JP3072433B2 - Method for producing high-purity maltose - Google Patents

Description

The present invention relates to a method for producing high-purity maltose.

(Prior art) Maltose, ie 4- [α-D-glucopyranosyl]
-D-glucose has long been known as a main component of maltose starch syrup and has good sweetness, and thus has been widely used in the food field.

In recent years, new characteristics of maltose have been clarified for use in food processing and medicine, and as the demand for high-purity products has further increased, an advantageous method for producing high-purity maltose has been desired.

Although many methods for producing high-purity maltose have been introduced in the past, most of the methods that can be carried out use underground starch as a raw material.

When ground starch such as corn starch, which is relatively inexpensive, was used as a raw material, the production of high-purity maltose was difficult, but the main problem was that the liquefaction and saccharification processes became turbid. Were generated and remained as turbidity of the product, filtration could not be performed due to high viscosity, and the maltose generation rate was low.

The cause is derived from the fact that the structure of the above-ground starch is relatively hard to saccharify, and is considered to be due to unreacted oligosaccharides and dextrin remaining during liquefaction, saccharification and subsequent production of the product.

A method of removing these unreacted oligosaccharides and dextrins to obtain high-purity maltose has been introduced. As the method, there is a method of saccharification as disclosed in JP-A-49-102854. A method for subsequently precipitating and removing oligosaccharides and dextrins with a solvent, JP-A-50-12244
JP-A-51-101141 and JP-A-52-57344 disclose a method of separating maltose and dextrin with an ion-exchange resin after saccharification. Later, there are a method of separating oligosaccharides and dextrins with a membrane, and a method of purifying a sugar solution by treating it with granular activated carbon as disclosed in JP-A-55-77896.

(Problems to be Solved by the Invention) However, the conventional method as described above has problems, and it is difficult to say that it is a sufficient method.

For example, when a solvent is used, if n-hexane approved for food is used, it is difficult to remove the solvent, and there is a problem that an odor or the like remains inevitably. There is a problem that it cannot be used during the process of use.

In addition, when chromatographic separation using an ion exchange resin is employed, the apparatus is extremely expensive, and a large amount of water is mixed during the separation, so that it is necessary to remove the large amount of water in a later step. There were challenges.

In addition, when a separation process of a sugar solution by a membrane is employed, clogging of the membrane is likely to occur and the production is interrupted. There was also a problem that a large amount of water was mixed in and a large amount of water had to be removed in a subsequent step.

Furthermore, in the method of removing and purifying oligosaccharides and dextrins with granular activated carbon, the storage capacity of oligosaccharides and dextrins in activated carbon is small, so it is necessary to increase the size of the equipment or to frequently replace or regenerate activated carbon. There was a problem that it could not be said to be a very practical method. Also, since a large amount of water is mixed during this step, the same problem as in the above-mentioned step is also present.

An object of the present invention is to produce high-purity maltose using ground starch, which is a relatively inexpensive raw material, and that turbidity of the liquid generated during liquefaction or saccharification cannot be removed even at the product stage. An object of the present invention is to solve problems such as a high viscosity and a low saccharification rate, and to enable a production process to be performed.

Another object of the present invention is to provide a method for producing high-purity maltose without using a process that leaves many problems, such as a chromatographic separation process, a honey crystallization process, a crystallization process using a solvent, and a separation process using a membrane. Is to make it possible.

(Means for Solving the Problems) In order to solve the various problems as described above, the present inventors have conducted intensive studies on a method for producing maltose. As a result, a calcium compound or a barium compound was added to starch milk prepared from ground starch. It has been found that by adding a heat treatment step, a substance causing turbidity can be aggregated in advance, and a substance that inhibits enzyme activity in a subsequent step such as saccharification can also be aggregated at the same time. The present invention was completed by successfully obtaining maltose.

