JP2009207462A - Method for producing sugar for synthetic raw material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To inexpensively provide high-purity L-arabinose for a synthetic raw material scarcely comprising D-xylose. <P>SOLUTION: A method for producing a sugar for the synthetic raw material is characterized by subjecting a plant body comprising arabinan as a raw material to following steps (a) to (e), and thereby affording the sugar for the synthetic raw material comprising ≥97 mass% of the L-arabinose, and ≤0.1 mass% of the D-xylose: (a) hydrolysis with an acid or an enzyme; (b) removal of a monosaccharide other than the L-arabinose; (c) deproteinization and/or removal of polysaccharides; (d) desalination; and (e) crystallization. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a sugar for synthetic raw material, which is high-purity L-arabinose used in the synthesis of pharmaceuticals, food additives, and other chemicals, and a sugar for synthetic raw material obtained by the production method. The sugar for synthetic raw materials has a feature that it hardly contains impurities such as xylose that can cause impurities in the synthesis reaction.

  L-arabinose is a pentasaccharide existing as a constituent sugar such as arabinan in hemicellulose of higher plants. It has a taste similar to sucrose, is a non-caloric saccharide showing poor absorbability, and has a disaccharide hydrolase inhibitory action, so it is used as a sweetener for diabetics or diets. L-arabinose is a rare L-type monosaccharide in nature and is also used as a raw material for the synthesis of L-type compounds. In particular, in the field of pharmaceuticals and the like, mixing of optical isomers becomes a big problem, so that high purity L-arabinose has been demanded.

  For example, Patent Document 1 discloses a method using L-arabinose for the synthesis of L-thymidine, and Patent Document 2 discloses a method using L-arabinose for the synthesis of L-2-deoxyribose. ing. All have the advantage that the number of steps is reduced by using L-arabinose, which is an L-type sugar, as a raw material. Non-Patent Document 1 discloses a method for synthesizing erythronic acid from L-arabinose.

  L-arabinose is obtained by acid hydrolysis or enzymatic degradation of hemicellulose obtained by alkaline extraction from a plant containing L-arabinose as a constituent sugar of hemicellulose (see, for example, Patent Document 3), or L-arabinose. What is liberated by direct acid hydrolysis (for example, see Patent Document 4) or enzymatic degradation (for example, see Patent Documents 5 and 6) of a plant body contained as a constituent sugar of hemicellulose is desalted and purified It is obtained through a process such as crystallization.

  However, L-arabinose used as a raw material for synthesis requires high purity in order to suppress the formation of impurities, and in particular when used as a raw material for the synthesis of optical isomers, other monosaccharides can be mixed. There was a problem that had to be reduced as much as possible. In general, other monosaccharides are known to be assimilated by microorganisms such as yeast and chromatographic separation methods. However, D-xylose cannot be consumed by yeast and has a structure similar to that of L-arabinose. Therefore, the chromatographic separation must be performed strictly, which is a factor of high cost.

  D-xylose is a sugar that is abundant in polysaccharides in the core and skin of plants such as wood, cereals, beans, and corn. In the method for producing L-arabinose using these as raw materials, acid hydrolysis, enzyme Any of the degradation methods makes it very difficult to remove and purify because it is released to the same level or higher than L-arabinose.

  For example, Patent Document 7 discloses a method of obtaining water-soluble saccharides by hydrolysis using wheat bran and corn fiber as raw materials. Here, D-xylose was released in substantially the same amount as L-arabinose. Patent Document 8 discloses a composition of a solution obtained by hydrolyzing corn hulls at various concentrations using various acids. However, even when a low concentration acid having a low D-xylose concentration is used, L -10% by mass or more of D-xylose was liberated with respect to arabinose. Furthermore, Patent Document 9 discloses a method for separating a sugar solution containing L-arabinose and D-xylose by simulated moving bed chromatography, but the L-arabinose fraction contains 4% or more of D-xylose. It can be seen that it is difficult to remove D-xylose using simulated moving bed chromatography. Patent Document 10 discloses separation of L-arabinose using corn fiber and barley fiber as raw materials, but D-xylose is liberated more than L-arabinose after acid hydrolysis, and two-stage chromatographic separation is performed. 2% or more of D-xylose remained in the L-arabinose fraction. Further, the process is complicated and not practical. Patent Document 11 discloses a method of treating a sugar solution containing L-arabinose and D-xylose with a yeast that selectively assimilate D-xylose. A sugar solution derived from corn hulls is treated with yeast for 4 days. Although D-xylose was reduced to 1.1% by mass before the treatment, 0.8% by mass of D-xylose still remained with respect to L-arabinose. Patent Document 12 discloses a method for producing high-purity L-arabinose crystals using beet pulp as a raw material, but it is eluted as crude araban in a strong alkali, subjected to acid treatment at high temperature, neutralized and filtered, This method is not practical because it involves many steps of chromatographic separation with a cation exchange resin, purification with a cation, an anion exchanger and an adsorption resin, and crystallization.

