WO2015111714A1

WO2015111714A1 - Sucrose solution refinement method and refinement device

Info

Publication number: WO2015111714A1
Application number: PCT/JP2015/051890
Authority: WO
Inventors: 英也八尾; 修大荻野; 浅野　伸; 直己越川; 学安田
Original assignee: オルガノ株式会社
Priority date: 2014-01-23
Filing date: 2015-01-23
Publication date: 2015-07-30
Also published as: JP2015136336A; CN105917009A; JP6265750B2

Abstract

The present invention refines a sucrose solution by successively passing the sucrose solution through a first column, which is filled with an OH-type strongly basic negative ion exchange resin and an Na-type or K-type positive ion exchange resin, and then a second column, which is provided to a later stage than that of the first column and is filled with a mixture of an OH-type strongly basic negative ion exchange resin and an H-type weakly acidic positive ion exchange resin. By means of the refining method, firstly it is possible to obtain a highly pure sucrose solution, to prevent scaling by suppressing the precipitation of calcium or the like within the device, and furthermore to reduce cost and reduce the amount of sweet water and waste water, and secondly it is possible to reduce the amount of waste water from regeneration liquid when regenerating the refining device.

Description

Method and apparatus for purifying sucrose solution

The present invention relates to a purification method and a purification apparatus for a sucrose solution.

1. Purification of sucrose solution In the process of purifying sucrose at a refined sugar factory, the raw material sugar is dissolved in warm water, and then lime and carbonic acid are added to this to aggregate colloidal impurities into the fine crystals of calcium carbonate that are formed. Process. Next, the sucrose solution after the carbonic acid saturation treatment is filtered, decolorized with bone charcoal or activated carbon, subjected to decolorization with a Cl-type anion exchange resin as final purification, and then crystallized to obtain a purified sucrose product. In some factories, in the sucrose purification process, the sucrose solution is desalted with an ion exchange resin to produce a sucrose crystal product or a liquid product.

The ion exchange resin equipment for desalting the sucrose solution includes (1) a reverse-bed single-bed single-bed tower, (2) a mixed-bed mixed-bed equipment, and (3) A -A single-bed / mixed-bed two-bed tower type apparatus is known.
(1) In the reverse method two-bed tower type apparatus, the sucrose solution is treated with a single bed tower of OH type strongly basic anion exchange resin and then treated with a single bed tower of H type weak acid cation exchange resin. To desalinate.
(2) In the mixed bed type mixed bed apparatus, the sucrose solution is treated in a mixed bed tower in which an OH-type strongly basic anion exchange resin and an H-type weakly acidic cation exchange resin are mixed. Perform desalting.
(3) In the two-bed tower type apparatus of the A-MB method, the sucrose solution is treated with a single-bed tower of OH type strongly basic anion exchange resin, and then OH type strongly basic anion exchange resin and H type weakly. Desalination is carried out by treatment with an acidic cation exchange resin in a mixed bed tower (Patent Document 1).

However, the above-described purification devices (1) to (3) cannot sufficiently remove the hardness component in the sucrose solution. Therefore, as shown below, a desalination apparatus in which a softening tower for removing hardness components is provided in the previous stage has been proposed.
(4) A desalting apparatus comprising a softening tower filled with a cation exchange resin and a two-bed tower type apparatus of A-MB method disposed in the subsequent stage (Patent Document 2).

2. Regeneration of sucrose solution purification equipment Regeneration of ion exchange resin filled in sucrose solution purification equipment involves passing an alkaline solution through a strongly basic anion exchange resin and an acid solution through a weakly acidic cation exchange resin. Do that. Regeneration of a mixed bed column packed with a strongly basic anion exchange resin and a weakly acidic cation exchange resin is carried out by separating the cation exchange resin and the anion exchange resin by their specific gravity difference, etc. Perform by replay. In Patent Document 3, first, an acid solution is introduced from the lower part of the tower and the weakly acidic cation exchange resin in the tower is fluidly regenerated, and at the same time, a strong basic anion exchange resin and a weakly acidic cation exchange resin are used. A method of isolating is presented.

Japanese Patent No. 2785833 Japanese Patent Laid-Open No. 11-70000 Japanese Patent No. 3765653

1. Purification of sucrose solution The sucrose solution after carbonation saturation in the sucrose purification step contains a large amount of calcium ions (Ca ²⁺ ), carbonate ions (CO ₃ ²⁻ ), and bicarbonate ions (HCO ₃ ⁻ ). When such a sucrose solution is desalted using an OH-type strongly basic anion exchange resin, calcium ions are precipitated as carbonate (CaCO ₃ ) or hydroxide (Ca (OH) ₂ ), and the sucrose solution It causes degradation of quality and scaling to equipment. In particular, in the sucrose purification process that does not use bone charcoal having calcium adsorption ability, the calcium ion concentration in the sucrose solution becomes high, which is a problem.

As a countermeasure against the above problems, as disclosed in Patent Document 2, a method of performing a softening treatment by disposing a softening tower for removing calcium ions in the previous stage of a desalting apparatus for a sucrose solution. Can be used. However, this method requires a total of three towers in order to increase the number of softening towers, and the initial introduction cost is high.

