KR20210052740A - Method for purifying sugar-containing solution using acrylic-based ion exchange resin and styrene-based ion exchange resin - Google Patents

Abstract

The present invention relates to a method for purifying a sugar-containing solution, and more specifically, to a method for purifying a sugar-containing solution, which can effectively remove impurities having different sizes to obtain the sugar-containing solution having a low color value and low electrical conductivity by bringing the sugar-containing solution into contact with the styrenic ion exchange resin after bringing the sugar-containing solution into contact with an acrylic ion exchange resin, or bringing the sugar-containing solution into contact with the acrylic ion exchange resin after bringing the sugar-containing solution into contact with the styrenic ion exchange resin.

Description

Purification method of sugar-containing solution using acrylic ion exchange resin and styrene ion exchange resin {METHOD FOR PURIFYING SUGAR-CONTAINING SOLUTION USING ACRYLIC-BASED ION EXCHANGE RESIN AND STYRENE-BASED ION EXCHANGE RESIN}

The present invention relates to a method for purifying a sugar-containing solution using an acrylic ion exchange resin and a styrene-based ion exchange resin that can be used for sugar production, and more particularly, unlike a method of purifying a sugar-containing solution using a conventional activated carbon, The present invention relates to a method for purifying a sugar-containing solution capable of obtaining a sugar-containing solution having a low color value and low electrical conductivity by effectively removing impurities of different sizes by sequentially contacting an acrylic ion exchange resin and a styrene-based ion exchange resin. .

In the case of purifying a sugar-containing solution, after performing purification processes such as a carbonic acid trapping step, an activated carbon filtration step, and a bone charcoal filtration step, an ion exchange treatment is performed as a post treatment. The ion exchange treatment includes an ion exchange treatment for the purpose of decolorization and an ion exchange treatment for the purpose of desalting.

Ion exchange treatment for the purpose of desalting is generally a two-phase shear desalination system using a strongly acidic cation exchange resin layer and a weakly basic anion exchange resin layer, and a mixture comprising a strong acidic cation exchange resin and a type II strongly basic anion exchange resin. It is constituted by a common sense downstream desalination system, and most of salts, pigments and other impurities in the sugar solution are removed in the front desalination system, and the final desalination, decolorization, and pH adjustment are performed in the subsequent desalination system.

The desalting treatment is widely used industrially and is a suitable method as a method for purifying a sugar solution in that it can obtain a sugar solution of high purity. This is because the final desalination using the mixed layer is proceeding smoothly and well. In addition, recently, a method of forming a mixed phase layer using a weakly basic anion exchange resin or an I type strongly basic anion exchange resin has been proposed instead of the II type strong basic anion exchange resin.

A method of purifying raw sugar using an ion exchange resin and activated carbon is generally known. For example, Korean Patent Publication No. 1993-0001318 describes a method of decolorizing and purifying by sequentially passing polydextrose, a food additive such as raw sugar, through activated carbon and ion exchange resin. However, in the decolorization and purification method, as activated carbon is used, it is difficult to remove impurities having a low molecular weight, and regeneration is also difficult.

In addition, a method of purifying raw sugar using anion exchange resin and cation exchange resin is also generally known. For example, Korean Patent Publication No. 1983-0001887 may be mentioned, and a method of purifying raw sugar using a strong basic anion exchange resin, a strong acidic cation exchange resin, and a weakly acidic cation exchange resin is described. However, the purification method is still inferior in bleaching and purification efficiency.

Accordingly, there is a need to develop a raw sugar purification method that can effectively remove impurities of various sizes, including impurities of low molecular weight, is easy to regenerate, is economically excellent, and has high efficiency of decolorization and purification.

The present invention is to solve the problems of the prior art as described above, by sequentially contacting an acrylic ion exchange resin and a styrene ion exchange resin, effectively removing impurities of different sizes, containing sugars having a low color value and low electrical conductivity. It is a technical problem to provide a method for purifying a sugar-containing solution that can obtain a solution.

In order to solve the above technical problem, the present invention includes the steps of: (a) contacting a sugar-containing solution with an acrylic ion exchange resin, and then contacting a styrene-based ion exchange resin; Or (b) contacting the sugar-containing solution with a styrene-based ion exchange resin, and then contacting the sugar-containing solution with an acrylic ion-exchange resin.

According to another aspect of the present invention, there is provided a purified sugar-containing solution that is purified by the above method, has a color value of 300 IU or less, and an electrical conductivity of 100 µs/cm or less.

