JP3089146B2 - Method for producing starch sugar - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a high purity maltose fraction, a maltotriose + maltose fraction and at least three fractions of dextrin having a molecular weight of maltotetraose or higher, simultaneously using a chromatographic separation apparatus 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 starch syrup obtained by saccharifying starch can obtain a saccharified solution having a high maltose content due to the development of an enzymatic saccharification method. However, glucose, maltotriose, etc. It contains a large amount of dextrin having a molecular weight higher than maltotetraose as an impurity. Conventionally, a method of purifying high-purity maltose by separating and removing these impurities by using a chromatographic separation method has been studied. Japanese Patent Application Laid-Open No. 57-209000 discloses a method for purifying by chromatographic separation using a Na-type cation exchange resin as a filler.
JP, JP-B-61-51120 and JP-A-60-670
No. 00 discloses a method for purifying maltose by simulated moving bed chromatography separation. They are classified into the following two.

[0003] "Oligosaccharides having a molecular weight of maltotriose or higher", "maltose", and "glucose" were selected as ones to be separated out of the chromatographic system by using a one-pass method or a chromatographic separation method using a circulation method and being extracted out of the chromatographic system. (Example 2 of JP-A-57-209000 and JP-A-4-227804)

[0004] Using a simulated moving bed system, the oligosaccharides are divided into "oligosaccharides having a molecular weight higher than maltotriose" and "maltose and glucose" (Japanese Patent Application Laid-Open No. 60-67000).

[0005]

When the saccharified solution is subjected to chromatographic separation using a column containing a strongly acidic cation exchange resin as a packing material, dextrin having a molecular weight of maltotetraose or higher usually flows out first. And then elute in the order of maltotriose, maltose and glucose.

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

In the table, the degree of separation (Rs) indicates the ease of separation of component A and component B. Larger ones are easier to separate.

As is apparent from the above, the degree of separation between maltose and glucose is about 0.55, which is relatively easy to separate, whereas the degree of separation between 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 pharmaceuticals, crystallization is attempted to improve purity, but in this case, maltotriose removal rate is lower than glucose, and in purification in chromatographic separation,
It was necessary to remove maltotriose as much as possible, and it was very difficult to obtain high-purity maltose for pharmaceutical use from a saccharified solution called maltose containing maltotriose by a conventional method. . The present inventors have studied to perform this separation efficiently. In recent years, it has been found that the taste differs depending on the sugar composition ratio. In the oligosaccharide field, which has been conventionally prepared using starch syrup, attempts have been made to obtain a useful sugar mixture by selecting the composition ratio of each sugar.

The present inventors have found that, among them, a sugar containing maltose and maltotriose as main components and having a maltose / maltotriose ratio of 1 to 3 and a total of maltose and maltotriose of 80% or more with respect to the solid content. The composition was found to be excellent in taste retention and the like, and to be excellent as sweeteners for pastes, soft drinks and the like. These sugar compositions cannot be efficiently produced by a conventional production method using an enzyme technique, and have been studied so as to be easily produced by the method of the present invention.

[0011]

The present invention uses the following three chromatographic separation methods using chromatographic separation with a strongly acidic cation exchange resin by intentionally distributing glucose to each compartment in separating a starch saccharified solution. Compartment: Component 1: dextrin having a molecular weight of maltotetraose or more (G4 ⁺ fraction) Component 2: sugar composition containing maltose and maltotriose as main components and having a maltose / maltotriose ratio of 1 to 3 ( (G3 + G2 fraction)-Component 3: easily obtains "sugar composition having maltose and maltotriose as main components and a maltose / maltotriose ratio of 1 to 3 which is 1 to 3" by separating into maltose (G2 fraction). While being able to
Since the mixed region of maltotriose and maltose can be effectively extracted, the maltotriose content in the “maltose” section could be reduced.

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

In the present invention, the reason that the glucose content in the stock solution is 4 wt% or less of the total solid content is that if it exceeds 4 wt%, the glucose content in the maltose fraction becomes too large, and it is not good. The maltose content in the stock solution was 65-80 wt% of the total solids because the maltose content was
This is because high purity maltose cannot be obtained if the stock solution is less than 65 wt%, and the economic effect is small if the stock solution exceeds 80 wt%. Next, the solid content concentration of the purified starch sugar stock solution to be separated by the chromatographic separation apparatus 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, resulting in 70 wt% This is because the method of the present invention cannot be carried out with a stock solution exceeding the above.

Although the glucose component in the stock solution is mixed in the maltose section, the glucose content can be easily reduced by the saccharification method, and the composition can be easily reduced in the subsequent crystallization step. Velocity of the substance between the "part" and the "maltose extraction part" (Um)
The relationship between the apparent moving speed (Us) of the packed bed is expressed by Um
(Glucose) <Us <Um (maltose) It was found that glucose in the maltose section could be reduced.

