JP2794040B2 - Method for producing high-purity isomaltose - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing high-purity isomaltose. [0002] Isomaltose is a low-sugar sugar that is present in trace amounts in fermented foods and the like, and is used for the reverse synthesis reaction of glucose by glucoamylase or acid catalyst, α-glucosidase ( Transglucosidase), a glucose transfer reaction from maltose or maltodextrin, a partial hydrolysis reaction of dextran, or the like, for 10 to 25 w / w% per solid.
(Unless otherwise specified, "%" herein means "w / w%" on a solids basis.) However, it can be suitably used industrially.
High purity isomaltose, preferably isomaltose
-Purity isomaltose with a content of more than 40% w / w
High-purity isomals that can be supplied stably in large quantities at low cost
There is no known method of producing toast. [0003] In recent years, it has been discovered that isomaltitol, a reduction product of isomaltose, is a low-calorie, low-cariogenic sweetener. It is desired to establish a production method that can be supplied at low cost. Means for Solving the Problems The present inventors have intensively studied a method for mass-producing high-purity isomaltose. As a result, a sugar solution containing 7% or more of the raw material isomaltose (hereinafter, simply referred to as a raw sugar solution) is applied to a column filled with an alkali metal or alkaline earth metal type strongly acidic cation exchange resin. The fraction is eluted with water and then eluted with water, and contains a high content of oligosaccharides having an isomaltosyl residue having a degree of glucose polymerization of 3 or more (hereinafter, simply referred to as isomatodextrin), and a high content of isomaltodextrin / isomaltose. Fraction, isomaltose-rich fraction, isomaltose / glucose-rich fraction and glucose-rich fraction in this order, and the isomaltose-rich fraction, preferably isomaltose having an isomaltose content of 40% or more It has been found that high-purity isomaltose can be easily mass-produced by collecting a high-content fraction. [0006] In addition, when the raw sugar solution is passed through a column for fractionation, the raw sugar solution is passed and fractionated together with the already obtained isomalt-dextrin / isomaltose-rich fraction and the isomaltose-glucose-rich fraction. By collecting the maltose-rich fraction and then flowing the isomaltodextrin / isomaltose-rich fraction obtained before and after that together with the next raw sugar solution, the target high-purity isomaltose can be concentrated at a high concentration. The present invention was found to be able to produce repeatedly and stably with a high yield, and that it can be mass-produced industrially at low cost. [0007] The raw sugar solution used in the present invention contains 7% or more of isomaltose.
It is sufficient that high-purity isomaltose containing 0% or more can be collected at a high yield. For example, glucoamylase (EC 3.2.1.3) or an acid-catalyzed glucose reverse synthesis product, α-glucosidase ( EC 3.2.
1.20) It is preferable to use a partially hydrolyzed product of glucosyl transfer product and dextran according to (1), which contains 7% or more of isomaltose. In preparing a raw sugar solution, in the case of glucoamylase, not only glucose but also partially decomposed products of starch such as maltose, maltotriose, starch syrup and dextrin are usually dissolved in a highly concentrated aqueous solution of about 40 to 80%. When it is made to act, glucoamylase produces not only isomaltose, but also isomaltdextrins such as isomalttriose, panose, and isomaltotetraose. In the case of α-glucosidase, a partially hydrolyzed starch such as maltose, maltotriose, starch syrup, dextrin or the like is usually allowed to act on a sugar solution of about 10 to 70% to obtain α-glucosidase. By the action of
In addition to isomaltose, isomalt dextrins such as isomalt triose, panose, isomalt tetraose, and isomaltosyl maltose are produced. On this occasion,
If necessary, make glucoamylase and the like work further,
An unreacted partially hydrolyzed starch that is present together can be decomposed into a raw sugar solution. When the raw sugar solution is a dextran hydrolyzate, for example, an acid is allowed to act on an aqueous dextran solution of about 10 to 50% to neutralize the dextran solution, or dextranase (EC 3.2.1. 11) or isomaltdextranase (EC 3.2.1.94)
It can be easily prepared by acting on them. The alkali metal type or alkaline earth metal type strongly acidic cation exchange resin used in the present invention includes, for example, Na ⁺ type styrene-divinylbenzene cross-linked copolymer resin having a sulfonic acid group bonded thereto. One or more of alkali metal type such as K ⁺ type or alkaline earth metal salt type such as Ca ^{++ type and Mg ++} type are appropriately used, and commercially available products include, for example, Dow Chemical Co., Ltd. X 50W × 2, Dowex 50W ×
4. Dowex 50W × 8, Amberlight CG-120 manufactured by Rohm & Haas, XT-1022E manufactured by Tokyo Organic Chemical Industry, Diaion SK1B, Diaion SK10 manufactured by Mitsubishi Kasei Kogyo
2. Diaion SK104. These resins are excellent not only in fractionation of a fraction containing high isomaltose, but also in heat resistance and abrasion resistance, and are extremely advantageous for mass production of high-purity isomaltose. In the present invention, usually 0.01 to 0.5 mm
A resin having a particle size of the order of magnitude may be packed in a column and used.
