KR100665127B1 - Method for preparing of membrane of reclaimed ion exchange resin - Google Patents

Abstract

A method for forming a recycled ion exchange resin membrane is provided to obtain an ion exchange resin membrane for simple water purification, which removes salt from sea water. The method for forming a recycled ion exchange resin membrane comprises the steps of: providing an acetone solution in which cellulose acetate is dissolved; mixing the acetone solution with powder of a waste cation exchange resin and a waste anion exchange resin to provide a recycled ion exchange resin solution; and forming a recycled ion exchange resin membrane from the recycled ion exchange resin solution by using a flat plate or a cylindrical container.

Description

Method for preparing recycled ion exchange resin membrane {Method for preparing of Membrane of Reclaimed ion exchange resin}

1 is a process chart for preparing a solution in which cellulose is dissolved to prepare a recycled ion exchange resin solution according to the present invention.

2 is a process chart for preparing a recycled ion exchange resin solution using a solution in which cellulose is dissolved according to the present invention.

The present invention relates to a method for producing a recycled ion exchange resin membrane using waste ion exchange resin powder, and more particularly, recycled ion exchange resin prepared by mixing the waste cation exchange resin and the powder of waste anion exchange resin with cellulose acetate The present invention relates to a method for producing a recycled ion exchange resin membrane, characterized in that for removing the salt contained in seawater using a membrane for use in simple water purification.

In general, ion exchange resins for removing various ions dissolved in water are generally in the form of small grains or pulverized amorphous particles absorbing translucent or transparent water, and include cation exchange resins, anion exchange resins and amphoteric ion exchange resins. Are distinguished. The ion exchange method using the ion exchange resin by using a cation resin or an anion resin to selectively exchange the cation or anion material dissolved in the water to exchange the ions contained in the water and the ions in the resin, The ionic substances dissolved in the water are removed. This ion exchange resin is usually recycled to the ion exchange resin using NaCl.

The regeneration method of the ion exchange resin as described above has been developed in a wide variety of applications have been applied for a variety of patents, but the development of a technology for recycling the ion exchange resin discarded after fully used such an ion exchange resin is very small situation.

Therefore, the present inventors powdered it using waste ion exchange resin, and then mixed with cellulose acetate to produce a recycled ion exchange resin membrane having excellent salt removal ability, so that the salt removal ability is excellent, the water is purified for simple water purification. The purpose of the present invention is to provide a method for producing a recycled ion-exchange resin membrane, which can be used to solve the drinking water shortage of islanders.

In addition, the present invention is characterized by an environmentally friendly manufacturing method that can recycle waste resources because it can be recycled ion exchange resin membrane having excellent salt removal ability by pulverizing it and then mixed with cellulose acetate using waste ion exchange resin. The purpose is to provide a method for producing a recycled ion exchange resin membrane.

The manufacturing method of the present invention for solving the above problems is manufactured through the following steps.

Method for producing a recycled ion exchange resin membrane of the present invention

Preparing an acetone solution in which cellulose acetate is dissolved,

And mixing the waste cation exchange resin and the powder of the waste anion exchange resin with the acetone solution to prepare a recycled ion exchange resin solution;

The recycled ion exchange resin solution is prepared through a step of preparing a recycled ion exchange resin membrane using a flat plate or a cylindrical container.

Hereinafter, the manufacturing method according to the present invention will be described in detail with reference to the accompanying drawings.

1 is a process chart for preparing a solution in which cellulose is dissolved to prepare a recycled ion exchange resin solution according to the present invention. The acetone solution in which cellulose acetate is dissolved is prepared as follows.

Iii) adding 15 to 20% by weight of swelling agent to 80 to 85% by weight of water (swelling agent solution preparation step);

Ii) 8 to 12% by weight of the swelling agent dissolution solution prepared in step iii) into 88-92% by weight of acetone solution, followed by mixing and dissolving (acetone mixed solution preparation step);

Iii) adding 20-25% by weight of cellulose acetate and 25-30% by weight of formamide solution to 45-55% by weight of the acetone mixed solution prepared in step ii) to dissolve and aged (cellulose cellulose solution dissolving step);

Through cellulose acetate is dissolved a solution is prepared.

