WO2011069391A1 - Method for extracting arabinose from mixed sugar - Google Patents

Method for extracting arabinose from mixed sugar Download PDF

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Publication number
WO2011069391A1
WO2011069391A1 PCT/CN2010/077749 CN2010077749W WO2011069391A1 WO 2011069391 A1 WO2011069391 A1 WO 2011069391A1 CN 2010077749 W CN2010077749 W CN 2010077749W WO 2011069391 A1 WO2011069391 A1 WO 2011069391A1
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arabinose
sugar
xylose
organic solvent
extracting
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PCT/CN2010/077749
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French (fr)
Chinese (zh)
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陈培豪
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Chen Peihao
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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
    • C07H1/06—Separation; Purification

Definitions

  • the present invention relates to the field of chemical industry, and in particular to a method for extracting arabinose from a mixed sugar containing arabinose, wherein the mixed sugar further contains xylose or rhamnose.
  • L-arabinose is a widely used five-carbon sugar mainly present in the form of a polymer in the plant hemicellulose. Higher plants generally contain about 20 to 35% hemicellulose in the dry matter, while hemicellulose is mainly composed of xylose and arabinose. In addition, L-arabinose is also abundantly present in plant gums such as gum arabic. Since hemicellulose is produced in a large amount, xylose and arabinose can be prepared in large quantities by hydrolyzing hemicellulose in higher plants.
  • the hemicellulose hydrolyzate contains a variety of monosaccharides, mainly xylose, as well as glucose, arabinose, galactose and the like. Since most of the monosaccharides in the hemicellulose hydrolyzate are xylose, the xylose crystals can be first separated by crystallization until the xylose cannot be recrystallized, and the remaining mother liquor which cannot be crystallized is called xylose mother liquor.
  • xylose mother liquor contains 38.10% xylose, 23.70% arabinose, 13.80% Glucose, 9.89% galactose.
  • the extraction of arabinose from xylose mother liquor is generally carried out by simulated moving bed chromatography. Due to the large investment in this technology, the production capacity is very small, which makes the arabinose unable to meet the market demand.
  • arabinose can also be prepared from some gum arabic-containing plant gums such as gum arabic.
  • the monomer composition of gum arabic is: galactose 42%, L-arabinose 31%, rhamnose 13%, glucuronic acid 13%, 4-0-mercaptogluonic acid 1%.
  • Chinese Patent No. 021 16353.7 discloses a method for extracting arabinose with gum arabic, but the mixed monosaccharide still needs to be separated by two-column chromatography to obtain arabinose, which is difficult to industrialize.
  • the present invention provides a method for extracting arabinose from a mixed sugar containing arabinose, wherein the mixed sugar further contains xylose or rhamnose, which utilizes xylose or rhamnose and arabinose
  • xylose or rhamnose which utilizes xylose or rhamnose and arabinose
  • step (2) when the arabinose in the initial sugar is completely dissolved, and the xylose or rhamnose is completely dissolved, the arabinose is extracted from the initial sugar from the step (5).
  • the method for extracting arabinose from a mixed sugar containing arabinose and xylose or rhamnose further comprises the following steps:
  • Step (3) solid or liquid separation of the mixture I and/or step (6) of solid and liquid separation of the mixture II is carried out under heat retention.
  • a third organic solvent is added to the sugar solution a or the sugar solution b as a crystallization accelerator, and the third organic solvent is selected from the group consisting of alcohols, Ethers and ketones.
  • the crystallization mother liquid a is reused as the aqueous solution of the step (2) or the aqueous solution of the first organic solvent, and the crystallization mother liquid b is reused as the second organic solvent or the solution described in the step (5).
  • the aqueous solution of the second organic solvent is described, but when the crystallization accelerator is added, the crystallization accelerator is first removed and reused.
  • the sugar solution a or the sugar solution b is evaporated to remove part or all of the solvent.
  • the arabinose-containing mixed sugar is a monosaccharide mixture prepared using a hemicellulose hydrolyzate.
  • the arabinose-containing mixed sugar is a monosaccharide mixture prepared from a xylose mother liquor obtained by crystallizing xylose with a hemicellulose hydrolyzate.
  • the arabinose-containing mixed sugar is a monosaccharide mixture prepared by fermenting glucose after the xylose mother liquor obtained by crystallizing xylose from the hemicellulose hydrolyzate.
  • the arabinose-containing mixed sugar is a monosaccharide mixture prepared by fermenting glucose and galactose after fermentation of the xylose mother liquor obtained by crystallizing xylose with a hemicellulose hydrolyzate.
  • the arabinose-containing mixed sugar is a monosaccharide mixture prepared by fermentation to remove galactose with an acacia hydrolyzate.
  • the first organic solvent and the second organic solvent are each selected from the group consisting of alcohols, ketones, carboxylic acids, nitrogen-containing organic solvents, polyfunctional compounds containing several functional groups of a hydroxyl group, a ketone group, and a carboxyl group, and a few of them.
  • the first organic solvent and the second organic solvent are each selected from the group consisting of alcohols, ketones, carboxylic acids, nitrogen-containing organic solvents, polyfunctional compounds containing several functional groups of a hydroxyl group, a ketone group, and a carboxyl group, and a few of them.
  • kind of mixture are examples of mixture.
  • the first organic solvent and/or the second organic solvent further contain other organic solvents.
  • the alcohol is selected from the group consisting of CI to C3 alcohols selected from the group consisting of acetone and methyl ethyl ketone, the carboxylic acid being selected from the group consisting of CI to C4 carboxylic acids, and the nitrogen-containing organic solvent being selected from the group consisting of acetonitrile and pyridine.
  • the crystal a is mixed with an aqueous solution of the second organic solvent or the second organic solvent, and the aqueous solution of the first organic solvent is washed with a cold organic solvent or an aqueous solution of a cold organic solvent.
  • the crystal a is dried before being mixed with the aqueous solution of the second organic solvent or the second organic solvent; before the crystal b is mixed with the water or the aqueous solution of the first organic solvent Dry.
  • the resulting crude arabinose, crude xylose or crude rhamnose is recrystallized to give pure arabinose, pure xylose or pure rhamnose.
  • the present invention uses a mixed sugar obtained by hydrolysis of hemicellulose as a raw material, or a monosaccharide mixture prepared from a xylose mother liquor obtained by crystallizing xylose from a hemicellulose hydrolyzate as a raw material, or a mixed sugar obtained by hydrolysis of gum arabic as a raw material. Extract arabinose.
  • the remaining mixed sugar mainly contains xylose, arabinose, glucose and galactose, and the highest content of xylose and arabinose.
  • the hexoses such as glucose and galactose can be removed by fermentation, while xylose and arabinose are difficult to separate by fermentation. Therefore, the separation of xylose and arabinose is a key point of the present invention.
  • monosaccharides are generally insoluble in organic solvents, while xylose is soluble in hot ethanol and pyridine.
  • Lober sugar is soluble in glycerin, but it is also difficult to achieve the separation of xylose and arabinose using these common general knowledge.
  • the mixed sugar obtained by hydrolysis of hemicellulose has a xylose content of at least 1.5 times that of the arabinose. Therefore, the mixed sugar obtained by hydrolyzing hemicellulose cannot separate the arabinose by ordinary dissolution and crystallization. .
  • solubility increases, but the increase in arabinose solubility is greater than the increase in xylose solubility until the solubility of the two is close to each other; when the hot mixed sugar solution in which the solubility of the two is close to each other and both are saturated, Since the solubility of arabinose is greater than the decrease in the solubility of xylose, a crystal having a ratio of xylose to arabinose of less than or equal to about 1:1 can be obtained; after obtaining such crystallization, xylose is utilized.
  • the solubility in the organic solvent is greater than the solubility of the arabinose, so that the xylose is completely dissolved and the arabinose is only partially dissolved, thereby isolating the arabinose in the form of insoluble matter.
  • the solubility of arabinose is greater than the solubility of xylose. Therefore, it is also possible to prepare a hot mixed sugar solution in which both xylose and arabinose are saturated by using water as a solvent, and then obtain the xylose content by cooling and crystallization.
  • the ratio of arabinose content is less than or approximately equal to 1:1 crystals.
  • the mixed sugar obtained by hydrolysis of hemicellulose is an initial sugar
  • the aqueous solution of the first organic solvent is mixed with the initial sugar
  • the water content in the aqueous solution of the organic solvent is such that the ratio of the xylose content to the arabinose content is less than or
  • the water content required for crystal a is approximately equal to 1:1.
  • the water content may be selected between 0% and 100% depending on the organic solvent.
  • the amount of water or the first organic solvent aqueous solution is adjusted, and heated to make the Arabian
  • the sugar is completely dissolved or nearly completely dissolved, while the xylose is partially dissolved in the solution, and the other part is in the form of insoluble matter to obtain the mixture I; solid and liquid are separated, thereby obtaining the crude xylose and sugar solution a; the sugar solution a is cooled.
  • crystal a and crystallization mother liquid a wherein the ratio of xylose content to arabinose content in crystal a is less than or equal to about 1:1, that is, the mixed sugar is dissolved by hot water or a hot first organic solvent aqueous solution.
  • the purpose is to separate the solubility of xylose and arabinose in the solvent or the solubility of xylose is less than the solubility of arabinose.
  • Xylose two It is the use of the solvent to crystallize the crystal a having a ratio of xylose content to arabinose content of less than or about equal to 1:1.
  • crystal a While crystal a will be used as the starting sugar for the next separation process; the crystal a is added to the hot second organic solvent or the second organic solvent solution, and the solubility of xylose in the second solvent or second organic solvent solution And greater than the solubility of the arabinose in the second organic solvent or the second organic solvent aqueous solution, adjusting the amount of the second organic solvent or the second organic solvent aqueous solution, so that the xylose is completely dissolved or nearly completely dissolved, and the arabinose is partially Dissolved in the solvent, another part is in the form of insoluble matter, to obtain a mixture II; solid and liquid separation, thereby obtaining crude arabinose and sugar solution b; sugar solution b is cooled and crystallized to obtain crystal b and crystal mother liquid b; The crystal b is an initial sugar, and the above steps are repeated to completely separate the xylose and the arabinose in the mixed sugar obtained by the hydrolysis of hemicellulose; the obtained crude xylose and crude arabinose can
  • the initial sugar when the initial sugar is dissolved in hot water or a hot aqueous solution of the first organic solvent, it is also possible that the xylose is completely dissolved when the arabinose is completely dissolved. At this time, the initial sugar should first be combined with the hot one.
