JP2622695B2 - Maltitol manufacturing method - Google Patents

Description

The present invention relates to a method for producing maltitol having a low oligosaccharide alcohol content of DP3 or higher.

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

A number of methods have been reported for attempts to obtain high-purity maltitol, but they are broadly classified into the following three methods.

That is, the first method is, for example, as described in JP-A-57-134498, in which starch is reduced with α-amylase to low DE.
Β-amylase and isoamylase are allowed to act on a liquefied starch liquefied liquid (dextrose equivalent) to obtain a saccharified saccharified solution containing maltose, which is hydrogenated to obtain high-purity maltitol.

The second method is disclosed in JP-A-57-209000 and JP-A-58-2379.
No. 9, No. 60-67000, No. 62-19210, etc., using a high-purity maltose obtained by fractionation of a saccharified solution as a raw material, that is, a method having a low glucose content, Maltose purity (indicated by weight% per solid matter; hereinafter simply referred to as purity) 75-85% of saccharified solution is chromato-fractionated, for example, 93% or more maltose fraction is obtained and hydrogenated. .

As a third method, as disclosed in JP-A-61-180797, starch milk having a concentration of 25 to 45% is first liquefied, saccharification conditions are selected and saccharification is performed, and maltose purity is 50 to 80. %
The above saccharified solution is obtained. This is hydrogenated, and a sugar alcohol solution having a maltitol purity of 87 to 97.5% is obtained by chromatographic fractionation, followed by concentration and crystallization to obtain maltitol of the same purity.

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

For example, in the case of the first method as disclosed in Japanese Patent Application Laid-Open No. 574-134498, it is necessary to obtain high-purity maltose first, and for that purpose, it is necessary to minimize the DE of starch liquefaction as much as possible. That is, in order to obtain high purity maltose, the liquefied DE is required to be 2 or less, preferably 0.5 to 1.0. For this purpose, it is necessary to limit the raw material starch to expensive underground starch (such as potato starch) and further reduce the liquefaction concentration to 20% or less. This method requires a very large saccharification apparatus as compared to the apparatus used for producing high-maltose syrup and glucose syrup which are produced and sold in large quantities. In addition, since a large amount of water is concentrated, there is a disadvantage that the cost of concentration is increased.

Furthermore, there is a disadvantage that the use of expensive isoamylase is required for saccharification.

In short, the first method has a drawback in that it is necessary to use expensive starch of a type limited to the production of high-purity maltitol as a raw starch and to prepare it by a special method. In other words, it is difficult to use inexpensive high-maltose syrup that is produced and sold in large quantities.

Further, the second method disclosed in JP-A-57-209000, JP-A-58-23799, JP-A-60-67000, JP-A-62-121010, etc. uses starch (e.g. Corn starch, which is an above-ground starch, also has the advantage that it can be used as a raw starch, but this chromatographic fractionation method separates maltose from glucose and oligosaccharides with DP3 or higher, especially maltose and maltotriose. Is difficult to separate because the 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
A 300 ml column is filled with a sodium-type strongly acidic cation exchange resin (Diaion FRK-01, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) as an adsorbent, and the temperature is kept at 50 ° C., and maltose and maltotriose are mixed at 1:50. This shows the change in the amount of sugar in the effluent when 30 ml of the mixture mixed with 1 was passed at an SV (Specific Velocity: the ratio of the volume velocity of the circulating fluid to the apparent volume of the packing material) of 0.5. It is a thing.
As is apparent from FIG. 1, the outflow times of maltose and maltotriose are close, and this separation requires a large amount of eluted water. Therefore, the cost of concentrating this water is a major problem industrially, and furthermore, glucose of the saccharified solution enters the maltose fraction as it is, which has the disadvantage of reducing the purity of maltose.

