KR19980069011A - Method of manufacturing high purity maltose - Google Patents

Abstract

The present invention operates an improved pseudo mobile phase separation device in which four columns filled with a cation exchange resin are continuously circulated under specific conditions, and the maltose sugars from the starch saccharification solution containing maltotriose or higher polymer oligosaccharides and maltose are maltose. It relates to a process for producing high purity maltose with a content of at least 90% with a recovery of at least 70%.

In addition, the production method of the present invention is an economical method of producing a high-purity maltose per unit resin in a large amount by increasing the separation yield of maltose with a small number of floors, or by reducing the amount of resin used by reducing the number of packed columns. .

Description

Method of manufacturing high purity maltose

The present invention relates to a method for producing high purity maltose. More specifically, the present invention is a starch saccharified solution containing maltotriose or higher polymer oligosaccharides and maltose by operating an improved pseudo mobile phase separation device in which four columns filled with a cation exchange resin are continuously circulated under specific conditions. It relates to a method for producing maltose of high purity maltose content per solid content from 90% or more from.

In recent years, maltose has low sweetness and excellent moisturizing property and has been widely applied to food and beverages and pharmaceuticals. In addition, as sugar alcohols having low-calorie and hard tooth decay properties have been spotlighted as food materials, the demand of maltini, a honeycomb, has increased greatly, and the demand of maltose, which is a direct raw material thereof, has also increased. As a result, maltose of high purity can be used as a maltose powder product using the properties of maltose itself and at the same time can be used as a raw material necessary for conversion to a high value-added product such as maltitol.

The production of this important maltose in high purity was urgently needed first of all. Generally, maltose is added to liquefied starch simultaneously with maltose enzymes such as beta amylase and starch degrading enzyme alpha-1,6 glucosidase that attacks the 1,6 bond of amylopectin, resulting in a maltose content of at least 70%. It can be produced relatively easily by preparing starch saccharified solution. In addition, when maltogenase is added together with the above enzymes, maltotriose is decomposed, thereby increasing the maltose content by more than 85%. It is known that the addition of an enzyme produced and produced by an officer can produce maltose syrup having a maltose content of about 88%. However, direct production of high purity maltose having a maltose content of 90% or more by using starch glycosylation method alone involves various economic and technical problems.

Therefore, a method of preparing maltose of high purity by preparing starch saccharified solution using an enzyme and then separating maltose only from it has been developed.

Japanese Patent Publication No. 56-17078 discloses a method of eluting and separating maltose sugar solution using a dialysis membrane, and Japanese Patent Publication No. 56-11437 adds 30-50% of acetone. A method of producing high purity maltose by removing the insoluble material generated by the present invention is disclosed. In addition, Korean Patent Publication No. 82-1788 discloses high purity maltose without using an organic solvent or the like by selectively adsorbing oligosaccharides or dextrins by passing a starch saccharified solution through a column filled with granular activated carbon.

However, the above-described method has not been put into practical use because of various technical and economic problems to be applied industrially for mass production of maltose.

Subsequently, a method of producing maltose of high purity was developed by passing starch saccharified liquid through a column filled with an ion exchange resin. For example, Japanese Patent Publication No. 52-46290 discloses high purity maltose by passing starch saccharified liquid through an anion exchange resin. However, when the anion exchange resin is used, the thermal stability (up to 40 ° C) of the resin is lowered, so that the work must be performed at a lower temperature, so that the viscosity of the stock solution is increased, and then the pressure inside the column is increased, so that the work at a high concentration is performed. There was a problem that was difficult.

In order to make up for the disadvantages of the anion exchange resin, Japanese Patent Publication No. 6-14880 manufactures high purity maltose using a highly productive alkali metal type strong acid cation exchange resin. However, this method requires a very high column, and the separation method is a batch method, which results in a long working time and reduced maltose resolution per unit resin, making it inefficient for producing large-scale high-purity maltose.

