JPH07100000A - Production of starch saccharide - Google Patents

Abstract

PURPOSE:To provide a production method markedly simplified in production process and reduced in production cost, also capable of easily and simultaneously obtaining high-purity maltose and a maltose-maltotriose mixed sugar liquor of high added value. CONSTITUTION:This starch saccharide production method to obtain high-purity maltose, a maltose + maltotriose mixed liquor and dextrins comprises the combination of a liquefying and saccharifying processes to obtain saccharide liquors consisting mainly of maltose of low glucose content by hydrolyzing starch with beta-amylose with a chromatographic separation process to separate the saccharide liquors into a dextrin fraction, the maltose + maltotriose fraction and high-purity maltose fraction.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a high-purity maltose fraction, a maltotriose + maltose fraction, and at least 3 fractions of dextrin having a molecular weight of maltotetraose or more at the same time by using a chromatographic separation device from starch sugar. The present invention relates to a method for producing the obtained starch sugar.

[0002]

2. Description of the Related Art Edible maltose syrup obtained by saccharifying starch has made it possible to obtain a saccharified solution having a high maltose content by the development of an enzymatic saccharification method. However, in the saccharified solution, glucose or maltotriose or It contains a large amount of dextrin having a molecular weight of maltotetraose or more as an impurity. Conventionally, a method of purifying high-purity maltose by separating and removing these impurities using a chromatographic separation method has been studied. As a method for purifying by chromatographic separation using a Na-type cation exchange resin as a filler, JP-A-57-209000.
Japanese Patent Publication No. 61-51120 and Japanese Patent Laid-Open No. 60-670.
No. 00 discloses a maltose purification method by simulated moving bed chromatography separation. They are classified into the following two categories.

"Oligosaccharides having a molecular weight higher than maltotriose", "maltose" and "glucose" were selected as those to be extracted out of the chromatographic system by dividing into three sections by using chromatographic separation using a one-pass method or a circulation method. (Example 2 of JP-A-57-209000 and JP-A-4-227804)

· Using an artificial moving bed system to divide into “oligosaccharides having a molecular weight higher than maltotriose” and “maltose and glucose” (JP-A-60-67000)

[0005]

When the above saccharified solution is chromatographically separated by a chromatographic separation using a column having a strongly acidic cation exchange resin as a packing material, dextrin having a molecular weight of maltotetraose or more usually flows out first. Then, maltotriose, maltose, and glucose flow out in this order.

As an example of the basic performance in the above chromatographic separation, Table 1 shows the degree of separation between each component.

[0007]

[Table 1] "Example of separation of glucose, maltose, maltotriose, and dextrin having a molecular weight of maltotetraose or more using a strongly acidic cation exchange resin (Na type)" Amberlite CG-6000 Na type (9.8φ *) Ten
00H) Stock solution: Bx60, ME65, Eluent: Pure water LV =
5

In the table, the degree of separation (Rs): the ease with which the components A and B are separated. Larger is easier to separate.

As is apparent from the above, the degree of separation of maltose and glucose is about 0.55, which is relatively easy to separate, whereas the degree of separation of maltose and maltotriose is about 0.28, which is difficult to separate. In addition, as a final purification in producing high-purity maltose used for medicine, crystallization is performed to improve the purity, but in this case, the removal rate of maltotriose is lower than that of glucose, and in purification by chromatographic separation,
It is necessary to remove maltotriose as much as possible, and it was very difficult to obtain high-purity maltose for pharmaceuticals from a saccharified solution containing maltotriose, which is commonly known as "edible maltose", in the conventional method. . The present inventors have conducted extensive studies to efficiently perform this separation. Further, in recent years, it has been found that the taste varies depending on the sugar composition ratio, and in the field of oligosaccharides that have been conventionally summarized with starch syrup, attempts have been made to obtain useful sugar mixtures by selecting the composition ratio of each sugar.

The inventors of the present invention are sugars in which maltose and maltotriose are the main components, the ratio of maltose / maltotriose is 1 to 3, and the total content of maltose and maltotriose is 80% or more based on the solid content. It has been found that the composition has excellent taste retention and the like and is excellent as a sweetener for pastes, soft drinks and the like. These sugar compositions could not be efficiently produced by conventional production methods using enzyme technology, and studies were conducted to make it easy to produce them by the method of the present invention.