That is, the present invention provides (1) a first step in which starch milk is prepared by adding water to ground starch and heat-treated in the presence of a calcium compound or a barium compound; (2) a heat treatment obtained in the first step After neutralizing the liquid, the second step of liquefying the enzyme, (3) enzymatic saccharification of the liquefied liquid obtained in the second step,
A method for producing high-purity maltose, which comprises sequentially performing three steps of a third step of increasing the purity of maltose in a solid to 85% by weight or more.

In the present invention, the concentration of the starch milk in the first step is 5 to 15% by weight, and the calcium compound or the barium compound is calcium hydroxide, calcium carbonate, calcium chloride, calcium sulfate, calcium lactate, calcium citrate, glucone. The method for producing high-purity maltose as described above, which is one or a mixture of two or more kinds selected from the group consisting of calcium oxide, calcium acetate, calcium oxide, barium hydroxide, barium chloride, and barium oxide.

In the present invention, the heat treatment in the first step is performed at a temperature of 105 to 1
The method for producing high-purity maltose according to the above or the above, which is carried out at 40 ° C. for a time of 5 to 30 minutes.

Further, the present invention is the method for producing high-purity maltose according to any one of the above-mentioned items, wherein the enzyme liquefaction in the second step is performed under a condition of 100 ° C. or lower.

Further, in the present invention, the saccharification in the third step is carried out under the conditions of 15 to 48 hours, and any one of the above-mentioned items which is carried out by adding α-amylase and / or maltogenic α-amylase as necessary. The method for producing high-purity maltose described in (1).

The high-purity maltose obtained through the above steps, per se known purification, concentration, crystallization, solidification, reduction, drying, powdering, etc., by subjecting it to a high-purity maltose liquid, The product can be made into various forms such as a crystalline form and a powdery mass, and it is also possible to easily produce high-purity maltose and high-purity maltitol.

 Hereinafter, the contents of the present invention will be described in more detail.

In carrying out the present invention, it is a great advantage that ground starch can be used, but it goes without saying that underground starch that has been conventionally used can also be used.

In practicing the present invention, the composition of amylose and amylopectin in the starch does not need to be particularly considered. Specific examples of usable starches include corn starch, wheat starch, barley starch, and the like. Ground starch may be mentioned.

In the first step of the present invention, starch milk is prepared by adding water to these ground starches and heat-treated in the presence of a calcium compound or a barium compound. The concentration of the starch milk is 5 to 15% by weight ( Hereinafter, it may be simply referred to as%.).

If the concentration of starch milk is less than 5%, the amount of water is increased more than necessary, and it becomes necessary to remove water in a later process.
In the subsequent enzyme liquefaction and enzymatic saccharification steps, the enzymatic reaction rate is slow, and the saccharification reaction does not proceed further at low maltose purity, resulting in lower purity of maltose as a product This is not preferred because of the tendency to cause

Further, the calcium compound or the barium compound used in the first step of the present invention is not particularly limited in quality, and specifically, calcium hydroxide, calcium carbonate,
Various industrial, food, and pharmaceutical grade materials such as calcium chloride, calcium sulfate, calcium lactate, calcium citrate, calcium gluconate, calcium acetate, calcium oxide, barium hydroxide, barium chloride, and barium oxide are used. it can.

The use amount of the calcium compound or the barium compound is preferably from 0.1 to 1% based on the weight of the solid substance of starch milk. If the amount used is less than 0.1%, the effect of the present invention cannot be sufficiently obtained, so that it is not preferable. If the amount exceeds 1%, side reactions are likely to occur and the load to be removed during purification is reduced. If it exceeds 1%, the effect of the present invention is not greatly affected and is not economically meaningful.

The heat treatment conditions in the first step are 105-140 ° C, 5
It is preferable to carry out in a range of up to 30 minutes.

When the treatment temperature is lower than 105 ° C, it is not preferable because the removal of the turbidity-causing substance and the saccharification reaction inhibitor tends to be insufficient, and the starch milk may not form a paste. If it exceeds, undesired side reactions such as decomposition of starch and sugar, polymerization, isomerization, etc. will proceed.