As described above, although L-arabinose as a synthetic raw material is desired to reduce impurities, particularly D-xylose, as much as possible, such L-arabinose is difficult to obtain and can be obtained. There was a problem that it was very expensive.
JP 2002-241390 A JP 2006-232861 A Japanese Patent No. 3031534 JP-A-11-313700 JP 2001-286294 A JP 2002-95491 A Carbohydrate Res. , 4, 157-164 (1967) Japanese Patent Laid-Open No. 11-113600 JP-A-11-313700 JP 2000-201700 A JP 2000-157300 A JP 2002-262899 A JP-T-2001-514018

  This invention is made | formed in view of the above problems, The objective is to provide the L-arabinose for synthetic raw materials which is highly purified and hardly contains D-xylose at low cost.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have used plant structures having a relatively small amount of D-xylose release as a raw material, and have at least protein-free and / or polysaccharide-removed polysaccharides and other monosaccharides. It has been found that high-purity L-arabinose that can be suitably used as a synthetic raw material can be obtained by purification in the steps of removal, desalting and crystallization.

That is, in the first aspect of the present invention, a plant body containing arabinan is used as a raw material, and the following steps (a) to (e) are performed to contain 97% by mass or more of L-arabinose and D-xylose. Is a synthetic raw material sugar production method characterized in that a sugar for synthetic raw material is obtained, wherein the plant body containing arabinan is preferably beet pulp, beet fiber And at least one selected from the group consisting of apple candy, apple fiber and citrus candy.
(a) hydrolysis by acid or enzyme, (b) removal of monosaccharides other than L-arabinose, (c) deproteinization and / or polysaccharide removal, (d) desalting, (e) crystallization of the present invention Is based on the sugar for synthetic raw material obtained by the above-described production method.

  ADVANTAGE OF THE INVENTION According to this invention, the highly purified L-arabinose which hardly contains D-xylose which can be used conveniently in the synthesis | combination of a pharmaceutical raw material etc. can be obtained at low cost.

  Hereinafter, the present invention will be described in detail.

  Any plant can be used as a raw material in the present invention as long as the effects of the present invention are not impaired, but those containing a large amount of hemicellulose, particularly those containing a large amount of arabinan are preferred, and arabinoxylan, xylan, mannan. Those containing a large amount of sugars other than L-arabinose, such as galactomannan and rhamnogalacturonan, are preferred.

  Examples include citrus fruits, apples, beets (bean sugar beet), soybeans, peanuts, etc., as well as citrus fruits orange juice, orange juice fruits, apple fruits apple juice, apple juice fruits, beet fiber, beets. By-products such as pulp, soybean meal, peanut ginger, peanut oil cake and the like. The use of wastes and by-products as raw materials is a very preferable method not only for the purpose of manufacturing at low cost but also from the environmental protection aspect of effective use of industrial waste. Orange fiber and tangerine juice lees are residues after squeezing juice from tangerines and oranges, and contain about 3 to 10% by mass of L-arabinose in the form of arabinan. Apple fiber is a residue after squeezing apple juice from an apple, and contains about 4 to 7% by mass of L-arabinose in the form of arabinan or the like. Beet pulp is a residue after beet sugar liquid is extracted from beet, and contains about 12 to 18% by mass of L-arabinose in the form of arabinan or the like. Peanut pods are from peanuts and the like, and contain about 5% by mass of L-arabinose in the form of arabinan.