The length of the resin layer filled in the column is desirably 7 m or more in total length. At this time, even if the length is 7 m or more in one column,
Further, two or more columns may be connected in series to have a length of 7 m or more. [0012] If necessary, even in the case of a resin layer of 7 m or less, the obtained isomaltose-rich fraction is separated by repeatedly flowing the obtained eluted fraction through the same resin layer again in the order of elution. A method may be employed in which the raw sugar solution is substantially in contact with the resin layer length of 7 m or more before collection. The material and shape of the column can be freely selected as long as the object of the present invention is achieved. The material is, for example, glass, plastic, stainless steel or the like can be used, the shape is as laminar as possible liquid in the filled resin layer, for example, cylindrical,
A prismatic shape or the like can be appropriately used. Hereinafter, the method of implementing the present invention will be described more specifically. An alkali metal or alkaline earth metal type strongly acidic cation exchange resin is suspended in water and packed in a column so that the total length of the resin layer is 7 m or more.
While maintaining the temperature in the column usually at 45 to 85 ° C., about 1 to 60 v / v% of a raw sugar solution having a concentration of about 10 to 70 w / w% is added to the resin, and water is added to the solution at about SV .1 to
The eluate was eluted by flowing at a flow rate of 2.0 by the ascending method or the descending method, and the raw sugar solution was subjected to isomaltodextrin-rich fraction, isomaltodextrin / isomaltose-rich fraction, isomaltose-rich fraction, isomaltose / A plurality of fractions, usually 5 to 100, desirably 5 to 30 in order of the glucose-rich fraction and the glucose-rich fraction.
The fractions may be fractionated, and a fraction containing isomaltose containing at least 40% of isomaltose may be collected. At this time, the eluate is usually collected at a rate of about 1 to 20 v / v% based on the resin used. However, it is easy to automate this and to distribute the eluate to the fractions. When the raw sugar solution is passed through a column for fractionation, the isomalt-dextrin-isomaltose-rich fraction and the isomaltose-glucose-rich fraction, which have already been obtained, are added before and after the raw sugar solution. Alternatively, by flowing together with the raw sugar solution, the amount of water required for fractionation can be reduced, and isomaltose in the raw sugar solution can be collected with high purity, high concentration and high recovery, which is convenient. In general, a raw sugar solution is flowed after the isomalt dextrin / isomaltose-rich fraction already obtained is flowed, and then the already obtained isomaltose / isomaltose.
It is preferable to adopt an order of flowing a glucose-rich fraction. Further, the fractionation method used in the present invention may be any of a fixed bed method, a moving bed method, and a simulated moving bed method. The fraction thus separated and the collected isomaltose-rich fraction can be used as it is, but if necessary, for example, filtered, decolorized, desalted, purified, and then concentrated, for example, according to a conventional method. It is also possible to collect the powder by syrup or spray-drying. The high-purity isomaltose thus produced preferably contains isomaltose in a high purity of at least 40%, and is a sweetener, a humectant, a thickener, a shine-imparting agent, an antioxidant. It is used as a bulking agent, excipient, and the like in various foods and drinks, cosmetics, medicines, and the like, and is also advantageously used as a raw material for isomaltitol. Hereinafter, the present invention will be described in detail by experiments. [Experiment 1] Comparison of raw sugar solution [0021] Glucose was used as a 60 w / w% aqueous solution of glucose, and glucoamylase immobilized by the method disclosed in JP-A-55-124494 was added thereto. 50
A reverse synthesis reaction was caused at pH 4.8 ° C. After the reaction solution was sampled with time, it was diluted to 45 w / w% to obtain a raw sugar solution for this experiment. Table 1 shows the sugar composition of each raw sugar solution. [Table 1] The resin is an alkali metal type strongly acidic cation exchange resin (manufactured by Dow Chemical Company, trade name: Dowex 50)
W.times.4, Na.sup. ⁺ Type) was used as a water suspension, and packed into a stainless steel column with a jacket having an inner diameter of 5.4 cm so as to have a resin layer length of 10 m. While maintaining the temperature in the column at 75 ° C., the raw sugar solution was added to the resin at 5 v / v.