In the sucrose purification process, sweet water is generated. Sweet water is a low-concentration sucrose solution that is discharged from the desalinator during the initial flow when the sucrose solution is passed through a desalinator that has been previously filled with water, and the desalinator is washed after completion of purification. This represents a low-concentration sucrose solution discharged from the desalting apparatus. In general, in order to increase the yield in the purification step, the sweet water is concentrated and then added back to the raw sugar solution to return to the purification step. As described above, in the desalination apparatus consisting of three towers, the amount of sweet water increased by the number of towers. Since concentration of sweet water requires energy and costs increase, it has been desired to reduce the amount of sweet water generated during the purification process.

2. Regeneration of Sucrose Solution Purification Device Patent Document 3 discloses a method of separating two types of ion exchange resins in a mixed bed tower. However, there has been a demand for a method for efficiently regenerating a sucrose solution purification apparatus including a tower filled with an ion exchange resin for removing calcium ions. Since the purification apparatus described in Patent Document 2 is composed of three towers, the amount of drainage of the regenerated liquid tends to increase, and it has been desired to reduce the amount of wastewater.

The present invention has been made in view of the above problems. First, a purification apparatus is configured from two towers, and calcium ions and the like are removed in the first tower, thereby precipitating calcium and the like in the apparatus. The object is to obtain a high-purity sucrose solution while suppressing it to prevent scaling. Furthermore, an object of the present invention is to reduce the amount of sweet water and the amount of drainage and reduce the cost.

Secondly, the purpose is to reduce the amount of drainage of regenerated liquid when regenerating the purification equipment.

One embodiment is:
A first column packed with OH-type strongly basic anion exchange resin and Na-type or K-type cation exchange resin;
In the second tower arranged after the first tower and mixed and packed with OH type strong basic anion exchange resin and H type weak acid cation exchange resin,
The present invention relates to a method for purifying a sucrose solution characterized by passing the sucrose solution in this order.

Other embodiments are:
A first column packed with OH-type strongly basic anion exchange resin and Na-type or K-type cation exchange resin;
A second tower disposed after the first tower and filled with an OH-type strongly basic anion exchange resin and an H-type weakly acidic cation exchange resin;
The present invention relates to an apparatus for purifying a sucrose solution.

First, a purification apparatus is constructed from two towers, and calcium ions and the like are removed in the first tower, thereby suppressing the precipitation of calcium and the like in the apparatus to prevent scaling and a high-purity sucrose solution. Obtainable. Furthermore, the amount of sweet water and the amount of drainage can be reduced and the cost can be reduced.

Secondly, when the refining apparatus is regenerated, the amount of drainage of the regenerated liquid can be reduced.

It is a schematic diagram showing the refiner | purifier of the sucrose solution of one Embodiment of this invention. It is a schematic diagram showing the refiner | purifier of the sucrose solution of one Embodiment of this invention. It is a schematic diagram showing the purification method of the sucrose solution of one Embodiment of this invention. It is a schematic diagram showing the regeneration method of the refiner | purifier of the sucrose solution of one Embodiment of this invention. It is a figure showing the electrical conductivity of the sucrose solution of Example 1 and Comparative Examples 1 and 2. It is a figure showing pH of the sucrose solution of Example 1 and Comparative Examples 1 and 2. It is a figure showing the color value of the sucrose solution of Example 1 and Comparative Examples 1 and 2. It is a figure showing the light absorbency in 720 nm of the sucrose solution of Example 1 and Comparative Examples 1 and 2.

Hereinafter, the present invention will be described based on embodiments. The following embodiment is an example of the present invention, and the present invention is not limited to the following embodiment.

(Sucrose solution purification equipment)
1 and 2 are schematic views showing a sucrose solution purifying apparatus according to the present embodiment. In the purification apparatus of FIG. 1, the first column 2 is a mixed bed column in which OH type strong basic anion exchange resin and Na type or K type cation exchange resin are mixed and packed, and the second column 4 is OH type strong base. It is a mixed bed tower in which a mixed anion exchange resin and an H-type weakly acidic cation exchange resin are mixed and packed. In the purification apparatus of FIG. 2, the first column 2 is a multi-layered bed column in which an Na-type or K-type cation exchange resin 2a is arranged in the upper stage and an OH type strongly basic anion exchange resin 2b is arranged in the lower stage. The column 4 is a mixed bed column of OH type strong basic anion exchange resin and H type weak acid cation exchange resin.

As shown in FIGS. 1 and 2, the first tower may be a mixed bed tower or a multi-layer bed tower, but a mixed bed tower is preferred because the purity of the sucrose solution can be further increased. As shown in FIG. 2, when the first column is a multi-layered column, an Na-type or K-type cation exchange resin is used in the upper stage (upstream side), and an OH type strongly basic anion exchange resin is used in the lower stage (downstream side) Is preferably arranged. By arranging the ion exchange resin as shown in FIG. 2, it is possible to prevent the sucrose solution from becoming a high alkali (high pH) state upstream of the first tower, and to remove calcium ions and the like. Scaling can be prevented by suppressing the precipitation of calcium carbonate or the like in the refiner.