The swelling agent added to the water in step iii) uses magnesium perchlorate (Mg (ClO ₄ ) ₂ ) as a compound for swelling the cellulose acetate, and the amount of the swelling agent added to the water is 15 to 20% by weight. Is preferred. If the added amount is less than 15% by weight, the cellulose acetate may not be sufficiently swollen. If the added amount is more than 20% by weight, the swelling effect of the cellulose acetate does not significantly increase with the increase of the amount of the swelling agent added. Do not.

And the acetone solution used in the step ii) and iii) serves to dissolve cellulose acetate, there is a fear that the cellulose acetate may not be sufficiently dissolved when the amount of the acetone is less than the amount of the used amount, When the amount exceeds the above-mentioned range, the concentration of cellulose acetate is thinner than that of the acetone solution, so that it may not be easy to form a membrane of recycled ion exchange resin.

In addition, the formamide solution added in step iii) is a compound that serves to enhance the effect of aging while dissolving cellulose acetate. There is a concern that, when the amount of the used amount is exceeded, the dissolution and aging effects of cellulose acetate with the increase of the amount of use are not particularly increased.

And, Figure 2 relates to a process for producing a recycled ion exchange resin membrane using a solution in which cellulose is dissolved in accordance with the present invention, the recycled ion exchange using a solution in which cellulose acetate is dissolved and waste ion exchange resin powder The method of manufacturing a resin solution is as follows.

Iii) separately adding 8-12% by weight of waste ion exchange resin powder to 88-92% by weight of water (mixing of waste ion-exchange resin solvent);

Iii) dissolving 15-25 wt% of the waste ion exchange resin mixed solvent prepared in step iii) in 75-85 wt% of the acetone solution (preparing waste ion exchange resin mixed acetone solution);

Iii) mixing 20-30% by weight of the waste ion exchange resin mixed acetone solution prepared in step iii) into 70-80% by weight of a solution of cellulose acetate acetate prepared in step c), and then mixing the mixture to 70-80% by weight to mature in a homogeneous state (recycling). Ion exchange resin solution manufacturing step);

Waste ion-exchange resin solution is prepared through.

      The amount of the waste ion exchange resin added to the water in the step iii) is preferably 8 to 12% by weight. When the amount of the waste ion exchange resin is less than the amount added, the performance of the ion exchange resin membrane used for recycling decreases. There is a possibility that the salt contained in the seawater may not be sufficiently removed, and if the added amount exceeds the above added amount range, the ability to remove the salt contained in the seawater does not improve in proportion to the added amount of the waste ion exchange resin. In this case, the amount of waste ion exchange resin used is preferably contained in seawater, so that the amount of cation exchange resin and the amount of anion exchange resin are mixed in the same amount in order to efficiently remove salts.

In addition, the amount of the mixed solvent of the waste ion exchange resin added to the acetone solution in the step iii) is preferably 15 to 25% by weight, and when the amount is less than the amount of the added amount, the waste ion exchange resin is added to the acetone solution. Although the mixture is sufficiently mixed, the performance of the recycled ion exchange resin membrane may be deteriorated due to the lack of the content of the ion exchange resin, so that the salts contained in the sea water may not be sufficiently removed. The ability to remove salts contained in seawater does not improve in proportion to the amount of exchange resin added.

In the step iii), the amount of the acetone solution mixed with the waste ion exchange resin added to the cellulose acetate solution is preferably 20 to 30% by weight. If the added amount of acetone solution is less than the range of the added amount, the seawater may not be sufficiently purified due to lack of content of the waste ion exchange resin, and if it exceeds the range of the added amount, the viscosity of the waste ion exchange resin solution is exceeded. This is because not only the manufacturing efficiency of the waste ion exchange resin membrane is decreased, but also the water purification capacity of the seawater does not increase due to the increase in the amount added.

