high yield by using the method of the present invention.

Example 12:
A mannose aqueous solution (0.4% by mass) was used as a raw material, and the reaction was carried out under atmospheric pressure at a reaction temperature of 260 ° C. and a reaction time of 0.13 seconds. GPC analysis of the reaction product gave anhydrosugars, ie mannosan and 1,6-anhydromannofuranose, in 53% and 19% yields, respectively.

Example 13:
An aqueous galactose solution (0.4% by mass) was used as a raw material, and the reaction was carried out at atmospheric pressure with a reaction temperature of 260 ° C. and a reaction time of 0.13 seconds. According to GC analysis of the reaction product (column: Shimadzu Corporation CBP10-S25-050, detector: flame ionization detector), 59% each of anhydrosugars, ie, galactosan and 1,6-anhydrogalactofuranose And a yield of 36%.

Example 14:
180 mL of the reaction mixture obtained in Example 11 was concentrated under reduced pressure at a water temperature of 40 ° C. or lower to obtain 1460 mg of a crude reaction product. The crude reaction product was purified by silica gel column chromatography (silica gel, 30 mL). Anhydro sugars (levoglucosan and 1,6-anhydroglucofuranose) were eluted with a mixed solvent of ethyl acetate / methanol (20/1 → 10/1). The elution solvent was distilled off under reduced pressure to obtain 1050 mg of anhydrosugar (yield 65%). By recrystallizing this anhydrosugar from a mixed solvent of isopropyl alcohol / ethyl acetate, 820 mg (yield 51%) of crystals of levoglucosan and 220 mg of mother liquor (levoglucosan / 1,6-anhydroglucofuranose = 1/2, yield 14) %).

  Therefore, according to the present invention, a biodegradable bioplastic, a chemical raw material such as a bioadhesive, a raw material for an anticancer agent or an anti-HIV agent, an optical isomer resolving agent, and a sugar-derived safe medicine based on a multibranched polysaccharide Anhydro sugar useful as various functional polymer materials such as materials can be supplied at low cost.

It is the schematic of an example of the reaction apparatus which can be used with the method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Raw material (aqueous solution) tank 2 Pump 3 Reactor 4, 5 Heater 6, 7 Thermocouple 8 Cooler 9 Pressure regulating valve 10 Recovery device 11 Preheater

Claims (5)

An aqueous solution containing at least one water-soluble saccharide compound selected from monosaccharides, oligosaccharides or glycosides thereof, polysaccharides and mixtures thereof is heated to a temperature of 100 to 460 ° C. at atmospheric pressure in a steam atmosphere. The following general formula (1), general formula (2) and / or general formula (3)

The manufacturing method of the anhydrosugar shown by these.   The water-soluble sugar compound is glucose, mannose, galactose, growth, allose, altrose, idose, talose, ribose, xylose, arabinose, and lyxose, monosaccharide, sucrose, maltose, isomaltose, cellobiose, trehalose, trehalulose, Palatinose, nigerose, lactose, lactulose, glycosyl sucrose, lactosucrose, panose, raffinose, cyclodextrins and their glycosides, branched cyclodextrins, cyclodextran, maltooligosaccharides, isomaltooligosaccharides, cellooligosaccharides, galactooligosaccharides, mannooligosaccharides , Oligosaccharides, xylo-oligosaccharides, fructooligosaccharides, palatinose oligosaccharides, nigerooligosaccharides, gentio-oligosaccharides and soybean oligosaccharides And soluble starch, pullulan, gum arabic, dextran, dextrin and at least one method for producing anhydro sugar according to claim 1, wherein the water-soluble sugar compound selected from a polysaccharide selected from glucomannan.   The method for producing an anhydrosugar according to claim 1, wherein the raw material containing the water-soluble sugar compound is selected from honey, molasses, molasses, starch syrup, brown sugar product and maple syrup. An aqueous raw material solution containing a water-soluble sugar compound is continuously supplied to a heated flow reactor and heated to a temperature of 100 to 460 ° C. at atmospheric pressure to react in a steam atmosphere , and the reaction mixture is cooled and recovered. A method for continuously producing the anhydrosugar according to claim 1. The method for continuously producing an anhydrosugar according to claim 4 , wherein the preheated raw material aqueous solution is supplied to the flow reactor.

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