In order to improve this, pseudo mobile phase separation methods have been developed (see Japanese Patent Publication No. 5-9080 and Japanese Patent Publication No. 4-334503). In a manner designed to provide a separation performance equivalent to, it is basically a method of moving the feed position of the feed solution in the moving direction of the eluent instead of moving the filler. Since a part of the unit packed phase in the concentration distribution curve is discharged and the composition of each fraction is constantly vibrated during discharge, a larger number of unit packed phases leads to better separation. However, as the number of industrially packed phases increases, the device becomes more complicated and the production cost is high.

In order to solve the above-mentioned shortcomings, that is, an improved pseudo mobile phase separation method has been developed with a high separation yield regardless of the number of unit packed phases (see Japanese Patent Publication No. 7-46097). This method focuses on the conventional pseudo-mobile phase separation method, in which the supply-discharge proceeds simultaneously while the concentration distribution curve moves through the unit packed phase, so that the flow rate of this supply-discharge is small compared to the circulation flow in each region. Is divided into two parts, first supplying-discharging the required liquid at a large flow rate close to the circulation flow in each region, then stopping supply-discharging, and then circulating only to move the predetermined amount of the concentration distribution curve.

However, the improved pseudo mobile phase separation method has many operating variables for separating only the necessary components from the stock solution containing two or more components (the operation method varies depending on each separation device or resin type). Since the separation aid varies depending on the composition and properties of the stock solution, various conditions must be considered for the high-purity production of a specific substance. For this reason, when a specific substance is manufactured at high purity using an electrically improved pseudo mobile phase separation method, Very limited is reported. For example, it is known that glucose and fructose are separated to produce high purity fructose by an improved pseudo mobile phase separation method, and fructooligosaccharides of high purity are prepared by separating fructooligosaccharide and oligosaccharide. However, there have been no reports of maltose of high purity using the above-described improved pseudo mobile phase separation method.

Therefore, the present inventors have diligently researched to produce a large amount of high purity maltose at low cost, and as a result, by operating an improved pseudo mobile phase separation device connected to four columns filled with a cation exchange resin under continuous conditions, The present invention has been completed by discovering that high purity maltose having a maltose content of solid content of 90% or more can be produced on an economical and industrial scale from starch saccharification liquid containing at least oligosaccharide and maltose.

After all, it is an object of the present invention to provide a method for producing maltose of high purity by applying an improved pseudo mobile phase separation method.

1 shows a schematic diagram of an improved pseudo mobile phase separation apparatus used in the present invention.

FIG. 2 shows the concentration distribution curve formed in the packed bed when the separator of FIG. 1 is operated.

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

The improved pseudo mobile phase separator used in the present invention is composed of four packed phases (columns), in which fluid flows circulating in one direction and a set of raw material supply ports, non-adsorbent material discharge ports, desorbent supply ports and adsorption depending on the flow direction. The material discharge port is installed in order, and the whole device is located between the raw material supply port and the non-adsorbed material discharge port, the adsorption zone between the non-adsorbed material discharge port and the desorbent supply port, and the adsorption area between the desorbent supply port and the adsorbent material discharge port, It is divided into four zones consisting of refining zone between adsorbent outlet and desorbent supply port, desorbent zone between desorbent supply and adsorbent outlet, and enrichment zone between adsorbent outlet and raw material supply port. The passed liquid is chromatographed to move to another set of feed ports in the downstream direction after a certain period of time. Device. 1 shows a schematic diagram of a separator used in the present invention.

Within the above-mentioned constant working time, two steps of the supply-discharge process and the circulation process are performed. ① The supply-discharge process introduces a part of the fluid discharged from the desorption zone into the concentration zone, and then transfers the fluid from the concentration zone to the adsorption zone. Feeding the starch saccharified liquid through the raw material supply port and the desorbent through the desorbent supply port while moving; The process of discharging the fluid discharged from the adsorption zone through the non-adsorption material discharge port and the part of the fluid discharged from the desorption area through the adsorption material discharge port, respectively. ② The circulation process is performed in the packed bed without supplying or discharging fluid to the packed bed. It is a process of moving a fluid downstream.