%, And hot water at 75 ° C. was flowed at a flow rate of SV 0.2 to fractionate, and a high isomaltose-containing fraction having an isomaltose content of 40% or more was collected. The results are shown in Table 2. [Table 2] As is evident from the results in Table 2, the raw sugar solution has an isomaltose content of 7% or more, especially 7 to 25.5%, and a 40% isomaltose content.
It has been found that isomaltose can be collected in the above isomaltose-rich fraction in a high yield of 70% or more of the raw sugar solution isomaltose. Experiment 2 Comparison of resin layer length In the same manner as in Experiment 1, one or two columns were filled with an alkali metal type strongly acidic cation exchange resin, and the resin layer length was 1 to 20 m. And In each of these columns having different resin layer lengths, the raw sugar solution No. 1 prepared by the method of Experiment 1 was maintained while maintaining the temperature in the column at 75 ° C. 3 (isomaltose content: 7.1%) or raw sugar solution No. 3 5 (25.5% isomaltose content)
Was added to the resin at 5 v / v%, and hot water at 75 ° C was added to the SV.
Fractionation at a flow rate of 0.2 yields an isomaltose content of 4
Fractions high in isomaltose of 0% or more were collected. The results are shown in Table 3. [Table 3] As is clear from the results in Table 3, the raw sugar solution was applied to a resin layer having a length of 7 m.
By contacting with the above, it was found that isomaltose can be collected in the isomaltose-rich fraction having an isomaltose content of 40% or more with a high yield of 70% or more of the isomaltose in the raw sugar solution. Hereinafter, a few embodiments will be described. Example 1 A glucose reverse synthesis product (concentration: 45 w / w%) having an isomaltose content of 25.5% and prepared by the method described in Experiment 1 was used as a raw sugar solution. The resin is an alkali metal type strongly acidic cation exchange resin (manufactured by Tokyo Organic Chemical Industry,
(Trade name: XT-1022E, Na ⁺ type), and packed in a water-suspended form into a jacketed stainless steel column having an inner diameter of 5.4 cm. At this time, four columns with a resin layer length of 5 m were packed, and the four columns were connected so that the liquid flowed in series, so that the total length of the resin layer was 20 m. While maintaining the temperature in the column at 75 ° C., a raw sugar solution was added at 5 v / v% to the resin, and hot water at 75 ° C. was flowed at a flow rate of SV 0.13 to fractionate the fraction, containing isomaltose. Isomaltose-rich fractions with an amount of 40% or more were collected. This isomaltose-rich fraction contained 233 g of isomaltose, and had a high yield of 75.1% based on isomaltose in the raw sugar solution. This fraction was decolorized and desalted and purified according to a conventional method to obtain 580 g of syrup having a water content of 15%. The product contained 46.4% of isomaltose and 43.0% of isomaltdextrins such as isomalttriose, panose and isomaltetrate. Example 2 Dextran was dissolved in 1N sulfuric acid to a concentration of 20%, kept at 100 ° C. for 60 minutes, neutralized with 6N caustic soda solution, and then ion exchange resin of H type and OH type , And concentrated to prepare a raw sugar solution containing 60% w / w% and 12.2% isomaltose. The resin used in Example 1 was changed to K ⁺ type and used. The resin was packed in one jacketed stainless steel column having an inner diameter of 6.2 cm so that the resin layer length became 10 m or more. While maintaining the temperature in the column at 60 ° C., the raw sugar solution was added at 3 v / v% to the resin, and hot water at 60 ° C. was flowed at a flow rate of SV 0.2 to fractionate the fraction, containing isomaltose. The isomaltose-rich fraction having an amount of 40% or more contained 66.0 g of isomaltose, and had a high yield of 79.1% based on isomaltose in the raw sugar solution. This fraction was purified and concentrated in the same manner as in Example 1 to obtain 43.2% of isomaltose having a water content of 15% and 48.6% of isomaltdextrin such as isomalttriose and isomalttetraose.
