JPH0193597A - Production of multitol - Google Patents

Abstract

PURPOSE:To enable mass production of the title compound of high purity from inexpensive starting materials, by hydrogenating the starch-saccharified product containing maltose, allowing glucoamylase to act on the hydrogenation product to hydrolyze the sugar alcohol, and hydrogenating, before fractionation by chromatography. CONSTITUTION:A starch-saccharified product containing more than 50wt.% of maltose is hydrogenated, then glucoamylase is allowed to act on the hydrogen ated product to hydrolyze sugar alcohols of 3 or more polymerization degree into multitol and glucose. The hydrolyzate is hydrogenated, and the product is subjected to chromatography using a sodium type cation exchange resin as an adsorbent to separate into one fraction rich in multitol and another one rich in sorbitol whereby multitol of high purity is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing maltitol having a DP of 3 or more and having a low oligosaccharide alcohol content.

(Prior Art) Maltitol is a sugar alcohol obtained by hydrogenating maltose.

Many methods have been published in attempts to obtain highly pure maltitol, but they can be broadly classified into the following three methods.

■That is, the first method is, for example, disclosed in Japanese Patent Application Laid-Open No. 57-134498.
As shown in the publication, β-amylase and isoamylase are applied to a starch liquefied liquid obtained by liquefying starch to a low DB (dextrose equivalent) with α-amylase to obtain a maltose-rich saccharified liquid. High purity maltitol is obtained by hydrogenation.

■The second method is disclosed in Japanese Unexamined Patent Publication No. 57-209000, No. 58-23799, No. 60-67ooo,
A method using high-purity maltose obtained by fractionation of a saccharified liquid as shown in Publication No. 62-19210, etc. , hereinafter simply referred to as purity.
) 75-85% of the saccharified liquid is chromatographically fractionated 9 e.g. 93
This method involves obtaining a maltose fraction of % or more and hydrogenating it.

■The third method is as shown in Japanese Patent Application Laid-Open No. 180797, after first liquefying starch milk having a concentration of 25 to 45%, saccharification is performed by selecting II conversion conditions, and the maltose purity is 50 to 80%. % or more of the saccharified liquid. This was hydrogenated, and the purity of maltitol was 87 to 97 in the chromatographic fraction.
．． Highly pure maltitol is obtained by obtaining a 5% sugar alcohol solution, concentrating it, and crystallizing it.

(Problems to be Solved by the Invention) However, the conventional methods have many drawbacks and are not satisfactory as a commercial method for producing high-purity maltitol.

For example, in the case of the first method as disclosed in JP-A-57-134498, it is first necessary to obtain high purity maltose, and for this purpose it is necessary to suppress the DH of starch liquefaction as low as possible. That is, in order to obtain high purity maltose, the liquefaction DE should be 2 or less, preferably D B 0.5.
~1.0 is required.

7. For this purpose, it is necessary to limit the raw material starch to expensive underground starches (potato starch, etc.), and furthermore, it is necessary to lower the liquefaction concentration to 20% or less. This method requires a much larger 111 converter than the equipment used to produce high maltose syrup and glucose syrup, which are produced and sold in large quantities. Furthermore, since a large amount of water is concentrated, there are drawbacks such as an increase in concentration cost.

A further disadvantage is that it requires the use of expensive isoamylase during II conversion.

In summary, the first method has the disadvantage that it uses a limited type of expensive starch for producing high-purity maltitol as the raw material starch, and that it needs to be prepared by a special method. In other words, instead of using cheap high maltose syrup that is produced and sold in large quantities.

Also, Japanese Patent Application Laid-open No. 57-209000, 58-23
No. 799, No. 60-67000.

The second method disclosed in Publication No. 62-19210 has the advantage that starch that is easy to use industrially (such as corn starch, which is ground starch) can be used as raw material starch, but this chromatographic fractionation method teeth.

It separates maltose from glucose and oligosaccharides with a DP of 3 or more, and it is particularly difficult to separate maltose and maltotriose because their molecular weight ratio is small.

For example, FIG. 1 is a graph showing an example of separation of maltose and maltotriose by a column test. This is 3
A sodium type strongly acidic cation exchange resin (Diaion FRK-01, manufactured by Mitsubishi Chemical Industries, Ltd.) was packed in a 00■E column as an adsorbent, the temperature was maintained at 50℃, and maltose and maltotriose were mixed in 1:1. 1 to a concentration of 5
0%, and the 30+wJ is S V (Specifi
c Velocity: This shows the change in the amount of sugar in the effluent when the circulating fluid is passed at a volumetric velocity (ratio of the apparent volume of the filler) of 0.5. As is clear from Figure 1.