In the purification apparatus shown in FIGS. 1 and 2, the sucrose solution is softened (removal of calcium ions, etc.), anions are removed, and decolorized in the first tower 2. Specifically, the cation (calcium ion (Ca ²⁺ ), etc.) in the sucrose solution is formed by the Na-type or K-type cation exchange resin in the first tower 2, and the OH-type strongly basic anion exchange resin is used in the sucrose solution. An anion (carbonate ion (CO ₃ ²⁻ ), hydrogen carbonate ion (HCO ₃ ⁻ ), etc.) is adsorbed. Furthermore, the dye in the sucrose solution is adsorbed by these ion exchange resins. For this reason, precipitation of calcium etc. in a refiner | purifier can be suppressed and scaling can be prevented. Accordingly, it is possible to obtain a high-purity sucrose solution by suppressing the desalting ability of the purification apparatus from being reduced by precipitation or scaling of calcium or the like. Conventionally, since a single tower for softening the sucrose solution was provided, it was necessary to use a purification apparatus consisting of three towers in total. On the other hand, in this embodiment, the sucrose solution can be purified (desalted and decolorized) by two towers. Therefore, the space for installing the apparatus can be reduced, and the amount of sweet water and the amount of drainage generated in the refining process can be reduced, thereby reducing the cost.

Furthermore, the sucrose solution contains anionic impurities such as amino acids, organic acids and polysaccharides in addition to pigments and inorganic ions. These anionic impurities may form complexes with cations such as calcium ions. Even if the sucrose solution containing this complex is passed through a purification apparatus having a single column for softening and a single column filled with an anion exchange resin, calcium ions and the like do not dissociate from the complex. In this tower, calcium ions and the like cannot be removed. In contrast, in the purification apparatus of the present embodiment, the first column 2 is filled with both OH-type strongly basic anion exchange resin and Na-type or K-type cation exchange resin. . For this reason, since anion impurities are adsorbed on the OH-type strongly basic anion exchange resin, calcium ions and the like in the complex are liberated. The liberated calcium ions and the like are adsorbed on the Na-type or K-type cation exchange resin. Therefore, even when the sucrose solution contains anionic impurities, it can be effectively removed in the first tower 2 and the sucrose solution can be made highly pure.

The H-type weakly acidic cation exchange resin of the second column 4 adsorbs sodium ions (Na ⁺ ) or potassium ions (K ⁺ ) desorbed by adsorption of calcium ions (Ca ²⁺ ) and the like in the first column 2, The OH type strongly basic anion exchange resin adsorbs carbonate ions (CO ₃ ²⁻ ), bicarbonate ions (HCO ₃ ⁻ ), etc. that could not be removed in the first column 2. Further, the sucrose solution can be decolorized in the second tower 4.

The type of the OH type strong basic anion exchange resin charged in the first tower 2 and the second tower 4 is not particularly limited, but the first tower 2 includes an acrylic OH type strong basic anion exchange resin, the second tower. 4 is preferably filled with a styrenic OH type strongly basic anion exchange resin. Usually, the sucrose solution contains a dye, but the acrylic OH-type strongly basic anion exchange resin has a characteristic that the affinity with the dye is low and the adsorptive power with the dye is weak. On the other hand, the styrenic OH type strongly basic anion exchange resin has a high affinity with a dye and a strong adsorbing power with the dye. Here, the pigments contained in the sucrose solution exist from those having a high adsorption power to the ion exchange resin to those having a low adsorption power.

Therefore, the acrylic OH-type strongly basic anion exchange resin mainly absorbs a dye having a high adsorbing power with the ion exchange resin. Since the acrylic OH type strongly basic anion exchange resin originally has a weak adsorption power with the dye, the dye adsorbed on the ion exchange resin can be easily detached from the ion exchange resin by the regenerant. As a result, the acrylic OH type strongly basic anion exchange resin can be regenerated and used without deteriorating.

As described above, in the first tower 2, the dye having a high adsorptive power with the ion exchange resin is mainly adsorbed. Therefore, what remains in the sucrose solution after passing through the first tower 2 is mainly ion exchange. The dye has a low adsorption power with the resin. For this reason, the styrenic OH type strongly basic anion exchange resin in the second column 4 mainly adsorbs a dye having a low adsorption power with the ion exchange resin. Therefore, even a dye adsorbed on a styrene-based OH type strongly basic anion exchange resin having a high adsorbing power with the dye can be easily detached by the regenerant. As a result, the styrenic OH type strongly basic anion exchange resin can be regenerated and used without deteriorating.

As described above, the first column 2 is filled with acrylic OH type strongly basic anion exchange resin, and the second column 4 is filled with styrene type OH type strongly basic anion exchange resin. The sucrose solution can be desalted with high capacity without deteriorating the resin by decolorization (dye adsorption).