  • the two organic solvents or the second organic solvent aqueous solution are mixed to completely dissolve or nearly completely dissolve the xylose, and the arabinose is partially dissolved in the solvent, and the other portion is in the form of insoluble matter, thereby obtaining insoluble matter by solid and liquid separation. Crude arabinose.
  • the crystallization mother liquid a reuse can increase the amount of the arabinose dissolved by the unit solvent, that is, the amount of the solvent can be reduced, thereby speeding up the separation speed; similarly, the reuse of the crystallization mother liquid b can increase the dissolution of the xylose per unit solvent. The amount, that is, the amount of solvent can be reduced, thereby speeding up the separation.
  • the gum arabic hydrolysate contains three monosaccharides, galactose, arabinose and rhamnose, wherein galactose can be removed by fermentation, and the separation of arabinose and rhamnose is also the key to extracting arabinose.
  • the Applicant's research has found that when rhamnose and arabinose coexist in hot water or organic solvent, they have the same solubility characteristics and crystallization characteristics as when xylose and arabinose coexist in hot water or organic solvent. The same method of separating xylose and arabinose was used to separate rhamnose and arabinose.
  • the method for extracting arabinose from the mixed sugar containing arabinose and xylose or rhamnose according to the present invention only through the mixed sugar containing arabinose and xylose or rhamnose in an organic solvent of different water content
  • the dissolution and crystallization process completes the complete separation of xylose or rhamnose from arabinose, frees the dependence on chromatographic separation methods, and lays the foundation for large-scale preparation of arabinose.
  • the xylose mother liquor obtained by crystallizing the mixed sugar obtained by hydrolysis of hemicellulose is diluted with glucose and added to Saccharomyces cerevisiae for fermentation until the glucose and galactose are substantially utilized, and the yeast cells are separated by centrifugation, and the supernatant is at 70 ° C.
  • the non-fermented monosaccharide in the xylose mother liquor is basically Crystallized, the crystals contained xylose and arabinose, wherein the xylose content was about 1.6 times that of arabinose, and was used as the initial sugar of the examples and Examples 2, 3, 4, and 5.
  • the product is crude xylose, and the crude xylose is washed twice with a small amount of cold 90% ethanol and stored for later; the sugar solution a is allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation, to obtain crystal a and supernatant, wherein, crystallization a, the xylose content is 0.5 times the arabinose content, and the crystal a is washed twice with a small amount of cold 90% ethanol; 1.0 g of crystal a is added and 1.8 g of 90% ethanol is added, and the mixture is kept in a water bath at 70 ° C for 1 hour, wherein The xylose is completely dissolved, and only a part of arabinose is dissolved; in the state of heat preservation, the solid solution and the liquid are separated into a sugar solution b and an insoluble matter, the insoluble matter is crude arabinose, and the crude arabinose is washed twice with a small amount of cold 90% ethanol.
  • the sugar solution b Stored in standby; the sugar solution b is allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation, to obtain crystal b and supernatant, and wash crystal b twice with a small amount of cold 90% ethanol; repeat with crystal b Separation process, so that the initial sugar is continuously separated into coarse xylose and crude arabinose; crude xylose and crude arabinose are separately dissolved in 80 ° (90% ethanol to form a saturated solution, and then left to stand at room temperature for 36 hours for crystallization The crystals were washed twice with cold 90% ethanol and dried to obtain pure xylose and arabinose.
  • the crude xylose is washed twice with a small amount of cold 90% ethanol and stored for later use; the sugar solution a is allowed to stand at room temperature for 72 hours for crystallization, and solid and liquid separation is carried out by centrifugation to obtain crystal a and supernatant, wherein, in crystal a, The xylose content and the arabinose content are close to 1:1, and the crystal a is washed twice with a small amount of cold 90% ethanol; 1.0 g of crystal a is added and 2.8 g of 90% ethanol is added, and the mixture is kept in a water bath at 70 ° C for 1 hour, wherein the wood The sugar is completely dissolved, and the arabinose is only partially dissolved.
  • the solid solution and the liquid are separated into a sugar solution b and an insoluble matter, and the insoluble matter is crude arabinose.
  • the crude arabinose is washed twice with a small amount of cold 90% ethanol and stored for use.
  • the sugar solution b is allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation to obtain crystal b and supernatant, and the crystal b is washed twice with a small amount of cold 90% ethanol; the above separation process is repeated with crystal b, thereby continuously initializing
  • the sugar is separated into coarse xylose and crude arabinose; the crude xylose and crude arabinose are separately dissolved in 90% isopropanol at 80 ° C to form a saturated solution, and then allowed to stand at room temperature for 24 hours for crystallization, and the crystal is cooled.
  • 90% The isopropyl alcohol was washed twice and dried to obtain pure xylose and arabinose.
  • the solid solution and the liquid are separated into a sugar solution b and an insoluble matter, the insoluble matter is crude arabinose, and the crude arabinose is washed with a small amount of cold 90% ethanol.
  • the sugar solution b was allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation, and the crystal b and the supernatant were obtained, and the crystal b was washed twice with a small amount of cold 90% ethanol; the crystal b was repeated to repeat the above separation process.
  • the solid solution and the liquid are separated into a sugar solution b and an insoluble matter, the insoluble matter is crude arabinose, and the crude arabinose is washed twice with a small amount of cold 99.5% pyridine for storage; the sugar solution b is distilled to dryness at 70 ° C under reduced pressure. Crystallization b is obtained; crystal b repeats the above separation process, thereby continuously separating the initial sugar into crude xylose and crude arabinose; and the crude xylose and crude arabinose are separately dissolved in 90% ethanol at 80 ° C to form a saturated solution. Then room temperature For 48 hours. The crystals were washed with cold 90% ethanol twice, to give after drying Pure xylose and arabinose.
  • the gum arabic is hydrolyzed with dilute sulfuric acid to obtain a hydrolyzate, and the acid is extracted with a diisooctylamine solution to obtain a hydrolyzate of pH 5.6. Then, the galactose is removed by fermentation with Saccharomyces cerevisiae, and the yeast cell is removed by centrifugation, and then reduced at 70 ° C. Press distillation to a sugar concentration of about 80%, crystallize and crystallize after cooling, and the crystallization mother liquor continues to be used to crystallize the mixed sugar substantially.
  • the arabinose content in the crystal is about twice that of rhamnose, ie rhamnose. It is 0.5 times of arabinose as the initial sugar of this example.
  • the initial sugar is mixed with 90% ethanol, heated to 70 ° C and stirred to dissolve a portion of the sugar.
  • 90% ethanol is added in an amount necessary to completely dissolve the rhamnose in the mixed sugar to obtain a mixture II, wherein a part of the arabinose is In the form of insoluble matter, and then subjected to solid-liquid separation to obtain insoluble crude arabinose and sugar solution b; the sugar solution b is distilled under reduced pressure at 70 ° C to dryness to obtain crystal b, the content of rhamnose in crystal b About 2.5 times the arabinose content; crystal b is mixed with 90% isopropanol, heated to 70 ° C and stirred to dissolve part of the sugar, 90% of the isopropanol is added in the mixed sugar, the arabinose is just completely dissolved
  • the required amount is such that a mixture I is obtained in which part of the rhamnose is present in the form of an insoluble matter, followed by solid-liquid separation to obtain an insoluble crude rhamnose and a
  • the content of arabinose in crystal a is about 1.2 times the rhamnose content, that is, rhamnose is about 0.8 times that of arabinose, that is, Her. Rhamnose sugar content greater than the content.
  • the crystal a is re-mixed with 90% ethanol, heated to 70 ° C and stirred to dissolve a portion of the sugar, and 90% ethanol is added in an amount required to completely dissolve the rhamnose in the crystal a to obtain a mixture II, a part of the arabinose.
  • insoluble crude arabinose and sugar solution b In the form of insoluble matter, and then subjected to solid-liquid separation to obtain insoluble crude arabinose and sugar solution b; the sugar solution b is distilled under reduced pressure at 70 ° C to dryness to obtain crystal b, crystal b in rhamnose The content is about 2.5 times of the arabinose content; the crystal b is mixed with the crystallization mother liquid a, heated to 70 ° C and stirred to dissolve a part of the sugar, and the crystallization mother liquid a is added in an amount required for the arabinose in the mixed sugar to be completely dissolved.
  • a mixture I is obtained, wherein part of the rhamnose is present as an insoluble matter, and then subjected to solid-liquid separation to obtain an insoluble crude rhamnose and a sugar solution a; the sugar solution a is cooled to room temperature and left for 24 hours. Crystallization, obtaining crystal a and crystallization mother liquid a, and drying crystal a, the content of arabinose in crystal a is about 1.3 times that of rhamnose, that is, rhamnose is about 0.8 times that of arabinose, that is, arabinose The content is greater than the rhamnose content. Repeat the above steps until the arabinose and rhamnose are completely separated.
  • the crude arabinose and crude rhamnose were recrystallized from 90% ethanol to give pure arabinose and pure rhamnose.

Abstract

A method for extracting arabinose from mixed sugar is provided. The mixed sugar comprises arabinose admixed with xylose or rhamnose. Based on the different solubility and crystallinity of arabinose and xylose or rhamnose in organic solvent with different water content, the method completely separates arabinose from xylose or rhamnose. In comparison with chromatographic separation, the method is cost effective and can be carried out in large scale.

Description

一种从混合糖中提取阿拉伯糖的方法  Method for extracting arabinose from mixed sugar
技术领域 Technical field
本发明属于化工领域， 具体地， 涉及一种从含阿拉伯糖的混合糖中提取阿 拉伯糖的方法， 其中， 混合糖中还含有木糖或鼠李糖。 背景技术  The present invention relates to the field of chemical industry, and in particular to a method for extracting arabinose from a mixed sugar containing arabinose, wherein the mixed sugar further contains xylose or rhamnose. Background technique
L一阿拉伯糖是用途广泛的五碳糖， 主要以聚合物的形式存在于植物的半纤 维素中。 高等植物的干物质中一般含有约 20 ~ 35%的半纤维素， 而半纤维素主 要由木糖和阿拉伯糖组成。 另外， L一阿拉伯糖也大量地存在于阿拉伯胶等植物 胶质中。 由于半纤维素的产量巨大， 故通过水解高等植物中的半纤维素可以大 量制备木糖和阿拉伯糖。  L-arabinose is a widely used five-carbon sugar mainly present in the form of a polymer in the plant hemicellulose. Higher plants generally contain about 20 to 35% hemicellulose in the dry matter, while hemicellulose is mainly composed of xylose and arabinose. In addition, L-arabinose is also abundantly present in plant gums such as gum arabic. Since hemicellulose is produced in a large amount, xylose and arabinose can be prepared in large quantities by hydrolyzing hemicellulose in higher plants.
