KR101367409B1 - Method of liquid composition comprising cyclodextrin with improved turbidity - Google Patents

Abstract

The method for preparing a cyclodextrin-containing liquid composition with improved turbidity according to the present invention is to hydrolyze a cyclodextrin-containing saccharified solution obtained from starch by enzymatic conversion of cyclodextrin glycosyltransferase, and then to cyclodextrin-containing hydrolyzate before ion purification. Adjusting the pH of the decomposition solution and adjusting the temperature of the ion exchange resin column when the cyclodextrin-containing hydrolysis solution is passed.
The method for preparing a cyclodextrin-containing liquid composition according to the present invention may provide a cyclodextrin-containing liquid composition in which cloudiness hardly occurs, and wherein the cyclodextrin content is at least 15% by weight or more based on the total weight of the saccharides. In addition, the method for preparing a cyclodextrin-containing liquid composition according to the present invention can be applied to a cyclodextrin saccharified solution obtained from starch having an amylopectin content of less than 90%, and it is possible to remarkably improve the turbidity of the cyclodextrin-containing liquid composition by only an ion purification process. Very economical.

Description

Method for preparing cyclodextrin-containing liquid composition with improved turbidity {Method of liquid composition comprising cyclodextrin with improved turbidity}

The present invention relates to a method for preparing a cyclodextrin-containing liquid composition, and more particularly, to the cyclodextrin-containing saccharified solution obtained from starch by enzymatic conversion of cyclodextrin glycosyltransferase through pH adjustment and temperature control during ion purification. It relates to a method for preparing a cyclodextrin-containing liquid composition capable of improving cloudiness.

Cyclodextrin is a polymer of glucose first discovered by Villier in 1891. It is a cyclic oligosaccharide in which at least six glucoses have alpha-1,4-glucoside linkage. to be. In particular, cyclodextrins with 6, 7, and 8 glucose units are of commercial importance, and they are α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, respectively. Cyclodextrin). Cyclodextrins with glucose units of 9, 10, and 11, on the other hand, are less commercially important, which are called δ-cyclodextrin, ε-cyclodextrin, and ζ-cyclodextrin, respectively. Cyclodextrins are all cyclic and have molecular pores that can contain various organic and metal compounds in the center. Due to these characteristics, cyclodextrin is one of the new functional substances that are in the spotlight for the purpose of stabilizing volatiles, eliminating bitters, solubilizing insoluble substances, stabilizing colors, and the like in food, medicine, pesticides, fragrances and the like.

Cyclodextrins are usually prepared by reacting cyclodextrin glycosyltransferase (EC 2.4.1.19), which is a cyclodextrin synthase, or the producing microorganism of the enzyme. Specifically, cyclodextrins are produced by treating starch suspensions with liquefaction enzymes at high temperatures and by treating the starch liquors with cyclodextrin glycosyltransferase, a cyclodextrin synthase. At this time, the final product is a liquid composition containing a predetermined amount of cyclodextrin, and other sugars will include glucose, maltose, oligosaccharides. In addition, the cyclodextrin-containing liquid composition prepared by the conventional manufacturing method is a situation that the use of various applications due to the occurrence of turbidity is limited. For example, in opaque beverages and pesticides, the syrup whitening does not have a negative effect, but in other fields, for example, in the food and pharmaceutical sectors, transparency is important and consumers have a turbid syrup in the market. Can cause negative perception.

Looking at methods for improving the cloudiness of cyclodextrins, Japanese Patent Laid-Open No. 2634951 contains starch having an amylopectin content of at least 90% by dextrose equivalents (by acid or enzyme) of about 10 or less. A method of hydrolyzing to a DE) value and converting the starch hydrolysate to cyclodextrins using a cyclodextrin glycosyltransferase is disclosed. However, the method is applied only to starch having a very high amylopectin content, so there is a problem of low economic efficiency. Also, Japanese Patent Publication No. 3055565 adds a hydrogen bond inhibitor to prevent precipitation of noncyclodextrin material between crystallization processes of cyclodextrin and adjusts the pH of the aqueous cyclodextrin solution to between about 9 and 11. A method for producing cyclodextrin crystals, in which no clouding occurs, is then disclosed. However, the method is a method of improving by clouding rather than improving the turbidity of the aqueous solution of cyclodextrin itself has the disadvantage of requiring additional equipment investment and the use of chemicals.

The present invention was derived to solve the conventional problems, the object of the present invention is applicable to cyclodextrin saccharification liquid obtained from starch having an amylopectin content of less than 90%, and requires a separate hydrogen bond inhibitor and crystallization step The present invention provides a method for preparing a cyclodextrin-containing liquid composition in which the cyclodextrin saccharification solution itself is purified under specific conditions so that no clouding occurs.