As the chromatographic separation apparatus used in the present invention, various types of equipment conventionally proposed can be used, but it is necessary to use an apparatus which 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, or the load is small and the production becomes low, making production impossible from an economical viewpoint.

[0016]

According to the present invention, there is an apparatus developed by the applicants as a chromatographic separation apparatus capable of efficiently separating three or more fractions by one operation and proposed in Japanese Patent Application Laid-Open No. 4-227804. Although the performance is somewhat reduced, the three-component separation method using a circulation method (JP-A-56-92127 and JP-A-63-158105) can be 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 with reference to examples, but the present invention is not limited to the following examples unless 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 chromatograph separation apparatus.

In FIG. 2, reference numerals 1 to 12 denote unit packed beds each filled with the same adsorbent, and the unit packed beds are connected by pipes so that fluid can flow therethrough.
The rear end of the last packed layer 12 is connected to the front end of the first unit packed layer 1. Reference numeral 14 denotes a circulation pump provided on the channel between the unit packed bed 12 and 1. 13 is the unit packed bed 6
And a shut-off valve provided in the connecting pipe between 7 and 7, which is controlled to open and close by a control device (not shown). On the downstream side of the unit packed layer 6, an outlet 6a for the component A (dextrin fraction), an outlet 6b for the component B (maltose + maltotriose fraction) and an outlet 6 for the component C (maltose fraction).
c, and an inlet 7 f for the undiluted solution and an inlet 7 d for the eluent are provided upstream of the unit packed layer 7. An extraction port a for component A and an extraction port c for component C are provided downstream of the unit packed bed other than 6, and an inlet d for eluent is provided upstream 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 shown above, this figure is an example of a schematic configuration of a chromatographic separation apparatus provided for carrying out the method of the present invention. In place of the apparatus shown in this figure, a circulating 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 and the simulated moving bed device. The equipment shown in FIG.
Although used for 12 unit packing layers, the number of the unit packing layers is “G2 section” (maltose fraction) and “G2 + G3 section”.
Needless to say, the ratio can be changed depending on the ratio of (maltose + maltotriose fraction), the respective purity, and the target value of the recovery rate.

Example 1 In the production process shown in FIG. 1, corn starch was used as a raw starch, α-amylase was used as a liquefaction enzyme, liquefied to DE2, and saccharified with pullulanase and β-amylase to give an aqueous starch sugar solution. This solution was desalted and decolorized using activated carbon and an ion exchange resin, and then concentrated to obtain an undiluted solution for chromatography. This was subjected to chromatographic separation using the chromatographic separation equipment shown in FIG. 2 in the operation steps shown in Table 2 to obtain fractionated liquids shown in Table 3.

The apparatus shown in FIG. 2 uses 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.
In addition, 12 inner diameters of 108.3 mm connected in series, packed bed height of 1200
133 liters of adsorbent is packed in a packed bed of
The separation operation was repeated while maintaining the temperature. In this separation experiment, “G4 ⁺ ” was obtained from the A-section extraction valve (1a to 12a).
(Dextrin) as a main component, a fraction mainly composed of “G2 + G3” (maltose + maltotriose) from the B-section extraction valve (6b), and “High-purity G2” ( (Maltose) fraction is extracted. The flow rates in each step of the chromatographic separation are as follows.

Flow rate in step 1 Supply flow rate of raw material liquid 27.1 L / h Supply flow rate of elution 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 Supply flow rate of eluent water 21.3 L / h G4 ⁺ fraction extraction flow rate 15.0 L / h G2 fraction extraction flow rate 6.3 L / h G2 extraction section and G4 ⁺ extraction section Liquid flow rate 55.2 L / h

The results are shown in Table 3. High purity maltose and maltose + maltotriose could be easily obtained. In this example, there is no G1 (glucose) classification,
Are divided into a G4 ⁺ section, a G3 + G2 section, and a G2 section. As a result, the G2 content of the G2 section (maltose section) can be increased, and the G1 content can be reduced.

[0025]

[Table 2]

[0026]

[Table 3]

(Comparative Example 1) As a conventional method, "oligosaccharides having a molecular weight of maltotriose or more", "maltose", and "glucose" were selected as materials to be extracted out of the chromatographic system, and operated under the following flow conditions. The equipment used was the same as in Example 1, and the opening and closing of the 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 eluent 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 Supply flow rate of elution water 29.6 L / h G4 ⁺ fraction extraction flow rate 21.3 L / h G2 fraction extraction flow rate 8.3 L / h G2 extraction section and G4 ⁺ extraction section Liquid flow rate 55.2 L / h

Table 5 shows the experimental results. It can be seen that the G2 content of the G2 category is high. In this example, the classification of G3 and above and G2
And G1. However, the content of G3 (maltotriose) in the G2 (maltose) category becomes large, and the content of G2 becomes insufficient. Therefore, in this example, it is difficult to obtain a pharmaceutical grade maltose.