According to the present invention, without performing a conventional activated carbon treatment, a sugar-containing solution is brought into contact with an acrylic ion exchange resin and a styrene ion exchange resin in the order of contact, or in the opposite order, thereby effectively removing impurities of low molecular weight. , Impurities of various sizes can be effectively removed due to the difference in pore size between the acrylic ion exchange resin and the styrene ion exchange resin, thereby obtaining a purified sugar-containing solution having a low color value and electrical conductivity.

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

The method for purifying a sugar-containing solution of the present invention includes the steps of: (a) contacting the sugar-containing solution with an acrylic ion exchange resin, and then contacting a styrene-based ion exchange resin; Or (b) contacting the sugar-containing solution with a styrene-based ion exchange resin, followed by contacting with an acrylic-based ion exchange resin; Includes.

The sugar-containing solution to be purified by the purification method in the present invention is not particularly limited, and generally, an aqueous solution containing saccharides such as starch sugar solution, beet sugar solution, or sucrose solution, or an aqueous solution containing a saccharide-based product, etc. Can be Specifically, a glucose solution prepared from starch as a raw material, a starch sugar solution such as an isomerized sugar solution, and starch syrup, a sugar alcohol sugar solution such as sorbitol and maltitol, a lactose-containing sugar solution, or various oligosaccharide solutions, and the like may be mentioned.

The sugar-containing solution generally contains various impurities derived from raw materials and manufacturing processes, and these may degrade the performance of the ion exchange resin, so it is preferable to perform the purification process after pretreatment.

In one embodiment, the sugar-containing solution includes (1) a step of washing raw sugar, and (2) preparing a solution by dissolving the resultant product of step (1) in a solvent; And (3) the solution of step (2) is reacted with lime and carbon dioxide gas to remove foreign substances.

The sedan step [Step (1)] may be performed by washing the raw sugar in a separator (preferably a centrifugal separator), and specifically, the raw sugar is kneaded with syrup and added to the separator, and then the syrup is first removed. It can be carried out by secondly adding hot water to clean foreign substances on the surface of the raw sugar. The sedan method and apparatus are not particularly limited, and those commonly used in this field may be used without limitation. For example, a batch type separator may be used as the separator, or a continuous type separator may be used.

Sugarcane may be used as a raw sugar for the raw sugar, and the raw sugar may have a color value of 3,000 to 4,000 IU.

The solution preparation step [step (2)] may be performed by dissolving the resultant (washed raw sugar) of step (1) in a solvent. Although not particularly limited, hot water (specifically, hot water of 70 to 80° C.) may be used as the solvent used in the above step.

The carbonic acid trapping step [step (3)] may be performed by reacting the solution obtained in step (2) with lime and carbon dioxide gas to remove foreign substances. The sesaccharide solution obtained through the steps (1) and (2) contains a polymeric organic substance and a pigmented substance as impurities, and the polymeric organic substance can be removed by carbonic acid insects.

Lime and carbon dioxide gases cause the following chemical reactions.

Ca(OH) ₂ + CO ₂ → CaCO ₃ + H ₂ O

When the sedan solution is reacted with carbonic acid gas (CO ₂ gas) and slaked lime (Ca(OH) ₂ ), colored substances and impurities contained in the sedan solution are removed, and at this time, about 45% to 55% of the colored substances are removed. I can. The sugar-containing solution obtained after the carbonic acid insect step generally has a color value of 800 to 1,000 IU.

The sugar-containing solution obtained through steps (1) to (3) may be filled in a constant temperature reactor to maintain the temperature at 60°C or higher, preferably 70°C or higher.

In one embodiment, the purification method of the present invention comprises the steps of (a) contacting the sugar-containing solution with an acrylic ion exchange resin and then contacting a styrene-based ion exchange resin; Or (b) contacting the sugar-containing solution with a styrene-based ion exchange resin, followed by contacting with an acrylic-based ion exchange resin.

Conventionally, in the purification of a sugar-containing solution, impurities such as pigments and silicic acid compounds have been removed together with anions using an anion exchange resin.

Among the above anion exchange resins, suitable for use in the present invention are strongly basic anion exchange resins having a highly porous structure, mechanically installing countless tools on resin particles, or resin particles easily swelling by a sugar-containing solution. Acrylic ion exchange resins can be used.

In the purification method of the present invention, since activated carbon is not used, the sugar-containing solution contains many pigment components that must be removed by an ion exchange resin.

In the purification method of the present invention, when the sugar-containing solution is brought into contact with the acrylic ion-exchange resin before the sugar-containing solution is brought into contact with the styrene-based ion exchange resin, a long service life can be expected due to increased decolorization ability and excellent organic contamination resistance. .