On the other hand, Japanese Patent Application Laid-Open No.
In this method, ground starch can be used as raw material starch, and liquefaction and saccharification do not require any special operation. However, the sugar solution used for fractionation is a mixture of sorbitol, maltitol, and a sugar alcohol of DP3 or higher. In order to extract maltitol as a main component from the inside, an eight-column type chromatographic apparatus is used in an extremely complicated flow rate operation. Nevertheless, the resulting maltitol solution contains about 8% maltotriitol. Oligosaccharide alcohols above DP3 have a very significant effect on the crystallization rate of maltitol, which makes the next crystallization step difficult. In addition, calcium-type ion exchangers, which are adsorbents for fractionation, have remarkably different adsorption capacities for each saccharide component. ,
This has the disadvantage of significantly increasing the enrichment in subsequent steps.

As described above, the conventional method for producing high-purity maltitol has many inadequacies, and it has been desired to develop an easy and economical method for producing maltitol. An object of the present invention is to provide a new method for producing high-purity maltitol which overcomes these disadvantages.

(Means for Solving the Problems) The present inventors have conducted intensive studies in order to solve the above problems, and as a result, using corn starch or the like which is available at a low cost as a raw material starch and using isoamylase. Even without this, a method for economically and easily producing high-purity maltitol was found, and the present invention was completed.

That is, the present invention sequentially comprises a) a first step of hydrogenating a starch saccharified product having a maltose content of 50% by weight or more, b) a glucoamylase acting on the hydrogenated product to give a degree of polymerization of 3 or more. A second step of hydrolyzing the sugar alcohol to maltitol and glucose, c) a third step of hydrogenating the hydrolyzate, d) converting the hydrogenated product obtained in the third step to maltitol mainly by chromatographic fractionation. And a fourth step of separating into a fraction containing sorbitol as a main component and a fraction containing sorbitol as a main component.

A powder can be easily obtained by purifying and concentrating the above-mentioned maltitol fraction by a known method, drying and pulverizing, or precipitating and separating crystals.

 Hereinafter, the present invention will be described in detail.

First, the saccharified starch used as a raw material in the present invention will be explained. Any saccharified starch may be used as long as the maltose content in the solid content is 50% or more, preferably 65% or more. Liquefied or saccharified with a conventional commercial product [for example, Maltrich (manufactured by Showa Sangyo Co., Ltd., maltose content: 58%), eclipse high maltose (Nihon Shokuhin Kako Co., Ltd., maltose content: 72%) %) Can also be used as a raw material. This means that the liquefaction of the raw starch to obtain the starch saccharified product is carried out at a general liquefaction concentration of 20 to 40%, and the use of enzymes such as isoamylase is not required.
Further, it also means that it is not necessary to use expensive potato starch or the like, which was indispensable for obtaining high-purity maltose, as a raw material starch. Accordingly, the raw material starch used for obtaining the starch saccharified product used as the raw material in the present invention is not limited to potato starch, but also common starches such as corn starch, potato starch, rice starch, wheat starch, tapioca starch and the like. Available.

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

First step A starch saccharified product is hydrogenated in a batch or continuous manner by a known method in the presence of a nickel or noble metal catalyst to form a maltitol solution. The hydrogenation reaction condition may be any condition as long as maltose does not decompose. Usually, the concentration of the sugar solution is 40 to 60%, and the
g / cm ² or more, preferably under a hydrogen pressure of 50 to 150 kg / cm ² ,
It is preferable to carry out at a temperature of up to 150 ° C. It is not necessary to extremely reduce the amount of unreducing sugar in the maltitol solution, and preferably 1% or less, more preferably 0.5% or less, is sufficient for obtaining the effects of the present invention.

・ Second step The maltitol solution separates the hydrogenation catalyst if necessary,
Activated carbon treatment is performed if necessary, and the following enzyme treatment is performed.

