JP2663134B2 - Method for producing high purity maltitol - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing high-purity maltose useful as food.

(Prior art) Maltose obtained by hydrogenating maltose, that is, 4- [α-D-glucopyranosyl] -D-glucitol, is difficult to ferment by microorganisms and has a sweetness close to that of sugar. It is a sugar alcohol that has many advantages such as high moisture retention,
It is used for a wide range of applications in the field of cosmetics and the like.

Conventionally, it has been difficult to obtain high-purity maltitol compared to obtaining high-purity products of other saccharides.However, maltitol is a chromatographic separation method often used to increase the purity of other saccharides. Attempts have been made to reduce the difficulty by applying it to the manufacturing process.

Many attempts to obtain high-purity maltitol have been reported. Among them, representative ones using a chromatographic separation technique are as follows.

JP-A-57-209000, JP-A-58-23799, and JP-A-62-2799.
Nos. 0-67000 and 62-19210, which have a low glucose content and a maltose purity of 75.
About 85% (in the present specification,% is% by weight per solid content)
Is shown. Hereinafter, it may be simply referred to as purity. )) By separating the components of the liquefied liquid containing maltose as a main component with an alkali metal type strongly acidic cation exchange resin,
A method of producing high-purity maltose of 93% or more and then hydrogenating it to high-purity maltitol.

As disclosed in JP-A-61-180797,
After liquefying starch milk having a concentration of 25 to 45%, saccharification is performed by adjusting saccharification conditions to obtain a saccharified solution having a maltose purity of 50 to 80% or more.
There is a method of producing high-purity maltitol by hydrogenation and then chromatographic separation.

However, the conventional method has a number of drawbacks,
It was not satisfactory as a method for industrially producing maltitol.

For example, the gist of the method is to separate maltose from oligosaccharides having a DP (degree of polymerization of sugar) of 3 or more, that is, trisaccharide or more. Particularly, maltose and maltotriose have a small molecular weight ratio and other separation methods. Since the separation is difficult due to the small difference in required properties, a large-capacity separation tower is required, and a large amount of eluted water is required for separation, and as a result, the cost of concentrating this water is increased. There is a benefit.
Further, since separation is difficult, impurities such as glucose are often mixed in the maltose fraction, and there is a disadvantage that maltose purity is hardly increased.

In addition, in the method (1), the saccharide composition of the liquid to be fractionated is a mixture of sorbitol, maltitol, and a sugar alcohol having a DP of 3 or more. The separation device is used in a very complicated operation. Nevertheless, the separation state of each sugar component is poor, and particularly, a maltitol-based fraction contains about 8% of maltotriitol. The presence of a sugar alcohol having a DP of 3 or more inhibits the precipitation of maltitol, which is the target substance, and causes problems such as a long crystallization step and a low yield of maltitol. Furthermore, the calcium-type ion exchanger used for fractionation has an extremely strong adsorptive power to sorbitol, and its elution is significantly delayed compared to maltitol or sugar alcohols with DP3 or higher. There is also a drawback that elution water is required five times as much as the raw sugar solution. This means that a large amount of water needs to be concentrated and removed in the subsequent concentration step, which is extremely disadvantageous industrially. From the above, there has been a strong demand for improvements in the chromatographic separation step and the steps before and after it.

(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted intensive studies and as a result, have found that the fraction of sorbitol and maltitol and DP
Focusing on the relative ease of separation from the fraction of 3 or more oligosaccharide alcohols, to achieve this advantage, focus only on increasing the sugar composition before hydrogenation to increase the purity of maltose as before. It is considered that it is effective to reduce the oligosaccharide component of trisaccharide or more even if the glucose component is increased when increasing the purity of maltose, instead of the method described above. Was produced, hydrogenated, and then subjected to chromatographic separation to easily, efficiently and economically produce high-purity maltitol, thereby completing the present invention.

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

An object of the present invention is to provide an efficient method for producing high-purity maltitol useful as food.

The process of the present invention comprises the steps of: (1) liquefying starch and then selecting from a group consisting of β-amylase, isoamylase and pullulanase;
Maltose purity in solids using more than 70 enzymes
A first step in which glucoamylase is added to the mixture prepared at a concentration of not less than% by weight and saccharification is performed until the value of the following formula is given; (2) a second step of reducing the obtained saccharified product, and (3) a third step of separating the obtained reduced product into a fraction containing maltitol as a main component and other fractions by a chromatographic separation method. It consists of three main steps.

