KR0165737B1 - Process for preparing high-purity cyclodextrin - Google Patents

Abstract

The present invention concentrates the cyclodextrin products produced from raw starch or starch subjected to physical treatment at high temperature, and then cools them to produce crystals of beta-cyclodextrin, thereby producing high purity beta-cyclodextrin in high yield. When the beta-cyclodextrin is prepared by the method of the present invention, the manufacturing process is simple, economical, and high purity beta-cyclodextrin can be produced in high yield. In addition, the beta-cyclodextrin prepared by the method of the present invention can be used in food, medicine, pesticides and flavoring for the purpose of stabilizing volatiles, elimination of bitterness, solubilization of insoluble substances and stabilization of color will be.

Description

Method for preparing high purity beta-cyclodextrin

The present invention relates to a method for producing high purity beta-cyclodextrin (β-cyclodextrin). More specifically, the present invention concentrates high-temperature beta-cyclodextrins by concentrating the cyclodextrin product produced from raw starch or physically treated starch at high temperature and then cooling to produce beta-cyclodextrin crystals. It relates to a process for producing in yield.

Cyclodextrin is a polymer of glucose that was first discovered by Billier in 1891. It is an illusion in which six or more glucose forms alpha-1,4-glucoside linkage. Oligosaccharides. Particularly, those consisting of 6, 7, and 8 glucose are called alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin, respectively.

Cyclodextrins have cavities capable of encapsulating hydrophobic substances, which are used in foods, medicines, pesticides, and fragrances to stabilize volatiles, remove bites, solubilize insoluble materials, and stabilize colors. It is known to be a very useful material used.

Cyclodextrins are prepared by reacting starch cyclodextrin glucanotransferase (EC 2.4.1.19.) Or its producing microorganisms with starch, usually liquefying starch with liquefied enzyme, and then cyclodextrin It is prepared by the method of obtaining.

As an improved cyclodextrin manufacturing method, a method of treating starch such that DE (dextrose equivalent) of substrate starch is less than 15 in Japanese Patent Publication No. 46-2380 has been proposed. 52-25043 discloses a method for increasing the production rate of cyclodextrin by using cyclodextrin glucanotransferase as a liquefaction enzyme. However, this method requires the substrate to be liquefied within a range that minimizes the production of by-products, some by-products are generated before the reaction, and when cyclodextrin glucanotransferase is used as the liquefaction enzyme, The production of dextrin was very low.

In Japanese Patent Laid-Open No. 52-43897, a mixture of alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin can be obtained by performing a concentrated crystallization process with a cyclodextrin production solution containing a large amount of such by-products. In this case, since the purity of the beta-cyclodextrin is about 72%, the problem that the recrystallization process is necessary to produce a high purity beta-cyclodextrin was exposed.

Thus, there is a need for another method that can selectively separate beta-cyclodextrins in one process. Japanese Patent Publication No. 46-9223, Patent Publication No. 56-805, Patent Publication No. 63-3002, Patent Publication No. 63-154701, Patent Publication No. 63-154702, Patent Publication 63-159403 and JP-A 2-218702 describe a method for separating cyclodextrins by adsorption. However, these methods are not selective separation methods of alpha-cyclodextrin, beta-cyclodextrin, and gamma-cyclodextrin, respectively, and they also increase the production cost due to the use of adsorptive resins, and the disadvantage that the separated cyclodextrin must be concentrated. It has

In addition, Japanese Patent Laid-Open Nos. 55-156595 and 60-120998 disclose methods for selectively separating cyclodextrins by adding alcohols, ethers, and esters to the reaction solution of the cyclodextrin manufacturing process. This method also did not selectively separate each of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin. In addition, these methods have caused a problem that the organic solvent must be removed after the cyclodextrin has been separated.