%. Example 3 An aqueous solution of syrup was prepared at a concentration of 45 w / w%, and the immobilized glucoamylase prepared by the method of Experiment 1 was added thereto and hydrolyzed at 50 ° C. and pH 4.8 to cause a reverse synthesis reaction. Then, a raw sugar solution containing 16.5% of isomaltose was obtained. The resin is an alkaline earth metal type strongly acidic cation exchange resin (manufactured by Dow Chemical Co., trade name: Dowex 50W
× 4, Mg ⁺⁺ type) and packed in the same column as in Example 1 so that the total length of the resin layer was 15 m. 5. While maintaining the temperature in the column at 55 ° C.,
6% (v / v) was added thereto, and hot water at 55 ° C. was flowed at a flow rate of SV 0.13 to fractionate, and a fraction containing isomaltose with a high isomaltose content of 40% or more was collected. This isomaltose-rich fraction contained 156 g of isomaltose, and had a high yield of 78.1% based on isomaltose in the raw sugar solution. This fraction was purified and concentrated in the same manner as in Example 1, dried under reduced pressure, and pulverized to obtain a powder 320 having a water content of 1% or less.
g was obtained. This product contained 47.7% of isomaltose and 20.3% of isomaltdextrins such as isomalttriose, panose, and isomaltotetraose. Example 4 A glucose reverse synthesis product (concentration: 45 w / w%) having an isomaltose content of 25.5% and prepared by the method described in Experiment 1 was used as a raw sugar solution. First, in the first fractionation, fractionation was carried out in the same manner as in Example 1 except that the raw sugar solution was used in an amount of 20 v / v% based on the resin. The elution pattern of the fractions is shown in FIG. In FIG. 1, A shows a fraction containing high isomalt dextrin, B shows a fraction containing high isomalt dextrin / isomaltose, C shows a fraction containing high content of isomaltose, and D shows a fraction containing high isomaltose. -A glucose-rich fraction is shown, and E shows a glucose-rich fraction. The elution order was A, B, C, D, E. Fraction C (isomaltose-rich fraction) was collected and Fractions A and E were removed. For the second and subsequent fractions, fraction B was added to the same column, then a raw sugar solution of about 10 v / v% based on the resin, fraction root D were added in that order, and hot water at 75 ° C. was further added. In the same manner as in Example 1, an isomaltose-rich fraction containing at least 50% isomaltose was collected. The second and subsequent fractionation operations were repeated a total of 50 times, and the average result was determined. The fraction containing high isomaltose content contained 519 g of isomaltose.
The yield was as high as 83.7% based on isomaltose in the raw sugar solution. 50 fractions of this fraction were collected and treated in the same manner as in Example 3 to obtain 43 kg of powder. This product contained 58.4% of isomaltose and 29.3% of isomaltdextrin such as isomalttriose, panose and isomaltetrate. The fraction A removed outside the system by the above method
And E were collected and concentrated to a concentration of about 60% w / w, and immobilized glucoamylase was allowed to act on it. As a result, the sugar composition became almost the same as that of the raw sugar solution, and it was found that the sugar solution could be used. It has been found that by employing this method, the raw glucose can be practically and completely converted into high-purity isomaltose. Example 5 A glucose reverse synthesis product (concentration: 60 w / w%) having an isomaltose content of 25.5% and prepared by the method described in Experiment 1 was used as a raw sugar solution. As the resin, an alkaline earth metal type strongly acidic cation exchange resin (manufactured by Rohm & Haas Co., Ltd., trade name: Amberlite CG-120, Ca ⁺⁺ type) was used. Filling was performed so that the total length became 10 m. While maintaining the temperature in the column at 80 ° C., at the time of the first fractionation, the raw sugar solution was added to the resin at 15 v / v%, and hot water at 80 ° C. was flowed at a flow rate of SV 0.6 to fractionate. Then, the fractionation pattern shown in the figure was obtained in the same manner as in Example 4. The fraction C (isomaltose-rich fraction) was collected. Fractions A and E were collected, concentrated to a concentration of 60 w / w%, and allowed to act on immobilized glucoamylase, and returned to the original sugar solution with almost the same sugar composition as the original sugar solution. For the second and subsequent fractions, fraction B, fractional sugar solution of about 7 v / v% based on the resin, and fraction D were added to the same column in this order, and hot water at 80 ° C. was further added to SV0. At a flow rate of 0.6, an isomaltose-rich fraction having an isomaltose content of 60% or more was collected. FIG. 2 shows the steps of this embodiment. A, B, C, D and E in FIG. 2 indicate each fraction of the elution pattern as in FIG. G indicates glucose, GA indicates a reaction with glucoamylase, S indicates a raw sugar solution, R indicates fractionation using a resin, V indicates a concentration, and P indicates a high-purity isomaltose product. The second and subsequent fractionation operations were repeated a total of 200 times, and the average result was determined. The fraction containing high isomaltose content contained 256 g of isomaltose, and The yield was as high as 83.4% based on isomaltose. 