In order to solve the above object of the present invention, the present invention comprises the steps of (a) treating the starch suspension or starch liquor with a cyclodextrin glycosyltransferase to obtain a cyclodextrin-containing glycosylated solution; (b) treating the cyclodextrin-containing saccharified solution with starch hydrolase to obtain a cyclodextrin-containing hydrolyzed solution; And (c) injecting the cyclodextrin-containing hydrolyzate into an ion exchange resin column and passing the ion to purify the ions, thereby providing a method for preparing a cyclodextrin-containing liquid composition having improved turbidity. In this case, the cyclodextrin-containing hydrolyzate has a Dextrose equivalent (DE) value of 15 to 35 of the total sugars, and the cyclodextrin content is at least 15% based on the total peak area of the sugars shown in the liquid chromatography. It is characterized by the above. In addition, the pH of the cyclodextrin-containing hydrolysis solution is characterized in that it is adjusted to 4.5 ~ 11 before being injected into the ion exchange resin column. In addition, the ion exchange resin column is composed of a column filled with a cation exchange resin and a column filled with an anion exchange resin, characterized in that maintained at a temperature of 45 ~ 70 ℃ when passing through the cyclodextrin-containing hydrolysis solution.

The method for preparing a cyclodextrin-containing liquid composition according to the present invention may provide a cyclodextrin-containing liquid composition in which cloudiness hardly occurs, and wherein the cyclodextrin content is at least 15% by weight or more based on the total weight of the saccharides. In addition, the method for preparing a cyclodextrin-containing liquid composition according to the present invention can be applied to a cyclodextrin saccharified solution obtained from starch having an amylopectin content of less than 90%, and it is possible to remarkably improve the turbidity of the cyclodextrin-containing liquid composition by only an ion purification process. Very economical.

1 is a photograph of the purified cyclodextrin-containing liquid composition obtained in Example 2 of the present invention, Figure 2 is a photograph of the purified cyclodextrin-containing liquid composition obtained in Comparative Example 2 of the present invention.

Before describing the present invention in detail, terms used in the present invention are defined. In the present invention, "cyclodextrin" is a concept of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin or a mixture thereof. In addition, in the present invention, "CGTase" refers to cyclodextrin glycosyltransferase.

Hereinafter, the present invention will be described in detail. The method for preparing a cyclodextrin-containing liquid composition having improved turbidity according to the present invention includes obtaining a cyclodextrin-containing saccharified solution, obtaining a cyclodextrin-containing hydrolyzed solution, and ionizing the cyclodextrin-containing hydrolyzed solution. It consists of steps. Hereinafter, the present invention will be described by dividing step by step.

Cyclodextrin  contain Saccharification  Obtaining Step

Obtaining the cyclodextrin-containing saccharified solution in the method for preparing the cyclodextrin-containing liquid composition of the present invention consists of treating the starch suspension or the starch liquified solution with cyclodextrin glycosyltransferase to generate cyclodextrin. .

Starch in the present invention is not limited in kind, and considering the economics, it is preferable that the amylopectin content is 70 ~ 85%. Such starches include corn starch and tapioca starch.

In the present invention, the starch liquefied liquid is about 2 to 10, preferably hydrolyzed by adding starch hydrolase such as amylase, preferably α-amylase or cyclodextrin glycosyltransferase, to the starch suspension. Liquefied to have a dextrose equivalent (DE) of about 3-6.

In addition, in the present invention, the cyclodextrin-containing saccharified solution preferably has a dextrose equivalent (DE) value of the entire sugars of 2 to 10, more preferably 3 to 7, and the cyclodextrin content is determined in liquid chromatography. It is characterized by at least 15% or more (e.g. 15-30%), more preferably 18% or more (e.g. 18-25%), based on the peak area of the total sugars shown. The amount of cyclodextrin glycosyltransferase added to obtain the cyclodextrin-containing glycosylated solution is about 0.05 to 0.5% by weight based on the dry weight of the starch contained in the starch suspension or the starch used to obtain the starch liquefied liquid. It is preferable that it is and it is more preferable that it is about 0.1 to 0.2 weight%. Moreover, it is preferable that it is about 80-100 degreeC, and, as for the saccharification reaction temperature, it is more preferable that it is 85-95 degreeC. Moreover, it is preferable that it is about 10-20 hours, and, as for saccharification reaction time, it is more preferable that it is 12-18 hours.