There is no particular limitation on the method of contacting the sugar-containing solution with the acrylic ion exchange resin, and for example, it may be carried out by passing the sugar-containing solution through a column filled with an acrylic ion exchange resin. It may be carried out in such a manner that it is introduced into the reactor and stirred for a predetermined time to mix.

In one embodiment, it may be desirable to perform decolorization treatment by passing a sugar-containing solution through a column filled with an acrylic ion exchange resin, and at this time, the color value of the sugar-containing solution may be 500 to 600 IU. The permeation rate of the sugar-containing solution may be ^{SV = 1 to 4 hr -1.}

After the sugar-containing solution and the acrylic ion exchange resin are brought into contact, the sugar-containing solution may be brought into contact with the styrene-based ion exchange resin.

In general, the acrylic ion exchange resin has a pore diameter in the range of several Å, whereas the styrene-based ion exchange resin has a pore diameter of several tens Å or hundreds of Å or more. Impurities that could not be removed when the sugar-containing solution is in contact with the acrylic ion exchange resin due to the difference in pore size may be removed when the sugar-containing solution is in contact with the styrene-based ion exchange resin.

The reason for using an ion exchange resin in the purification process of a sugar-containing solution is _{CaCl 2} , which is a form that can _{remove colored substances (pigment components) that cannot be removed only with activated carbon, and can dissolve ash (CaSO 4) better.} This is because the effect of the absorption of ash in the crystal is reduced by changing it.

Steel using Cl-type strongly basic anion exchange resin in basic anion exchange resin can be maintained when the temperature of the sugar-containing solution is treated with 70~80 ℃, Cl to SO ₄ ^2- ions in the sugar containing solution ^- to exchange ions and have. Therefore, it is possible to suppress the formation of _{CaSO 4} scale that may occur when a sugar-containing solution is boiled.

Similar to the method of contacting a sugar-containing solution with an acrylic ion exchange resin, there is no particular limitation on the method of contacting a sugar-containing solution with a styrene-based ion exchange resin. For example, a sugar-containing solution is placed in a column filled with a styrene-based ion exchange resin. It may be carried out in a manner of passing through, or may be carried out in a manner in which a sugar-containing solution and a styrene-based ion exchange resin are introduced into a reactor and stirred for a predetermined time to be mixed.

In one embodiment, it may be desirable to perform decolorization treatment by passing a sugar-containing solution through a column filled with a styrene-based ion exchange resin, and at this time, the color value of the sugar-containing solution may be 200 to 300 IU. The permeation rate of the sugar-containing solution may be ^{SV = 1 to 4 hr -1.}

In one embodiment, in the purification method of the present invention, instead of contacting a sugar-containing solution with an acrylic ion exchange resin and then contacting a styrene-based ion exchange resin, vice versa, contacting a styrene-based ion exchange resin, and then acryl-based ion exchange. It can be brought into contact with the resin. Also in this case, as described above, a decolorization effect when contacted with a styrene-based ion exchange resin and an acrylic-based ion exchange resin can be obtained, effectively reducing the color value of the sugar-containing solution, and lowering the electrical conductivity.

Further, according to another aspect of the present invention, there is provided a purified sugar-containing solution that is purified by the above method, has a color value of 300 IU or less, and an electrical conductivity of 100 μs/cm or less.

The purified sugar-containing solution according to the present invention may have a color value of 300 IU or less, preferably 250 IU or less, more preferably 230 IU or less, even more preferably 226 IU or less, and 100 μs/cm or less, Preferably, it may have an electrical conductivity of 90 µs/cm or less, more preferably 80 µs/cm or less, even more preferably 70 µs/cm or less, and even more preferably 65 µs/cm or less.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these examples.

[ Example ]

<Preparation of sugar-containing solution>

Manufacturing example One

Raw sugar made from sugar cane was kneaded with syrup and put into a batch-type centrifuge, and then the syrup was first removed, and hot water was secondarily added to wash foreign substances on the surface of the raw sugar. Thereafter, the washed raw sugar was dissolved in hot water at 70°C to 80°C to prepare a raw sugar solution. Subsequently, the raw sugar solution was reacted with lime and carbon dioxide gas to remove foreign substances through a carbonic acid trapping step to obtain a sugar-containing solution. After filling the obtained sugar-containing solution into a constant temperature reactor, the temperature of the constant temperature reactor was maintained at 70°C.