200 fractions of this fraction were collected and treated in the same manner as in Example 3 to obtain 77 kg of powder. This product contained 65.3% of isomaltose and 22.7% of isomaltdextrins such as isomalttriose, panose and isomaltetrate. As is evident from the above, the present invention makes it possible to easily produce high-purity isomaltose in high yield, and the high-purity isomaltose obtained by the present invention is: It is used as a sweetener, humectant, thickener, illuminant, anti-aging agent, bulking agent, excipient, etc. in various foods, drinks, cosmetics, medicines, etc., and is also advantageously used as a raw material for isomaltitol be able to.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing an example of an elution pattern of a raw sugar solution. The symbol A in the figure is an isomalt dextrin high content fraction, B is an isomalt dextrin / isomaltose high content fraction,
C is a fraction containing high isomaltose, D is isomaltose
The glucose-rich fraction and E indicate the glucose-rich fraction. FIG. 2 is a diagram showing an example of a process for producing high-purity isomaltose from glucose. Symbols A, B, C, D and E in the figure indicate each fraction of the elution pattern as in FIG. G
Is glucose, GA is a reaction by glucoamylase, S is raw sugar solution, R is fractionation by resin, V is concentration,
P indicates a high purity isomaltose product.

Claims (1)

(57) [Claims] Glucose amylase reverse glucose synthesis reaction, α
-Glucose transfer reaction by glucosidase or
A sugar solution containing 7% or more of the isomaltose obtained by the partial hydrolysis reaction of the stran per solid is passed through a column packed with an alkali metal type or alkaline earth metal type strongly acidic cation exchange resin to a total length of 7 m or more, Then, the fraction was eluted with water and the fraction containing high isomalt dextrin,
Fractions high in rutodextrin / isomaltose, isomers
High lactose-rich fraction, high isomaltose / glucose content
A method for producing high-purity isomaltose , comprising fractionating in the order of a fraction having a high glucose content and collecting a fraction having a high isomaltose content. 2. 2. The isomaltose-rich fraction contains at least 40% of isomaltose based on solids.
The method for producing high-purity isomaltose according to the above. 3. 3. The method for producing high-purity isomaltose according to claim 1, wherein an immobilized enzyme is used as glucoamylase. 4. Claim 1, 2 or 3 the method of producing a high-purity isomaltose, wherein the maintaining the inner column temperature in the range of 45 to 85 ° C.. 5. When a sugar solution containing 7% or more of isomaltose per solid is flowed through the column, the sugar solution is flown together with the already obtained isomaltdextrin / isomaltose-rich fraction and isomaltose / glucose-rich fraction. The method for producing high-purity isomaltose according to claim 1, 2 , 3, or 4 . 6. When a sugar liquid containing 7% or more of isomaltose per solid is passed through a column, a sugar containing 7% or more of isomaltose per solid is passed after flowing a fraction having a high content of isomaltdextrin / isomaltose already obtained. claim, characterized in that flow flowing liquid, then the already isomaltose, glucose-rich fraction is obtained 1,2,3
Or the method for producing high-purity isomaltose according to 4 . 7. When a sugar solution containing 7% or more of isomaltose per solid is passed through the column, the already obtained isomaltdextrin / isomaltose-rich fraction and / or glucose-rich fraction are treated with glucoamylase to give isomaltose. claim 2, 3, 4, 5 or, characterized in that used to convert the sugar solution containing maltose solids per 7% or more
6. The method for producing high-purity isomaltose according to 6 . 8. The isomaltose-rich fraction contains isomaltdextrin together with at least 40% isomaltose per solid, and isomaltdextrin is characterized in that :
8. The method for producing high-purity isomaltose according to 5, 6, or 7 . 9. 9. The method for producing high-purity isomaltose according to claim 8, comprising 20% or more of isomalt-dextrin.