Cyclodextrin  Obtaining a Hydrolyzate Containing

In the method for preparing a cyclodextrin-containing liquid composition of the present invention, the step of obtaining a cyclodextrin-containing hydrolyzate may be performed by treating the cyclodextrin-containing saccharified solution with starch hydrolase and the dextrose of all the saccharides contained in the cyclodextrin-containing saccharified solution. It consists of increasing the value of Dexrose equivalent (DE). The cyclodextrin-containing saccharified liquid having a Dextrose equivalent (DE) value of 2 to 10 of all sugars lacks filtering power, and thus, it is not smooth to pretreat with filter paper before ion purification as described below. When the filtrate is passed through the ion exchange resin column, clogging may occur and there is a fear that the flow rate may drop significantly. In addition, in order to solve this problem, the cyclodextrin-containing saccharified solution is greatly diminished in terms of economic efficiency of passing through the ion exchange resin column.

The cyclodextrin-containing hydrolyzate of the present invention is very similar to the cyclodextrin-containing saccharified solution in terms of the composition of the cyclodextrin, and is characterized in that the monosaccharide glucose composition is increased than the cyclodextrin-containing saccharified solution. From this point of view, the cyclodextrin-containing hydrolyzate preferably has a Dextrose equivalent (DE) value of the entire sugars of 15 to 35, more preferably 18 to 30, and the cyclodextrin content is shown in liquid chromatography. It is characterized by at least 15% or more (eg 15-30%), more preferably 17% or more (eg 17-25%) based on the peak area of the entire sugar. The starch hydrolase used to obtain such cyclodextrin-containing hydrolyzate is preferably an amylase, more preferably α-amylase. In this case, the amount of α-amylase added is preferably about 0.01 to 0.1% by weight, and more preferably about 0.02 to 0.05% by weight, based on the dry weight of starch or starch used to obtain the starch liquefied liquid contained in the starch suspension. Do. Moreover, it is preferable that it is about 80-100 degreeC, and, as for a hydrolysis reaction temperature, it is more preferable that it is 85-95 degreeC. Moreover, it is preferable that it is about 15-30 hours, and, as for a hydrolysis reaction time, it is more preferable that it is 18 to 28 hours.

In the method for preparing a cyclodextrin-containing liquid composition of the present invention, the step of obtaining a cyclodextrin-containing hydrolyzate is preferably a cyclodextrin-containing hydrolyzate obtained by treating the cyclodextrin-containing saccharified solution with starch hydrolase to activated carbon. The process further includes the process of bleaching and filtration. By the above process, the load on the ion exchange resin column during the ion purification of the cyclodextrin-containing hydrolysis solution described later can be reduced.

Cyclodextrin  Ion Purification of Hydrolyzate Containing

In the method for preparing a cyclodextrin-containing liquid composition of the present invention, the ion purification of the cyclodextrin-containing hydrolyzate comprises injecting and passing the cyclodextrin-containing hydrolyzate into an ion exchange resin column. The cyclodextrin-containing liquid composition obtained through the ion purification treatment hardly produces turbidity, and the saccharide composition does not show a significant difference from the cyclodextrin-containing hydrolyzate.

In the step of ion-purifying the cyclodextrin-containing hydrolyzate of the present invention, the cyclodextrin-containing hydrolyzate has a pH of 4.5-11, preferably 4.7-10, more preferably 5--10 before being injected into the ion exchange resin column. Is adjusted to 7. In addition, the ion exchange resin column is composed of a column filled with a cation exchange resin and a column filled with an anion exchange resin, wherein the cation exchange resin is preferably a strong acid cation exchange resin, the anion exchange resin is a weakly basic anion exchange resin It is preferable. The type of the strongly acidic cation exchange resin and the anion exchange resin is not particularly limited and can be purchased commercially, for example. In addition, the ion exchange resin column is maintained at a temperature of 45 to 70 ° C, and preferably at a temperature of 50 to 60 ° C when the cyclodextrin-containing hydrolyzate passes. In addition, the rate at which the cyclodextrin-containing hydrolyzate passes through the ion exchange resin column is not particularly limited, but is preferably about 1 to 2 based on the space velocity (SV) in consideration of purification efficiency and productivity. In the ion purification process, the space velocity (SV) is a value obtained by dividing the amount of liquid per hour (m 3 / hr) by the volume of the ion exchange resin (m 3) and having a dimensionless unit. When the pH of the cyclodextrin-containing hydrolysis solution injected into the ion exchange resin column and the temperature of the ion exchange resin column in the ion purification process satisfy the above range, a cyclodextrin-containing liquid composition having improved turbidity may be obtained.