  The arabinan contained therein is characterized by having a linear structure in which L-arabinose is linked, and L-arabinose production by an enzyme occurs relatively easily. In that respect, beet pulp, beet fiber, apple fiber, apple koji, orange fiber, citrus koji, etc., which easily release L-arabinose are good raw materials, and especially beet pulp is easy to release L-arabinose and has good workability. Most preferred. On the other hand, rice, wheat, corn containing a large amount of arabinoxylan, and rice bran, wheat bran, corn fiber, corn cob and the like, which are residues thereof, are slightly inferior as raw materials.

  In hydrolyzing these plants, hemicellulose obtained by alkali extraction from these plants can be used as it is, but it is preferable to perform hydrolysis as it is because the process becomes complicated. .

  A plant body containing the above-described arabinan of the present invention is used as a raw material, and the following steps (a) to (e) are performed. Note that the order of the steps (b), (c), and (d) is not limited to this.

(A) Step of hydrolysis In the present invention, the step of hydrolysis is first performed. The method of hydrolysis is not particularly limited as long as the effects of the present invention are not impaired, and acid hydrolysis and / or hydrolysis using an enzyme can be performed.

  Although it does not specifically limit as an acid used by the hydrolysis by an acid, Hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, an acetic acid, an oxalic acid, a citric acid, malic acid etc. are mentioned. The concentration of the acid to be used is not particularly limited, but is preferably 0.01 N to 2.5 N, more preferably 0.1 N to 2.0 N, and most preferably 0.16 N to 1.5 N. At lower concentrations, the efficiency is poor, and at higher concentrations, it is no longer possible to increase the amount of L-arabinose released.

  The amount of acid used is preferably 2 to 30 times, more preferably 3 to 20 times, and most preferably 5 to 10 times the dry weight of the raw material. If it is less than this range, it may not be sufficiently uniform, or the amount of liberation may decrease, and if it is more than this range, no further increase in the amount of liberation can be expected.

  The temperature at which hydrolysis with an acid is performed is preferably 50 ° C to 160 ° C, more preferably 70 ° C to 130 ° C, and most preferably 80 ° C to 110 ° C. If the temperature is lower than this range, the efficiency is poor. If the temperature is higher than this range, there is a danger and there is a possibility of an increase in impurities and decomposition of L-arabinose. Although the time for performing hydrolysis with an acid is not particularly limited, it is preferably 30 minutes to 18 hours, more preferably 1 hour to 10 hours, and most preferably 4 hours to 8 hours. If it is shorter than this range, the liberated amount of L-arabinose will be low, and if it is longer than this range, a significant increase in the liberated amount can no longer be expected.

  After hydrolyzing with an acid, neutralization with an alkali is preferable to show strong acidity. The alkali used for neutralization is not particularly limited, and sodium hydroxide, potassium hydroxide, sodium bicarbonate, barium hydroxide, calcium hydroxide, magnesium hydroxide, aqueous ammonia, etc. can be used, but they are relatively inexpensive. It is preferable to use sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate or calcium hydroxide. In particular, calcium hydroxide is preferable because it can be easily removed as a precipitate when an acid that does not require calcium salt such as sulfuric acid is used in water.

  The enzyme used in the hydrolysis by the enzyme is not particularly limited as long as it has an activity of acting on arabinan contained in the plant body as a raw material to release L-arabinose, and examples thereof include arabinase (arabanase) and arabinofurano. Examples include arabinan degrading enzymes such as sidases. The origins of arabinan-degrading enzymes include bacteria (Bacillus subtilis, Streptomyces spp.), Yeasts (Rodtorula spp.), Filamentous fungi (Aspergillus niger, Aspergillus oryzae, Aspergillus pleurentas, Aspergillus tereus, Aspergillus japonicas, Aspergillus flavus, Trichoderma reesei, Trichoderma viride, Trichosporon penicillatum, Rhizopus genus) and the like. Enzymes derived from Aspergillus are preferred. In particular, an enzyme derived from Aspergillus niger is preferable.

  These enzymes are produced in the culture supernatant or cells obtained by culturing the above-mentioned strains by a conventionally known method. In the present invention, any fraction containing these enzymes is used. It may be used. Moreover, the fractions containing these enzymes can be used after purification or partial purification by a conventional method, if necessary. Moreover, you may use a commercially available enzyme.