半纤维素水解液中含有多种单糖， 以木糖为主， 以及葡萄糖、 阿拉伯糖、 半乳糖等。 由于半纤维素水解液中的单糖绝大部分为木糖， 所以可以通过结晶 的方法首先把木糖结晶分离出来， 直到木糖无法再结晶， 余下无法结晶的母液 称为木糖母液。 根据液相色谱分析（安徽农业科学， 2009, 37 ( 5 ): 1881-1882, "PHLC法测定木糖母液的组成"）， 木糖母液中含有 38.10%木糖， 23.70%阿拉 伯糖， 13.80%葡萄糖， 9.89%半乳糖。 目前从木糖母液中分离提取阿拉伯糖， 一 般是釆用模拟移动床色谱分离技术， 由于该技术设备投资大， 但产能却非常小， 使阿拉伯糖无法满足市场的需求。  The hemicellulose hydrolyzate contains a variety of monosaccharides, mainly xylose, as well as glucose, arabinose, galactose and the like. Since most of the monosaccharides in the hemicellulose hydrolyzate are xylose, the xylose crystals can be first separated by crystallization until the xylose cannot be recrystallized, and the remaining mother liquor which cannot be crystallized is called xylose mother liquor. According to liquid chromatography analysis (Anhui Agricultural Sciences, 2009, 37 (5): 1881-1882, "PHLC method for determining the composition of xylose mother liquor"), xylose mother liquor contains 38.10% xylose, 23.70% arabinose, 13.80% Glucose, 9.89% galactose. At present, the extraction of arabinose from xylose mother liquor is generally carried out by simulated moving bed chromatography. Due to the large investment in this technology, the production capacity is very small, which makes the arabinose unable to meet the market demand.
阿拉伯糖除主要从半纤维素水解制备外， 还可以从一些含有阿拉伯糖的植 物胶如阿拉伯胶中制备。 根据分析， 阿拉伯胶的单体组成为： 半乳糖 42%, L— 阿拉伯糖 31%, 鼠李糖 13%, 葡萄糖醛酸 13%, 4— 0—曱基葡萄糖醛酸 1%。 如中国专利 021 16353.7公开了一种用阿拉伯胶提取阿拉伯糖的方法，但 混合单糖仍需要通过两柱色谱法才能分离得到阿拉伯糖，难以工业化。 论文"从阿拉伯胶水解液中结晶分离 L一阿拉伯糖"（化学工业与工程， 2007 , 24 ( 5 ): 398-400 ) 描述的分离方法为： 阿拉伯胶稀硫酸水解并 中和后的水解液经发酵除去半乳糖， 然后在曱醇中结晶分离制得粗阿 拉伯糖， 接着在粗阿拉伯糖水溶液中加入乙醇而结晶得到 97.5%的阿 拉伯糖。 该方法由于曱醇结晶母液和乙醇结晶母液中的阿拉伯糖无法 分离回收， 所以得率不高， 最高只有理论得率的 50% , 从而成本较高。 In addition to being primarily prepared from the hydrolysis of hemicellulose, arabinose can also be prepared from some gum arabic-containing plant gums such as gum arabic. According to the analysis, the monomer composition of gum arabic is: galactose 42%, L-arabinose 31%, rhamnose 13%, glucuronic acid 13%, 4-0-mercaptogluonic acid 1%. For example, Chinese Patent No. 021 16353.7 discloses a method for extracting arabinose with gum arabic, but the mixed monosaccharide still needs to be separated by two-column chromatography to obtain arabinose, which is difficult to industrialize. Paper "Crystal separation of L-arabinose from gum arabic hydrolysate" (Chemical Industry and Engineering, 2007, 24 (5): 398-400) The separation method described is as follows: The hydrolysate after hydrolysis and neutralization of the gum arabic is fermented to remove galactose, and then crystallized in decyl alcohol to obtain crude arabinose, followed by Ethanol was added to the crude arabinose aqueous solution to obtain 97.5% arabinose. In this method, since the arabinose in the mother liquor of the sterol crystal and the mother liquor of the ethanol crystal cannot be separated and recovered, the yield is not high, and the highest is only 50% of the theoretical yield, so that the cost is high.
由于釆用现有的方法制备阿拉伯糖不仅产量小而且成本居高不下， 从而限 制了这种具备良好保健功能的功能糖的普及使用。 为此， 需要开发阿拉伯糖的 大规模生产方法。 发明内容  Since the preparation of arabinose by the existing method is not only small in yield but also high in cost, it limits the popular use of such functional sugar having good health care functions. To this end, it is necessary to develop a large-scale production method of arabinose. Summary of the invention
为了克服上述缺点， 本发明提供了一种从含阿拉伯糖的混合糖中提取阿拉 伯糖的方法， 其中， 混合糖中还含有木糖或鼠李糖， 其利用木糖或鼠李糖与阿拉 伯糖在不同含水量的热的有机溶剂中的溶解度和冷却后结晶率的不同， 通过简 单的溶解和结晶过程实现了木糖或鼠李糖与阿拉伯糖的完全分离， 为大规模制 备阿拉伯糖奠定了基础。  In order to overcome the above disadvantages, the present invention provides a method for extracting arabinose from a mixed sugar containing arabinose, wherein the mixed sugar further contains xylose or rhamnose, which utilizes xylose or rhamnose and arabinose The solubility of hot water in different organic solvents and the crystallization rate after cooling, the complete separation of xylose or rhamnose from arabinose by simple dissolution and crystallization process, laid the foundation for the large-scale preparation of arabinose. basis.
本发明的技术方案如下： 一种从含阿拉伯糖的混合糖中提取阿拉伯糖的方 法， 其中， 混合糖中还含有木糖或鼠李糖， 该方法包括以下步骤：  The technical solution of the present invention is as follows: A method for extracting arabinose from a mixed sugar containing arabinose, wherein the mixed sugar further contains xylose or rhamnose, the method comprising the steps of:
( 1 )取上述含阿拉伯糖的混合糖为初始糖；  (1) taking the above-mentioned arabinose-containing mixed sugar as an initial sugar;
( 2 )将初始糖与水或第一有机溶剂的水溶液混合，加热使初始糖部分溶解， 所述第一有机溶剂的水溶液的含水量为得到木糖含量与阿拉伯糖含量之比或鼠 李糖含量与阿拉伯糖含量之比小于或约等于 1 : 1的结晶 a所需要的含水量， 所 述水或所述第一有机溶剂的水溶液的用量约为该加热条件下初始糖中阿拉伯糖 完全溶解所需要的量， 得混合物 I；  (2) mixing the initial sugar with water or an aqueous solution of the first organic solvent, and heating to partially dissolve the initial sugar, wherein the aqueous solution of the first organic solvent has a water content of a ratio of xylose to arabinose or rhamnose. The ratio of the content to the arabinose content is less than or equal to the water content required for the crystallization a of 1:1, and the aqueous solution or the aqueous solution of the first organic solvent is used in an amount sufficient to completely dissolve the arabinose in the initial sugar under the heating condition. The amount required to obtain a mixture I;
( 3 )将混合物 I固、 液分离， 得到糖溶液 a和粗木糖， 或得到糖溶液 a和 粗鼠李糖；  (3) separating the mixture I and the liquid to obtain a sugar solution a and crude xylose, or obtaining a sugar solution a and crude rhamnose;
( 4 )糖溶液 a冷却后结晶， 分离得到结晶 a和结晶母液 a, 其中， 所述结 晶 a 中， 木糖含量与阿拉伯糖含量之比或鼠李糖含量与阿拉伯糖含量之比小于 或约等于 1 : 1 ; (4) The sugar solution a is cooled and crystallized, and the crystal a and the crystal mother liquid a are separated, wherein the ratio of the xylose content to the arabinose content or the ratio of the rhamnose content to the arabinose content in the crystal a is smaller than Or about equal to 1: 1 ;
( 5 )将结晶 a与第二有机溶剂或第二有机溶剂的水溶液混合， 加热使结晶 a部分溶解 ,所述第二有机溶剂或所述第二有机溶剂的水溶液的用量约为该加热 条件下结晶 a中木糖或鼠李糖完全溶解所需要的量， 得混合物 II；  (5) mixing the crystal a with an aqueous solution of the second organic solvent or the second organic solvent, heating to partially dissolve the crystal a, and the aqueous solution of the second organic solvent or the second organic solvent is used under the heating condition. The amount required for the complete dissolution of xylose or rhamnose in crystal a, to obtain a mixture II;
( 6 )将混合物 II固、 液分离， 得到糖溶液 b和粗阿拉伯糖。  (6) The mixture II is solid and liquid separated to obtain a sugar solution b and crude arabinose.
在步骤（2 ) 中， 初始糖中的阿拉伯糖完全溶解时， 木糖或鼠李糖也完全溶 解， 则从步骤（5 )开始从初始糖中提取阿拉伯糖。  In the step (2), when the arabinose in the initial sugar is completely dissolved, and the xylose or rhamnose is completely dissolved, the arabinose is extracted from the initial sugar from the step (5).
所述从含阿拉伯糖和木糖或鼠李糖的混合糖中提取阿拉伯糖的方法， 还包 括以下步骤：  The method for extracting arabinose from a mixed sugar containing arabinose and xylose or rhamnose further comprises the following steps:
( 7 )将糖溶液 b冷却后结晶， 分离得到结晶 b和结晶母液 b;  (7) cooling the sugar solution b, crystallizing, separating the crystal b and the crystal mother liquid b;
( 8 ) 以结晶 b为初始糖， 重复上述步骤（2 ) ~ ( 7 ), 直到将含阿拉伯糖 的混合糖中的阿拉伯糖全部提取出。  (8) The above steps (2) to (7) are repeated with the crystal b as the initial sugar until all the arabinose in the arabinose-containing mixed sugar is extracted.
步骤（ 3 )将混合物 I固、 液分离和 /或步骤（ 6 )将混合物 II固、 液分离在 保温状态下进行。  Step (3) solid or liquid separation of the mixture I and/or step (6) of solid and liquid separation of the mixture II is carried out under heat retention.
所述糖溶液 a或所述糖溶液 b难以结晶时 ,向所述糖溶液 a或所述糖溶液 b 中加入第三种有机溶剂作为结晶促进剂， 所述第三种有机溶剂选自醇、 醚和酮。  When the sugar solution a or the sugar solution b is difficult to crystallize, a third organic solvent is added to the sugar solution a or the sugar solution b as a crystallization accelerator, and the third organic solvent is selected from the group consisting of alcohols, Ethers and ketones.