Examples of the acrylic OH type strongly basic anion exchange resin charged in the first tower 2 include Amberlite (registered trademark, hereinafter the same) 同様 IRA958, IRA458 (manufactured by Dow Chemical Co.), PUROLITE (registered trademark, the same hereinafter). ) A860, A850 (manufactured by Purolite) and the like. Of the acrylic OH type strongly basic anion exchange resins, the gel type resin is particularly advantageous because it has a large exchange capacity and increases the amount of sucrose solution that can be processed. Examples of the gel-type acrylic strongly basic anion exchange resin include Amberlite® IRA458 (manufactured by Dow Chemical Co.) and PUROLITE A850 (manufactured by Purolite).

The Na-type or K-type cation exchange resin packed in the first tower 2 may be a strong acid cation exchange resin or a weak acid cation exchange resin. Examples of Na-type strongly acidic cation exchange resins include Amberlite IR120B Na, IR124 Na, 200CT Na, 252 Na (manufactured by Dow Chemical), Diaion (registered trademark, hereinafter the same) SK1B, PK216 (manufactured by Mitsubishi Chemical Corporation) ), PUROLITE C100E (manufactured by Purolite). A known H-type strongly acidic cation exchange resin may be converted into a Na-type or K-type strongly acidic cation exchange resin by regenerating with a regenerating agent such as NaOH or KOH. Similarly, a known H-type weakly acidic cation exchange resin converted into a Na-type or K-type weakly acidic cation exchange resin by regenerating with a regenerating agent such as NaOH or KOH may be used.

Examples of the styrenic OH type strongly basic anion exchange resin charged in the second tower 4 include, for example, Amberlite IRA900, IRA402, IRA402BL (manufactured by Dow Chemical Co.), PUROLITE A500S (manufactured by Purolite), Diaion SA10A, PA308. (Mitsubishi Chemical Corporation).

Examples of the H-type weakly acidic cation exchange resin used in the second column 4 include Amberlite IRC76, Dowex (registered trademark, hereinafter the same), MAC-3 (manufactured by Dow Chemical), PUROLITE C115E (manufactured by Purolite). And Diaion WK10, WK11 (Mitsubishi Chemical Corporation).

(Purification method of sucrose solution)
FIG. 3 is a schematic diagram showing a method for purifying a sucrose solution using the purification apparatus of FIG. In this purification method, the sucrose solution is passed through in the direction of the arrow in the figure, the sucrose solution is first passed through the first tower 2, and the sucrose solution after passing through the first tower 2 is passed through the second tower 2. 4 is passed through. The Na-type or K-type cation exchange resin of the first tower 2 is a cation (calcium ion Ca ²⁺ etc.) in a sucrose solution, and the OH type strongly basic anion exchange resin is an anion (carbonate ion (CO ₃ ²⁻ ) And bicarbonate ions (HCO ₃ ⁻ ) and the like. These ion exchange resins can adsorb the dye in the sucrose solution. Accordingly, the precipitation of calcium or the like in the first column 2 is suppressed to prevent scaling in the purification apparatus, and the decrease in the demineralization ability of the first column 2 is thereby suppressed, thereby desalting and decolorization. A high-purity sucrose solution can be obtained. Compared with the conventional refinement | purification apparatus, while being able to reduce the space which installs an apparatus, the quantity of the sweet water and drainage amount which arise in a refinement | purification process can be reduced, and cost can be reduced. Furthermore, when a complex such as an anionic impurity and calcium ion is contained in the sucrose solution, the OH-type strongly basic anion is removed from the complex by passing the sucrose solution through the first column 2. Since anion impurities are adsorbed on the exchange resin, calcium ions and the like are liberated. Since the liberated calcium ions and the like are adsorbed on the Na-type or K-type strongly acidic cation exchange resin, the complex can be effectively removed in the first column 2 and the sucrose solution can be made highly pure.

The H-type weakly acidic cation exchange resin in the second column 4 removes sodium ions (Na ⁺ ) or potassium ions (K ⁺ ) desorbed by adsorption of calcium ions (Ca ²⁺ ) and the like in the first column 2. The OH type strongly basic anion exchange resin removes carbonate ions (CO ₃ ²⁻ ), hydrogen carbonate ions (HCO ₃ ⁻ ) and the like remaining in the sucrose solution after passing through the first column 2. Further, the sucrose solution can be decolorized in the second tower 4.

The sucrose solution used for purification is not particularly limited, but the sucrose solution used for purification is a filtrate after carbonation saturation and filtration treatment, after further activated carbon treatment after the filtration treatment, or other treatment. A solution from which impurities have been removed is preferable. These sucrose solutions contain a large amount of impurities such as calcium ions and magnesium ions. Therefore, a high-purity sucrose solution can be obtained by purifying these sucrose solutions with the purification apparatus of this embodiment. The sucrose solution before passing through the first tower 2 preferably has a sum of calcium ion and magnesium ion concentrations of 0.001 mol / L or more, more preferably 0.002 mol / L or more. preferable. In the present embodiment, even a sucrose solution containing high-concentration calcium ions and magnesium ions as described above, these ions are effectively removed in the first tower 2 to obtain a high-purity sucrose solution. be able to.