The cyclodextrin-containing liquid composition prepared by the method of the present invention may then be provided in the form of a concentrate through a concentration process, or may be provided in the form of particles through a crystallization process.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to clearly illustrate the present invention and do not limit the scope of protection of the present invention.

One. Cyclodextrin  contain Saccharified  Produce

Production Example 1

A starch suspension having a tapioca starch content (based on dry starch weight) of 30% was prepared by mixing tapioca starch (about 20% amylose content and about 80% amylopectin content) and water. Thereafter, the pH of the starch suspension was adjusted to about 5.3 to 5.8, and heat-resistant alpha-amylase (product name: Liquozyme supra; supplier: Novozyme) was added at about 0.03% by weight based on the dry weight of the starch, and then the temperature of the starch suspension was adjusted. It heated up to about 95 degreeC, pregelatinized, and made it liquefy for 10 minutes at about 105 degreeC. After the liquefaction of starch was completed, the liquefaction reaction product was heated to about 125 ° C. and maintained for about 20 minutes to inactivate heat-resistant alpha-amylase to obtain a starch liquefied liquid. After cooling the starch liquor to about 85 ~ 90 ℃ and adjust the pH to about 5.0 ~ 5.5, add CGTase (product name: Tourzyme 3.0; supplier: Novozyme) to about 0.12% by weight relative to the dry weight of the starch and The reaction was carried out for 15 hours to obtain a cyclodextrin-containing saccharified solution. The solid concentration of the obtained cyclodextrin-containing saccharified solution was about 18 Brix, and the Dextrose equivalent (DE) value was about 4.71.

Production Example 2

A starch suspension having a tapioca starch content (based on dry starch weight) of 30% was prepared by mixing tapioca starch (about 20% amylose content and about 80% amylopectin content) and water. Thereafter, the pH of the starch suspension was adjusted to about 5.3 to 5.8, and CGTase (product name: Tourzyme 3.0; supplier: Novozyme) was added thereto at about 0.12% by weight based on the dry weight of the starch, and then the temperature of the starch suspension was adjusted to about 95 ° C. It heated up to pregelatinization (pregelatinization), it liquefied at about 105 degreeC for 10 minutes, and the starch liquefied liquid was obtained. After cooling the starch liquor to about 85 ~ 90 ℃ and adjust the pH to about 5.0 ~ 5.5, add CGTase (product name: Tourzyme 3.0; supplier: Novozyme) to about 0.12% by weight relative to the dry weight of the starch and The reaction was carried out for 15 hours to obtain a cyclodextrin-containing saccharified solution. The solid concentration of the obtained cyclodextrin-containing saccharified solution was about 18 Brix and the dextrose equivalent (DE) value was about 2.03.

Production Example 3

A starch suspension having a tapioca starch content (based on dry starch weight) of 30% was prepared by mixing tapioca starch (about 20% amylose content and about 80% amylopectin content) and water. Thereafter, the temperature of the starch suspension was raised to about 85 to 90 ° C. and the pH was adjusted to about 5.0 to 5.5. Then, CGTase (product name: Tourzyme 3.0; supplier: Novozyme) was added at about 0.12% by weight based on the dry weight of the starch. And reacted for about 16 hours to obtain a cyclodextrin-containing saccharified solution. The solid concentration of the obtained cyclodextrin-containing saccharified solution was about 18 Brix.

Production Example 4

Cyclodextrin-containing saccharified solution in the same manner as in Example 2 except that CGTase (product name: Tourzyme 3.0; supplier: Novozyme) was added to the starch liquor at about 0.1 wt% based on the dry weight of the starch and reacted for about 13 hours. Obtained. The solid concentration of the obtained cyclodextrin-containing saccharified solution was about 18 Brix, and the Dextrose equivalent (DE) value was about 4.87.

Production Example 5

Cyclodextrin-containing saccharified solution in the same manner as in Example 2 except that CGTase (product name: Tourzyme 3.0; supplier: Novozyme) was added to the starch liquor at about 0.1 wt% based on the dry weight of the starch and reacted for about 13.5 hours. Obtained. The solid concentration of the obtained cyclodextrin-containing saccharified solution was about 18 Brix and the Dextrose equivalent (DE) value was about 4.97.