The enzyme is usually a commercially available glucoamylase [eg, glucozyme (manufactured by Nagase Seikagaku Co., Ltd.), glycozyme (manufactured by Amano Pharmaceutical Co., Ltd.), etc.], in a batch system or by various methods of immobilizing the enzyme. The treatment can also be performed in a continuous manner using the immobilized immobilized enzyme. Of course, commercially available immobilized glucoamylase [BRIMAC amyloglucosidase (Tat
e & Lyle) etc.] can also be used.

The treatment conditions are usually a sugar solution concentration of 10 to 60% and a pH of 4
Adjust the temperature to 35 to 65 ° C, add the above glucoamylase to the solid of the sugar solution at 0.1 to 1.0%, and add 12 to 7
Perform by gentle stirring for 2 hours. When the immobilized enzyme is used, the sugar solution prepared as described above is passed through a column filled with the immobilized enzyme at SV = 0.1 to 5.0.

By this glucoamylase treatment, sugar alcohols of DP3 or higher in the maltitol solution are hydrolyzed to maltitol and glucose. Glucoamylase also acts on maltitol to produce glucose and sorbitol,
Since this reaction rate is much slower than the rate at which sugar alcohols of DP3 or more intended by the present invention are decomposed into maltitol and glucose, the decomposition of multilol is small unless glucoamylase and maltitol solution are contacted more than necessary. Thus, sugar alcohols with DP3 or higher are almost quantitatively converted to maltitol and glucose.

The sugar solution after enzyme treatment generally contains maltitol at 65-85.
% Glucose, sorbitol and a small amount of DP3
A composition comprising the above sugar alcohol is obtained. The content of maltitol here depends on the content of maltose and maltotriose in the raw starch saccharified solution, and the extremely advantageous point of the present invention is that the raw starch saccharified solution is obtained by converting the raw starch saccharified solution into a sugar having a high maltose content. Without limiting to a liquid, a sugar liquid having a high maltotriose content, which is inexpensive and easy to produce, can also be used as a useful raw material.

-Third step The sugar solution containing glucose 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 that of the raw starch saccharified solution, the amount of hydrogen used during hydrogenation can be reduced, and hydrogenation can be performed under milder reaction conditions than in the first step. This hydrogenation can be carried out either batchwise or continuously.

-Fourth step The above-mentioned hydrogenated solution is subjected to chromatographic fractionation after removing the catalyst if necessary, and, if necessary, after treatment with activated carbon.

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

FIG. 3 is a schematic view of one example of a fractionating apparatus used in the method of the present invention. In FIG. 3, the separation columns, which are the main parts of the fractionation apparatus, are designated by 10, 20, 30, and 40. Usually, these columns are packed with, for example, salt type cation exchangers of sodium type, calcium type, potassium type and lithium type sugar. 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 to be subjected to the fractionation consists almost exclusively of maltitol and sorbitol. Usually, a sodium type of a strongly acidic cation exchange resin in which a sulfonic acid group is bonded to a crosslinked polymer of styrene-divinylbenzene is used. Fractionation with sodium-type packing material can reduce the capacity of the separation column compared to calcium-type packing material, and it is possible to fractionate with even less eluted water. It has the advantage that it can be kept.

This will be described with reference to FIG. FIG. 2 is a graph comparing the results of column tests when using a sodium type and a calcium type as an adsorbent. In this test, a strongly acidic cation exchange resin (Diaion FR
K-01, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.). 300 ml of each of these two types of cation exchange resins were packed in separate columns, and a 1: 1 mixture of sorbitol and maltitol with a concentration of 50% was used as a fractionated sugar solution. Put 30 ml of each into a column, then
Water was flowed at a flow rate of SV 0.5. FIG. 2 shows the change in the amount of each sugar in the effluent, and the abscissa plots the point at which the same amount of effluent as the filler was obtained at 1.0. According to FIG. 2, the calcium type has a strong affinity between the adsorbent and sorbitol, so the outflow is extremely slow, and a large amount of eluted water is required, so that economical continuous fractionation cannot be performed. On the other hand, fractionation with the sodium-type adsorbent has a rapid outflow and very little tailing, so that separation can be performed using only 1/5 of the amount of eluted water as compared with fractionation with the calcium-type. The fact that fractionation is possible with such a small amount of elution water means that fractionated fractions can be obtained at a high concentration, which reduces the cost of enrichment in the subsequent steps and increases the cost. It brings economic benefits.