A two-step process consisting of such a supply-discharge process and a circulating process is made one step, and when this is completed, the process in the downstream direction is repeatedly repeated stepwise as in one step. Return to the valve tank and complete one cycle.

In the supply-discharge process, the feed flow rate of the starch saccharified solution is 0.3 to 0.5 L / hr, most preferably 0.35 L / hr: The feed rate of the desorbent is 0.9 to 1.5 L / hr, most preferably 1.05 L / hr: The discharge flow rate of the adsorbent material is 0.4 to 0.67 L / hr, preferably 0.467 to 0.562 L / hr, and the discharge flow rate of the non-adsorbed material is 0.8 to 1.34 L / hr, preferably 0.83 to 0.93 L / hr. Do it yourself. In addition, the operating time of the feed-discharge process is adjusted to 100 to 500 seconds.

In addition, the flow rate of the fluid flowing in each region during the circulation process is adjusted to 0.9 to 1.5l / hr, most preferably 1.05l / hr, the operating time of the circulation process is adjusted to 900 to 1500 seconds.

On the other hand, the raw material of saccharified liquid used in the present invention is a starch saccharified solution containing maltotriose or higher polymer oligosaccharides and maltose, preferably a starch saccharified liquid having a maltose content of solid sugar of at least 70%. A cation exchange resin, preferably an alkali metal type strong acid cation exchange resin, is used, and a desorbent is water, which is desorbed depending on the resin used to prevent degradation of the resin and to prevent maltose decomposition during the separation process. Adjust pH of agent appropriately.

When maltose is prepared by the improved pseudo-mobile phase separation method under the above-described conditions of the present invention, the maltose fraction contains maltose of high purity of maltose content of 90% or more per solid content, and its recovery rate is maltose in starch saccharified solution. It can be seen that more than 70% for.

In addition, the high-purity maltose manufacturing method of the present invention described above discharges oligosaccharides, which are a part of maltose and non-adsorbing substances, only in the supply-discharge process of the concentration distribution curve of the starch saccharified liquid, so that the change in the liquid composition of the discharge liquid is less over time In addition, a small packing column can increase the separation yield of maltose. In addition, reducing the number of filling towers means a reduction in the amount of resin used, and it is economical to produce a large amount of high purity maltose per unit resin.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention more specifically, 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

In order to prepare high purity maltose using the improved pseudo mobile phase separation apparatus shown in FIG. 1, the glycosylated solution used in the present invention is starch decomposition such as alpha amylase, beta amylase, alpha-1,6 glucosidase, etc. A commercially available starch saccharified solution Sunhaimalto ^TM (Samyang Genex, South Korea) having a maltose content of 70% or more and a glucose content of 5% or less was prepared by adding an enzyme.

In addition, the separation resin used in the present invention is Na-type strongly acidic cation exchange resin UBK 530 (Mitsubishi, Japan), and this resin has a small particle size and uniform particle size to separate fructose and glucose or GF3 in fructooligosaccharide. In addition to being widely used to separate high molecular weight oligosaccharides having a molecular weight, it is known to have excellent resolution, heat resistance and abrasion resistance. The resin was filled in a column of glass 5 cm inside and 51.5 cm long, and the temperature in the column was kept constant at 60 ° C.

The water used as the desorbent was distilled water, and the pH was adjusted to 9 to 10 in order to prevent degradation of the Na-type resin and to prevent maltose decomposition during the separation process.

When the improved pseudo mobile phase separation apparatus was operated under the above-described conditions, the concentration distribution curve formed in the packed phase was as shown in FIG. 2, and the operation of the apparatus was advanced as described below. At this time, the pump P10CA disclosed in FIG. 1 serves to flow the solution showing the concentration distribution curve of FIG. 2 downstream in the circulating process downstream by one packed phase, and the pump P10S supplies the starch saccharified solution (S) and the pump. P10W is responsible for the supply of desorbent (water) (W), pump P10P for the discharge of maltose (P) and pump P10R for the discharge of oligosaccharides (R). Among these, the pump P10P may be replaced with a PIC (pressurre indicator controller) in which the opening and closing degree of the valve is adjusted according to the pressure in the filling tower.