较佳地， 所述结晶母液 a回用作为步骤（2 )所述的水或所述的第一有机溶 剂的水溶液， 结晶母液 b回用作为步骤（5 )所述的第二有机溶剂或所述的第二 有机溶剂的水溶液， 但当加入了结晶促进剂时首先分离除去结晶促进剂后再回 用。  Preferably, the crystallization mother liquid a is reused as the aqueous solution of the step (2) or the aqueous solution of the first organic solvent, and the crystallization mother liquid b is reused as the second organic solvent or the solution described in the step (5). The aqueous solution of the second organic solvent is described, but when the crystallization accelerator is added, the crystallization accelerator is first removed and reused.
所述糖溶液 a或所述糖溶液 b难以结晶时 ,将所述糖溶液 a或所述糖溶液 b 蒸发除去部分或全部溶剂。  When the sugar solution a or the sugar solution b is difficult to crystallize, the sugar solution a or the sugar solution b is evaporated to remove part or all of the solvent.
所述含阿拉伯糖的混合糖为用半纤维素水解液制备的单糖混合物。  The arabinose-containing mixed sugar is a monosaccharide mixture prepared using a hemicellulose hydrolyzate.
较佳地， 所述含阿拉伯糖的混合糖为用半纤维素水解液结晶出木糖后的木 糖母液制备的单糖混合物。  Preferably, the arabinose-containing mixed sugar is a monosaccharide mixture prepared from a xylose mother liquor obtained by crystallizing xylose with a hemicellulose hydrolyzate.
较佳地， 所述含阿拉伯糖的混合糖为用半纤维素水解液结晶出木糖后的木 糖母液经过发酵除去葡萄糖后制备的单糖混合物。 优选地， 所述含阿拉伯糖的混合糖为用半纤维素水解液结晶出木糖后的木 糖母液经过发酵除去葡萄糖和半乳糖后制备的单糖混合物。 Preferably, the arabinose-containing mixed sugar is a monosaccharide mixture prepared by fermenting glucose after the xylose mother liquor obtained by crystallizing xylose from the hemicellulose hydrolyzate. Preferably, the arabinose-containing mixed sugar is a monosaccharide mixture prepared by fermenting glucose and galactose after fermentation of the xylose mother liquor obtained by crystallizing xylose with a hemicellulose hydrolyzate.
所述含阿拉伯糖的混合糖为用阿拉伯胶水解液经发酵除去半乳糖后制备的 单糖混合物。  The arabinose-containing mixed sugar is a monosaccharide mixture prepared by fermentation to remove galactose with an acacia hydrolyzate.
所述第一有机溶剂和所述第二有机溶剂均选自醇， 酮， 羧酸， 含氮有机溶 剂， 含羟基、 酮基、 羧基中的几种官能团的多官能团化合物， 和它们中的几种 的混合物。  The first organic solvent and the second organic solvent are each selected from the group consisting of alcohols, ketones, carboxylic acids, nitrogen-containing organic solvents, polyfunctional compounds containing several functional groups of a hydroxyl group, a ketone group, and a carboxyl group, and a few of them. Kind of mixture.
所述第一有机溶剂和 /或所述第二有机溶剂还含有其他有机溶剂。  The first organic solvent and/or the second organic solvent further contain other organic solvents.
所述醇选自 CI ~ C3的醇， 所述酮选自丙酮和丁酮， 所述羧酸选自 CI ~ C4 的羧酸， 所述含氮有机溶剂选自乙腈和吡啶。  The alcohol is selected from the group consisting of CI to C3 alcohols selected from the group consisting of acetone and methyl ethyl ketone, the carboxylic acid being selected from the group consisting of CI to C4 carboxylic acids, and the nitrogen-containing organic solvent being selected from the group consisting of acetonitrile and pyridine.
较佳地， 所述结晶 a与所述第二有机溶剂或所述第二有机溶剂的水溶液混 所述第一有机溶剂的水溶液混合前先用冷的有机溶剂或冷的有机溶剂的水溶液 洗涤。  Preferably, the crystal a is mixed with an aqueous solution of the second organic solvent or the second organic solvent, and the aqueous solution of the first organic solvent is washed with a cold organic solvent or an aqueous solution of a cold organic solvent.
较佳地， 所述结晶 a与所述第二有机溶剂或所述第二有机溶剂的水溶液混 合前先进行干燥； 所述结晶 b与所述水或所述第一有机溶剂的水溶液混合前先 进行干燥。  Preferably, the crystal a is dried before being mixed with the aqueous solution of the second organic solvent or the second organic solvent; before the crystal b is mixed with the water or the aqueous solution of the first organic solvent Dry.
较佳地， 所得粗阿拉伯糖、粗木糖或粗鼠李糖经过重结晶而得到纯的阿拉伯 糖、 纯的木糖或纯的鼠李糖。  Preferably, the resulting crude arabinose, crude xylose or crude rhamnose is recrystallized to give pure arabinose, pure xylose or pure rhamnose.
本发明是以半纤维素水解所得的混合糖作为原料， 或以半纤维素水解液结 晶出木糖后的木糖母液制备的单糖混合物作为原料， 或以阿拉伯胶水解所得的 混合糖作为原料提取阿拉伯糖。  The present invention uses a mixed sugar obtained by hydrolysis of hemicellulose as a raw material, or a monosaccharide mixture prepared from a xylose mother liquor obtained by crystallizing xylose from a hemicellulose hydrolyzate as a raw material, or a mixed sugar obtained by hydrolysis of gum arabic as a raw material. Extract arabinose.
半纤维素水解所得的混合糖结晶出木糖后， 余下的混合糖中， 主要含有木 糖、 阿拉伯糖、 葡萄糖和半乳糖， 其中以木糖和阿拉伯糖含量最高。 葡萄糖、 半乳糖等六碳糖可以通过发酵的方法除去， 而木糖和阿拉伯糖却难以通过发酵 方法进行分离， 因此， 木糖与阿拉伯糖的分离是本发明的关键点。 根据本领域 的公知常识， 单糖一般难溶于有机溶剂， 而木糖却能溶于热乙醇和吡啶中， 阿 拉伯糖能溶于甘油中， 但利用这些公知常识也难以实现木糖和阿拉伯糖的分离。 另外， 在一般情况下， 半纤维素水解所得混合糖中木糖含量至少大于阿拉 伯糖含量 1.5倍， 因此， 将半纤维素水解所得混合糖仅仅通过一般的溶解和结晶 是无法分离出阿拉伯糖的。 After the mixed sugar obtained by the hydrolysis of hemicellulose crystallizes xylose, the remaining mixed sugar mainly contains xylose, arabinose, glucose and galactose, and the highest content of xylose and arabinose. The hexoses such as glucose and galactose can be removed by fermentation, while xylose and arabinose are difficult to separate by fermentation. Therefore, the separation of xylose and arabinose is a key point of the present invention. According to common knowledge in the art, monosaccharides are generally insoluble in organic solvents, while xylose is soluble in hot ethanol and pyridine. Lober sugar is soluble in glycerin, but it is also difficult to achieve the separation of xylose and arabinose using these common general knowledge. In addition, in general, the mixed sugar obtained by hydrolysis of hemicellulose has a xylose content of at least 1.5 times that of the arabinose. Therefore, the mixed sugar obtained by hydrolyzing hemicellulose cannot separate the arabinose by ordinary dissolution and crystallization. .
本申请人研究发现， 当木糖与阿拉伯糖共存时， 它们在热水或热的有机溶 剂水溶液中的溶解与冷却后结晶特性与它们单独存在时有很大的差别。 在有机 溶剂中， 木糖的溶解度大于阿拉伯糖的溶解度， 但当木糖与阿拉伯糖共存于热 的有机溶剂水溶液中时， 随着溶液中含水量的增大， 阿拉伯糖的溶解度和木糖 的溶解度都增大， 然而阿拉伯糖溶解度增加的幅度比木糖溶解度增加的幅度大， 直到两者溶解度互相接近； 当两者溶解度互相接近而且两者均处于饱和状态的 热的混合糖溶液冷却时， 由于阿拉伯糖溶解度下降的幅度比木糖溶解度下降的 幅度大， 所以就可以得到木糖含量与阿拉伯糖含量之比小于或约等于 1 : 1的结 晶； 得到这种结晶后， 再利用木糖在有机溶剂中溶解度比阿拉伯糖溶解度大的 特性， 使木糖完全溶解而阿拉伯糖只能部分溶解， 从而分离出以不溶物形式存 在的阿拉伯糖。 另外， 在水中， 阿拉伯糖的溶解度大于木糖的溶解度， 因此， 也可以用水作为溶剂， 制备木糖和阿拉伯糖均处于饱和状态的热的混合糖溶液， 再通过冷却结晶来得到木糖含量与阿拉伯糖含量之比小于或约等于 1 : 1的结晶。  The Applicant's study found that when xylose and arabinose coexist, their dissolution and cooling crystallization characteristics in hot water or hot organic solvent aqueous solution are quite different from those when they are present alone. In organic solvents, the solubility of xylose is greater than the solubility of arabinose, but when xylose and arabinose coexist in a hot aqueous solution of organic solvents, the solubility of arabinose and xylose increase with the increase of water content in the solution. The solubility increases, but the increase in arabinose solubility is greater than the increase in xylose solubility until the solubility of the two is close to each other; when the hot mixed sugar solution in which the solubility of the two is close to each other and both are saturated, Since the solubility of arabinose is greater than the decrease in the solubility of xylose, a crystal having a ratio of xylose to arabinose of less than or equal to about 1:1 can be obtained; after obtaining such crystallization, xylose is utilized. The solubility in the organic solvent is greater than the solubility of the arabinose, so that the xylose is completely dissolved and the arabinose is only partially dissolved, thereby isolating the arabinose in the form of insoluble matter. In addition, in water, the solubility of arabinose is greater than the solubility of xylose. Therefore, it is also possible to prepare a hot mixed sugar solution in which both xylose and arabinose are saturated by using water as a solvent, and then obtain the xylose content by cooling and crystallization. The ratio of arabinose content is less than or approximately equal to 1:1 crystals.