  Preferred examples of such commercially available enzymes include Sumiteam PX (manufactured by Shinnippon Chemical Co., Ltd.), Sumiteam AP2 (manufactured by Shinnippon Chemical Co., Ltd.), Sumiteam ARS (manufactured by Shinnippon Chemical Co., Ltd.), and Sumiteam SPC (new NIPPON CHEMICAL INDUSTRY CO., LTD., Sumiteam MC (manufactured by Shinnippon Chemical Industry Co., Ltd.), Sumiteam PMAC (manufactured by Shinnippon Chemical Industry Co., Ltd.), Sumiteam CXC (manufactured by Shin Nippon Chemical Industry Co., Ltd.), Sumiteam PTE (Nippon Chemical Co., Ltd.) Industrial Co., Ltd.), Sumiteam LC (manufactured by Shin Nippon Chemical Industry Co., Ltd.), neutral pectinase (manufactured by Shin Nippon Chemical Industry Co., Ltd.), pectinase PL “Amano” (manufactured by Amano Enzyme Co., Ltd.), pectinase G “Amano” ( Amano Enzyme), Pectinase GL “Amano” (Amano Enzyme), Pe Tinase A “Amano” (manufactured by Amano Enzyme), cellulosin PC5 (manufactured by HBI), cellulosin PE60 (manufactured by HBI), cellulosin PEL (manufactured by HBI), soluble pectinase T (manufactured by HBI), Cellulosin ME (HBI Co., Ltd.), Pectinase SS (Yakult Pharmaceutical Co., Ltd.), Pectinase 3S (Yakult Pharmaceutical Co., Ltd.), Pectinase HL (Yakult Pharmaceutical Co., Ltd.), Macero Team A (Yakult Pharmaceutical Co., Ltd.) ), ROHAPECT D5L (manufactured by Higuchi Shokai Co., Ltd.), ROHAPECT D5S (manufactured by Higuchi Shokai Co., Ltd.), ROHAPECT MA PLUS (manufactured by Higuchi Shokai Co., Ltd.), ROHAPECT MAX (manufactured by Higuchi Shokai Co., Ltd.), ROHAPECT PTE (manufactured by Higuchi Co., Ltd.) ), ROHAPECT PL (manufactured by Higuchi Shokai), ROHAPECT B1 (manufactured by Higuchi Shokai), ROCAPECT VR-C (manufactured by Higuchi Shokai), ROHAPECT 7104 (manufactured by Higuchi Shokai), ROHAPECT DA6L (stock) Company Higuchi Shokai), ROHAPECT 10L (Higuchi Shokai Co., Ltd.), ROAPECT AP1 (Higuchi Shokai Co., Ltd.), Sucrase N (Sankyo Co., Ltd.), Sucrase S (Sankyo Co., Ltd.), Pectinex (Novozymes Japan) Pecchinex Ultra SP-L (manufactured by Novozymes Japan), Ultrazyme (manufactured by Novozymes Japan), Vinozyme (manufactured by Novozymes Japan), Peelzyme (Novozymes Japan) SIT) Zyme (Novozymes Japan), Olivex (Novozymes Japan), Novo Farm 12 (Novozymes Japan), Vinoflow (Novozymes Japan), Beerzyme (Novozyme) Zymes Japan Co., Ltd.), pectinase Nagase (manufactured by Nagase ChemteX Corp.), pectinase XP-534 (manufactured by Nagase ChemteX Corp.), and the like. Company-made), Sumiteam ARS (manufactured by Shin Nippon Chemical Industry Co., Ltd.), cellulosin PE60 (manufactured by HBI Co., Ltd.), Pectinex Ultra SP-L (manufactured by Novozymes Japan Co., Ltd.).

  In the present invention, the amount of the enzyme having L-arabinose releasing activity to act is 10 to 100,000 units, preferably 100 to 50,000 units, more preferably, in the case of arabinase (arabanase) per 1 kg of the raw material. 500 to 10,000 units. In the case of arabinofuranosidase, it is 10 to 100,000 units, preferably 100 to 50,000 units, and more preferably 100 to 10,000 units. If it is less than this range, L-arabinose may not be sufficiently liberated, and if it is more than this range, an increase in the amount of L-arabinose released can no longer be expected.