(Regeneration method of sucrose solution purification equipment)
4A to 4D are schematic diagrams showing a method for regenerating the purification apparatus of FIG. By refinement of the sucrose solution, Na ions (Na ⁺ ) or K ions (K ⁺ ) are desorbed from the Na-type or K-type cation exchange resin in the first tower 2, mainly calcium ions (Ca ²⁺ ), etc. Adsorbs. Hydroxide ions (OH ⁻ ) are desorbed from the OH type strongly basic anion exchange resin in the first column 2, and mainly carbonate ions (CO ₃ ²⁻ ), bicarbonate ions (HCO ₃ ⁻ ) and chloride. Object ions (Cl ⁻ ) and the like are adsorbed. Hydrogen ions (H ⁺ ) and hydroxide ions (OH ⁻ ) are desorbed from the H-type weakly acidic cation exchange resin and the OH-type strongly basic anion exchange resin in the second column 4 respectively, and mainly Na. Ions (Na ⁺ ) or K ions (K ⁺ ), carbonate ions (CO ₃ ²⁻ ), and bicarbonate ions (HCO ₃ ⁻ ) are adsorbed. That is, after purification of the sucrose solution, the OH type strongly basic anion exchange resin in the first column 2 is mainly CO ₃ ²⁻ -strongly basic anion exchange resin, HCO ₃ ⁻ -strongly basic anion exchange resin. And Cl ⁻ -strongly basic anion exchange resin, and Na-type or K-type cation exchange resin mainly becomes Ca ²⁺ -cation exchange resin. After purification, the H-type weakly acidic cation exchange resin in the second column 4 is mainly Na ⁺ -weakly acidic cation exchange resin or K ⁺ -weakly acidic cation exchange resin, and OH type strongly basic anion exchange resin. Are mainly CO ₃ ²⁻ -strongly basic anion exchange resins and HCO ₃ ⁻ -strongly basic anion exchange resins.

In the regeneration method of the present embodiment, first, as shown in FIG. 4A, the first regeneration solution for the H-type weakly acidic cation exchange resin is passed through the second column 4. At this time, the first regenerating liquid flows from the bottom of the second tower 4 toward the top. Thereby, the strongly basic anion exchange resin and the weakly acidic cation exchange resin in the second column 4 flow and are separated by the difference in specific gravity of these ion exchange resins. In the present embodiment, a strong basic anion exchange resin 4a is arranged at the upper part and a weak acidic cation exchange resin 4b is arranged at the lower part in the second tower 4 by the separation. By the first regeneration solution, Na ions (Na ⁺ ) or K ions (K ⁺ ) are desorbed from the weakly acidic cation exchange resin in the second column 4 and regenerated to become an H-type weakly acidic cation exchange resin. .

Next, the first regenerated liquid is recovered from the top of the second tower 4 and passed from the top of the first tower 2 toward the bottom. At this time, since the first regenerating liquid flows from the bottom to the top of the second column 4, it is not necessary to flow a solution such as water so as to be countercurrent to the first regenerating liquid. Therefore, it can be recovered from the second column 4 without reducing the concentration of the first regenerated solution with water or the like. By passing the first regeneration solution through the first column 2, calcium ions (Ca ²⁺ ) and the like adsorbed on the cation exchange resin in the first column 2 are desorbed, and instead hydrogen ions (H ⁺ ) Is adsorbed to form an H-type cation exchange resin.
The first regenerating solution is not particularly limited as long as it is an acid solution, and an aqueous hydrochloric acid solution can be preferably used. The hydrochloric acid concentration in the aqueous hydrochloric acid solution is not particularly limited as long as it does not deteriorate the ion exchange resin, but is preferably 0.05 to 2.0 N, more preferably 0.1 to 1.0 N. As described above, when an aqueous hydrochloric acid solution is used as the first regeneration solution, carbonate ions (CO ₃ ²⁻ ) and bicarbonate ions (HCO ₃ ) are introduced by passing the first regeneration solution into the second column 4. ^-) strongly basic anion exchange resin from carbonate ions in the second column 4 was adsorbed _(CO ^{3 2-)} and bicarbonate ions (HCO ₃ ^-) is eliminated, chloride ion (Cl ^-) adsorption Cl ⁻ -strongly basic anion exchange resin. Similarly, strong basicity in which carbonate ions (CO ₃ ²⁻ ) and hydrogen carbonate ions (HCO ₃ ⁻ ) in the first column 2 are adsorbed by passing the first regenerating solution into the first column 2. anion exchange resin, Cl - ^- a strongly basic anion exchange resin.

In the above process, the strongly basic anion exchange resin in the first column 2 and the second column 4 is regenerated. That is, this regeneration removes impurities (such as dyes) adsorbed on the base structure of the strongly basic anion exchange resin.

Next, as shown in FIG. 4B, a second regeneration solution for OH type strongly basic anion exchange resin containing sodium ions or potassium ions is passed from the top of the second column 4 and second Water is passed from the bottom of the tower 4. By making this water counter-current with the second regenerating liquid, the water reaches the H-type weakly acidic cation exchange resin separated from the lower part of the second tower 4, and H It is possible to prevent the ion form of the weakly acidic cation exchange resin from being converted into the Na form or the K form. By passing the second regeneration solution into the second column 4, chloride ions (Cl ⁻ ) are desorbed from the strongly basic anion exchange resin in the second column 4, and instead hydroxide ions ( OH ⁻ ) is adsorbed and converted to an OH-type strongly basic anion exchange resin.