The efflux times of maltose and maltotriose are close, and this separation requires a large amount of elution water. Therefore,
Industrially, the cost of concentrating this water is a major problem, and furthermore, glucose in the saccharification solution enters the maltose fraction as it is, reducing the purity of maltose.

On the other hand, the third method disclosed in JP-A No. 61-180797 uses ground starch as the raw material starch, liquefies it,
Saccharification also requires no special operations.

The sugar solution used for fractionation is sorbitol and maltitol.

and a mixture of sugar alcohols with a DP of 3 or more.

In order to extract maltitol as the main component from these, an eight-column chromatography device is used with complicated flow control. Nevertheless, the maltitol solution obtained contains around 8% maltotriitol. DP
Oligosaccharide alcohols of three or more have a very large effect on the crystallization rate of maltitol, which makes the next crystallization step difficult. Furthermore, the calcium-type ion exchanger, which is the adsorbent for the 9 fractions, has significantly different adsorption performance for each sugar component, so the elution water for the 9 fractions is required to be about 5 times that of the raw sugar solution. This causes the disadvantage that the amount of concentration in subsequent steps is significantly increased.

As mentioned above, conventional methods for producing high-purity maltitol have many insufficiencies, and there has been a desire to develop an easier and more economical method for producing maltitol.

The object of the present invention is to provide a new method for producing high-purity maltitol that overcomes these drawbacks.

(Means for Solving the Problems) As a result of extensive research in order to solve the above-mentioned problems, the present inventors used inexpensively available corn starch, etc. as a raw material starch, and also used isoamylase. The present invention has been completed by discovering a method for producing high-purity maltitol economically and easily even without the use of maltitol.

That is, 1 the present invention is sequential.

b) The first step of hydrogenating starch saccharide having a maltose content of 50% by weight or more.

(1) A second step of causing glucoamylase to act on the hydrogenated product to hydrolyze sugar alcohols with a degree of polymerization of 3 or more into maltitol and glucose.

c) A third step of hydrogenating the hydrolyzate.

2) A fourth step in which the hydrogenated product obtained in the third step is separated into a fraction containing maltitol as a main component and a fraction containing sorbitol as a main component by chromatographic fractionation.

It is constructed by implementing the following.

The above-mentioned maltitol fraction can be easily obtained into a powder by purifying and concentrating, drying, and powdering by a known method, or by precipitating crystals and condensing the fraction.

The present invention will be explained in detail below.

First, the starch saccharide used as a raw material in the present invention will be explained.

The saccharified starch may be of any kind as long as the maltose content in the solid content is 50% or more, preferably 65% or more, and can be either one that has been liquefied and saccharified by a method such as boat fishing, or one that has been commercially available. For example, Maltrich (manufactured by Showa Sangyo ■, maltose content 58%).

Eclipse High Maltose (manufactured by Nihon Shokuhin Kako ■, maltose content 72%), etc. can also be used as a raw material. This means that the liquefaction of raw starch to obtain starch saccharide is 20%
It is carried out at a general liquefaction concentration of ~40%, and does not require the use of an enzyme such as iso7-mylase, and uses expensive potato starch, etc., as the raw material starch, which is indispensable to obtain high-purity maltose. It also means that it is not necessary.

Therefore, the raw material starch used to obtain the starch saccharide used as a raw material in the present invention includes, in addition to potato starch, corn starch, horsetail starch, and rice starch.

Common starches such as barley starch and tapioca starch can be used.

Next, each step of the present invention will be explained.

- In the first step, starch saccharide is hydrogenated as a raw material by a known method in a batchwise or continuous manner in the presence of a nickel-based or noble metal-based catalyst to obtain a maltitol solution. The hydrogenation reaction conditions may be any conditions as long as the decomposition of maltose does not occur.1 Usually, the concentration of the sugar solution is 40 to 60%,
Under hydrogen pressure of 20 kg/- or more, preferably 50 to 150 kg/-.

It is preferable to carry out the reaction at a temperature of 100 to 150°C.

The content of unreduced sugar in the maltitol solution does not need to be extremely reduced, and a content of preferably 1% or less, more preferably 0.5% or less is sufficient to obtain the effects of the present invention.