If the heat treatment time is less than 5 minutes, it is not preferable for the same reason as when the processing temperature is low, and if it exceeds 30 minutes, it is preferable for the same reason as when the processing temperature exceeds 140 ° C. Absent.

The liquid after the heat treatment contains the generated aggregates, and the aggregates grow during the liquefaction and saccharification steps,
Since there is a filtration step at the stage of purifying the sugar solution after the saccharification is completed, it is economically advantageous to remove aggregates after the saccharification is completed.

By passing through this simple and economical process, the causative substances of turbidity and high viscosity and the enzyme reaction inhibitory factors are aggregated in advance, so that the liquid in the subsequent processes is clear except for the sedimentation part of the aggregate, In addition, the viscosity is relatively low, and the effect that the enzymatic reaction proceeds smoothly to a maltose purity of 85% or more is obtained.

Next, in the second step of the present invention, the heat treatment liquid obtained in the first step is neutralized, and the type and quality of the neutralizing agent may be any as long as the heat treatment liquid can be adjusted to a desired pH. There is no particular restriction on the type and quality, and specific types such as oxalic acid, sulfuric acid, phosphoric acid and the like for industrial use, food use, pharmaceutical use and the like can be used.

In addition, since the enzymatic liquefaction and enzymatic saccharification which are subsequent steps are performed, the end point of the neutralization is adjusted to a pH at which the activity of the enzyme to be used is sufficiently exhibited, for example, 5.5 to 7.
5, and more preferably, the pH range is about 6.0 to 6.5.

For the enzyme liquefaction in the second step, a normal liquefaction enzyme, for example,
Nova Termamyl (registered trademark), Nagase & Co., Ltd. spinase HS (registered trademark) and the like can be used. The liquefaction reaction is carried out under ordinary conditions, for example, a reaction for about 3 to 15 minutes and a DE of 0.1.
It is preferable to perform the reaction until the concentration becomes about 2 to 1.5 in order to obtain maltose with high purity.

As a guide for the end point of the reaction at this time, it is preferable that the color of the iodine / starch reaction be blue to purple.

The liquefaction enzyme can be inactivated by ordinary means such as heating or pH change, but can be achieved by, for example, setting the temperature to about 120 ° C.

After neutralization and liquefaction, aggregates formed to the extent that they can be observed with the naked eye can be removed by a method known per se, for example, filtration or centrifugation. It is economically advantageous to remove them all at once.

In the next third step, the liquefied liquid obtained in the second step is enzymatically saccharified to make the maltose purity in the solid substance 85% or more, but as an enzyme used in the saccharification reaction, a normal maltose production enzyme is used. Enzymes are sufficient, for example β-amylase,
One or a combination of two or more selected from pullulanase, maltogenic α-amylase, glucoamylase and α-amylase can be used.

Among the combinations of saccharifying enzymes, a combination of soybean-derived β-amylase and pullulanase which can obtain maltose of relatively high purity and is economically advantageous is provided.

Saccharification conditions are not limited as long as high-purity maltose is obtained.For example, when using 15 units of soybean-derived β-amylase per 1 g of solid substrate and 1.5 units of pullulanase, the pH is about 5.0. It is preferable to react at a temperature of about 55 ° C. for 24 hours. In this case,
High-purity maltose having a maltose purity of about 90% in a solid material can be obtained.

Since the high-purity maltose obtained after saccharification has a sufficiently high maltose purity as compared with commercially available high-purity maltose, it can be commercialized by purifying it by a method known per se.

In addition, before completion of the saccharification reaction, maltogenic-
93-95% by supplementary treatment with α-amylase etc.
It is also possible to produce high-purity maltose of a higher degree of purity, and by using α-amylase in combination during the saccharification or supplementation treatment, the viscosity of the sugar solution is further reduced, and the filterability is improved. You can also.

(Example) Next, the content of the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Example 1 (First step) 2.0 kg of corn starch yellow (trade name: corn starch Y) manufactured by Nippon Shokuhin Kako Co., Ltd. was dissolved in water and the solid content concentration was 1
0% starch milk was added and mixed with 4.25 g of calcium hydroxide, and gelatinized by heating at 125 ° C. for 15 minutes, and then the gelatinized product was cooled to 90 ° C.