The present invention can be used irrespective of above-ground starch and underground starch, and there is no need to worry about the composition of amylose and amylopectin in the starch. Specific examples of the starch that can be used in the present invention include corn starch, wheat starch, potato starch, and starches derived from barley, sweet potato, tapioca, and the like.

Next, these starches are liquefied, but the liquefaction method and conditions do not need to be particularly limited. However, in order to improve economic efficiency by keeping the concentration high and to make DE (dextrose equivalent) relatively high, In order to prevent aging of the liquefied product, it is advantageous to perform liquefaction by a jet cooker using a heat-resistant liquefying enzyme at a substrate concentration of 20 to 35%, for example, and to inactivate the liquefied enzyme at a DE of about 5 to 15.

Further, the liquefied liquid is saccharified at 55 to 60 ° C., and at this time, two or more enzymes selected from the group consisting of β-amylase, isoamylase and pullulanase are used. Next, 1 to 10 hours after the start of the saccharification step, liquefaction enzyme was added to further promote saccharification, and the maltose purity in the solid was reduced to 70% by weight.
Above.

By the second addition of the liquefying enzyme, oligosaccharides of mainly tetrasaccharide or more are hydrolyzed. As a result, the purity of maltose and the filterability of the solution are improved. Commercially available enzymes are sufficient for the saccharifying enzyme used at this time. Examples of β-amylase include maltozyme manufactured by Nagase Sangyo Co., Ltd., BBA1500 manufactured by Finsugar Co., and biozyme manufactured by Amano Pharmaceutical Co., Ltd. Novo's Promozyme, Amano CKL, a pullulanase from Amano Pharmaceutical Co., Ltd. can be used.

Next, treatment with glucoamylase is performed. Examples of usable enzymes include Gluczyme manufactured by Amano Pharmaceutical Co., Ltd., and AMG200L manufactured by Novo. The enzyme used in this step is not limited to glucoamylase. For example, Novo's β-amylase SP that degrades oligosaccharides of three or more sugars
−295 and the like are also very effective in practicing the present invention.

The purpose of this treatment with glucoamylase is to reduce the ratio of oligosaccharides of three or more sugars to maltose. At this time, disaccharides are partially hydrolyzed, but hydrolysis of oligosaccharides of three or more sugars proceeds. The sugar composition is adjusted to a maltose purity of 70% or more in the solid, It is preferable to stop at the point where the condition is satisfied.

Next, this treatment solution is subjected to hydrogenation in the presence of a nickel-based or noble metal-based catalyst in a manner known per se, using a batch-type or continuous-type method to form a sugar containing maltitol as a main component. Use alcohol solution. The hydrogenation condition may be any condition as long as maltose does not decompose, but usually, the concentration of the sugar solution is set to 40 to 60% by weight, and 20 kg / c
m ² or more, more preferably under a hydrogen pressure of 50 to 200 kg / cm ² ,
It is preferable to carry out at a temperature of 00 to 150 ° C. It is not necessary to extremely reduce the unreduced sugar after hydrogenation, but 1%
Hereinafter, it is more preferable that the content be 0.5% or less.

The obtained hydrogenated liquid is subjected to a chromatographic separation step after removing a catalyst as necessary and further performing an activated carbon treatment if necessary.

The chromatographic separation carried out in the present invention can be carried out batchwise or continuously using various adsorbents by a method known per se. An example of such a chromatographic separation is disclosed in
It is shown in Japanese Patent No. 180795.

The ion exchanger used in the present invention is not particularly limited as long as it is a cation exchanger, such as an ion exchange resin, an ion exchange fiber, and zeolite.
A strongly acidic cation exchange resin in which a sulfonic acid group is bonded to a crosslinked polymer of divinylbenzene is widely used as a commercial product, so that it is convenient to use. In addition, this product has a better separation state when each substance to be adsorbed is eluted than the calcium type, and since the elution is not delayed, it is possible to reduce the capacity of the separation column, and therefore, the chromatograph with less elution water. Since separation is possible, the concentration of the separated fraction can be kept high. This makes it possible to reduce the amount of water to be concentrated in the subsequent concentration step, which constitutes a great economic advantage of the present invention.

Further, since the sugar alcohol composition of the composition according to the present invention is separated into a fraction mainly composed of maltitol and a fraction composed of sorbitol, the conventional fraction mainly composed of maltitol and a sugar alcohol of DP3 or more The separation efficiency is extremely high compared to the separation of a fraction containing as a main component, and the results also contribute to a reduction in the amount of eluted water and a reduction in the capacity of the separation column.