Supplying starch saccharified liquid through valve HV102S disclosed in FIG. 1 through valve HV104W; After the supply-discharge process of discharging oligosaccharides through the valve HV102R and maltose through the valve HV104P, the supply to the packed bed and the discharge valve are closed, and the valves HV101C, HV102C, HV103V and HV104C are opened and only the pump P10CA is opened. A circulation process was performed to run the fluid in the packed bed in the downstream direction. The flow rates of the fluids moving the adsorption, purification, desorption, and concentration zones downstream in the feed-discharge process are represented by R1, R2, R3, and R4, respectively. (See; FIG. 2).

The two-step process consisting of the above-described supply-discharge process and the circulation process is made one step, and when this is completed, the process in the downstream direction is repeated in steps as in the one step, and the liquid having passed the four steps is The cycle returned to the tank and completed one cycle (see Table 1).

Table 1: Valves Opened in Each Process by Step

Example 1-1

A 60% (w / w) aqueous solution prepared by dissolving Sun Hai Malto ^TM (Samyang Genex, South Korea) having a maltose content of 76.9% in water was used as a stock solution to be supplied to a separator. Maltose separation was carried out in the process sequence disclosed in Table 1 and the operating conditions shown in Table 2 below, and the sugar composition of each fraction when the steady state was reached is shown in Table 3 below.

[Table 2] Operation Conditions in Supply-Discharge Process and Circulation Process

[Table 3] Composition of sugars contained in each fraction of steady state

*: DPI is glucose, DP2 is maltose, DP3 is maltotriose, and DP4 + represents maltotriose or higher oligosaccharides, respectively.

**:% represents weight% per solid content.

As shown in Table 3, the maltose fraction contained maltose of high purity of 94.3% maltose per solid content, and the recovery rate was 83% relative to maltose in the starch saccharified solution.

Example 1-2

A 60% (w / w) aqueous solution prepared by dissolving Sun Hai Malto ^TM (Samyang Genex, South Korea) having a maltose content of 77.2% in water was used as a stock solution to be supplied to a separator. Maltose separation was carried out using the process sequence disclosed in Table 1 and the operating conditions shown in Table 4 below, and the sugar composition of each fraction when the steady state was reached is shown in Table 5 below.

[Table 4] Operation Conditions in Supply-Discharge Process and Circulation Process

[Table 5] Composition of sugars contained in each fraction of steady state

*: DPI is glucose, DP2 is maltose, DP3 is maltotriose, and DP4 + represents maltotriose or higher oligosaccharides, respectively.

**:% represents weight% per solid content.

As shown in Table 5, the maltose fraction contained maltose of high purity of maltose per solid content of 91.84%, and the recovery rate was 91% of maltose in the starch saccharified solution.

Example 1-3

A 60% (w / w) aqueous solution prepared by dissolving Sun Hai Malto ^TM (Samyang Genex, South Korea) having a maltose content of 77.2% in water was used as a stock solution to be supplied to a separator. Maltose separation was carried out using the process sequence disclosed in Table 1 and the operating conditions shown in Table 6 below, and the sugar composition of each fraction when the steady state was reached is shown in Table 7 below.

[Table 6] Operation Conditions in Supply-Discharge Process and Circulation Process

[Table 7] Composition of sugars contained in each separated fraction in steady state

*: DPI is glucose, DP2 is maltose, DP3 is maltotriose, and DP4 + represents maltotriose or higher oligosaccharides, respectively.

**:% represents weight% per solid content.

As shown in Table 7, the maltose fraction contained maltose of high purity of 90.76% maltose per solid content, and the recovery rate was 72% of maltose in the starch saccharified solution.