2. Cyclodextrin  contain Saccharified  Sugar composition analysis

The sugar composition of the cyclodextrin-containing saccharified solution in Preparation Examples 1 to 5 was analyzed using high performance liquid chromatography (HPLC 1200 series, Agilent). Specifically, the diluted saccharified liquid was prepared by diluting with distilled water such that the solid content concentration of the cyclodextrin-containing saccharified liquid became 2 Brix. Then, 2.5 ml of glucoamylase solution (toyobo's GLA-111 enzyme product diluted 1000-fold with distilled water) was added to 10 ml of diluted saccharified solution, and reacted at 40 ° C. for 1 hour, and then the enzyme was inactivated with boiling water. , And filtered with a 0.45㎛ syringe filter to prepare a sample for high performance liquid chromatography analysis. Thereafter, high performance liquid chromatography analysis was performed, and the composition of the sugar was calculated based on the cyclodextrin content analysis method of the Republic of Korea food additives. The sugar composition analysis results are shown in Table 1 below, and high performance liquid chromatography analysis conditions are shown in Table 2 below.

division Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Glucose 75.74 66.85 80.71 69.95 70.29 α-CD 6.43 8.82 7.22 7.86 7.86 β-CD 8.45 8.66 7.45 7.24 7.32 γ-CD 3.18 3.77 1.51 3.41 3.21 Total CD 18.06 21.25 16.2 18.51 18.28

In Table 1, the sugar content is based on the total sugars, that is, the solids contained in the saccharification liquid, not the entire saccharification liquid, and specifically, shows the peak area of each sugar as a percentage of the total peak area of the high performance liquid chromatography. Is% and usually has a value almost equal to the weight%. In addition, most of the glucose in Table 1 is generated in the process of preparing a sample for high performance liquid chromatography analysis. In addition, in Table 1, "CD" means cyclodextrin.

Column Aminex HPX-42A Carbohydrate 7.8 × 300㎜, BIO-RAD Flow rate (ml / min) 0.6 Column temperature (캜) 80 Mobile phase eluent Deionized Water (DW) Detector Refractive Index Detector

3. Cyclodextrin  Preparation of the Hydrolyzate Containing

Production Example 6

The temperature of the cyclodextrin-containing saccharified solution obtained in Preparation Example 1 was maintained at about 85-90 ° C., the pH was adjusted to about 5.3-5.8, and then alpha-amylase (product name: Liquozyme supra; supplier: Novozyme) was added thereto. About 0.02% by weight relative to the dry weight of starch was added and hydrolyzed for about 22 hours. Thereafter, the hydrolysis reaction product was filtered through a filter paper (Whatman filter paper No. 2), and activated carbon was added to the filtrate at about 5% by weight based on the dry weight of the starch, and then about 1 hour at a pH of about 4.5 and a temperature of 72 ° C. And the decolorized filtrate was filtered again with filter paper (Whatman filter paper No. 6) to obtain a cyclodextrin-containing hydrolyzate. The value of Dextrose equivalent (DE) of the obtained cyclodextrin-containing hydrolyzate was about 24.07.

Production Example 7

Using the cyclodextrin-containing saccharified solution obtained in Preparation Example 2, a cyclodextrin-containing hydrolysis solution was obtained in the same manner as in Preparation Example 6 except that the hydrolysis reaction time was about 24 hours. The value of Dextrose equivalent (DE) of the obtained cyclodextrin-containing hydrolyzate was about 20.92.

Production Example 8

Using the cyclodextrin-containing saccharified solution obtained in Preparation Example 3, a cyclodextrin-containing hydrolysis solution was obtained in the same manner as in Preparation Example 6 except that the hydrolysis reaction time was about 21 hours.

Production Example 9

Using the cyclodextrin-containing saccharified solution obtained in Preparation Example 4, alpha-amylase (product name: Liquozyme supra; supplier: Novozyme) was added to the cyclodextrin-containing saccharified solution at about 0.04% by weight based on the dry weight of the starch, and the hydrolysis reaction. A cyclodextrin-containing hydrolyzate was obtained in the same manner as in Preparation Example 6, except that the time was about 24 hours. The value of Dextrose equivalent (DE) of the obtained cyclodextrin-containing hydrolyzate was about 25.08.

Production Example 10.

Using the cyclodextrin-containing saccharified solution obtained in Preparation Example 5, a cyclodextrin-containing hydrolysis solution was obtained in the same manner as in Preparation Example 6 except that the hydrolysis reaction time was about 25.5 hours. The value of Dextrose equivalent (DE) of the obtained cyclodextrin-containing hydrolyzate was about 23.07.

Production Example 11.

Using the cyclodextrin-containing saccharified solution obtained in Preparation Example 5, alpha-amylase (product name: Liquozyme supra; supplier: Novozyme) was added to the cyclodextrin-containing saccharified solution at about 0.04% by weight based on the dry weight of the starch, and the hydrolysis reaction. A cyclodextrin-containing hydrolyzate was obtained in the same manner as in Preparation Example 6, except that the time was about 19 hours. The value of Dextrose equivalent (DE) of the obtained cyclodextrin-containing hydrolyzate was about 26.66.