The fraction containing maltitol as a main component obtained from this step has a sufficient purity as compared with maltitol currently on the market, and is purified and concentrated by a known method, and remains in a liquid state as it is. As a product, it can be further concentrated, crystallized, or powdered to obtain a powdered or crystalline maltitol product. As a method of powdering, for example, a spray granulation method, a kneader method, a fluid granulation method, a block pulverization method, various methods such as a crystallization honey method or a combination thereof can be adopted, but according to the method of the present invention. Maltitol solution
Since it contains only a small amount of an oligosaccharide alcohol of DP3 or more, which is considered to inhibit crystallization most greatly, 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 more specifically with reference to Examples.
The present invention is not limited by the following examples.

Example 1 First Step (Liquefaction / Saccharification Step) Corn starch was adjusted to a concentration of 32% and pH 6.3, and a heat-resistant liquefying enzyme [Spinase PN4, manufactured by Nagase Sangyo Co., Ltd.] 20 u / g substrate solid content (hereinafter DS) And the mixture was liquefied at 105 ° C. with a jet cooker. The liquefaction reaction was stopped at DE12 by inactivating the enzyme, and after adjusting to a temperature of 57 ° C. and pH 5.5, 1 ml / kg DS Finsugar β-amylase BBA1500 and 1 u / g DS Novo Pullulanase from Novo were used. The saccharification reaction was allowed to proceed by adding Promozyme TM 200L, and after 6 hours, the above-mentioned liquefaction enzyme spinase PN4 was added at 20 u / g DS, and the saccharification reaction was allowed to proceed for an additional 30 hours. The result of analysis of the saccharified component at this time by high performance liquid chromatography was as follows.

(1.7% monosaccharide) (71.5% disaccharide) (21.4% trisaccharide) (5.4% oligosaccharide over tetrasaccharide) The process of adding liquefaction enzyme in the middle of the above 6 hours is mainly oligosaccharide over tetrasaccharide. Is decomposed to produce maltose and trisaccharide, which is an effective method for improving maltose purity and filterability.

Next, 1 u / g DS of glucoamylase (Amagno Pharmaceutical Co., Ltd., Gluczyme) was added, and the reaction was further proceeded for 10 hours. In this reaction, disaccharides are also hydrolyzed, but oligosaccharides more than trisaccharides are decomposed. Since the value decreases when the reaction is further advanced, this value increases. The reaction was terminated by heating 10 hours after the minimum of this value.

The result of analysis of the sugar component at this time by high performance liquid chromatography was as follows.

(Monosaccharide 23.9%) (Disaccharide 70.6%) (Trisaccharide 1.5%) (Oligosaccharide more than tetrasaccharide 4.0%) Second step (hydrogenation step) Decolorization and decolorization of the saccharified solution obtained above according to the usual method Salt, concentrated to obtain a purified sugar solution having a concentration of 50%, 20 kg of the purified sugar solution and 200 g of Raney nickel catalyst were charged into an autoclave having an internal volume of 25 liters, the hydrogen pressure was maintained at 120 kg / cm ^2, and the mixture was stirred at 120 ° C. for 2 hours, The addition was made. The obtained liquid is separated from the catalyst,
The result of analysis by high performance liquid chromatography after passing through the column of granular activated carbon was as follows.

Sorbitol 24.6% Maltitol 70.2% Trisaccharide or higher oligosaccharide alcohol 5.2% Third step (Chromatographic separation step) Continuous separation of the above-mentioned sugar solution containing sorbitol and maltitol as main components by chromatographic separation is disclosed in US Pat. No. 426704.
The method disclosed in Example 4 of the above-mentioned publication, that is, a method of separating fructose and glucose using a four-column type column was modified and carried out so as to be suitable for the above-mentioned separation of sugar solution.

FIG. 1 shows the configuration of the column and the piping. In FIG. 1, reference numerals 40, 30, 20, and 10 denote separation columns, each of which is a strongly acidic cation exchange resin in the form of sodium [Diaion FRK-01 (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)]. Each 75 liters was filled, and the temperature in the column was kept at 70 ° C. R is the entrance of the raw sugar liquid for chromatographic separation obtained in the second step,
W is the inlet of the elution water, A is the maltitol fraction, B
Is a receiving tank for the sorbitol fraction. 12, 52, 62 are preset flow meters, 13, 17 are circulating pumps, 1
1,21,31,41 are filters, and the others are valves for controlling the flow path.

The apparatus shown in FIG. 1 was operated according to the procedure shown in Table 1 below.