[0011]

The present invention uses a chromatographic separation using a strongly acidic cation exchange resin, and when separating a starch saccharified solution, the following three methods are used by intentionally distributing glucose in each compartment. Partitioning-Component 1: Dextrin having a molecular weight of maltotetraose or higher (G4 ⁺ fraction) -Component 2: Maltose containing maltose and maltotriose as main components / a sugar composition having a maltotriose ratio of 1 to 3 ( G3 + G2 fraction) -Component 3: Maltose (G2 fraction) is separated to easily obtain "a sugar composition containing maltose and maltotriose as the main components and having a maltose / maltotriose ratio of 1 to 3". While being able to
Since the mixed region of maltotriose and maltose can be extracted in an effective form, the maltotriose content in the "maltose" section could be reduced.

That is, the gist of the present invention is to liquefy starch,
A saccharified dextrin having a glucose content of 4 wt% or less of the total solid content and maltose of 65 wt% to 80 wt% of the total solid content and the balance of maltotriose and maltotetraose and a starch sugar aqueous solution as an impurity After getting
A filtration step for removing impurities such as fats, proteins, and SS,
Purification process for desalting and decolorizing, solid content concentration 40 ~ 70 wt
At least once each concentration step to concentrate to
The purified starch sugar aqueous solution thus obtained was used as a stock solution, and a chromatographic separation device using a strongly acidic cation exchange resin as an adsorbent, the dextrin fraction while distributing glucose to all fractions without separating the glucose fraction, The present invention provides a method for producing a starch sugar in which a maltose + maltotriose fraction and a high-purity maltose fraction are separated into at least three fractions.

In the present invention, the glucose content in the undiluted solution is set to 4 wt% or less of the total solid content because if it exceeds 4 wt%, the glucose content in the maltose fraction will not be too large, and The maltose content in the undiluted solution was 65-80 wt% of the total solid content because the maltose content was
This is because a high-purity maltose cannot be obtained if a stock solution of less than 65 wt% is used, and an economical effect is small with a stock solution of more than 80 wt%. Next, the solid content concentration of the purified starch sugar stock solution to be separated by the chromatographic separation device was set to 40 to 70 wt% because the use of a stock solution having a solid content concentration of less than 40 wt% reduces the production amount of the maltose fraction to 70 wt%. This is because the method of the present invention cannot be carried out with a stock solution of more than 10%.

The glucose component in the undiluted solution is mixed in the maltose fraction, but the glucose content can be easily reduced by the saccharification method, and the composition can be easily reduced in the subsequent crystallization step. Part "and" Maltose Extraction Part "transfer speed (Um)
The apparent moving speed (Us) of the packed bed is Um
It was found that glucose in the maltose compartment can be reduced by setting (glucose) <Us <Um (maltose).

The chromatographic separation device used in the present invention can use various types of equipment that have been proposed so far, but it is necessary to use a device that can efficiently separate into three or more fractions. If a device with poor separation efficiency is used, "G3 +
This is because a large amount of dextrin of G4 or more enters the "G2 fraction", maltose of high purity cannot be obtained, the load is small, the productivity is low, and the production is not economical.

[0016]

EFFECT OF THE INVENTION There is a facility developed by the applicants as a chromatographic separation device capable of efficiently separating into three or more fractions by one operation and proposed in Japanese Patent Laid-Open No. 4-227804. Although the performance is somewhat deteriorated, the three-component separation method using the circulation method (JP-A-56-92127, JP-A-63-158105) and the like are used to efficiently separate the above three fractions, High-purity maltose and maltotriose + maltose mixed sugar solution can be efficiently obtained at the same time.

[0017]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples without departing from the gist thereof. FIG. 1 shows an example of a manufacturing process for carrying out the method of the present invention, and FIG.
1 shows an outline of the configuration of an example of a component separation chromatographic separation device.

In FIG. 2, 1 to 12 are unit packed beds filled with the same adsorbent, and the unit packed beds are connected by a pipe so that a fluid can flow therethrough.
The rear end of the final packed bed 12 is connected to the front end of the frontmost unit packed bed 1. Reference numeral 14 is a circulation pump provided on the flow path of the unit packed bed 12 and 1. 13 is a unit packing layer 6
It is a shutoff valve provided in a connecting pipe between and and is opened / closed by a control device (not shown). On the downstream side of the unit packed bed 6, an A component (dextrin fraction) outlet 6a, a B component (maltose + maltotriose fraction) outlet 6b, and a C component (maltose fraction) outlet 6a.
c is provided, and an inlet 7f for the undiluted solution and an inlet 7d for the eluent are provided on the upstream side of the unit packed bed 7. A component extraction port a and a C component extraction port c are provided on the downstream side of the unit packed bed other than 6, and an eluent inlet d is provided on the upstream side of the packed bed other than 7. . The opening and closing of these valves can be appropriately switched by a control device (not shown).