In addition, Japanese Patent Application Laid-Open No. 3-83592 discloses a method for selectively separating beta-cyclodextrin using naphthalene monosulfonic acid, but this method is followed by selective separation of beta-cyclodextrin and naphthalene monosulfate. There is a need for a process for removing phonic acid and its use is limited when naphthalene monosulfonic acid remains in beta-cyclodextrin.

On the other hand, in recent years, we have improved the former method of producing cyclodextrins by treating enzymes with starch, converting starch into a form that can react with cyclodextrin glucanotransferase without degrading the substrate using physical methods. Methods for preparing cyclodextrins have been proposed.

In other words, Korean Patent Publication No. 92-937 uses crushing friction instead of liquefaction, and Japanese Patent Publication No. Hei 1-168295 uses a starch extrusion method to form a substrate in which enzymes can be used. A method of switching is disclosed.

In addition, the inventors have reported a method for preparing cyclodextrin from raw starch or heat-treated starch (see Korean Patent Application Nos. 93-20680 and 93-26531), which method is a by-product of preparing cyclodextrins. By lowering the production of dextrins, the yield of cyclodextrin per enzyme can be increased, and the unreacted starch, which remains in the form of particles even after the production reaction of cyclodextrin, can be provided to provide high-purity cyclodextrin. .

Therefore, the inventors of the present invention crystallize the cyclodextrin product produced from starch subjected to electric raw starch or physical treatment by concentrating and cooling to separate only beta-cyclodextrin, and thus, highly purified by one crystallization step. It has been found that beta-cyclodextrin can be prepared and the present invention has been completed.

It is an object of the present invention to provide high purity beta-cyclodextrins by concentrating the cyclodextrin products produced from raw starch or physically treated starch at high temperature and then cooling to produce beta-cyclodextrin crystals. It is to provide a method for producing in yield.

Another object of the present invention is to provide a beta-cyclodextrin produced by the electric method.

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

Activated charcoal is added to the cyclodextrin product produced from raw starch or starch subjected to physical treatment and heated to remove the enzyme protein, preferably at 70 ° C. to 90 ° C., most preferably at 80 ° C., up to 80 Bx, preferably Was concentrated to 30Bx to 70Bx, crystal nuclei were added, cooled to 50 ° C or below, preferably 30 ° C to 50 ° C, most preferably 40 ° C, and stirred to form crystals of beta-cyclodextrin. The resulting beta-cyclodextrin crystals were separated by centrifugation or filtration, and then analyzed by the content of beta-cyclodextrin, and thus, high purity beta-cyclodextrin can be selectively prepared by the method of the present invention. It was confirmed.

In the present invention, 'raw starch' refers to starch which has not been subjected to any pretreatment, and 'physically treated starch' means physical reactions such as crushed friction, extrusion, ultrasonic and heat treatment, and reacts with cyclodextrin synthase. It means each starch converted to a form that can be.

On the other hand, the method of the present invention provides a high purity beta-cyclodextrin by one crystallization process, several crystallization processes may be further performed as necessary. In addition, the beta-cyclodextrin prepared by the method of the present invention is far superior in purity and yield in terms of purity and yield than the beta-cyclodextrin obtainable by a crystallization process from a cyclodextrin product prepared by a known method of pretreating enzymes in starch. Excellent.

In addition, the method for preparing beta-cyclodextrin according to the present invention has the following advantages: First, high purity beta-cyclodextrin can be produced in one simple crystallization process that does not require a recrystallization process. ; Second, no pretreatment is required to prevent the by-products from separating simultaneously with cyclodextrins during concentration; Third, since a separate material is not used for selective separation of the beta-cyclodextrin, a process for removing the material is unnecessary, and the use range of the beta-cyclodextrin is not limited according to the remaining of the electric material.

Therefore, when the beta-cyclodextrin is produced by the method of the present invention, the manufacturing process is simple, economical, and can be produced in high yield of high purity beta-cyclodextrin. In addition, the beta-cyclodextrin prepared by the method of the present invention can be used in food, medicine, pesticides and fragrances for the purpose of stabilizing volatiles, eliminating bitterness, solubilizing insoluble substances and stabilizing color. will be.