Production Example 12.

The cyclodextrin-containing saccharified solution obtained in Preparation Example 5 was used, except that alpha-amylase (product name: Liquozyme supra; supplier: Novozyme) was added to the cyclodextrin-containing saccharified solution at about 0.04% by weight based on the dry weight of the starch. Was obtained in the same manner as in Preparation Example 6 cyclodextrin-containing hydrolysis solution. The value of Dextrose equivalent (DE) of the obtained cyclodextrin-containing hydrolyzate was about 23.98.

4. Cyclodextrin  Analysis of Sugar Composition of Containing Hydrolysate

In Preparation Examples 6 to 12, the saccharide composition of the cyclodextrin-containing hydrolyzate was analyzed in the same manner as the above-described method of analyzing the saccharide composition of the cyclodextrin-containing saccharified solution, and the results are shown in Table 3 below.

division Production Example 6 Production Example 7 Production Example 8 Production Example 9 Production Example 10 Production Example 11 Production Example 12 Glucose 77.17 74.62 74.99 78.43 78.12 77.80 78.34 α-CD 7.24 8.64 8.87 8.15 7.80 7.92 7.82 β-CD 9.25 8.61 8.85 7.43 7.29 7.49 7.30 γ-CD 3.46 4.68 4.25 2.87 2.48 2.63 2.99 Total CD 19.95 21.92 22.0 18.44 17.57 18.04 18.11

As shown in Table 3, the cyclodextrin-containing hydrolyzate obtained in Preparation Examples 6 to 12 had a total cyclodextrin content of about 17.5 to 22% based on the entire sugar.

5. Cyclodextrin  Ion Purification of Hydrolyzate Containing Liquid and Its Physical Properties Analysis-Ⅰ

(1) Ion Purification of Cyclodextrin-containing Hydrolysis Solution

Example 1.

The pH of the cyclodextrin-containing hydrolyzate obtained in Preparation Example 7 was adjusted to 4.7, and the ions were purified by passing through an ion exchange resin column. At this time, as the ion exchange resin column, a column filled with a strong acid cation exchange resin (product name: Lewatit S2568; supplier: LANXESS) and a column filled with a weakly basic anion exchange resin (product name: Lewatit S4428; supplier: LANXESS) The connection was used, the temperature of the ion exchange resin column was maintained at 60 ° C., and the flow rate was about 2 based on the space velocity (SV). The liquid passed through the ion exchange resin column was collected to obtain a purified cyclodextrin-containing liquid composition. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Example 2.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 1 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 7 was adjusted to 5.0. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Example 3.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 1 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 7 was adjusted to 6.0. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Example 4.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 1 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 7 was adjusted to 7.0. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Example 5.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 1 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 7 was adjusted to 8.0. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Example 6.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 1 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 7 was adjusted to 9.0. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Example 7.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 1 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 7 was adjusted to 10.0. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Comparative Example 1

A cyclodextrin-containing liquid composition purified in the same manner as in Example 1 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 7 was not adjusted. At this time, the pH of the cyclodextrin-containing hydrolyzate supplied to the ion exchange resin column was about 4.1-4.2. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

Comparative Example 2

The cyclodextrin-containing hydrolyzate obtained in Preparation Example 7 was adjusted to 5.0 and the cyclodextrin-containing purified in the same manner as in Example 1 except that the temperature of the ion exchange resin column was maintained at about 25 ° C. A liquid composition was obtained. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 15 Brix.

(2) Physical property analysis of purified cyclodextrin-containing liquid composition

The final pH, color, turbidity, and turbidity of the purified cyclodextrin containing liquid compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were analyzed. In this case, chromaticity and turbidity were measured using a spectrophotometer, specifically, chromaticity was obtained by measuring absorbance at a wavelength of 420 nm, and turbidity was measured by measuring absorbance at a wavelength of 720 nm. In addition, the occurrence of cloudiness was visually examined. Table 4 shows the analysis results.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Final pH 6.2 6.2 7.6 7.2 6.2 6.6 7.0 5.6 6.5 Chromaticity at 420nm 0.015 0.002 0.010 0.012 0.031 0.035 0.045 0.083 0.997 Turbidity at 720 nm 0.001 0.012 0.026 0.011 0.000 0.000 0.008 0.079 0.953 Cloudiness occurs Not occurring Not occurring Not occurring Not occurring Not occurring Not occurring Not occurring Slightly Badly