As described above, this figure is an example of the outline of the constitution of the chromatographic separation apparatus provided for carrying out the method of the present invention. Instead of the apparatus shown in this figure, a circulation tank system is used. Any device can be used as long as it can be efficiently separated into three or more fractions by combining two devices, a simulated moving bed device. The equipment shown in Figure 2
It is used for 12 unit packed beds, but the number of the unit packed beds is "G2 classification" (maltose fraction) and "G2 + G3 classification".
It goes without saying that it can be changed depending on the ratio of (maltose + maltotriose fraction), the respective purities, and the target values of the recovery rate.

Example 1 In the manufacturing process shown in FIG. 1, cornstarch was used as a raw material starch, α-amylase was used as a liquefying enzyme to liquefy DE2, and saccharification was performed with pullulanase and β-amylase to prepare an aqueous starch sugar solution. This solution was desalted and decolorized using activated carbon and an ion exchange resin, and then concentrated to obtain a chromatographic supply stock solution. This was chromatographed in the operating steps shown in Table 2 using the chromatographic separation equipment shown in FIG. 2 to obtain the fractionated liquids shown in Table 3.

The apparatus shown in FIG. 2 is a strongly acidic cation exchange resin of Na type (Amberlite CG-60) as an adsorbent.
00: trade name) and soft water was used as an eluent,
Also, twelve serially connected inner diameters 108.3 mm, packed bed height 1200
The packed column of mm was packed with 133 liters of adsorbent, and the packed bed was packed with 60
The separation operation was repeated while keeping the temperature at ℃. In this separation experiment, "G4 ⁺ " was extracted from the A-section extraction valve (1a to 12a).
The fraction mainly composed of (dextrin), the fraction mainly composed of “G2 + G3” (maltose + maltotriose) from the B compartment extraction valve (6b) and the “high purity G2” (from the C compartment extraction valve) ( The maltose) fraction is extracted. The flow rate in each step of chromatographic separation is as follows.

Flow rate in step 1 Supply flow rate of raw material liquid 27.1 L / h Supply flow rate of eluting water 31.2 L / h G4 ⁺ fraction extraction flow rate 14.9 L / h G2 + G3 fraction extraction flow rate 43.5 L / h

Flow rate in step 2 Eluent water supply flow rate 21.3 L / h G4 ⁺ fraction extraction flow rate 15.0 L / h G2 fraction extraction flow rate 6.3 L / h G2 in the packed bed between the extraction section and the G4 ⁺ extraction section Liquid flow rate 55.2 L / h

The results of passing the liquid are shown in Table 3. High-purity maltose and maltose + maltotriose could be easily obtained. In this example, there is no G1 (glucose) section,
Are distributed to the G4 ⁺ section, the G3 + G2 section, and the G2 section, respectively. This makes it possible to increase the G2 content in the G2 classification (maltose classification) and reduce the G1 content.

[0025]

[Table 2]

[0026]

[Table 3]

(Comparative Example 1) As a conventional method, "oligosaccharide having a molecular weight of maltotriose or more", "maltose", or "glucose" was selected as a product to be extracted from the chromatographic system, and the operation was performed under the following flow rate conditions. The equipment used was the same as in Example 1, and the opening / closing of valves in each step was based on Table 4.

Flow rate in step 1 Supply flow rate of raw material liquid 27.7 L / h Supply flow rate of eluting water 29.6 L / h G4 ⁺ fraction extraction flow rate 21.2 L / h G2 + G3 fraction extraction flow rate 36.0 L / h

Flow rate in step 2 Elution water supply flow rate 29.6 L / h G4 ⁺ fraction extraction flow rate 21.3 L / h G2 fraction extraction flow rate 8.3 L / h G2 in the packed bed between the extraction section and the G4 ⁺ extraction section Liquid flow rate 55.2 L / h

The experimental results are shown in Table 5. It can be seen that the G3 content in the G2 category is high. In this example, G3 and above categories and G2
However, the content of G3 (maltotriose) in the G2 (maltose) classification becomes large and the content of G2 becomes insufficient. Therefore, in this example, it is difficult to obtain medical grade maltose.

[0031]

[Table 4]

[0032]

[Table 5]

(Comparative Example 2) "Dextrin having a molecular weight higher than maltotetraose", "maltotriose + maltose", and "maltose + glucose" were extracted from the chromatographic system using the same equipment and stock solution as in Example 1. The operation was performed under the following flow rate conditions obtained. The opening and closing of the valve in each step was based on Table 6.