  The amount of water added during the enzyme reaction is not particularly limited, but is preferably 2 to 30 times, more preferably 3 to 20 times, and more preferably 5 to 15 times the dry weight of the raw material. Most preferred. If the amount is less than this range, it may not be evenly distributed or the release amount may decrease, and if it is more than this range, no further increase in the release amount can be expected.

  The temperature at which the enzyme reaction is carried out is preferably carried out at the optimum temperature of the enzyme to be used. For example, when an enzyme derived from Aspergillus niger is used, it is preferably 35 ° C to 65 ° C, more preferably 45 to 55 ° C. The pH of the reaction solution is preferably adjusted under the optimum conditions for the enzyme, but may be reacted as it is. When adjusting, pH 2-7 is preferable and pH 3-6 is more preferable. Outside these ranges, there is a problem that the enzyme does not work effectively. While the reaction time depends on the amount of substrate and enzyme used, it is usually preferably 1 to 72 hours, more preferably 8 to 48 hours, and most preferably 15 to 24 hours. If it is shorter than this range, the amount of liberated L-arabinose decreases, and if it is longer than this range, a significant increase in the amount of liberation can no longer be expected.

  What liberated L-arabinose by acid hydrolysis and / or enzymatic hydrolysis as described above can be transferred to the next purification step as it is. Here, although depending on the next purification step, solid-liquid separation is not necessarily required. For example, if the next work is neutralization, deproteinization by carbonation saturation method, which will be described later, removal of polysaccharides, removal of other monosaccharides by microorganisms, etc., it should be carried out with the residue of the plant after hydrolysis present. Can do. As a result, the solid-liquid separation step can be omitted once and the production can be performed at a lower cost. However, it is preferable to perform solid-liquid separation when performing deproteinization, polysaccharide removal, chromatographic separation, and the like using an ultrafiltration membrane.

  The solid-liquid separation performed in the present invention can be performed by a conventionally known apparatus or method. For example, it is preferable to use a device such as a filter press, a screw press, a vacuum filter, a centrifuge, or a screw decanter. Moreover, conventionally well-known filter aids, such as diatomaceous earth and a cellulose, can also be used as needed.

(B) Step of removing monosaccharides other than L-arabinose In the present invention, a step of removing monosaccharides other than L-arabinose is then performed. As a method for removing other monosaccharides other than L-arabinose, any method can be used as long as the effects of the present invention are not impaired. As a preferred example, L-arabinose is not assimilated and D-xylose is used. , D-glucose, D-fructose, D-galactose, D-rhamnose and other monosaccharide-assimilating microorganisms, L-arabinose alone, or other sugars that are easily separated And a method using an enzyme that converts to L-arabinose, and separation of L-arabinose fractions by chromatography. Particularly preferred examples include the action of microorganisms that assimilate all other monosaccharides without assimilating L-arabinose. The method of letting it be mentioned.

  Examples of such microorganisms include lactic acid bacteria, Bacillus subtilis, yeasts and molds, and particularly preferred examples include yeasts. Among yeast, Saccharomyces cerevisiae, which is generally used as baker's yeast, is preferable because it is easily available and inexpensive, operates at a high sugar concentration and a wide pH range, and can be easily deactivated by applying temperature. Microorganisms can be added from those that have been pre-cultured in a conventionally known medium, or commercially available live yeast, dry yeast, lactic acid bacteria beverages, yogurt, and dry cells can be added as they are.

(C) Deproteinization and / or polysaccharide removal process In the present invention, the processed product that has been subjected to the hydrolysis process or the monosaccharide removal process other than L-arabinose is subjected to solid-liquid separation as it is or as necessary. The obtained supernatant is subjected to a deproteinization and / or polysaccharide removal step. The method is preferably membrane filtration using an ultrafiltration membrane or reverse osmosis membrane, separation by chromatography or gel filtration, precipitation using a flocculant, carbonation saturation by blowing calcium hydroxide and carbon dioxide. More preferred examples include membrane filtration using an ultrafiltration membrane and a carbonic acid saturation method. The ultrafiltration membrane preferably has a fractional molecular weight in the range of 3000 to 10,000. Carbonation satisfactorily precipitates proteins and polysaccharides together with calcium carbonate precipitation by simultaneously blowing carbon dioxide and adding calcium hydroxide while maintaining the pH at preferably 7 to 10, more preferably 8 to 9.5. This method is described in detail in Japanese Patent Application Laid-Open No. 2004-59475.