As shown in Table 4, when the pH of the cyclodextrin-containing hydrolyzate supplied to the ion exchange resin column during ion purification is less than 4.5 or the temperature of the ion exchange resin column is around 25 ° C., the purified cyclodextrin-containing liquid composition Haze occurred. 1 is a photograph of the purified cyclodextrin-containing liquid composition obtained in Example 2 of the present invention, Figure 2 is a photograph of the purified cyclodextrin-containing liquid composition obtained in Comparative Example 2 of the present invention. As shown in FIGS. 1 and 2, the turbidity of the purified cyclodextrin-containing liquid composition was worse when the ion exchange resin column was maintained at a low temperature. In addition, as the pH of the cyclodextrin-containing hydrolysis solution supplied to the ion exchange resin column during ion purification increases the chromaticity of the purified cyclodextrin-containing liquid composition, and when the pH of the cyclodextrin-containing hydrolysis solution is 8.0 or higher, It was observed that the color of the cyclodextrin-containing liquid composition became dark when viewed visually.

6. Cyclodextrin  Ion Purification of Hydrolyzate Containing Liquids and Their Physical Properties- Ⅱ

(1) Ion Purification of Cyclodextrin-containing Hydrolysis Solution

Example 8.

The pH of the cyclodextrin-containing hydrolyzate obtained in Preparation Example 10 was adjusted to 4.7, and ion-purified by passing through an ion exchange resin column. At this time, as the ion exchange resin column, a column filled with a strong acid cation exchange resin (product name: Lewatit S2568; supplier: LANXESS) and a column filled with a weakly basic anion exchange resin (product name: Lewatit S4428; supplier: LANXESS) The connection was used, the temperature of the ion exchange resin column was maintained at 60 ° C., and the flow rate was about 1.0 based on the space velocity (SV). The liquid passed through the ion exchange resin column was collected to obtain a purified cyclodextrin-containing liquid composition. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 20.60. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Example 9.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 8 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 11 was adjusted to 5.0 and then passed through an ion exchange resin column. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 20.75. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Example 10.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 8 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 11 was adjusted to 6.0 and then passed through an ion exchange resin column. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 20.78. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Example 11.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 8 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 11 was adjusted to 7.0 and then passed through an ion exchange resin column. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 22.85. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Example 12.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 8 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 12 was adjusted to 8.0 and then passed through an ion exchange resin column. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 22.08. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Example 13.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 8 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 12 was adjusted to 9.0 and then passed through an ion exchange resin column. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 22.16. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Example 14.

A cyclodextrin-containing liquid composition purified in the same manner as in Example 8 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 12 was adjusted to 10.0 and then passed through an ion exchange resin column. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 22.23. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Example 15.

The pH of the cyclodextrin-containing hydrolyzate obtained in Preparation Example 11 was adjusted to 5.0, and then passed through an ion exchange resin column, except that the temperature of the ion exchange resin column was maintained at 50 ° C. The cyclodextrin containing liquid composition purified by the method was obtained. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Comparative Example 3

A cyclodextrin-containing liquid composition purified in the same manner as in Example 8 was obtained except that the pH of the cyclodextrin-containing hydrolysis solution obtained in Preparation Example 9 was adjusted to 4.3 and then passed through an ion exchange resin column. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix, and the dextrose equivalent (DE) value was about 23.27. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Comparative Example 4

The pH of the cyclodextrin-containing hydrolyzate obtained in Preparation Example 9 was adjusted to 4.3, and then passed through an ion exchange resin column, except that the temperature of the ion exchange resin column was maintained at 50 ° C. The cyclodextrin containing liquid composition purified by the method was obtained. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Comparative Example 5

The pH of the cyclodextrin-containing hydrolyzate obtained in Preparation Example 9 was adjusted to 4.3, and then passed through an ion exchange resin column, except that the temperature of the ion exchange resin column was maintained at 40 ° C. The cyclodextrin containing liquid composition purified by the method was obtained. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

Comparative Example 6

The pH of the cyclodextrin-containing hydrolyzate obtained in Preparation Example 11 was adjusted to 5.0, and then passed through an ion exchange resin column. The cyclodextrin containing liquid composition purified by the method was obtained. At this time, the solid concentration of the purified cyclodextrin-containing liquid composition was about 17 Brix. It was again concentrated to about 75 Brix using a vacuum concentrator (Model: Rotavapor R-210; supplier: Buchi).