根据上述发现， 以半纤维素水解所得的混合糖为初始糖， 用水或第一有机 溶剂水溶液与初始糖混合， 其中有机溶剂水溶液中的含水量为得到木糖含量与 阿拉伯糖含量之比小于或约等于 1 : 1的结晶 a所需要的含水量， 根据不同的有 机溶剂该含水量可在 0%〜100%之间选择， 此时调节水或第一有机溶剂水溶液的 用量， 并加热使阿拉伯糖完全溶解或接近完全溶解， 而木糖则一部分溶解于溶 液中， 另一部分以不溶物的形式存在， 得到混合物 I； 固、 液分离， 从而得到粗 木糖和糖溶液 a; 糖溶液 a冷却后结晶得结晶 a和结晶母液 a, 其中结晶 a中， 木糖含量与阿拉伯糖含量之比小于或约等于 1 : 1 , 即混合糖用热水或热的第一 有机溶剂水溶液进行溶解有两个目的， 一是利用该溶剂中木糖与阿拉伯糖溶解 度趋于接近或者木糖溶解度小于阿拉伯糖溶解度的性质而分离得到粗木糖， 二 是利用该溶剂结晶出木糖含量与阿拉伯糖含量之比小于或约等于 1 : 1的结晶 a。 而结晶 a将作为下一分离过程的起始混合糖；将结晶 a加入热的第二有机溶剂或 第二有机溶剂水溶液中， 木糖在第二有溶机或第二有机溶剂水溶液中的溶解度 大于阿拉伯糖在所述第二有溶机或第二有机溶剂水溶液中的溶解度， 调节第二 有机溶剂或第二有机溶剂水溶液的用量， 使木糖完全溶解或接近完全溶解， 而 阿拉伯糖则一部分溶解于所述溶剂， 另一部分以不溶物的形式存在， 得混合物 II； 固、 液分离， 从而得到粗阿拉伯糖和糖溶液 b; 糖溶液 b冷却后结晶得结晶 b和结晶母液 b; 再以结晶 b为初始糖， 重复上述步骤就可以把半纤维素水解所 得的混合糖中的木糖和阿拉伯糖完全分离； 所得粗木糖和粗阿拉伯糖经过重结 晶就可以得到纯的木糖和纯的阿拉伯糖。 According to the above findings, the mixed sugar obtained by hydrolysis of hemicellulose is an initial sugar, and the aqueous solution of the first organic solvent is mixed with the initial sugar, wherein the water content in the aqueous solution of the organic solvent is such that the ratio of the xylose content to the arabinose content is less than or The water content required for crystal a is approximately equal to 1:1. The water content may be selected between 0% and 100% depending on the organic solvent. At this time, the amount of water or the first organic solvent aqueous solution is adjusted, and heated to make the Arabian The sugar is completely dissolved or nearly completely dissolved, while the xylose is partially dissolved in the solution, and the other part is in the form of insoluble matter to obtain the mixture I; solid and liquid are separated, thereby obtaining the crude xylose and sugar solution a; the sugar solution a is cooled. After crystallization, crystal a and crystallization mother liquid a, wherein the ratio of xylose content to arabinose content in crystal a is less than or equal to about 1:1, that is, the mixed sugar is dissolved by hot water or a hot first organic solvent aqueous solution. The purpose is to separate the solubility of xylose and arabinose in the solvent or the solubility of xylose is less than the solubility of arabinose. Xylose, two It is the use of the solvent to crystallize the crystal a having a ratio of xylose content to arabinose content of less than or about equal to 1:1. While crystal a will be used as the starting sugar for the next separation process; the crystal a is added to the hot second organic solvent or the second organic solvent solution, and the solubility of xylose in the second solvent or second organic solvent solution And greater than the solubility of the arabinose in the second organic solvent or the second organic solvent aqueous solution, adjusting the amount of the second organic solvent or the second organic solvent aqueous solution, so that the xylose is completely dissolved or nearly completely dissolved, and the arabinose is partially Dissolved in the solvent, another part is in the form of insoluble matter, to obtain a mixture II; solid and liquid separation, thereby obtaining crude arabinose and sugar solution b; sugar solution b is cooled and crystallized to obtain crystal b and crystal mother liquid b; The crystal b is an initial sugar, and the above steps are repeated to completely separate the xylose and the arabinose in the mixed sugar obtained by the hydrolysis of hemicellulose; the obtained crude xylose and crude arabinose can be recrystallized to obtain pure xylose and pure. Arabic sugar.
当然， 当用热的水或热的第一有机溶剂水溶液溶解初始糖时， 也可能出现 阿拉伯糖刚好完全溶解时， 木糖也完全溶解的情况， 此时， 应将初始糖首先与 热的第二有机溶剂或第二有机溶剂水溶液混合， 使木糖完全溶解或接近完全溶 解， 而阿拉伯糖则一部分溶解于所述溶剂， 另一部分以不溶物的形式存在， 从 而通过固、 液分离得到不溶物粗阿拉伯糖。  Of course, when the initial sugar is dissolved in hot water or a hot aqueous solution of the first organic solvent, it is also possible that the xylose is completely dissolved when the arabinose is completely dissolved. At this time, the initial sugar should first be combined with the hot one. The two organic solvents or the second organic solvent aqueous solution are mixed to completely dissolve or nearly completely dissolve the xylose, and the arabinose is partially dissolved in the solvent, and the other portion is in the form of insoluble matter, thereby obtaining insoluble matter by solid and liquid separation. Crude arabinose.
优选的， 结晶母液 a回用可以增加单位溶剂对阿拉伯糖的溶解量， 亦即可 以减少溶剂的用量， 从而加快分离速度； 同理， 结晶母液 b 的回用可以增加单 位溶剂对木糖的溶解量， 亦即可以减少溶剂的用量， 从而加快分离速度。  Preferably, the crystallization mother liquid a reuse can increase the amount of the arabinose dissolved by the unit solvent, that is, the amount of the solvent can be reduced, thereby speeding up the separation speed; similarly, the reuse of the crystallization mother liquid b can increase the dissolution of the xylose per unit solvent. The amount, that is, the amount of solvent can be reduced, thereby speeding up the separation.
相似地， 阿拉伯胶水解液中含有三种单糖即半乳糖、 阿拉伯糖和鼠李糖， 其中半乳糖可以通过发酵除去， 而阿拉伯糖与鼠李糖的分离也是提取阿拉伯糖 的关键。 本申请人研究发现， 鼠李糖和阿拉伯糖共存于热的水或有机溶剂时， 具有与木糖和阿拉伯糖共存于热的水或有机溶剂中时一样的溶解特性和结晶特 性， 因此， 可以使用分离木糖和阿拉伯糖相同的方法来分离鼠李糖和阿拉伯糖。  Similarly, the gum arabic hydrolysate contains three monosaccharides, galactose, arabinose and rhamnose, wherein galactose can be removed by fermentation, and the separation of arabinose and rhamnose is also the key to extracting arabinose. The Applicant's research has found that when rhamnose and arabinose coexist in hot water or organic solvent, they have the same solubility characteristics and crystallization characteristics as when xylose and arabinose coexist in hot water or organic solvent. The same method of separating xylose and arabinose was used to separate rhamnose and arabinose.
本发明所述的从含阿拉伯糖和木糖或鼠李糖的混合糖中提取阿拉伯糖的方 法， 仅通过含阿拉伯糖和木糖或鼠李糖的混合糖在不同含水量的有机溶剂中的 溶解和结晶过程就实现了木糖或鼠李糖与阿拉伯糖的完全分离， 摆脱了对色谱 分离方法的依赖， 为大规模制备阿拉伯糖奠定了基础。 具体实施方式 The method for extracting arabinose from the mixed sugar containing arabinose and xylose or rhamnose according to the present invention, only through the mixed sugar containing arabinose and xylose or rhamnose in an organic solvent of different water content The dissolution and crystallization process completes the complete separation of xylose or rhamnose from arabinose, frees the dependence on chromatographic separation methods, and lays the foundation for large-scale preparation of arabinose. detailed description
以下将结合具体实施例对本发明做进一步说明和描述。  The invention will be further illustrated and described below in conjunction with specific embodiments.
实施例 1  Example 1
将半纤维素水解所得的混合糖结晶出木糖后的木糖母液稀释后加入酿酒酵 母进行发酵， 直到葡萄糖和半乳糖基本利用完毕， 离心分离出酵母菌体， 上清 液在 70°C下减压蒸馏， 浓缩至糖浓度约 80%, 冷却结晶， 离心分离出结晶， 分 离出结晶的母液重复减压蒸馏一冷却结晶一分离结晶的过程， 最终把木糖母液 中的非发酵单糖基本结晶出来， 该结晶含有木糖和阿拉伯糖， 其中木糖含量约 为阿拉伯糖的 1.6倍， 作为本实施例和实施例 2、 3、 4、 5的初始糖。  The xylose mother liquor obtained by crystallizing the mixed sugar obtained by hydrolysis of hemicellulose is diluted with glucose and added to Saccharomyces cerevisiae for fermentation until the glucose and galactose are substantially utilized, and the yeast cells are separated by centrifugation, and the supernatant is at 70 ° C. Distillation under reduced pressure, concentration to a sugar concentration of about 80%, cooling the crystals, separating the crystals by centrifugation, separating the crystallized mother liquor, repeating the vacuum distillation, cooling the crystal, separating and crystallizing, and finally, the non-fermented monosaccharide in the xylose mother liquor is basically Crystallized, the crystals contained xylose and arabinose, wherein the xylose content was about 1.6 times that of arabinose, and was used as the initial sugar of the examples and Examples 2, 3, 4, and 5.