(D) Desalting step In the present invention, a desalting step is performed. As a desalting method, any method can be used as long as the effects of the present invention are not impaired. Preferred examples include a cation / anion exchange resin, an ion exchange membrane, electrodialysis, and a reverse osmosis membrane. Examples thereof include a method and a method in which a precipitated salt is formed and then precipitated and removed. These may be performed alone or in combination of two or more methods. Among these, a method using an ion exchange resin is particularly preferable. The type of ion exchange resin to be used is not particularly limited. For example, a resin such as Diaion Series from Mitsubishi Chemical Corporation, Amberlite Series from Organo Corporation, Dowex Series from Muromachi Chemical Co., Ltd. may be used. it can. The size of the resin is not particularly limited, but it is not particularly necessary to use an expensive one having fine particles for chromatographic separation, and a general desalting resin may be used. The type of the resin is not particularly limited, but a porous type having pores is particularly preferable because it can simultaneously perform decolorization and adsorption removal of a polymer component.

(E) Crystallization Step In the present invention, a crystallization step is finally performed. As a crystallization method, a conventionally known method can be adopted. A high-purity L-arabinose sugar solution is obtained by the steps (a) to (d) described above. For example, the sugar solution is obtained at a solid content concentration of 50% by mass to 80% by mass, preferably 55% by mass to Concentrate to 70% by weight, more preferably 57% to 65% by weight, 5 to 48 hours, preferably 8 to 35 hours, more preferably 15 to 24 hours, 0 ° C. to 35 ° C., preferably 2 ° C. to The crystals can be precipitated by cooling at 25 ° C. Addition of the seed crystal promotes crystallization, but it does not have to be added. The L-arabinose purity of the sugar solution used before crystallization is preferably 70% to 100%, and more preferably 80% to 100%. If the purity is lower than this range, there are problems such as the purity of the recovered crystals being lowered and the recovery amount being reduced.

  The precipitated crystals can be collected by a conventionally known method. For example, a centrifugal filter, a vacuum filter, a pressure filter and the like are preferable, and a centrifugal filter is particularly preferable. The crystals may be recovered and dried as they are, but can be further purified by washing with a small amount of ethanol. Ethanol may be absolute ethanol, or may contain 50% by volume or less, preferably 30% by volume or less, and more preferably 13% by volume or less of water.

  In the white powder or aqueous solution obtained by the production method of the present invention as described above, the proportion of L-arabinose in the solid content is 97% by mass or more, preferably 98% by mass or more, and more preferably 99% by mass. % Or more. As the remaining impurities, oligosaccharides, organic acids, D-glucose, D-galactose, glycerin, ethanol, and sugar alcohols are each at most 1% by mass, preferably 0.5% by mass or less, more preferably 0 0.1 mass% or less, and D-xylose is at most 0.1 mass%, preferably 0.05 mass% or less, more preferably 0.01 mass% or less.

  Such a white powder or aqueous solution is suitably used as a raw material for the synthesis of pharmaceuticals, food additives, and other chemicals.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the content of this invention is not limited.
In the reference examples, comparative examples, and examples shown here, each carbohydrate is analyzed by high performance liquid chromatography (column: Aminex HPX-87P manufactured by Bio-Rad, column temperature: 60 ° C., mobile phase: ion-exchanged water. , Detection; differential refractometer).