(Second step) Thereafter, oxalic acid having a concentration of 10% was dropped to neutralize the solution to pH 6.2.

To the gelatinized / neutralized solution obtained above, a heat-resistant liquefying enzyme [Nipase Sangyo Co., Ltd., Spitase HS] 3 u / g substrate solid content (hereinafter abbreviated as DS) is added, and the mixture is added at 92 ° C. for about 10 minutes. After liquefaction by heating, the reaction was stopped to obtain a liquefied product of DE1.0.

(Third Step) Next, after adjusting the liquefied product obtained in the second step to a temperature of 55 ° C. and a pH of 5.0, the β-amylase # 1500 and 1.5u / gDS of 20u / gDS manufactured by Nagase Sangyo Co., Ltd. As a result of adding Novo's Promozyme TM 200L and saccharifying for about 24 hours, the enzymatic reaction proceeded smoothly and a saccharified product with maltose purity of about 90% was obtained.

The result of measuring the composition of the saccharified product by high performance liquid chromatography was as follows.

Monosaccharide 0.0% Disaccharide 90.6% Trisaccharide 5.8% Tetrasaccharide or higher oligosaccharide 3.6% After this, powdered activated carbon is added to decolorize and deodorize, deionized with ion exchange resin, and the maltose purity in the solid is 90.6% % Pure maltose purified product.

The liquid of the purified product was clear and free of turbidity, and there was no difficulty in filtering activated carbon or passing the solution through an ion exchange resin tower.

Example 2 (First Step) Using the same corn starch as in Example 1, the solid content of starch milk was set to 6%, and 14 g of calcium hydroxide was used.
The mixture was added, mixed and gelatinized by heating at 115 ° C. for 9 minutes.

 Next, the gelatinized product was cooled to 95 ° C.

(Second step) Thereafter, oxalic acid having a concentration of 10% was added dropwise to neutralize the solution to pH 6.0.

Add 4u / gDS to the gelatinized / neutralized solution obtained above and heat-resistant liquefying enzyme [Spinase HS, manufactured by Nagase & Co., Ltd.].
After heating and liquefying for 1 minute, the reaction was stopped to obtain a liquefied product having a DE of about 1.4.

(Third step) Next, the liquefied product obtained in the second step is subjected to a temperature of 50 to 55 ° C and a pH of 5.1.
After adjusting to 20 u / gDS, β-amylase # 1500 from Nagase & Co., Ltd. and Promozyme TM200L from Novo with 1.5 u / gDS
Was added and saccharified for about 24 hours to obtain a saccharified product having a maltose purity of about 90%.

The result of measuring the composition of the saccharified product 24 hours after the start of the reaction by high performance liquid chromatography was as follows.

Monosaccharide 0.0% Disaccharide 90.2% Trisaccharide 5.7% Oligosaccharide with more than tetrasaccharide 4.1% In addition, 24 hours after the start of the reaction, 3u / gDS Nagase & Co., Ltd.
After adding Novo's maltogenase of Sputase PN4 and 7u / gDS and continuing the saccharification reaction for 22 hours, the sugar solution was purified with activated carbon and an ion exchange resin.
A high-purity maltose having a maltose purity of 94.0% in the solid was obtained.

Monosaccharide 3.3% Disaccharide 94.0% Trisaccharide 0.4% Oligosaccharide with more than tetrasaccharide 2.3% Example-3 Using the same cornstarch as in Example-1, the solid content of starch milk was 13%, and calcium hydroxide was used as a substrate. Add and mix in an amount equivalent to 0.3% based on the solid content, then 130 ℃
For 4 minutes.

 Next, the gelatinized product was cooled to 90 ° C.

(Second step) Thereafter, oxalic acid having a concentration of 10% was dropped to neutralize the solution to pH 6.2.