Further, by selecting a fractionation parameter, a maltitol fraction having a desired maltitol purity can be obtained from one raw material. The sorbitol fraction can be efficiently used as a raw material for producing maltitol by refractionation or as it is as a commercial product.

This maltitol solution can be purified and concentrated by a well-known method, and can be directly converted into a liquid product, or further concentrated and powdered to obtain a powdered maltitol product.

Various methods such as a spray granulation method, a kneader method, a flow granulation method, a block pulverization method, and a crystal honey separation method can be used as a powdering method. Since it contains only a small amount of oligosaccharide alcohol of DP3 or more, which is considered to inhibit the crystallization most, the crystallization speed is high and the powder state can be extremely easily obtained by any method.

(Examples) Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 Corn starch was liquefied by a known method to give DE5 and a liquefied liquid, and saccharified by a known method to obtain a saccharified liquid.

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 more 13.3% ・ First step (first hydrogenation step) Concentrate the saccharified solution obtained above to 50% and concentrate it to 400k
g and 4 kg of Raney nickel catalyst were charged into an autoclave with a capacity of 500, and the hydrogen pressure was kept at 120 kg / cm ² at 120 ° C.
The mixture was stirred for an hour and hydrogenated. After separating the obtained liquid from the catalyst, a maltitol liquid was obtained through a column of activated carbon on granules. This was analyzed by liquid chromatography, and the results were as follows.

Glucose 0.2% Sorbitol 1.5% Maltitol 77.0% Maltotriitol 8.7% Oligosaccharide alcohol with DP4 or more 12.6% ・ Second step (enzyme treatment step) The above maltitol solution was treated with an enzyme by the following method.

A stainless steel column having an inner volume of 5 was filled with immobilized glucoamylase [BRIMAC amyloglucosidase (manufactured by Tate & Lyle)], and the temperature was kept at 55 ° C. The maltitol solution of the first step was adjusted to pH 4.5 with acetic acid and passed through the column with SV 2.0. The analysis results of sugar components by effluent liquid chromatography were as follows.

Glucose 11.3% Sorbitol 1.8% Maltitol 85.6% Maltotriitol 1.0% Oligosaccharide alcohol with DP4 or more 0.3% ・ Third step (second hydrogenation step) Continuously use the above enzyme-treated sugar solution as it is using a fixed bed catalyst Hydrogenated again. The catalyst used was ruthenium supported on activated carbon. This was filled in a continuous autoclave with an internal volume of 5, and hydrogenation was performed by flowing the enzyme-treated sugar solution and hydrogen in countercurrent while maintaining the temperature at 120 ° C. . The results of analysis of the sugar components after rehydrogenation by liquid chromatography were as follows.

Glucose 0.2% Sorbitol 13.2% Maltitol 85.5% Oligosaccharide alcohol with DP3 or more 1.1% ・ Fourth step (fractionation step) Continuous separation of the sugar solution containing maltitol and sorbitol as main components by chromatographic fractionation US Patent 4267
The method shown in Example 4 of No. 054, that is, the method of fractionating fructose and glucose in a four-column system was modified and used so as to be suitable for the fractionation of the above-mentioned sugar solution.

FIG. 3 shows the configuration of the column and the piping. In FIG. 3, reference numerals 40, 30, 20, and 10 denote columns for separation, each of which is a strongly acidic cation exchange resin (Diaion FRK-01 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)) in the form of sodium. And the temperature inside the column was kept at 70 ° C. R is the inlet of the fraction raw material liquor obtained in the third step, W is the inlet of the elution water, A is the maltitol fraction, B is the sorbitol and the receiving tank for the fraction. Also, 12, 52 and 62 are preset flow meters, and 13, 17
Is a circulation pump, 11,21,31,41 are filters,
Others show valves for flow control.