Hereinafter, the present invention will be described in more detail with reference to Examples.

These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1

[Preparation of High Purity Beta-cyclodextrin from Raw Starch (I)]

According to the method described in Korean Patent Application No. 93-20680, the content of beta-cyclodextrin by adding cyclodextrin synthase to 7.5% corn starch and reacting at 65 ° C., followed by centrifugation to remove unreacted starch. One liter of this cyclodextrin product, 22.5%, was prepared. To this product, activated carbon of dry solid content was added to 0.05% (weight ratio) and boiled to remove activated carbon to which enzyme protein was adsorbed. Then, partially purified by passing through an ion exchange resin tower filled with a mixed form of cation and anion exchange resin, concentrated at 30 ℃, 30Bx, 50Bx, 70Bx respectively at 80 ℃, and then passed through 400 mesh (mesh) 1% was added, cooled to 40 ° C and stirred to form crystals of beta-cyclodextrin. It was washed by filtration to give beta-cyclodextrin of crystals.

The content of beta-cyclodextrin was analyzed by high performance liquid chromatography, and the contents thereof were 98.3%, 98.2% and 97.5%, respectively. Therefore, it was found that the beta-cyclodextrin of high purity can be prepared by performing one crystallization process from the cyclodextrin product produced from raw starch.

Example 2

[Preparation of High Purity Beta-Cyclodextrin from Raw Starch (II)]

400L of cyclodextrin product was prepared in the same manner as in Example 1, partially purified by treatment with activated carbon treatment and ion exchange resin tower, concentrated to 70Bx at 80 ° C, and then beta-cyclodextrin was prepared in the same manner as in Example 1. Crystals were obtained. As a result of analyzing the content of beta-cyclodextrin by high performance liquid chromatography, its content was 98.1% and the amount of beta-cyclodextrin produced was 2.5 kg. Therefore, it can be seen that by performing a single crystallization process from the cyclodextrin product produced from raw starch, high purity beta-cyclodextrin can be produced in high yield.

Example 3

[Preparation of High Purity Beta-Cyclodextrin from Heat Treated Starch]

According to the method described in Korean Patent Application No. 93-26531, by heating the 7.5% corn starch at 65 ℃, then reacted at 55 ℃ by adding cyclodextrin synthase, centrifuged to remove the unreacted starch, One liter of cyclodextrin product was prepared having a content of beta-cyclodextrin of 20.3%. Then, crystals of beta-cyclodextrin were obtained in the same manner as in Example 1. The content of beta-cyclodextrin was analyzed by high performance liquid chromatography, and the contents thereof were 97.5%, 97.0%, and 97.5%, respectively. Therefore, it was found that the beta-cyclodextrin of high purity can be prepared by performing one crystallization process from the cyclodextrin product produced from the heat-treated starch.

As described and demonstrated in detail above, the present invention concentrates the cyclodextrin products produced from raw starch or physically treated starch at high temperature, and then cools them to produce crystals of beta-cyclodextrin, thereby providing high purity beta- Provided are methods for preparing cyclodextrins in high yield. When the beta-cyclodextrin is prepared by the method of the present invention, the manufacturing process is simple, economical, and high purity beta-cyclodextrin can be produced in high yield. In addition, the beta-cyclodextrin prepared by the method of the present invention can be used in food, medicine, pesticides and flavoring for the purpose of stabilizing volatiles, elimination of bitterness, solubilization of insoluble substances and stabilization of color will be.

Claims (1)

Cyclodextrin products from cyclodextrin products produced from raw starch or starch converted to a form capable of reacting with cyclodextrin synthase by crushing friction, extrusion, ultrasonication or heat treatment were subjected to cyclodextrin products at a temperature of 70 ° C. to 90 ° C. up to 80 Bx. And to crystallize by cooling the concentrated cyclodextrin product to 50 ° C. to room temperature.