As shown in FIG. 4B, the second regenerated solution and water passed through the second column 4 as described above are separated from each other as OH-type strongly basic anion exchange resin and H-type weakly acidic cation. Collect with an intermediate collector located at the boundary of the exchange resin. Next, the second regenerated liquid and water that have passed through the second tower 4 are passed from the top of the first tower 2 toward the bottom. Thus, strongly basic anion exchange resin in the first column 2 is rough play, a part of the chloride ion (Cl ^-) was desorbed, hydroxide ions instead - adsorb ^(OH) OH type strongly basic anion exchange resin. At the same time, the hydrogen ions (H ⁺ ) of the H-type cation exchange resin in the first column 2 are desorbed, and instead sodium ions (Na ⁺ ) or potassium ions (K ⁺ ) are adsorbed, respectively. Or K-type cation exchange resin. The second regenerating solution is not particularly limited as long as it is an alkaline solution containing sodium ions or potassium ions, preferably an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, more preferably an aqueous sodium hydroxide solution. . The concentration of sodium hydroxide in the aqueous sodium hydroxide solution is not particularly limited as long as it does not degrade the ion exchange resin, but is preferably 0.05 to 3.0 normal, more preferably 0.5 to 2.0 normal.

Next, as shown in FIG. 4C, a third regeneration solution for OH type strongly basic anion exchange resin is passed from the top to the bottom of the first column 2. As a result, carbonate ions (CO ₃ ²⁻ ), bicarbonate ions (HCO ₃ ⁻ ), and chloride ions (Cl ⁻ ) adsorbed on a part of the strongly basic anion exchange resin in the first column 2. Is converted to an OH-type strongly basic anion exchange resin by adsorbing hydroxide ions (OH ⁻ ) instead. The third regenerating solution is not particularly limited as long as it is an alkaline solution, but preferably the same as the second regenerating solution.

Next, as shown in FIG. 4D, compressed air is allowed to flow from the bottom of the second column 4 into the second column 4, and the OH type strong basic anion exchange resin and the H type separated and arranged in the second column 4. A weakly acidic cation exchange resin is flowed and mixed. Thereby, in the 2nd tower 4 after completion | finish of inflow of compressed air, OH type strong basic anion exchange resin and H type weakly acidic cation exchange resin are mixed and filled, and the 2nd tower 4 becomes a mixed bed.

In the above regeneration method, it is not necessary to flow a solution such as water in the process of FIG. 4A. Furthermore, the amount of regenerated liquid can be reduced as compared with the case of regenerating the conventional three-column purification apparatus.

After passing each regenerated liquid through each tower, water is passed through each tower, and the regenerated liquid remaining in each tower is pushed out and discharged outside the tower. After the step of FIG. 4D, water may be passed through each tower to wash the ion exchange resin in the tower. Since the purification apparatus of this embodiment consists of two towers, the amount of water used in the above process can also be reduced compared to a purification apparatus consisting of three towers. In the above embodiment, the process of FIG. 4D is performed after the process of FIG. 4C. However, the process of FIG. 4C may be performed after the process of FIG. 4D, or the processes of FIGS. 4C and 4D may be performed simultaneously. good.

Example 1
As the sucrose solution, a solution obtained by subjecting the filtrate after carbonation saturation treatment and filtration treatment to activated carbon treatment (Brix sugar content 55%, conductivity 250 μS / cm, color value 80 ICUMSA (International Commission for Uniform Methods of Sugar Analysis), Abs720 0.002 (100 mm cell measurement)). This sucrose solution was passed through the purification apparatus of FIG. 1 in the order of the first column 2 and the second column 4 at 50 ° C. and 300 mL / h. Then, the conductivity, pH, color value, and turbidity (absorbance at 720 nm) of the sucrose solution at the outlet of the second tower 4 were monitored. For the first column 2 and the second column 4, ion exchange resins shown in Table 1 below were used.

Next, 500 mL of a 0.5 N aqueous hydrochloric acid solution (first regeneration solution) was passed from the bottom of the second tower 4 toward the top at 800 mL / h. As a result, the Amberlite IRC76 and 402BL were flowed in the second tower 4 to separate the Amberlite IRA402BL in the upper part of the second tower 4 and the Amberlite IRC76 in the lower part. Thereafter, the waste liquid (first regenerated liquid) discharged from the top of the second tower 4 was passed from the top of the first tower 2 toward the bottom. Subsequently, 300 mL of pure water was allowed to flow into the second tower 4 at the same flow rate, and the aqueous hydrochloric acid solution in the tower was extruded. Subsequently, 800 mL of pure water was poured into the second tower 4 to wash the ion exchange resin in the tower.