Flow rate in step 1 Supply flow rate of raw material liquid 31.5 L / h Supply flow rate of eluting water 31.5 L / h G4 ⁺ fraction extraction flow rate 14.1 L / h G2 + G3 fraction extraction flow rate 45.9 L / h

Flow rate in steps 2 to 12 Eluent water supply flow rate 22.3 L / h G4 ⁺ fraction extraction flow rate 14.1 L / h G2 fraction extraction flow rate 8.1 L / h G2 filling between extraction section and extraction section of G4 or more Liquid flow rate in bed 55.2 L / h

The experimental results are shown in Table 7. It can be seen that the G1 content in the G2 category is high. In this example, G2 (maltose) was extracted by adding G1 (glucose) to the G2 (maltose) section.
Since the section contains a large amount of G1, the G2 + G1 section naturally has a high glucose content, and the G2 content is insufficient.

[0037]

[Table 6]

[0038]

[Table 7]

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a manufacturing method for carrying out the method of the present invention.

FIG. 2 is a schematic configuration diagram showing an example of a three-component separation chromatographic separation device used in the method of the present invention.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 29, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

[Table 2]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

[0031]

[Table 4]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

[0037]

[Table 6]

Claims (3)

[Claims] 1. Liquefaction and saccharification of starch so that the glucose content is 4 wt% or less of the total solid content and maltose is 65 wt% of the total solid content.
After obtaining the aqueous dextrin containing ~ 80wt% and the balance of maltotriose and maltotetraose and the starch starch aqueous solution as an impurity, a filtration step for removing impurities such as fats and oils, proteins, SS, desalting and decolorization The purification step for carrying out the method and the concentration step for concentrating the solid content to 40 to 70 wt% are carried out at least once each, and the strong starch cation exchange resin is used as a stock solution of the purified starch sugar aqueous solution thus obtained. , The dextrin fraction having a molecular weight of maltotetraose or more, the maltose + maltotriose fraction and the maltotriose content while distributing the glucose to all fractions without separating the glucose fraction. Is less than 1 wt% and maltose content is 95
High-purity maltose fraction of at least wt% is at least 3
A method for producing starch sugar, which comprises obtaining a fraction. 2. The starch is liquefied and saccharified so that the glucose content is 4 wt% or less of the total solid content and the maltose is 65 wt% of the total solid content.
After obtaining the aqueous dextrin containing ~ 80wt% and the balance of maltotriose and maltotetraose and the starch starch aqueous solution as an impurity, a filtration step for removing impurities such as fats and oils, proteins, SS, desalting and decolorization The purification step for carrying out the method and the concentration step for concentrating the solid content to 40 to 70 wt% are carried out at least once each, and the strong starch cation exchange resin is used as a stock solution of the purified starch sugar aqueous solution thus obtained. With the chromatographic separation device described above, the dextrin fraction, the maltose + maltotriose fraction, and the maltotriose content having a molecular weight of maltotetraose or more while distributing glucose to all fractions without separating the glucose fraction are Less than 1 wt% and maltose content 95
A method for producing a starch sugar in which a high-purity maltose fraction of wt% or more is separated into at least three fractions, wherein the maltose +
A starch sugar characterized in that as a maltotriose fraction, a sugar composition is obtained in which the weight ratio of maltose / maltotriose is 1 to 3 and the total content of maltose and maltotriose is 80% by weight or more based on the solid content. Manufacturing method. 3. A chromatographic separation device comprises a plurality of column groups filled with an adsorbent, wherein each column is connected by a fluid passage so as to form an endless series circulation passage and the circulation passage can be disconnected. And a pseudo moving bed type or a form similar thereto, in which the undiluted solution is allowed to flow into the latter stage of the dextrin + maltotriose mixing zone, and the maltotriose + maltose fraction is eluted from the end of the flow path, Without flowing the undiluted solution, the eluent water flows in from the upstream of the maltose zone and the maltose is extracted from its downstream,
Forming a separation zone of maltose, maltotetraose, and dextrin having a molecular weight of maltotetraose or more downstream thereof, and extracting the dextrin from the downstream thereof and intermittently moving the feeding part and the extracting part to the second step in the downstream direction. Holding and repeating one and two steps, maltose fraction, maltose + maltotriose fraction,
And the dextrin fraction having a molecular weight of maltotetraose or higher, to obtain the starch sugar according to claim 1 or 2.