Example 1
10 L of 0.2 N sulfuric acid was added to 1 kg of beet pulp, and heat treatment was performed at 95 ° C. for 3 hours with stirring to perform acid hydrolysis. After the reaction, the liquid was subjected to solid-liquid separation with a press filter, and the pH was adjusted to 4.5 while gradually adding calcium hydroxide. The produced precipitate was subjected to diatomaceous earth filtration using Radiolite # 700 (manufactured by Showa Kagaku Kogyo) on diatomaceous earth. While maintaining this filtrate at 35 ° C., 30 g of baker's yeast: Kaneka yeast RED (manufactured by Kaneka Foods) was added, and the mixture was stirred and aerated for 12 hours to remove monosaccharides other than L-arabinose. After the reaction, baker's yeast was removed by diatomaceous earth filtration, passed through an ultrafiltration membrane with a molecular weight cut off of 6000, and the permeate was recovered to remove proteins and polysaccharides. The permeate was concentrated to a solid content concentration of 30% by mass, 10 g of powdered activated carbon Dazai SA1000 (manufactured by Nimura Chemical) was added, stirred for 60 minutes, and filtered through diatomaceous earth. The filtrate was passed through 5 L each of ion-exchange resin Diaion PK216 and Diaion WA30 (Mitsubishi Chemical) for desalting, and the resulting liquid was concentrated to a solid concentration of 60% by mass and stirred to room temperature. When allowed to cool, white crystals were precipitated. White crystals were separated with a centrifugal filter, rinsed with 5 ml of 99% ethanol, and dried under reduced pressure at 50 ° C. for 17 hours. The obtained crystals were 48 g, L-arabinose purity was 99.9%, and D-xylose was not detected by HPLC and was at least less than 0.01%.

Example 2
In Example 1, L-arabinose was similarly used except that acid hydrolysis was performed using 0.2N nitric acid instead of 0.2N sulfuric acid, and neutralization after the reaction was performed with sodium hydroxide. Manufactured. The obtained crystals were white and 48 g, L-arabinose purity was 99.8%, and D-xylose was not detected by HPLC and was at least less than 0.01%.

Example 3
Add 9L of water to 1kg of beet pulp and keep it at 50 ° C, then add 15g of Sumiteam PX (manufactured by Shinnippon Chemical Co., Ltd.) dissolved in 1L of water and hydrolyze with enzyme at 50 ° C for 24 hours with stirring. Reaction was performed. After the reaction, the pH is adjusted to 4.5 with sodium hydroxide, and 30 g of baker's yeast: Kaneka Yeast RED (manufactured by Kaneka Foods) is added while maintaining 35 ° C., and agitation and aeration are performed for 12 hours. Sugar was removed. The yeast treatment liquid was subjected to solid-liquid separation with a press filter and further subjected to diatomaceous earth filtration using Radiolite # 700 (manufactured by Showa Chemical Industry) as diatomaceous earth. The obtained liquid was passed through an ultrafiltration membrane having a molecular weight cut off of 6000, and the permeate was collected to remove proteins and polysaccharides. The treatment after concentration of the permeate was performed as described in Example 1 to obtain white crystals. The obtained crystal was 42 g, L-arabinose purity was 99.9%, and D-xylose was not detected by HPLC, and was at least less than 0.01%.

Example 4
Add 18L of water to 2kg of Apple fiber (manufactured by Nichiro) and keep it at 50 ° C, then add 30g of Sumiteam PX (manufactured by Shin Nippon Chemical Industry) dissolved in 2L of water and stir at 50 ° C for 24 hours. An enzymatic hydrolysis reaction was performed. After the reaction, the pH is adjusted to 4.5 with sodium hydroxide, and 30 g of baker's yeast: Kaneka Yeast RED (manufactured by Kaneka Foods) is added while maintaining 35 ° C., and agitation and aeration are performed for 12 hours. Sugar was removed. The yeast treatment liquid was subjected to solid-liquid separation with a press filter and further subjected to diatomaceous earth filtration using Radiolite # 700 (manufactured by Showa Chemical Industry) as diatomaceous earth. The obtained liquid was passed through an ultrafiltration membrane having a molecular weight cut off of 6000, and the permeate was collected. The treatment after concentration of the permeate was performed as described in Example 1 to obtain white crystals. The obtained crystal was 43 g, L-arabinose purity was 98.7%, and D-xylose was 0.32%.