Next, 150 mL of 2N aqueous sodium hydroxide solution (second regeneration solution) is flowed from the top of the second column 4 at 400 mL / h, and at the same time, pure water is flowed from the bottom of the second column 4 at 400 mL / h. Washed away. The waste liquid (second regenerated liquid and pure water) extracted from the intermediate collector located at the boundary between Amberlite IRA402BL and Amberlite IRC76 was passed through the first tower 2. Thereafter, 200 mL of pure water was passed through the top and bottom of the second column 4 at 400 mL / h, and sodium hydroxide remaining in the second column 4 was extruded. Next, 1200 mL of pure water was allowed to flow from the top of the second column 4 at a flow rate of 800 mL / h and discharged from the bottom of the second column 4. Thereafter, compressed air was introduced from the bottom of the second tower 4, and Amberlite IRA402BL and Amberlite IRC76 were mixed to form a mixed bed again.

Next, 100 mL of a 1N aqueous sodium hydroxide solution (third regeneration solution) was passed through the top of the first tower 2 at 400 mL / h and discharged from the bottom of the first tower 2. Next, after 200 mL of pure water is flowed into the first tower 2 at the same flow rate to extrude sodium hydroxide in the first tower 2, 1200 mL of pure water is flowed into the first tower 2 at 800 mL / h, and the final washing is performed. Carried out.

The above-described purification of the sucrose solution and regeneration of the purification apparatus were repeated three times as one cycle. Table 1 shows the types of ion exchange resins used in the first column 2 and the second column 4, and FIGS. 5 to 8 show the results of the third cycle.

(Example 2)
As the sucrose solution, a solution obtained by subjecting the filtrate after carbonic acid saturation treatment and filtration treatment to activated carbon treatment (Brix sugar content 55%, conductivity 300 μS / cm, color value 725 ICUMSA) was used. This sucrose solution was passed through the purification apparatus of FIG. 1 in the same manner as in Example 1 at a total volume of 3.6 L at 50 ° C. and 300 mL / h. The whole amount of the sucrose solution after the purification treatment was recovered, and the conductivity, pH, and color value were measured. Next, the purification apparatus of FIG. 1 was regenerated in the same manner as in Example 1. The purification of the sucrose solution and the regeneration of the purification apparatus were repeated 20 times as one cycle. Table 2 shows the types of ion exchange resins used in the first column 2 and the second column 4, and Table 3 shows the results of the 1st cycle, 10th cycle, and 20th cycle. Table 4 shows the measurement results of the exchange capacity of each ion exchange resin before and after use (new and after 20 cycles).

Example 3
The sucrose was prepared in the same manner as in Example 2 except that the acrylic strongly basic anion exchange resin (Amberlite IRA458) shown in Table 2 was used as the strongly basic anion exchange resin in the first tower 2 of FIG. Purification of the solution and regeneration of the purification apparatus were performed. The ion exchange resins used in the first column 2 and the second column 4 are shown in Table 2, and the results of the 1st cycle, 10th cycle, and 20th cycle are shown in Table 5. Table 6 shows the measurement results of the exchange capacity of each ion exchange resin before and after use (new and after 20 cycles).

(Comparative Example 1)
As shown in Table 1, the sucrose solution was purified in the same manner as in Example 1 except that Na-type cation exchange resin (Amberlite IR120B) was not used in the first column 2 of FIG. .

The regeneration of the ion exchange resin in the first column 2 and the second column 4 was performed separately.
The regeneration of the ion exchange resin in the second tower 4 was performed as follows. 500 mL of 0.5 N hydrochloric acid aqueous solution was passed through the bottom of the second column 4 at 800 mL / h. As a result, Amberlite IRC76 and IRA402BL were flowed in the second tower 4 to separate Amberlite IRA402BL in the upper part of the second tower 4 and Amberlite IRC76 in the lower part. Subsequently, 300 mL of pure water was allowed to flow into the second column 4 at the same flow rate, and hydrochloric acid in the column was extruded. Subsequently, 800 mL of pure water was poured into the second tower 4 to wash the ion exchange resin in the tower.

Next, 150 mL of a 1N sodium hydroxide aqueous solution was flowed from the top of the second column 4 at 400 mL / h, and at the same time, pure water was flowed from the bottom of the second column 4 at 400 mL / h. Waste liquid was discharged from an intermediate collector located at the boundary between Amberlite IRA402BL and Amberlite IRC76. Thereafter, 200 mL of pure water was passed through the top and bottom of the second column 4 at 400 mL / h, and sodium hydroxide remaining in the second column 4 was extruded. Next, 1200 mL of pure water was allowed to flow from the top of the second column 4 at a flow rate of 800 mL / h and was discharged from the bottom of the second column 4. Thereafter, compressed air was introduced from the bottom of the second tower 4, and Amberlite IRA402BL and Amberlite IRC76 were mixed to form a mixed bed again.

The regeneration of the ion exchange resin in the first tower 2 was performed as follows. From the top of the first column 2, 300 mL of a 1N aqueous sodium hydroxide solution was passed at 400 mL / h and discharged from the bottom of the first column 2. Next, after 200 mL of pure water is flowed into the first tower 2 at the same flow rate to extrude sodium hydroxide in the first tower 2, 1200 mL of pure water is flowed into the first tower 2 at 800 mL / h, and the final washing is performed. Carried out.