・Second step Maltitol solution is separated from the hydrogenation catalyst if necessary, and if necessary, treated with activated carbon and subjected to a second enzyme treatment.

Enzymes are usually reprinted glucoamylases [e.g. Glucozyme (manufactured by Nagase Seikagaku Co., Ltd.), Glycozyme (manufactured by Amano Pharmaceutical Co., Ltd.], etc.) in a single-dose format or fixed enzymes immobilized by various immobilization methods. The treatment can also be carried out in a continuous manner using a converting enzyme. Of course, commercially available immobilized glucoamylase [BRIM^Camyloglucosida
se (manufactured by Tate & Lyle), etc. can also be used.

The processing conditions are usually a concentration of liquid II of 10 to 60%,
Adjust the 9H to 4 to 7, keep the temperature at 35 to 65°C, and add the above glucoamylase to the solids of the sugar solution at a rate of 0.1 to 1.
．． When using an immobilized enzyme, the sugar solution prepared in the same manner as above is added to a column filled with the immobilized enzyme by s v -o,
This is done by passing the sample at i~5.0.

By this glucoamylase treatment, sugar alcohols with a DP of 3 or higher in the maltitol solution are hydrolyzed into maltitol and glucose. Glucoamylase also acts on maltitol to produce glucose and sorbitol.
This reaction rate is extremely slower than the rate at which sugar alcohols with a DP of 3 or higher are decomposed into maltitol and glucose 1-ose, which is the intention of the present invention. Decomposition is small, and sugar alcohols with a DP of 3 or higher are almost quantitatively converted into maltitol and glucose.

The sugar solution after enzyme treatment generally contains maltitol from 65 to 8
Contains 5%, others include glucose, sorbitol and a small amount of D
The composition consists of a sugar alcohol of P3 or higher. The maltitol content here depends on the maltose and maltotriose contents in the raw material starch saccharification solution, but the extremely advantageous point of the present invention is that this raw material starch saccharification solution is converted into a sugar with a particularly high maltose content. One price is low without being limited to liquids (
Furthermore, a sugar solution with a high maltotriose content that is easy to produce can also be used as a useful raw material.

- Third step The glucose-containing sugar solution obtained by the enzyme treatment is treated with activated carbon if necessary, and then hydrogenated again by a known method. However, since the amount of reducing sugar in this sugar solution is smaller than the starch saccharified solution used as the raw material, the amount of hydrogen used during hydrogenation can be reduced, and hydrogenation can be carried out under milder reaction conditions than in the first step.

This hydrogenation can also be carried out in a 0-batch manner or in a continuous manner.

・Fourth process If necessary, remove the catalyst from the above hydrogenated solution.

Furthermore, if necessary, after treatment with activated carbon, chromatographic fractionation is performed.

Chromatographic fractionation can be carried out batchwise or continuously using various adsorbents by methods known per se. An example of such a romato fractionation method is shown in JP-A-61-180795.

FIG. 3 is a schematic diagram of an example of a fractionation apparatus used in the method of the present invention. In Figure 3, the separation columns, which are the main parts of the fractionation device, are indicated by 10, 20, 30.40. These columns usually contain, for example, sodium type, calcium type,
A salt type cation exchanger such as potassium type or lithium type is filled. As the cation exchanger, various commercially available cation exchange resins or zeolites can be used.

In the fractionation method in the fourth step of the present invention, the sugar component of the maltitol solution subjected to the 9 fractions consists almost only of maltitol and sorbitol, so the sodium type is the most preferable adsorbent among the above salt types. 1 Usually, a sodium type strongly acidic cation exchange resin is used, which is a crosslinked polymer of styrene-divinylbenzene with sulfonic acid groups bonded to it. Fractionation on the sodium type packing side allows the capacity of the separation column to be smaller than the calcium type, and it is possible to fractionate with less eluate water, so the concentration of the nine fractions remains high. It has the advantage of being able to be maintained.

This will be explained with reference to FIG. Figure 2 shows as an adsorbent,
It is a graph comparing the results of a column test using a sodium type and a calcium type. In this test, strongly acidic cation exchange resin (Diaion FRK)
-01. Sodium type and calcium type (manufactured by Mitsubishi Chemical Industries, Ltd.) are used.

These two types of cation exchange resins were each mixed with 300IIIn.

A 1:1 mixture of sorbitol and maltitol with a concentration of 50% was used as a 1-fraction sugar solution packed in separate columns. 30+wj each! was placed in the column, and then water was passed through the column at a flow rate of SVo and 5.