Example 5
After adding 18 L of water to 2 kg of dried crushed citrus peel of Unshu orange and keeping it at 50 ° C, a solution of 30 g of Sumiteam PX (manufactured by Shin Nippon Chemical Industry) dissolved in 2 L of water was added and stirred at 50 ° C. The enzyme reaction was performed for 24 hours. After the reaction, the pH was adjusted to 4.5 with sodium hydroxide, 30 g of baker's yeast: Kaneka Yeast RED (manufactured by Kaneka Foods) was added while maintaining 35 ° C., and the mixture was stirred and aerated for 12 hours. The yeast treatment liquid was subjected to solid-liquid separation with a press filter and further subjected to diatomaceous earth filtration using Radiolite # 700 (manufactured by Showa Chemical Industry) as diatomaceous earth. The obtained liquid was passed through an ultrafiltration membrane having a molecular weight cut off of 6000, and the permeate was collected to remove proteins and polysaccharides. The treatment after concentration of the permeate was performed as described in Example 1 to obtain white crystals. The obtained crystals were 43 g, L-arabinose purity was 99.1%, and D-xylose was 0.15%.

Comparative Example 1
18L of water is added to 2kg of dried soybean seed coat and kept at 50 ° C. Then, 30g of Sumiteam PX (manufactured by Shin Nippon Chemical Industry) dissolved in 2L of water is added and stirred for 24 hours at 50 ° C with stirring. Hydrolysis reaction was performed. After the reaction, the pH is adjusted to 4.5 with sodium hydroxide, and 30 g of baker's yeast: Kaneka Yeast RED (manufactured by Kaneka Foods) is added while maintaining 35 ° C., and agitation and aeration are performed for 12 hours. An attempt was made to remove sugar. The yeast treatment liquid was subjected to solid-liquid separation with a press filter and further subjected to diatomaceous earth filtration using Radiolite # 700 (manufactured by Showa Chemical Industry) as diatomaceous earth. The obtained liquid was passed through an ultrafiltration membrane having a molecular weight cut off of 6000, and the permeate was collected to remove proteins and polysaccharides. The treatment after concentration of the permeate was performed as described in Example 1 to obtain white crystals. The obtained crystal was 14 g, L-arabinose purity was 58.7%, and D-xylose was 41.2%.

Comparative Example 2
Add 18L of water to 2kg of dried maize husk and hold at 50 ° C, then add 30g of Sumiteam PX (manufactured by Shin Nippon Chemical Industry) in 2L of water and stir with stirring at 50 ° C for 24 hours. Hydrolysis reaction was performed. After the reaction, while adjusting the pH to 4.5 with sodium hydroxide and maintaining 35 ° C., 30 g of baker's yeast: Kaneka yeast RED (manufactured by Kaneka Foods) was added, stirred and aerated for 12 hours, and a monosaccharide other than L-arabinose Tried to remove. The yeast treatment liquid was subjected to solid-liquid separation with a press filter and further subjected to diatomaceous earth filtration using Radiolite # 700 (manufactured by Showa Chemical Industry) as diatomaceous earth. The obtained liquid was passed through an ultrafiltration membrane having a molecular weight cut off of 6000, and the permeate was collected to remove proteins and polysaccharides. The treatment after concentration of the permeate was performed as described in Example 1 to obtain white crystals. The obtained crystals were 72 g, L-arabinose purity was 92.1%, and D-xylose was 7.8%.

  Table 1 summarizes the raw materials used, the hydrolysis step, and the purity of the obtained crystals of L-arabinose and L-xylose for Examples 1 to 5 and Comparative Examples 1 and 2 described above.

Claims (4)

A plant body containing arabinan is used as a raw material, and the following steps (a) to (e) are performed to contain 97% by mass or more of L-arabinose and 0.1% by mass or less of D-xylose. A method for producing a synthetic raw material sugar, characterized by obtaining a synthetic raw material sugar.
(a) hydrolysis by acid or enzyme, (b) removal of monosaccharides other than L-arabinose, (c) deproteinization and / or depolysaccharide, (d) desalting, (e) crystallization   The method for producing a sugar for a synthetic raw material according to claim 1, wherein the purification step for obtaining the synthetic raw material sugar from the raw material does not include a purification step by chromatography or a purification step by two or more crystallization operations. .   The method for producing a sugar for synthetic raw material according to claim 1 or 2, wherein the plant containing arabinan is at least one selected from the group consisting of beet pulp, beet fiber, apple koji, apple fiber, and citrus koji. The sugar for synthetic raw materials obtained by the manufacturing method in any one of Claims 1-3.