(Comparative Example 2)
As shown in Table 1, the Na-type cation exchange resin (Amberlite IR120B) is not used in the first column 2 of FIG. A softening tower filled with light IR120B) was provided. Except for this, the sucrose solution was purified in the same manner as in Example 1.

The regeneration of the ion exchange resin in the first tower 2 and the second tower 4 was performed in the same manner as in Comparative Example 1. Amberlite IR120B in the first-stage softening tower was regenerated as follows. First, 100 mL of a 10 mass% NaCl aqueous solution was passed through the top of the softening tower at 200 mL / h and discharged from the bottom. Thereafter, 50 mL of pure water was flowed into the softening tower at the same flow rate, and 400 mL of pure water was passed through the softening tower at 400 mL / h to wash Amberlite IR120B.

5 to 8, it can be seen that the conductivity, color value, and absorbance at 720 nm are greatly reduced in Example 1 as compared with Comparative Example 1. From the results of Example 1 and Comparative Example 2, it is possible to achieve the same conductivity, color value, and absorbance at 720 nm as the two-column purification apparatus (Example 1) with the two-column purification apparatus (Example 1). I understand. Furthermore, the amount of sweet water having a Brix sugar content of 2 to 30% generated in the purification process was 450 mL in Comparative Example 2 but 360 mL in Example 1, and the amount of sweet water was reduced by 20%. We were able to.

From the results of Tables 3 and 5, it can be seen that in Examples 2 and 3, the pH of the sucrose solution hardly changed even after 20 cycles, and a sucrose solution having low conductivity and color value was obtained. Although the color value slightly increases as the number of cycles increases, the increase in color value is smaller in Example 3 than in Example 2, and the acrylic anion exchange resin is used in the first column. It can be seen that the rate of deterioration of the ion exchange resin becomes moderate.

From the results of Tables 4 and 6, when an acrylic anion exchange resin (Amberlite IRA458) was used in the first tower of Example 3, the acrylic anion exchange resin in the first tower was contaminated with pigments. Since it is difficult, it can be seen that a decrease in the total exchange capacity after use can be significantly suppressed as compared with the styrene-based anion exchange resin (Amberlite IRA402BL) in the first column in Example 2. Furthermore, for the styrene anion exchange resin (Amberlite IRA402BL) in the second tower, Example 3 using an acrylic anion exchange resin in the first tower used a styrene anion exchange resin in the first tower. It turns out that the fall of the total exchange capacity | capacitance after use can be suppressed compared with Example 2. FIG.

2 First column 2a Na-type or K-type cation exchange resin 2b OH type strongly basic anion exchange resin 4 Second column 4a Strongly basic anion exchange resin 4b Weakly acidic cation exchange resin

Claims

A first column packed with OH-type strongly basic anion exchange resin and Na-type or K-type cation exchange resin;
In the second tower arranged after the first tower and mixed and packed with OH type strong basic anion exchange resin and H type weak acid cation exchange resin,
A method for purifying a sucrose solution, wherein the sucrose solution is passed in this order.
The sucrose solution according to claim 1, wherein the first column is a mixed bed column in which the OH type strong basic anion exchange resin and the Na type or K type cation exchange resin are mixed and packed. Purification method.
The OH type strong basic anion exchange resin packed in the first tower is an acrylic OH type strong basic anion exchange resin,
The method for purifying a sucrose solution according to claim 1 or 2, wherein the OH type strongly basic anion exchange resin packed in the second column is a styrene type OH type strongly basic anion exchange resin. .
The sucrose solution before passing through the first tower has a sum of calcium ion and magnesium ion concentrations of 0.001 mol / L or more, according to any one of claims 1 to 3. Purification method of sucrose solution.
After passing the sucrose solution through the first and second towers,
Passing the first regeneration solution for the H-type weakly acidic cation exchange resin through the second column;
Passing the first regenerated liquid after passing through the second tower through the first tower;
Passing a second regeneration solution for OH type strongly basic anion exchange resin containing sodium ions or potassium ions into the second column;
Passing the second regenerated solution after passing through the second column through the first column;
The method for purifying a sucrose solution according to any one of claims 1 to 4, wherein the sucrose solution is contained in this order.
In the step of passing the first regenerating liquid into the second tower,
The first regeneration solution is passed through the second column, and the strong base anion exchange resin and the weakly acidic cation exchange resin are caused to flow and separate from each other in the second column. Item 6. A method for purifying a sucrose solution according to Item 5.
The method for purifying a sucrose solution according to claim 5 or 6, further comprising a step of passing a third regeneration solution for OH-type strongly basic anion exchange resin through the first column. .
A first column packed with OH-type strongly basic anion exchange resin and Na-type or K-type cation exchange resin;
A second tower disposed after the first tower and filled with an OH-type strongly basic anion exchange resin and an H-type weakly acidic cation exchange resin;
An apparatus for purifying a sucrose solution, comprising:
The OH type strong basic anion exchange resin packed in the first tower is an acrylic OH type strong basic anion exchange resin,
9. The apparatus for purifying a sucrose solution according to claim 8, wherein the OH type strongly basic anion exchange resin packed in the second tower is a styrene type OH type strongly basic anion exchange resin.