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

That is, in the order of the steps shown in Table 1, the indicated valves are opened, and the raw sugar solution and water flow into the predetermined column, and at the same time, the maltitol fraction and the sorbitol fraction flow out, and the flow meter is used.
After the counting of the predetermined flow rate is completed by 52 and 62, the flow automatically moves to the next step. In steps 3, 6, 9, and 12, all four towers are connected, and the entire inside of the towers is circulated by the circulation pump 17. After the flow meter 12 counts the predetermined flow rate, the process proceeds to the next step, and the process is repeated from step 12 to step 1. One cycle took about 2 hours.

The results after 24 hours of continuous operation are shown in Table 2 below. The sugar solution having a maltitol content of 96.5% was efficiently fractionated at a concentration of 28%.

The maltitol fraction obtained in the fourth step is purified and concentrated by a conventional method, and then powdered by, for example, a spray granulation method, a kneader method, a fluidized granulation method, a block pulverization method, a crystal honey separation method, and the like. Powder could be easily obtained by the method.

Example 2 Corn starch was liquefied into DE12 by a known method and saccharified by a known method to obtain a saccharified solution. Its sugar composition was as follows.

Glucose 0.5% Maltose 64.4% Maltotriose 18.7% Oligosaccharide with DP4 or more 16.4% This saccharified solution 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.

The hydrogenated solution obtained in the third step was fractionated by the following method.

The procedure was the same as in the fourth step of Example 1, except that the preset flow rate of the flow meter in the fourth step of Example 1 was changed as shown in Table 4 below.

The amount of eluted water required for this fractionation could be reduced by 20% as compared with Example 1, and a larger amount of hydrogenated solution could be treated. The results are shown in Table 5 below.

The maltitol purity of the maltitol fraction was 92.2%, and the concentration of the maltitol fraction was increased to 33%.

(Effects of the Invention) According to the method for producing maltitol of the present invention, easily available starch is used as a raw material starch, and a sugar liquid produced by a conventional liquefaction and saccharification method for producing starch syrup or glucose. Since maltitol having a desired purity can be obtained by selecting a fractionation parameter, a large amount of low-cost maltitol can be supplied.

The fractionation method in the fourth step of the present invention requires an extremely small amount of elution water as compared with the conventional method.
In order to obtain the same amount of maltitol product, fractionation can be performed with less than about 1/10 of the amount of eluted water compared with the conventional method, and the concentration of each fraction by the fractionation is extremely small.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of a separation test of maltose and maltotriose. The adsorbent used was sodium of a strongly acidic cation exchange resin [Diaion FRK-01 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)]. Type. FIG. 2 is a graph showing a comparison of the difference in the salt type of the adsorbent performed under the same test conditions as in FIG. 1, and sorbitol and maltitol are used as raw sugars. FIG. 3 is an example of a schematic view of a column and a pipe of a chromatographic fractionation apparatus used in the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Kazuaki Kato, Inventor 477 Nakasone, Yoshikawa-cho, Kita-Katsushika-gun, Saitama (72) Inventor Kensaburo Yoritomi 2-4-5 Hanazono, Chiba City

Claims (3)

(57) [Claims] 1. A first step of hydrogenating a saccharified starch having a maltose content of 50% by weight or more. B) A second step in which glucoamylase is allowed to act on the hydrogenated product to hydrolyze sugar alcohols having 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 mainly containing maltitol and a fraction mainly containing sorbitol by chromatographic fractionation. A method for producing maltitol, comprising the above four steps. 2. The method according to claim 1, wherein the maltitol purity of the fraction containing maltitol as a main component is 87% or more per solid. 3. The method according to claim 1, wherein the adsorbent used for the chromatographic fractionation is a sodium-type cation exchanger.