Heat-resistant liquefying enzyme [Novo Co., Ltd.
Termamyl] was added thereto, and the mixture was heated and liquefied at 88 ° C. for about 12 minutes. Then, the reaction was stopped to obtain a liquefied product having a DE of about 0.7.

(Third step) Next, the liquefied product obtained in the second step is subjected to a temperature of 50 to 55 ° C and a pH of 5.1.
After adjusting to 40 u / gDS, β-amylase # 1500 manufactured by Nagase & Co., Ltd. and Promozyme TM200L manufactured by Novo with 3.0 u / gDS
Was added and saccharified for about 24 hours to obtain a saccharified product having a maltose purity of about 84%.

The result of measuring the composition of the saccharified product 24 hours after the start of the reaction by high performance liquid chromatography was as follows.

Monosaccharide 0.0% Disaccharide 87.7% Trisaccharide 6.5% Oligosaccharide with more than tetrasaccharide 5.8% In addition, 24 hours after the start of the reaction, 10u / gDS Nagase & Co., Ltd. Spitase PN4 and 5u / gDS Novo maltogenase from Novo Was added thereto, and the saccharification reaction was continued for 15 hours. Then, the sugar solution was purified with activated carbon and an ion exchange resin. As a result, high-purity maltose having the following saccharide composition and a maltose purity in a solid of 92.8% was obtained.

Monosaccharide 3.7% Disaccharide 92.8% Trisaccharide 0.8% Oligosaccharide over tetrasaccharide 2.7% (Effect of the Invention) As described above, by implementing the present invention,
It is possible to use economically advantageous ground starch as a raw material, to use high-purity maltose by a simple and economical process without using a solvent, using an inexpensive apparatus, and having relatively little water in the process. Can be manufactured.

In addition, the liquefaction and saccharification processes are difficult because the causative substances of turbidity of the products, the causative substances of high viscosity of semi-finished products, and the enzyme reaction inhibitors, which have been difficult to remove economically, have been aggregated in advance. As a result, maltose purity of 85% or more can be obtained by proceeding smoothly, and an effect that agglomerated substances are easily separated, the viscosity in the filtration step is relatively low, and a product without turbidity can be obtained is obtained.

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Kazuaki Kato 477 Nakasone, Yoshikawa-cho, Kita-Katsushika-gun, Saitama (56) References Japanese Patent Publication No. 54-3937 (JP, B1) Japanese Patent Publication No. 57-2672 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C12P 19/00-19/64 BIOSIS (DIALOG) WPI (DIALOG)

Claims (5)

(57) [Claims] (1) a first step in which starch milk is prepared by adding water to ground starch and heat-treated in the presence of a calcium compound or a barium compound; (2) a heat-treated liquid obtained in the first step A third step of neutralizing and then liquefying the enzyme, and (3) a third step of enzymatically saccharifying the liquefied liquid obtained in the second step to make the maltose purity in the solid substance 85% by weight or more. The method for producing high-purity maltose is carried out sequentially. 2. The starch milk concentration in the first step is 5-15.
% By weight, and the calcium compound or the barium compound is calcium hydroxide, calcium carbonate, calcium chloride,
The composition according to claim 1, which is one or a mixture of two or more kinds selected from the group consisting of calcium sulfate, calcium lactate, calcium citrate, calcium gluconate, calcium acetate, calcium oxide, barium hydroxide, barium chloride, and barium oxide. Production method of high purity maltose. 3. The method for producing high-purity maltose according to claim 1, wherein the heat treatment in the first step is performed at a temperature of 105 to 140 ° C. for a time of 5 to 30 minutes. 4. The method for producing high-purity maltose according to claim 1, wherein the enzyme liquefaction in the second step is carried out at a temperature of 100 ° C. or lower. 5. The method according to claim 1, wherein the saccharification in the third step is carried out under a condition of 15 to 48 hours and, if necessary, is carried out by adding α-amylase and / or maltogenic α-amylase.
5. The method for producing high-purity maltose according to any one of items 4 to 4.