试管中加入 0.86克上述初始糖和 0.30克 60%乙醇， 70°C水浴中保温 1小时， 初始糖中的阿拉伯糖完全溶解； 保温状态下， 固、 液分离得糖溶液 a和不溶物， 不溶物为粗木糖， 用少量冷的 90%乙醇洗涤粗木糖 2次后保存备用； 糖溶液 a 室温下放置 36小时进行结晶， 固、 液分离， 得结晶 a和上清液， 其中， 结晶 a 中， 木糖含量为阿拉伯糖含量的 0.5倍， 用少量冷的 90%乙醇洗涤结晶 a 两次； 取 1.0克结晶 a并加入 1.8克 90%乙醇， 70°C水浴中保温 1小时， 其中的木糖完 全溶解， 阿拉伯糖仅溶解了一部分； 保温状态下， 固、 液分离得糖溶液 b和不 溶物， 不溶物为粗阿拉伯糖， 用少量冷的 90%乙醇洗涤粗阿拉伯糖 2次后保存 备用； 糖溶液 b室温下放置 36小时进行结晶， 固、 液分离， 得结晶 b和上清液， 用少量冷的 90%乙醇洗涤结晶 b 两次； 用结晶 b重复上述分离过程， 从而不断 将初始糖分离成粗木糖和粗阿拉伯糖； 粗木糖和粗阿拉伯糖分别重新溶解在 80 °( 的 90%乙醇中而成饱和溶液， 然后室温下放置 36小时进行结晶， 结晶用冷的 90%乙醇洗涤 2次， 烘干后得到纯的木糖和阿拉伯糖。  0.86 g of the above initial sugar and 0.30 g of 60% ethanol were added to the test tube, and the arabinose in the initial sugar was completely dissolved in a 70 ° C water bath for 1 hour; in the state of heat preservation, the sugar solution a and the insoluble matter were separated by solid and liquid, insoluble. The product is crude xylose, and the crude xylose is washed twice with a small amount of cold 90% ethanol and stored for later; the sugar solution a is allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation, to obtain crystal a and supernatant, wherein, crystallization a, the xylose content is 0.5 times the arabinose content, and the crystal a is washed twice with a small amount of cold 90% ethanol; 1.0 g of crystal a is added and 1.8 g of 90% ethanol is added, and the mixture is kept in a water bath at 70 ° C for 1 hour, wherein The xylose is completely dissolved, and only a part of arabinose is dissolved; in the state of heat preservation, the solid solution and the liquid are separated into a sugar solution b and an insoluble matter, the insoluble matter is crude arabinose, and the crude arabinose is washed twice with a small amount of cold 90% ethanol. Stored in standby; the sugar solution b is allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation, to obtain crystal b and supernatant, and wash crystal b twice with a small amount of cold 90% ethanol; repeat with crystal b Separation process, so that the initial sugar is continuously separated into coarse xylose and crude arabinose; crude xylose and crude arabinose are separately dissolved in 80 ° (90% ethanol to form a saturated solution, and then left to stand at room temperature for 36 hours for crystallization The crystals were washed twice with cold 90% ethanol and dried to obtain pure xylose and arabinose.
试管中加入 1.3克上述初始糖和 0.4克水， 70°C水浴中保温 0.5小时， 初始 糖中的阿拉伯糖完全溶解， 固、 液分离得糖溶液 a和不溶物， 不溶物为粗木糖， 用少量冷的 90%乙醇洗涤粗木糖 2次后保存备用； 糖溶液 a室温下放置 72小时 进行结晶， 通过离心进行固、 液分离， 得结晶 a和上清液， 其中， 结晶 a中， 木 糖含量与阿拉伯糖含量接近 1 : 1 , 用少量冷的 90%乙醇洗涤结晶 a 两次； 取 1.0 克结晶 a并加入 2.8克 90%乙醇，70°C水浴中保温 1小时，其中的木糖完全溶解， 阿拉伯糖仅溶解了一部分； 保温状态下， 固、 液分离得糖溶液 b和不溶物， 不 溶物为粗阿拉伯糖， 用少量冷的 90%乙醇洗涤粗阿拉伯糖 2次后保存备用； 糖 溶液 b室温下放置 36小时进行结晶， 固、 液分离， 得结晶 b和上清液， 用少量 冷的 90%乙醇洗涤结晶 b 两次； 用结晶 b重复上述分离过程， 从而不断将初始 糖分离成粗木糖和粗阿拉伯糖； 粗木糖和粗阿拉伯糖分别重新溶解在 80 °C的 90%异丙醇中而成饱和溶液，然后室温下放置 24小时进行结晶，结晶用冷的 90% 异丙醇洗涤 2次， 烘干后得到纯的木糖和阿拉伯糖。 实施例 3 1.3 g of the above initial sugar and 0.4 g of water were added to the test tube, and the mixture was incubated in a water bath at 70 ° C for 0.5 hour. The arabinose in the initial sugar was completely dissolved, and the sugar solution a and the insoluble matter were separated by solid and liquid, and the insoluble matter was crude xylose. The crude xylose is washed twice with a small amount of cold 90% ethanol and stored for later use; the sugar solution a is allowed to stand at room temperature for 72 hours for crystallization, and solid and liquid separation is carried out by centrifugation to obtain crystal a and supernatant, wherein, in crystal a, The xylose content and the arabinose content are close to 1:1, and the crystal a is washed twice with a small amount of cold 90% ethanol; 1.0 g of crystal a is added and 2.8 g of 90% ethanol is added, and the mixture is kept in a water bath at 70 ° C for 1 hour, wherein the wood The sugar is completely dissolved, and the arabinose is only partially dissolved. In the state of heat preservation, the solid solution and the liquid are separated into a sugar solution b and an insoluble matter, and the insoluble matter is crude arabinose. The crude arabinose is washed twice with a small amount of cold 90% ethanol and stored for use. The sugar solution b is allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation to obtain crystal b and supernatant, and the crystal b is washed twice with a small amount of cold 90% ethanol; the above separation process is repeated with crystal b, thereby continuously initializing The sugar is separated into coarse xylose and crude arabinose; the crude xylose and crude arabinose are separately dissolved in 90% isopropanol at 80 ° C to form a saturated solution, and then allowed to stand at room temperature for 24 hours for crystallization, and the crystal is cooled. 90% The isopropyl alcohol was washed twice and dried to obtain pure xylose and arabinose. Example 3
试管中加入 0.52克上述初始糖，逐步加入 70%乙酸， 70°C水浴中保温， 70% 乙酸的加入量使阿拉伯糖基本完全溶解， 固、 液分离得糖溶液 a和不溶物， 不 溶物为粗木糖， 用少量冷的 90%乙酸洗涤粗木糖 2次后保存备用， 糖溶液 a加 入结晶促进剂丁酮至形成浑浊， 室温下放置 48小时进行结晶， 固、 液分离， 得 结晶 a和上清液， 用少量冷的 90%乙酸洗涤结晶 a 两次， 即为结晶 a, 其中， 结 晶 a中， 木糖含量为阿拉伯糖含量的 0.5倍； 取 1.0克结晶 a并逐步加入 90%乙 酸， 70°C水浴中保温， 90%乙酸的加入量使木糖正好完全溶解， 固、 液分离得糖 溶液 b和不溶物， 不溶物为粗阿拉伯糖，用少量冷的 90%乙酸洗涤粗阿拉伯糖 2 次后保存备用； 糖溶液 b室温下放置 48小时进行结晶， 固、 液分离， 得结晶 b 和上清液，用少量冷的 90%乙酸洗涤结晶 b 两次；取结晶 b重复上述分离过程， 从而不断将混合糖分离成粗木糖和粗阿拉伯糖； 粗木糖和粗阿拉伯糖分别重新 溶解在 80°C的 90%乙醇中而成饱和溶液， 然后室温下放置 48小时进行结晶， 结 晶用冷的 90%乙醇洗涤 2次， 烘干后得到纯的木糖和阿拉伯糖。 试管中加入 0.52克上述初始糖和 0.50克 50%丙酮， 50°C水浴中保温 1小时， 其中的阿拉伯糖正好完全溶解， 固、 液分离得糖溶液 a和不溶物， 不溶物为粗 木糖， 用少量冷的 90%丙酮洗涤粗木糖 2次后保存备用； 糖溶液 a加入 1倍量 的无水乙醇作为结晶促进剂， 室温下放置 36小时进行结晶， 固、 液分离， 得结 晶 a和上清液， 其中， 结晶 a中， 木糖含量为阿拉伯糖含量的 1.1倍， 用少量冷 的 90%丙酮洗涤结晶 a 两次； 取 1.0克结晶 a并加入 2.9克 90%乙醇， 70 °C水浴 中保温 1小时， 其中的木糖正好完全溶解， 保温状态下， 固、 液分离得糖溶液 b 和不溶物， 不溶物为粗阿拉伯糖， 用少量冷的 90%乙醇洗涤粗阿拉伯糖 2次后 保存备用； 糖溶液 b室温下放置 36小时进行结晶， 固、 液分离， 得结晶 b和上 清液， 用少量冷的 90%乙醇洗涤结晶 b 两次； 取结晶 b重复上述分离过程， 从 而不断将混合糖分离成粗木糖和粗阿拉伯糖； 粗木糖和粗阿拉伯糖分别重新溶 解在 80°C的 90%乙醇中而成饱和溶液， 然后室温下放置 36小时进行结晶， 结晶 用冷的 90%乙醇洗涤 2次， 烘干后得到纯的木糖和阿拉伯糖。 实施例 5 0.52 g of the above initial sugar was added to the test tube, 70% acetic acid was gradually added, and the temperature was kept in a water bath at 70 ° C. The amount of 70% acetic acid was added to completely dissolve the arabinose, and the sugar solution a and the insoluble matter were separated by solid and liquid, and the insoluble matter was Rough xylose, washed with a small amount of cold 90% acetic acid for 2 times and stored for later use. The sugar solution a is added to the crystallization promoter butanone to form turbidity. It is allowed to stand at room temperature for 48 hours for crystallization, solid and liquid separation to obtain crystal a. And the supernatant, washed with a small amount of cold 90% acetic acid twice, that is, crystal a, wherein, in crystal a, the xylose content is 0.5 times the arabinose content; take 1.0 g of crystal a and gradually add 90% Acetic acid, 70 ° C water bath insulation, 90% acetic acid is added to make the xylose just completely dissolved, solid and liquid separation sugar solution b and insoluble matter, insoluble matter is crude arabinose, washed with a small amount of cold 90% acetic acid After the arabinose is stored for 2 times, the sugar solution b is allowed to stand at room temperature for 48 hours for crystallization, solid and liquid separation, and the crystal b and the supernatant are obtained, and the crystal b is washed twice with a small amount of cold 90% acetic acid; Separation process, The mixed sugar is continuously separated into coarse xylose and crude arabinose; the crude xylose and crude arabinose are separately dissolved in 90% ethanol at 80 ° C to form a saturated solution, and then left to stand at room temperature for 48 hours for crystallization, for crystallization The cold 90% ethanol was washed twice and dried to obtain pure xylose and arabinose. 0.52 g of the above initial sugar and 0.50 g of 50% acetone were added to the test tube, and the mixture was kept in a water bath at 50 ° C for 1 hour, wherein the arabinose was completely dissolved, and the solid solution and the insoluble matter were separated, and the insoluble matter was coarse xylose. Washing the xylose with a small amount of cold 90% acetone for 2 times and storing it for later; adding a 1 time amount of absolute ethanol as a crystallization accelerator to the sugar solution a, leaving it at room temperature for 36 hours for crystallization, solid and liquid separation, to obtain crystal a And the supernatant, wherein, in the crystal a, the xylose content is 1.1 times the arabinose content, and the crystal a is washed twice with a small amount of cold 90% acetone; 1.0 g of crystal a is taken and 2.9 g of 90% ethanol, 70 ° is added In the C water bath for 1 hour, the xylose is completely dissolved. In the state of heat preservation, the solid solution and the liquid are separated into a sugar solution b and an insoluble matter, the insoluble matter is crude arabinose, and the crude arabinose is washed with a small amount of cold 90% ethanol. After the second time, the sugar solution b was allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation, and the crystal b and the supernatant were obtained, and the crystal b was washed twice with a small amount of cold 90% ethanol; the crystal b was repeated to repeat the above separation process. Never The mixed sugar is separated into coarse xylose and crude arabinose; the crude xylose and crude arabinose are separately dissolved in 90% ethanol at 80 ° C to form a saturated solution, and then left to stand at room temperature for 36 hours for crystallization, and the crystal is cooled. Washed twice with 90% ethanol and dried to obtain pure xylose and arabinose. Example 5