<Purification of sugar-containing solution>

Example One

150ml of acrylic ion exchange resin (TRILITE ASP10, Samyang Co., Ltd.) was charged in the first column, and 150ml of styrene-based ion exchange resin (TRILITE AMP14, Samyang Co., Ltd.) was charged in the second column. Both the first column and the second column used a jacket type, and the internal temperature of the column was maintained at 70° C., so that the sugar-containing solution was maintained at 70° C. during the purification process.

^{SV = 2.5 hr -1} in the first column filled with acrylic ion exchange resin and the second column filled with styrene ion exchange resin. The sugar-containing solution of Preparation Example 1 was sequentially passed through at a rate of passage to remove moisture from the inside of the first column and the inside of the second column.

After removing all of the moisture inside the first column and the second column, the sugar-containing solution of Preparation Example 1 was sequentially passed through ^{the first column and the second column at a passing rate of SV = 2.5hr -1,} Sampling was performed 1 hour after passing the solution and 20 hours after passing the solution. The color value and electrical conductivity were measured for the samples 1 hour after passing through and 20 hours after passing through, and the results are shown in Table 1 below.

Example 2

In the purification process of the sugar-containing solution of Preparation Example 1, 150 ml of a styrene-based ion exchange resin (TRILITE AMP14, Samyang Corporation) was charged in the first column, and 150 ml of an acrylic ion exchange resin (TRILITE ASP10, Samyang Corporation) in the second column. Example 1, except that the sugar-containing solution was contacted with an acrylic ion exchange resin, and then contacted with a styrene-based ion exchange resin, and then contacted with an acrylic ion exchange resin, instead of contacting with a styrene-based ion exchange resin. The sugar-containing solution was purified by performing the same method as described above. Thereafter, in the same manner as in Example 1, the color value and electrical conductivity were measured for the sample after 1 hour of passing the liquid and the sample after 20 hours of passing the liquid, and the results are shown in Table 1 below.

Comparative example One

The sugar-containing solution of Preparation Example 1 was not subjected to a purification process, and the color value and electrical conductivity of the sugar-containing solution of Preparation Example 1 were measured, and the results are shown in Table 1 below.

Comparative example 2

After filling 300 ml of activated carbon into a jacket-type column, the internal temperature of the column was maintained at 70° C., so that the sugar-containing solution was maintained at 70° C. during the purification process.

The sugar-containing solution of Preparation Example 1 ^{was passed through the column filled with the activated carbon at a flow rate of SV=2.5 hr -1} , and sampling was performed 1 hour after the passage and 20 hours after the passage. The color value and electrical conductivity were measured for the samples 1 hour after passing through and 20 hours after passing through, and the results are shown in Table 1 below.

Comparative example 3

Except for filling both the first column and the second column with 150 ml of acrylic ion exchange resin (TRILITE ASP10, Samyang Co., Ltd.), contacting the sugar-containing solution with the acrylic ion exchange resin, and then contacting the acrylic ion exchange resin again. , In the same manner as in Example 1, a sugar-containing solution was purified. Thereafter, in the same manner as in Example 1, the color value and electrical conductivity were measured for the sample after 1 hour of passing the liquid and the sample after 20 hours of passing the liquid, and the results are shown in Table 1 below.

Comparative example 4

Filling both the first column and the second column with 150 ml of a styrene-based ion exchange resin (TRILITE AMP14, Samyang Co., Ltd.), contacting the sugar-containing solution with a styrene-based ion exchange resin, and then contacting the styrene-based ion exchange resin again. Except, the sugar-containing solution was purified in the same manner as in Example 1. Thereafter, in the same manner as in Example 1, the color value and electrical conductivity were measured for the sample after 1 hour of passing the liquid and the sample after 20 hours of passing the liquid, and the results are shown in Table 1 below.

Comparative example 5

After filling 150ml of mixed resin mixed with acrylic ion exchange resin (TRILITE ASP10, Samyang Co., Ltd.) and styrene ion exchange resin (TRILITE AMP14, Samyang Co., Ltd.) in a volume ratio of 1:1 in a jacket-type column, the internal temperature of the column Was maintained at 70° C., so that the sugar-containing solution could maintain 70° C. during the purification process.

The sugar-containing solution of Preparation Example 1 ^{was passed through the column filled with the mixed resin at a flow rate of SV = 2.5 hr -1} , and sampling was performed 1 hour after the flow and 20 hours after the flow. The color value and electrical conductivity were measured for the samples 1 hour after passing through and 20 hours after passing through, and the results are shown in Table 1 below.

<Physical property evaluation>

Color

Color values of the purified sugar-containing solutions of Examples 1 to 2 and Comparative Examples 1 to 5 were measured using UV/VIS Spectrophotometers (UV-1800).