Figure 2 shows the changes in the amount of each sugar in the effluent.

The horizontal axis is scaled to 1.0 at the point where the same amount of effluent as the filler was obtained. According to this figure 2, in the calcium type, the affinity between the adsorbent and sorbitol is strong, so the outflow is extremely slow.
For this reason, a large amount of elution water is required, making economical continuous fractionation impossible.On the other hand, fractionation using a sodium-type adsorbent has a rapid outflow and has very little tailing; Separation can be carried out using only 115 times the amount of eluate water compared to the fraction. The fact that fractionation is possible with a small amount of elution water means that nine fractions can be obtained at high concentrations, which reduces the cost of concentration in the subsequent step and requires a large amount of It brings economic benefits.

Furthermore, by selecting the fractionation parameters, a maltitol fraction with desired maltitol purity can be obtained from one raw material. Further, the sorbitol fraction can be efficiently utilized as a raw material for producing maltitol by refractionation, or as a commercial product as it is.

This maltitol liquid is purified and concentrated using well-known methods.
It can be made into a liquid product as it is, or it can be further concentrated and powdered to make a powdered maltitol product.

Various methods can be used for powdering, such as spray granulation, Niguu method, fluidized granulation, block pulverization, and crystallization granulation.1 The maltitol liquid according to the present invention is Since it contains only a small amount of oligosaccharide alcohol with a DP of 3 or higher, which is considered to be the biggest inhibitor of crystallization, the crystallization rate is fast and it can be easily ground into a powder by any method.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example 1 Corn starch was liquefied by a known method to obtain a liquefied DBS solution, and further saccharified by a known method to obtain a saccharified solution.

The analysis results of the sugar component by liquid chromatography were as follows.

Glucose 0.4% maltose
77.4% maltotriose
8.9% Oligosaccharides with DP4 or higher 13.3% 1st
Step (1st hydrogenation step) The saccharified liquid obtained above was concentrated to a concentration of 50%.

The 400 kg and 4 kg of Raney nickel catalyst were placed in an autoclave with an internal volume of 50 (liters), and the hydrogen pressure was increased to 120 kg.
g/- and stirred at 120° C. for 2 hours to perform hydrogenation. After separating the resulting liquid from the catalyst.

A maltitol solution was obtained through a column of granular activated carbon. When this was analyzed by liquid chromatography, the results were as follows.

Glucose 0.2% Sorbitol 1.5% Maltitol
77.0% maltotriitol
8.7% Oligosaccharide alcohol with a DP of 4 or more 12.6% 2nd step (enzyme treatment step) The above maltitol solution was treated with an enzyme by the following method.

Glucoamylase (BRIMACas+yloglucosidas) immobilized on a stainless steel column with an internal volume of 51
(manufactured by Tate & Lyle)) and the temperature was maintained at 55°C. The maltitol solution in the first step was adjusted to pH 4.5 with acetic acid and passed through the column at SV 2.0. The analysis results of sugar components of the effluent by liquid chromatography were as follows.

Glucose 11.3% Sorbitol 1.8% Maltitol
85.6% maltotriitol
1.0% DP4 or higher oligosaccharide alcohol 0.3% Third step (second hydrogenation step) The above enzyme-treated sugar solution was continuously hydrogenated again using a fixed bed catalyst. The catalyst used was ruthenium supported on activated carbon, which was packed into a continuous autoclave with an internal volume of 5J, and hydrogenation was carried out by flowing the enzyme-treated sugar solution and hydrogen in countercurrent while maintaining the temperature at 120°C. . The results of liquid chromatography analysis of sugar components after rehydrogenation were as follows.

Glucose 0.2% Sorbitol 13.2% Maltitol
85.5% DP3 or higher oligosaccharide alcohol 1.1% 4th step (fractionation step) Continuous separation by chromatographic fractionation of the above-mentioned sugar solution containing maltitol and sorbitol as main components was carried out in US Pat. No. 426
The method shown in Example 4 of No. 7047.

That is, a four-column method for fractionating fructose and glucose was modified to be suitable for fractionating the above-mentioned sugar solution.