试管中加入 0.52克上述初始糖， 加入 0.44克 50%吡啶水溶液， 70°C水浴中 保温， 使阿拉伯糖正好完全溶解， 保温状态下， 固、 液分离得糖溶液 a和不溶 物， 不溶物为粗木糖， 用少量冷的 90%乙醇洗涤粗木糖 2次后保存备用； 糖溶 液 a室温下放置 36小时进行结晶， 固、 液分离， 得结晶 a和上清液， 其中， 结 晶 a中， 木糖含量为阿拉伯糖含量的 1.2倍； 结晶 a用少量冷的 99.5%吡啶洗涤 2次； 取 1.0克结晶 a并加入 3.0克 99.5%吡啶， 60°C水浴中保温， 木糖正好完 全溶解， 固、 液分离得糖溶液 b和不溶物， 不溶物为粗阿拉伯糖， 粗阿拉伯糖 用少量冷的 99.5%吡啶洗涤 2次保存备用； 糖溶液 b在 70°C下减压蒸馏至干， 得到结晶 b; 结晶 b重复上述分离过程，从而不断将初始糖分离成粗木糖和粗阿 拉伯糖；粗木糖和粗阿拉伯糖分别重新溶解在 80°C的 90%乙醇中而成饱和溶液， 然后室温下放置 48小时进行结晶， 结晶用冷的 90%乙醇洗涤 2次， 烘干后得到 纯的木糖和阿拉伯糖。 Add 0.52 g of the above initial sugar to the test tube, add 0.44 g of 50% pyridine aqueous solution, and keep warm in a water bath at 70 ° C to dissolve the arabinose completely. In the state of heat preservation, the solid solution and the insoluble matter are separated, and the insoluble matter is Rough xylose, washed with a small amount of cold 90% ethanol for 2 times and stored for later use; the sugar solution a is allowed to stand at room temperature for 36 hours for crystallization, solid and liquid separation, to obtain crystal a and supernatant, wherein, crystal a The xylose content is 1.2 times the arabinose content; the crystal a is washed twice with a small amount of cold 99.5% pyridine; 1.0 g of crystal a is added and 3.0 g of 99.5% pyridine is added, and the temperature is kept in a water bath at 60 ° C, and the xylose is completely dissolved. The solid solution and the liquid are separated into a sugar solution b and an insoluble matter, the insoluble matter is crude arabinose, and the crude arabinose is washed twice with a small amount of cold 99.5% pyridine for storage; the sugar solution b is distilled to dryness at 70 ° C under reduced pressure. Crystallization b is obtained; crystal b repeats the above separation process, thereby continuously separating the initial sugar into crude xylose and crude arabinose; and the crude xylose and crude arabinose are separately dissolved in 90% ethanol at 80 ° C to form a saturated solution. Then room temperature For 48 hours. The crystals were washed with cold 90% ethanol twice, to give after drying Pure xylose and arabinose.
阿拉伯胶用稀硫酸水解得到水解液， 用二异辛胺溶液萃取酸， 得到 PH5.6 的水解液， 接着用酿酒酵母发酵除去半乳糖， 发酵液离心除去酵母菌体， 然后 在 70°C减压蒸馏至糖浓度约 80%, 冷却后结晶并干燥结晶， 而结晶母液继续回 用以把混合糖基本全部结晶出来， 该结晶中阿拉伯糖含量约为鼠李糖的两倍， 即鼠李糖为阿拉伯糖的 0.5倍， 作为本实施例的初始糖。 The gum arabic is hydrolyzed with dilute sulfuric acid to obtain a hydrolyzate, and the acid is extracted with a diisooctylamine solution to obtain a hydrolyzate of pH 5.6. Then, the galactose is removed by fermentation with Saccharomyces cerevisiae, and the yeast cell is removed by centrifugation, and then reduced at 70 ° C. Press distillation to a sugar concentration of about 80%, crystallize and crystallize after cooling, and the crystallization mother liquor continues to be used to crystallize the mixed sugar substantially. The arabinose content in the crystal is about twice that of rhamnose, ie rhamnose. It is 0.5 times of arabinose as the initial sugar of this example.
初始糖与 90%乙醇混合， 加热到 70 °C并搅拌使部分糖溶解， 90%乙醇的加 入量为混合糖中鼠李糖刚好完全溶解所需要的量，得到混合物 II,其中部分阿拉 伯糖以不溶物的形式存在， 然后进行固液分离， 得到不溶物粗阿拉伯糖和糖溶 液 b; 将糖溶液 b在 70°C下减压蒸馏至干， 得到结晶 b, 结晶 b中鼠李糖的含量 约为阿拉伯糖含量的 2.5倍； 结晶 b与 90%的异丙醇混合， 加热到 70°C并搅拌 使部分糖溶解， 90%的异丙醇加入量为混合糖中阿拉伯糖刚好完全溶解所需要的 量， 得到混合物 I, 其中部分鼠李糖以不溶物的形式存在， 然后进行固液分离， 得到不溶物粗鼠李糖和糖溶液 a; 将糖溶液 a冷却到室温并放置 24小时进行结 晶， 得到结晶 a和结晶母液 a, 并将结晶 a烘干， 结晶 a中阿拉伯糖的含量约为 鼠李糖含量的 1.2倍即鼠李糖约为阿拉伯糖的 0.8倍， 亦即阿拉伯糖的含量大于 鼠李糖含量。  The initial sugar is mixed with 90% ethanol, heated to 70 ° C and stirred to dissolve a portion of the sugar. 90% ethanol is added in an amount necessary to completely dissolve the rhamnose in the mixed sugar to obtain a mixture II, wherein a part of the arabinose is In the form of insoluble matter, and then subjected to solid-liquid separation to obtain insoluble crude arabinose and sugar solution b; the sugar solution b is distilled under reduced pressure at 70 ° C to dryness to obtain crystal b, the content of rhamnose in crystal b About 2.5 times the arabinose content; crystal b is mixed with 90% isopropanol, heated to 70 ° C and stirred to dissolve part of the sugar, 90% of the isopropanol is added in the mixed sugar, the arabinose is just completely dissolved The required amount is such that a mixture I is obtained in which part of the rhamnose is present in the form of an insoluble matter, followed by solid-liquid separation to obtain an insoluble crude rhamnose and a sugar solution a; the sugar solution a is cooled to room temperature and allowed to stand for 24 hours. Crystallization, obtaining crystal a and crystallization mother liquid a, and drying crystal a, the content of arabinose in crystal a is about 1.2 times the rhamnose content, that is, rhamnose is about 0.8 times that of arabinose, that is, Allah. Rhamnose sugar content greater than the content.
结晶 a重新与 90%乙醇混合， 加热到 70°C并搅拌使部分糖溶解， 90%乙醇 的加入量为结晶 a中鼠李糖刚好完全溶解所需要的量，得到混合物 II,其中部分 阿拉伯糖以不溶物的形式存在， 然后进行固液分离， 得到不溶物粗阿拉伯糖和 糖溶液 b; 将糖溶液 b在 70°C下减压蒸馏至干， 得到结晶 b, 结晶 b中鼠李糖的 含量约为阿拉伯糖含量的 2.5倍； 结晶 b与结晶母液 a混合， 加热到 70°C并搅 拌使部分糖溶解， 结晶母液 a 的加入量为混合糖中阿拉伯糖刚好完全溶解所需 要的量， 得到混合物 I, 其中部分鼠李糖以不溶物的形式存在， 然后进行固液分 离， 得到不溶物粗鼠李糖和糖溶液 a; 将糖溶液 a冷却到室温并放置 24小时进 行结晶， 得到结晶 a和结晶母液 a, 并将结晶 a烘干， 结晶 a中阿拉伯糖的含量 约为鼠李糖含量的 1.3倍即鼠李糖约为阿拉伯糖的 0.8倍， 亦即阿拉伯糖的含量 大于鼠李糖含量。 重复上述步骤， 直到把阿拉伯糖和鼠李糖完全分离。 The crystal a is re-mixed with 90% ethanol, heated to 70 ° C and stirred to dissolve a portion of the sugar, and 90% ethanol is added in an amount required to completely dissolve the rhamnose in the crystal a to obtain a mixture II, a part of the arabinose. In the form of insoluble matter, and then subjected to solid-liquid separation to obtain insoluble crude arabinose and sugar solution b; the sugar solution b is distilled under reduced pressure at 70 ° C to dryness to obtain crystal b, crystal b in rhamnose The content is about 2.5 times of the arabinose content; the crystal b is mixed with the crystallization mother liquid a, heated to 70 ° C and stirred to dissolve a part of the sugar, and the crystallization mother liquid a is added in an amount required for the arabinose in the mixed sugar to be completely dissolved. A mixture I is obtained, wherein part of the rhamnose is present as an insoluble matter, and then subjected to solid-liquid separation to obtain an insoluble crude rhamnose and a sugar solution a; the sugar solution a is cooled to room temperature and left for 24 hours. Crystallization, obtaining crystal a and crystallization mother liquid a, and drying crystal a, the content of arabinose in crystal a is about 1.3 times that of rhamnose, that is, rhamnose is about 0.8 times that of arabinose, that is, arabinose The content is greater than the rhamnose content. Repeat the above steps until the arabinose and rhamnose are completely separated.
将粗阿拉伯糖和粗鼠李糖在 90%乙醇中重结晶， 得到纯的阿拉伯糖和纯的 鼠李糖。  The crude arabinose and crude rhamnose were recrystallized from 90% ethanol to give pure arabinose and pure rhamnose.
上述实施例， 只是本发明的较佳实施例， 并非用来限制本发明实施范围， 故凡以本发明权利要求所述的特征及原理所做的等效变化或修饰， 均应包括在 本发明权利要求范围之内。  The above-described embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and equivalent changes or modifications made by the features and principles of the present invention should be included in the present invention. Within the scope of the claims.