Electrical conductivity

Electrical conductivity of the purified sugar-containing solutions of Examples 1 to 2 and Comparative Examples 1 to 5 was measured using a conductivity meter (Orion star A212).

[Table 1]

As shown in Table 1, in the case of Comparative Example 1 (sugar-containing solution before the purification process) in which the purification process was not performed on the sugar-containing solution, the color value was very high as 905 IU, and the electrical conductivity was 60 µs/cm.

In the case of Examples 1 and 2 according to the present invention, the electrical conductivity of the purified sugar-containing solution is 66 µs/cm or less initially (after 1 hour), and 61 µs/cm or less even after 20 hours, which is equivalent to that of Comparative Example 1. Despite this, the initial (after 1 hour) color value was 68 IU or less, and even after 20 hours, the color value was 226 IU or less, which was very low compared to Comparative Example 1.

However, in the case of Comparative Example 2, in which purification was performed using activated carbon, the electrical conductivity of the purified sugar-containing solution at the initial stage (after 1 hour) and after 20 hours satisfies the standard at the same level as Comparative Example 1, but the initial stage (1 hour After) the color value was 75 IU, and the color value after 20 hours was 340 IU, which was a very high level compared to Examples 1 and 2.

In the case of Comparative Example 3, in which purification was performed using only an acrylic ion exchange resin, the electric conductivity of the purified sugar-containing solution at the initial stage (after 1 hour) and after 20 hours satisfies the standard at the same level as Comparative Example 1, but the initial stage The color value (after 1 hour) was 88 IU, and the color value after 20 hours was 504 IU, which was a very high level compared to Examples 1 and 2.

In Comparative Example 4, in which purification was performed using only styrene-based ion exchange resin, the electric conductivity of the purified sugar-containing solution at the initial stage (after 1 hour) and after 20 hours satisfies the standard at the same level as Comparative Example 1. After the initial 1 hour) the color value was 95 IU, and the color value after 20 hours was 550 IU, which was a very high level compared to Examples 1 and 2.

In Comparative Example 5, in which purification was performed using a mixed resin of an acrylic ion exchange resin and a styrene ion exchange resin, the initial (after 1 hour) and 20 hours of the purified sugar-containing solution had the same electrical conductivity as Comparative Example 1. Although the standard was satisfied by the level, the initial (after 1 hour) color value was 75 IU, and the color value after 20 hours was 337 IU, which was a very high level compared to Examples 1 and 2.

Therefore, as in the present invention, the sugar-containing solution is first contacted with an acrylic ion exchange resin, and then a styrene-based ion exchange resin, or the sugar-containing solution is first contacted with a styrene-based ion exchange resin, and then the acrylic ion exchange It can be seen that the initial (after 1 hour) and 20 hours of electrical conductivity meets the criteria only when contacted with the resin, but the color value is significantly lowered, and thus the purification efficiency is excellent.

Claims (7)

(a) contacting the sugar-containing solution with an acrylic ion exchange resin and then contacting the styrene-based ion exchange resin; or
(b) contacting the sugar-containing solution with a styrene-based ion exchange resin, and then contacting the sugar-containing solution with an acrylic ion exchange resin. The method of claim 1, wherein the contact of the sugar-containing solution with the acrylic ion exchange resin is carried out by passing the sugar-containing solution through a column filled with the acrylic ion exchange resin, and the contact of the sugar-containing solution with the styrene-based ion exchange resin is styrene. A method for purifying a sugar-containing solution, performed by passing a sugar-containing solution through a column filled with a system ion exchange resin. The method of claim 1, wherein the contact of the sugar-containing solution with the acrylic ion exchange resin is carried out by introducing and mixing the acrylic ion exchange resin and the sugar-containing solution into the reactor, and the contact of the sugar-containing solution with the styrene-based ion exchange resin is styrene. A method for purifying a sugar-containing solution, performed by introducing and mixing a system ion exchange resin and a sugar-containing solution into a reactor. The method for purifying a sugar-containing solution according to claim 2, wherein the permeation rate of the sugar-containing solution is SV=1 to 4 hr ^-1. The method for purifying a sugar-containing solution according to claim 1, wherein the temperature of the sugar-containing solution is 60°C or higher. The method of claim 1, wherein the sugar-containing solution comprises: (1) a step of washing raw sugar; (2) dissolving the product of step (1) in a solvent; And (3) reacting the resultant solution of step (2) with lime and carbon dioxide gas to remove foreign substances. A purified sugar-containing solution that is purified by the method of any one of claims 1 to 6, has a color value of 300 IU or less, and an electrical conductivity of 100 µs/cm or less.