[0031]

[Table 4]

[0032]

[Table 5]

(Comparative Example 2) "Dextrin having a molecular weight of maltotetraose or higher", "maltotriose + maltose", and "maltose + glucose" were extracted out of the chromatographic system using the same equipment and stock solution as in Example 1. The operation was performed under the following flow 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 elution 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 Supply flow rate of eluent water 22.3 L / h G4 ⁺ fraction extraction flow rate 14.1 L / h G2 fraction extraction flow rate 8.1 L / h Filling between G2 extraction part and G4 or more extraction part Liquid flow rate in layer 55.2 L / h

Table 7 shows the experimental results. It can be seen that the G1 content of the G2 category is high. In this example, G2 (maltose) is divided into G1 (glucose) by the extraction method.
Since G1 is included in a large amount in the category, the G2 + G1 category naturally has a high glucose content and an insufficient G2 content.

[0037]

[Table 6]

[0038]

[Table 7]

[Brief description of the 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 structural diagram showing an example of a three-component separation chromatograph used in the method of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-108356 (JP, A) JP-A-60-67000 (JP, A) JP-B-63-64200 (JP, B2) (58) Field (Int.Cl. ⁷ , DB name) C13K 7/00 A23L 1/09

Claims (3)

(57) [Claims] 1. A starch is liquefied and saccharified to have a glucose content of not more than 4% by weight of the total solids and maltose to be 65% by weight of the total solids.
After obtaining a dextrin having a molecular weight of at least 80% by weight and a balance of maltotriose or maltotetraose or more and an aqueous solution of starch sugar as an impurity, a filtration step for removing impurities such as oils and fats, proteins, and SS, desalting and decolorization And a concentration step of concentrating the solid content concentration to 40 to 70 wt% at least once each. The purified starch sugar aqueous solution thus obtained is used as a stock solution, and a strongly acidic cation exchange resin is adsorbed. A dextrin fraction having a molecular weight of maltotetraose or more, a maltose + maltotriose fraction and a maltotriose content while distributing the glucose to all fractions without separating the glucose fraction by a chromatographic separation apparatus having Is less than 1 wt% and maltose content is 95
at least 3 of high purity maltose fraction of wt% or more
A method for producing starch sugar, comprising obtaining a fraction. 2. The starch is liquefied and saccharified to have a glucose content of 4% by weight or less of the total solids and maltose to 65% by weight of the total solids.
After obtaining a dextrin having a molecular weight of at least 80% by weight and a balance of maltotriose or maltotetraose or more and an aqueous solution of starch sugar as an impurity, a filtration step for removing impurities such as oils and fats, proteins, and SS, desalting and decolorization And a concentration step of concentrating the solid content concentration to 40 to 70 wt% at least once each. The purified starch sugar aqueous solution thus obtained is used as a stock solution, and a strongly acidic cation exchange resin is adsorbed. A dextrin fraction having a molecular weight of maltotetraose or more, a maltose + maltotriose fraction and a maltotriose content are obtained by distributing glucose to all fractions without separating the glucose fraction by a chromatographic separation apparatus. Not more than 1 wt% and maltose content of 95
The method for producing starch sugar, wherein at least 3 fractions of a high-purity maltose fraction of not less than wt% are separated, wherein the maltose +
A starch sugar, wherein a maltose / maltotriose weight ratio of 1 to 3 is obtained as a maltotriose fraction and a total sugar content of maltose and maltotriose is 80% by weight or more based on the solid content. Manufacturing method. 3. A chromatographic separation apparatus is a plurality of column groups packed with an adsorbent, so that each column can be connected to and shut off the circulation passage so as to form the circulation flow path of the endless series by fluid passages A simulated moving bed type or a form similar thereto, in which a stock solution flows into the latter stage of a dextrin + maltotriose mixed zone, and a maltotriose + maltose fraction is eluted from the end of the flow channel; , Without flowing the undiluted solution, eluted water flows in from the upstream of the maltose zone, and extracts maltose from the downstream,
A second step of forming a separation zone of maltose, maltotetraose and dextrin having a molecular weight of maltotetraose or more downstream thereof, extracting the dextrin from the downstream thereof, and intermittently moving the supply unit and the extraction unit downstream in the downstream direction. And maltose fraction, maltose + maltotriose fraction by repeating one and two steps,
3. The method for producing starch sugar according to claim 1, wherein a dextrin fraction having a molecular weight of maltotetraose or higher is obtained.