Claims

权 利 要 求 Rights request
1、 一种从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其中， 混合糖中 还含有木糖或鼠李糖， 其特征在于， 该方法包括以下步骤： 1. A method of extracting arabinose from arabinose-containing mixed sugar, wherein the mixed sugar also contains xylose or rhamnose, characterized in that the method includes the following steps:
( 1 )取上述含阿拉伯糖的混合糖为初始糖； (1) Take the above mixed sugar containing arabinose as the initial sugar;
( 2 )将初始糖与水或第一有机溶剂的水溶液混合，加热使初始糖部分溶解， 所述第一有机溶剂的水溶液的含水量为得到木糖含量与阿拉伯糖含量之比或鼠 李糖含量与阿拉伯糖含量之比小于或约等于 1 : 1的结晶 a所需要的含水量， 所 述水或所述第一有机溶剂的水溶液的用量约为该加热条件下初始糖中阿拉伯糖 完全溶解所需要的量， 得混合物 I； (2) Mix the initial sugar with water or an aqueous solution of the first organic solvent, and heat to partially dissolve the initial sugar. The water content of the aqueous solution of the first organic solvent is the ratio of the xylose content to the arabinose content or rhamnose. The ratio of content to arabinose content is less than or approximately equal to the water content required for crystallization a of 1:1. The amount of water or the aqueous solution of the first organic solvent is approximately the amount of arabinose in the initial sugar that is completely dissolved under the heating conditions. The required amount is obtained to obtain mixture I;
( 3 )将混合物 I固、 液分离， 得到糖溶液 a和粗木糖， 或得到糖溶液 a和 粗鼠李糖； (3) Separate the solid and liquid of the mixture I to obtain sugar solution a and crude xylose, or obtain sugar solution a and crude rhamnose;
( 4 )糖溶液 a冷却后结晶， 分离得到结晶 a和结晶母液 a, 其中， 所述结晶 a中，木糖含量与阿拉伯糖含量之比或鼠李糖含量与阿拉伯糖含量之比小于或约 等于 1 : 1； (4) The sugar solution a is crystallized after cooling, and the crystallization a and the crystallization mother liquor a are separated, wherein in the crystallization a, the ratio of the xylose content to the arabinose content or the ratio of the rhamnose content to the arabinose content is less than or about Equal to 1 : 1;
( 5 )将结晶 a与第二有机溶剂或第二有机溶剂的水溶液混合，加热使结晶 a 部分溶解， 所述第二有机溶剂或所述第二有机溶剂的水溶液的用量约为该加热 条件下结晶 a中木糖或鼠李糖完全溶解所需要的量， 得混合物 II； (5) Mix crystal a with a second organic solvent or an aqueous solution of a second organic solvent, and heat to partially dissolve crystal a. The amount of the second organic solvent or aqueous solution of the second organic solvent is approximately The amount of xylose or rhamnose required to completely dissolve in crystal a is obtained to obtain mixture II;
( 6 )将混合物 II固、 液分离， 得到糖溶液 b和粗阿拉伯糖。 (6) Separate the solid and liquid of mixture II to obtain sugar solution b and crude arabinose.
2、 如权利要求 1所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其 特征在于， 还包括以下步骤： 2. The method of extracting arabinose from arabinose-containing mixed sugar as claimed in claim 1, further comprising the following steps:
( 7 )将糖溶液 b冷却后结晶， 分离得到结晶 b和结晶母液 b; (7) Cool the sugar solution b and crystallize it, and separate the crystal b and the crystallization mother liquor b;
( 8 )以结晶 b为初始糖， 重复上述（2 ) ~ ( 7 )步骤， 直到将含阿拉伯糖的 混合糖中的阿拉伯糖全部提取出。 (8) Using crystal b as the initial sugar, repeat the above steps (2) ~ (7) until all the arabinose in the mixed sugar containing arabinose is extracted.
、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法, 其特征在于， 步骤（ 3 )将混合物 I固、 液分离和 /或步骤（ 6 )将混合物 II固、 液 分离在保温状态下进行。 . The method of extracting arabinose from arabinose-containing mixed sugar as claimed in claim 1 or 2, It is characterized in that step (3) of solid and liquid separation of mixture I and/or step (6) of solid and liquid separation of mixture II are performed in a heat preservation state.
4、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 结晶时， 向所述糖溶液 a或所述糖溶液 b中加入第三种有机溶剂作 为结晶促进剂， 所述第三种有机溶剂选自醇、 醚和酮。 4. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that, during crystallization, a third organic compound is added to the sugar solution a or the sugar solution b. The solvent serves as a crystallization accelerator, and the third organic solvent is selected from alcohols, ethers and ketones.
5、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述结晶母液 a回用作为步骤（2 )所述的水或所述的第一有机溶 剂的水溶液； 结晶母液 b 回用作为步骤（5 )所述的第二有机溶剂或所述的第二 有机溶剂的水溶液。 5. The method for extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the crystallization mother liquor a is reused as the water or the third water in step (2). an aqueous solution of an organic solvent; the crystallization mother liquor b is reused as the second organic solvent or the aqueous solution of the second organic solvent described in step (5).
6、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述结晶母液 a含有所述结晶促进剂时， 除去结晶促进剂后再回用 作为步骤（2 )所述的水或所述的第一有机溶剂的水溶液， 所述结晶母液 b含有 所述结晶促进剂时， 除去结晶促进剂后再回用作为步骤（5 )所述的第二有机溶 剂或所述的第二有机溶剂的水溶液。 6. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that when the crystallization mother liquor a contains the crystallization accelerator, the crystallization accelerator is removed and then reused. As the water in step (2) or the aqueous solution of the first organic solvent, when the crystallization mother liquor b contains the crystallization accelerator, the crystallization accelerator is removed and then reused as the third aqueous solution in step (5). Two organic solvents or an aqueous solution of the second organic solvent.
7、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于，结晶时，将所述糖溶液 a或所述糖溶液 b蒸发除去部分或全部溶剂。 7. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that during crystallization, part or all of the solvent is removed by evaporating the sugar solution a or the sugar solution b. .
8、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述含阿拉伯糖的混合糖为用半纤维素水解液制备的单糖混合物。 8. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the arabinose-containing mixed sugar is a monosaccharide mixture prepared by using hemicellulose hydrolyzate.
9、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于，所述含阿拉伯糖的混合糖为用半纤维素水解液结晶出木糖后的木糖 母液制备的单糖混合物。 9. The method for extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the arabinose-containing mixed sugar is obtained by crystallizing xylose from hemicellulose hydrolyzate. Monosaccharide mixture prepared from xylose mother liquor.
10、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于，所述含阿拉伯糖的混合糖为用半纤维素水解液结晶出木糖后的木糖 母液经过发酵除去葡萄糖后制备的单糖混合物。 10. The method for extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the arabinose-containing mixed sugar is obtained by crystallizing xylose from hemicellulose hydrolyzate. A monosaccharide mixture prepared by fermenting xylose mother liquor to remove glucose.
11、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于，所述含阿拉伯糖的混合糖为用半纤维素水解液结晶出木糖后的木糖 母液经过发酵除去葡萄糖和半乳糖后制备的单糖混合物。 11. The method for extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the arabinose-containing mixed sugar is obtained by crystallizing xylose from hemicellulose hydrolyzate. A monosaccharide mixture prepared by fermenting xylose mother liquor to remove glucose and galactose.
12、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于，所述含阿拉伯糖的混合糖为用阿拉伯胶水解液经发酵除去半乳糖后 制备的单糖混合物。 12. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the arabinose-containing mixed sugar is prepared by fermenting arabic gum hydrolyzate to remove galactose. of simple sugar mixtures.
13、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述第一有机溶剂和所述第二有机溶剂均选自醇， 酮， 羧酸， 含氮 有机溶剂， 含羟基、 酮基、 ½中的几种官能团的多官能团化合物， 和它们中的 几种的混合物。 13. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the first organic solvent and the second organic solvent are selected from alcohol, ketone, carboxyl Acids, nitrogen-containing organic solvents, multifunctional compounds containing several functional groups such as hydroxyl group, ketone group, and ½, and mixtures of several of them.
14、 如权利要求 13所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述第一有机溶剂和 /或所述第二有机溶剂还含有其他有机溶剂。 14. The method of extracting arabinose from arabinose-containing mixed sugar as claimed in claim 13, wherein the first organic solvent and/or the second organic solvent also contains other organic solvents.
15、 如权利要求 13所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述醇选自 CI ~ C3的醇， 所述酮选自丙酮和丁酮， 所述羧酸选自 CI ~ C4的羧酸， 所述含氮有机溶剂选自乙腈和吡啶。 15. The method of extracting arabinose from arabinose-containing mixed sugar as claimed in claim 13, wherein the alcohol is selected from CI to C3 alcohols, the ketone is selected from acetone and butanone, The carboxylic acid is selected from CI to C4 carboxylic acids, and the nitrogen-containing organic solvent is selected from acetonitrile and pyridine.
16、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述结晶 a与所述第二有机溶剂或所述第二有机溶剂的水溶液混合 所述结晶 b与所述水或所述 第一有机溶剂的水溶液混合前 16. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the crystal a is mixed with the second organic solvent or an aqueous solution of the second organic solvent. Before mixing the crystal b with the water or the aqueous solution of the first organic solvent
17、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所述结晶 a与所述第二有机溶剂或所述第二有机溶剂的水溶液混合 前先进行干燥； 所述结晶 b与所述水或所述第一有机溶剂的水溶液混合前先进行 干燥。 17. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the crystal a is mixed with the second organic solvent or an aqueous solution of the second organic solvent. The crystal b is dried before being mixed with the water or the aqueous solution of the first organic solvent.
18、如权利要求 1或 2所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其特征在于， 所得粗阿拉伯糖、 粗木糖或粗鼠李糖经过重结晶而得到纯的阿拉伯 糖、 纯的木糖或纯的鼠李糖。 18. The method of extracting arabinose from arabinose-containing mixed sugar according to claim 1 or 2, characterized in that the obtained crude arabinose, crude xylose or crude rhamnose is recrystallized to obtain pure arabinose. sugar, pure xylose or pure rhamnose.
19、如权利要求 1所述的从含阿拉伯糖的混合糖中提取阿拉伯糖的方法， 其 特征在于， 在步骤（2 ) 中， 初始糖中的阿拉伯糖完全溶解时， 木糖或鼠李糖也 完全溶解， 则从步骤（5 )开始从初始糖中提取阿拉伯糖。 19. The method of extracting arabinose from arabinose-containing mixed sugar as claimed in claim 1, wherein in step (2), when the arabinose in the initial sugar is completely dissolved, xylose or rhamnose If it is also completely dissolved, start from step (5) to extract arabinose from the initial sugar.
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