Figure 3 shows the structure of columns and piping. In Figure 3, 40, 30, 20, and 10 are separation columns, and each column is filled with a strongly acidic cation exchange resin in the sodium form [Diaion F12]. -01 (Mitsubishi Chemical Industries special product))
? The temperature inside the column was kept at 70℃.
Ta. R is the entrance of the fractionated raw material sugar solution obtained in the third step, W
is an inlet for elution water, A is a reservoir for the maltitol fraction, and B is a reservoir for the sorbitol fraction. Also 12,52.62
is a preset flowmeter, 13.17 is a circulation pump, 11, 21.31.41 are filters, and the others are valves for flow path control.

The apparatus shown in FIG. 3 was operated in the order of steps listed in Table 1 below.

(Left below) In other words, in the order of the steps shown in Table 1, the indicated valves open, the raw sugar solution and water flow into the specified column, and at the same time the maltitol fraction and sorbitol fraction flow out, and the flow meter 5
2.62 finishes counting the predetermined flow rate and then automatically moves to the next step. In steps 3, 6.9 and 12, all four towers are connected and 1w1 ring pump 17
The metal bodies inside the tower are circulated. After the flow meter 12 has counted a predetermined flow rate, the process proceeds to the first step, and the process repeats from step 12 to step 1. One cycle took approximately 2 hours.

The results after 24 hours of continuous operation are shown in Table 2 below.
It was efficiently fractionated at a concentration of

(Left below) The maltitol fraction obtained in the fourth step is purified and concentrated by a conventional method.2 For example, the spray granulation method.

It could be easily powdered by a powdering method such as the Niguu method, fluidized granulation method, block pulverization method, or crystallization separation method.

Example 2 Corn starch was liquefied to DE12 using a known method, and then saccharified using a known method to obtain a saccharified liquid.

Its sugar composition was as follows.

Glucose 0.5% maltose
64.4% maltotriose 1
8.7% DP4 or higher oligo $)! 16.4%
This saccharified liquid was treated in the same manner as in the first to third steps of Example 1. The sugar composition of the sugar solution at the end of each step is shown in Table 3 below.

(Margin below) The hydrogenated solution obtained in the third step was fractionated by the following method.

A single crop was produced in the same manner as in the fourth step of Example 1, except that the preset flow rate of the flowmeter in the fourth step of Example 1 was changed as shown in Table 4 below.

(Left below) The amount of eluate water required for this fractionation could be reduced by 20% compared to Example 1, and a larger amount of hydrogenated solution could be processed. The results are shown in Table 5 below.

(Margin below) The maltitol purity of this maltitol fraction is 92.2%
The concentration of maltitol fraction was increased to 33%.

(Effects of the Invention) According to the method for producing maltitol of the present invention, a sugar solution produced by the conventional liquefaction and saccharification method for producing starch syrup or glucose using easily available starch as the raw material starch This is because maltitol of desired purity can be obtained by selecting the fractionation parameters.

It will become possible to supply a large amount of low-priced maltitol.

The fractionation method in the fourth step of the present invention requires an extremely small amount of elution water compared to conventional methods. Fractionation can be carried out using the following amounts of elution water, and the decrease in concentration of each fraction due to two fractions is extremely small.

[Brief explanation of the drawing]

Figure 1 is a graph showing an example of a separation test of maltose and maltotriose. It is. FIG. 2 is a graph comparing the salt types of adsorbents conducted under the same test conditions as in FIG. 1, using sorbitol and maltitol as raw sugars. FIG. 3 is an example of a schematic diagram of columns and piping of the chromatographic fractionation apparatus used in the present invention. Patent Applicant: Towa Kasei Kogyo Co., Ltd. Agent: Futoshi Hitoshi 1) Megumi - Figure 1 ■ = Outflow production volume (*Q vR: ItlllglFll (*/) Figure 3

Claims (1)

[Scope of Claims] 1 a) A first step of hydrogenating starch saccharide having a maltose content of 50% by weight or more. b) A second step of causing glucoamylase to act on the hydrogenated product to hydrolyze the sugar alcohol with a degree of polymerization of 3 or more into maltitol and glucose. c) A third step of hydrogenating the hydrolyzate. D) A fourth step of separating the hydrogenated product obtained in the third step into a fraction containing maltitol as a main component and a fraction containing sorbitol as a main component by chromatographic fractionation. A method for producing maltitol, characterized by passing through the above four steps. 2. The production method according to claim 1, wherein the maltitol purity of the fraction containing maltitol as a main component is 87% or more based on solid matter. 3. The manufacturing method according to claim 1, wherein the adsorbent used for chromatographic fractionation is a sodium type cation exchanger.