(2) Physical property analysis of purified cyclodextrin-containing liquid composition

It was visually inspected whether turbidity occurred in the purified cyclodextrin-containing liquid composition obtained in Examples 8 to 15 and Comparative Examples 3 to 6, and the results are shown in Table 5 below.

division Cloudiness occurs Example 8 Does not occur Example 9 Does not occur Example 10 Does not occur Example 11 Does not occur Example 12 Does not occur Example 13 Does not occur Example 14 Does not occur Example 15 Does not occur Comparative Example 3 Slightly Comparative Example 4 Slightly Comparative Example 5 Severe Comparative Example 6 Slightly generated

In order to prevent turbidity of the purified cyclodextrin-containing liquid composition as shown in Table 5, the pH of the cyclodextrin-containing hydrolysis solution supplied to the ion exchange resin column during ion purification should be 4.5 or higher, preferably 4.7 or higher. At the same time, it can be seen that the temperature of the ion exchange resin column should be maintained at 45 ° C. or higher, preferably 50 ° C. or higher.

In addition, for the purified cyclodextrin-containing liquid compositions obtained in Examples 8 to 14 and Comparative Example 3, the sugar composition was analyzed using high performance liquid chromatography (HPLC 1200 series, Agilent), and the results are shown in the following table. 6 is shown.

division Sugar composition (%) Glucose α-CD β-CD γ-CD Total CD Example 8 75.94 8.29 7.56 1.93 17.78 Example 9 69.28 8.05 7.64 4.30 19.99 Example 10 69.55 8.48 7.79 3.03 19.29 Example 11 62.53 9.80 9.28 3.48 22.57 Example 12 76.21 8.15 7.26 4.18 19.59 Example 13 75.20 7.72 7.18 3.38 18.28 Example 14 60.12 9.84 7.78 3.38 21.00 Comparative Example 3 70.15 8.15 7.18 3.09 18.43

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. In addition, many modifications may be made to adapt a particular situation and material to the teachings of the invention without departing from the essential scope thereof. Accordingly, the protection scope of the present invention should not be construed as being limited to the particular embodiments disclosed as the best mode contemplated for carrying out the invention but to cover all embodiments falling within the scope of the appended claims.

Claims (8)

(a) treating a starch suspension or starch liquor with a cyclodextrin glycosyltransferase to obtain a cyclodextrin-containing saccharified solution;
(b) treating the cyclodextrin-containing saccharified solution with starch hydrolase to obtain a cyclodextrin-containing hydrolyzed solution; And
(c) injecting the cyclodextrin-containing hydrolysis solution into an ion exchange resin column and passing it through ion purification;
The starch has an amylopectin content of 70-85%,
The cyclodextrin-containing hydrolyzate has a Dextrose equivalent (DE) value of 15 to 35 of the total sugars, and the cyclodextrin content is at least 15% or more based on the peak area of the total sugars shown in the liquid chromatography. , The weight ratio of α-cyclodextrin (α-Cyclodextrin): β-cyclodextrin (β-Cyclodextrin): γ-cyclodextrin (γ-Cyclodextrin) constituting the cyclodextrin is 1: 1: based on the peak area shown in the liquid chromatography (0.91-1.28): (0.31-0.54),
PH of the cyclodextrin-containing hydrolysis solution is adjusted to 4.7 ~ 10.0 before being injected into the ion exchange resin column,
The ion exchange resin column is composed of a column filled with a strong acid cation exchange resin and a column filled with a weakly basic anion exchange resin, characterized in that it is maintained at a temperature of 45 ~ 70 ℃ when passing through the cyclodextrin-containing hydrolysis solution A method for preparing a cyclodextrin-containing liquid composition having improved turbidity.
According to claim 1, wherein the cyclodextrin-containing saccharified solution has a Dextrose equivalent (DE) value of 2 to 10 of the total sugars, cyclodextrin content based on the peak area of the total sugars shown in the liquid chromatography A process for producing a cyclodextrin-containing liquid composition with improved cloudiness, characterized in that at least 15% or more.
The cyclodextrin-containing glycosylated solution according to claim 2, wherein the cyclodextrin-containing glycosylated solution has a cyclodextrin content of 15 to 30% based on the peak area of the entire sugars shown in the liquid chromatography. Way.
The method according to claim 1, wherein the starch hydrolase is α-amylase.
The cyclodextrin-containing hydrolyzate of claim 1, wherein the cyclodextrin content of the cyclodextrin-containing liquid composition with improved turbidity is characterized in that the cyclodextrin content is 15 to 30% based on the peak area of the entire sugars shown in the liquid chromatography. Manufacturing method.
delete delete The method according to any one of claims 1 to 5, wherein the step (b) is performed by treating the cyclodextrin-containing hydrolyzate obtained by treating the cyclodextrin-containing saccharification enzyme with starch hydrolysis enzyme with activated carbon to decolorize and filter it. Process for producing a cyclodextrin-containing liquid composition with improved turbidity characterized in that it further comprises a process.

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