Example 1-4

A 60% (w / w) aqueous solution prepared by dissolving Sun Hai Malto ^TM (Samyang Genex, South Korea) having a maltose content of 77.2% in water was used as a stock solution to be supplied to a separator. Maltose separation was carried out using the process sequence disclosed in Table 1 and the operating conditions shown in Table 8 below, and the sugar composition of each fraction when the steady state was reached is shown in Table 9 below.

[Table 8] Operation Conditions in Supply-Discharge Process and Circulation Process

[Table 9] Composition of sugars contained in each separated fraction in steady state

*: DPI is glucose, DP2 is maltose, DP3 is maltotriose, and DP4 + represents maltotriose or higher oligosaccharides, respectively.

**:% represents weight% per solid content.

As shown in Table 9, the maltose fraction contained a high purity maltose of 90.4% maltose per solid content, the recovery was 71% of maltose in the starch saccharified liquid.

[Comparative Example]

Except for the operating conditions disclosed in Table 10, maltose separation was carried out in the same manner as in Example 1-2, the sugar composition of each fraction when the steady state is reached is shown in Table 11.

[Table 10] Operation Conditions in Supply-Discharge Process and Circulation Process

[Table 11] Composition of sugars contained in each separated fraction in steady state

*: DPI is glucose, DP2 is maltose, DP3 is maltotriose, and DP4 + represents maltotriose or higher oligosaccharides, respectively.

**:% represents weight% per solid content.

As shown in Table 7, the maltose fraction was found to contain maltose of 83.37%, the maltose content per solid content of 90% or less. Therefore, it was confirmed that the operating conditions used in the comparative example are not preferable for the production of maltose of high purity.

As described and demonstrated in detail above, the maltose manufacturing method of the present invention using an improved pseudo mobile phase separation apparatus can produce a high purity maltose having a maltose content of solids of 90% or more as a recovery rate of 70% or more. In addition, the production method of the present invention is an economical method of producing a high-purity maltose per unit resin in large quantities by increasing the separation yield of maltose with a small number of filling towers, reducing the amount of resin used by reducing the number of filling towers.

Claims (7)

Maltotriose is supplied using an improved pseudo mobile phase separator in which starch saccharified solution containing polymer oligosaccharide and maltose is used as a stock solution, water is used as a desorbent, and four columns filled with a cation exchange resin are continuously circulated. High purity maltose, characterized in that a high purity maltose having a maltose content of 90% or more per solid content is obtained by separating a high maltose fraction containing maltose as an adsorbent through a discharge process and a circulation process. Manufacturing method. The method of claim 1, Starch saccharification liquid is characterized in that the saccharification liquid content of maltose per solid content of 70% or more Method for producing high purity maltose. The method of claim 1, The cation exchange resin is an alkali metal type strong acid cation exchange resin Method for producing high purity maltose. The method of claim 1, In the feed-discharge process using the improved pseudo mobile phase separation apparatus, the feed flow rate of the starch saccharified solution is 0.3 to 0.5 L / hr: The feed flow rate of the desorbent is 0.9 to 1.5 L / hr; Discharge flow rate of the adsorbed material was 0.4 to 0.67 L / hr; And, the discharge flow rate of the non-adsorbed material is characterized in that it is adjusted to 0.8 to 1.34ℓ / hr Method for producing high purity maltose. The method of claim 1, In the supply-discharge process using the improved pseudo mobile phase separator, the operating time is characterized in that it is adjusted to 100 to 500 seconds Method for producing high purity maltose. The method of claim 1. In the circulation process using the improved pseudo mobile phase separation device, the flow rate of the fluid flowing through the adsorption, purification, desorption and concentration areas is controlled to be 0.9 to 1.5 l / hr. Method for producing high purity maltose. The method of claim 1, In the circulation process using the improved pseudo mobile phase separation device, the operating time is characterized in that it is adjusted to 900 to 1500 seconds Method for producing high purity maltose.