That is, the valve shown in the procedure shown in Table 1 is opened and the raw sugar liquid and water flow into a predetermined column, and at the same time, the maltitol fraction and the sorbitol fraction flow out. After the counting of the flow rate is completed, the procedure automatically proceeds 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 procedure proceeds to the next procedure, and the procedure 12 is repeated from the procedure 12. One cycle took about 2 hours.

The results after continuous operation for 24 hours are as shown in Table 2 below. The sugar solution having a maltitol content of 90.2% was efficiently separated at a concentration of 26.8% by chromatography.

The maltitol fraction obtained in the third step is purified and concentrated by a conventional method, and then easily purified by, for example, a spray granulation method, a kneader method, a fluid granulation method, a block pulverization method, a crystallization condensing method, or the like. It could be made into a powder.

Example 2 First step (liquefaction / saccharification step) In the same manner as in Example 1, the starch concentration was set to 30%, and the liquefaction reaction was stopped at DE7. β-amylase is 25 u / g of β-amylase # 1500 manufactured by Nagase & Co., Ltd., and pullulanase is pullulanase amano CKL2u / g manufactured by Amano Pharmaceutical Co., Ltd.
The saccharification reaction was carried out by adding DS, and after 6 hours, 10 u / g DS was added to the liquefying enzyme spitase PN4, and the saccharification reaction was further carried out for 48 hours. The result of analysis of the sugar component at this time by high performance liquid chromatography was as follows.

(0.7% monosaccharide) (76.6% disaccharide) 17.5% trisaccharide (5.2% oligosaccharide over tetrasaccharide) Next, 1 u / g of glucoamylase [NMG, AMG200L]
The reaction was allowed to proceed for an additional 8 hours after DS was added.

The result of analysis of the sugar component at this time by high performance liquid chromatography was as follows.

(Monosaccharide 21.0%) (Disaccharide 73.5%) (Trisaccharide 3.2%) (Tetrasaccharide or higher oligosaccharide 2.3%) Second step (hydrogenation step) Decolorization and decolorization of the saccharified solution obtained above in accordance with a conventional method The salt was concentrated and purified as a purified sugar solution having a concentration of 50%, and hydrogenated in the same manner as in Example 1 to obtain the following composition.

Sorbitol 21.7% Maltitol 73.0% Trisaccharide or higher oligosaccharide alcohol 5.3% Third step (Chromatographic separation step) The sugar alcohol solution was chromatographed in the same manner as in Example-1. At this time, the preset flow rate of the flow meter was changed and the flow rate ratio of the fraction was changed according to the sugar component as shown in Table 3 below.

Table 4 shows the results of the chromatographic separation.

The maltitol purity of the maltitol fraction was 91.3%, and the concentration was 25.9%.

Example 3 A sugar alcohol solution having undergone the first step and the second step was obtained in the same manner as in Example-1.

Third Step (Chromatographic Separation Step) Since oligosaccharide alcohols of three or more sugars move in the chromatographic separation tower more quickly than maltitol, three or more sorbitol fractions, maltitol fractions, and oligosaccharide alcohol fractions of three or more sugars are used. The fraction was separated and high-purity maltitol was taken out, and the sorbitol fraction and the oligosaccharide alcohol of three or more sugars were placed in the same receiving tank to carry out a step of preparing a low-purity sorbitol solution.

The same apparatus as in Example 1 was operated according to the procedure shown in Table 5.

The results are as shown in Table 6, and a sugar solution having a maltitol content of 95.1% was separated at a concentration of 29.6%.

(Effects of the Invention) As is apparent from the above description, according to the present invention, a high-purity maltitol can be obtained in a relatively easy operation with a high yield by using a general-purpose enzyme under certain conditions and performing each step. Obtainable.

[Brief description of the drawings]

FIG. 1 shows the configuration of columns and piping used in the present invention.

Claims (2)

(57) [Claims] (1) After starch is liquefied, the purity of maltose in the solid content is at least 70% by weight using two or more enzymes selected from the group consisting of β-amylase, isoamylase and pullulanase. A first step in which glucoamylase is added to the mixture prepared in step (1) and saccharified until the value of (2) a second step of reducing the obtained saccharified product, (3) a third step of separating the obtained reduced product into a fraction containing maltitol as a main component and other fractions by a chromatographic separation method, A method for producing high-purity maltitol, comprising three steps. 2. The method for producing high-purity maltitol according to claim 1, wherein the adsorbent used for chromatographic separation is a sodium-type ion exchanger.