And the method of producing a recycled ion exchange resin membrane using the waste ion exchange resin prepared in step iii) is as follows.

Iii) forming the ion exchange resin membrane using the waste ion exchange resin solution prepared in step iii) using a flat plate or a cylindrical container (recycled ion exchange resin membrane forming step);

Iii) when the recycled ion exchange resin membrane is dried, immersing the cooled ion exchange resin membrane in water for 2 to 3 hours to form a recycled ion exchange resin membrane in water (recycled ion exchange resin membrane formation step);

Iii) forming a recycled ion exchange resin membrane and then separating the membrane from a flat plate or cylindrical vessel and then heat treating at 60 to 100 ° C. (recycled ion exchange resin membrane heat treatment step);

Iii) drying the moisture by removing the heat-treated recycled ion exchange resin film from water (recycled ion exchange resin film drying step);

Through recycled ion exchange resin membrane is produced.

The method for forming the recycled ion exchange resin membrane in step (iii) can be largely divided into a method for producing a planar membrane and a method for producing a cylindrical tubular membrane.

First, the method of forming a planar membrane is carried out by pouring the recycled ion exchange resin solution into a flat plate such as a glass plate, pushing it with a round rod such as a glass rod, and then dipped the coolant immediately when the surface is dried, and then performing the steps iii) and iii). After forming the planar membrane formed through, the planar membrane is separated from the planar plate, and the separated planar membrane is placed on paper and wrapped with another paper. And dry.

Second, the method of forming a cylindrical tubular membrane is filled with a recycled ion exchange resin solution in a cylindrical container such as a test tube, and after a while empty the recycled ion exchange resin solution contained in a cylindrical container, and the cylindrical container is turned upside down to form a cylindrical container. Pour out the recycled ion-exchange resin solution contained in the container, and when the surface of the recycled ion-exchange resin solution attached to the inner wall of the cylindrical container is dried, soak it in 0 ° C. cooling water and go through the above steps iii) and iii) After separating the tubular membrane from the cylindrical container, the cylindrical tubular membrane is placed on paper, wrapped with another paper, and then naturally dried or forcedly dried.

     When the recycled ion exchange resin membrane is dried in step iii), it is immediately soaked in cooling water at 0 ° C. for 2-3 hours to solidify sufficiently. The solidified recycled ion exchange resin membrane is separated from the recycled ion exchange resin membrane formed in a flat plate or a cylindrical container in water as in step iii) to improve mechanical strength such as tensile strength of the recycled ion exchange resin membrane. The recycled ion exchange resin membrane is heat treated at a temperature of < RTI ID = 0.0 > At this time, the prepared recycled ion exchange resin membrane is adhered to the inner surface side of the flat plate or cylindrical container, and is a dense layer. The upper portion is solidified in a gel state, and the mechanical strength is weakened, which may lower the ability to remove salt. Therefore, in order to sufficiently harden the inside of the recycled ion exchange resin membrane to improve the mechanical strength, a heat treatment process is required. The heat treatment temperature is preferably 60 to 100 ° C., and the heat treatment must be performed in water. When the heat treatment temperature is less than 60 ℃ there is a fear that the inside of the recycled ion exchange resin membrane is not sufficiently hardened, so that the mechanical strength of the recycled ion exchange resin membrane is lowered and the ability to remove salts is reduced.

       In the step iii), the recycled ion exchange resin film heat-treated in the step iii) is taken out of water, the flat membrane or cylindrical tubular membrane is placed on paper, wrapped with another paper, and then naturally dried or forcedly dried.

Hereinafter, the configuration of the present invention will be described in detail with reference to the following examples, and the present invention is not necessarily limited to the following examples.

Example

One. Cellulose acetate  Dissolution solution preparation

      After dissolving 100 g of magnesium perchlorate as a swelling agent in 500 g of water and dissolving, 600 g of this solution was added to 5 kg of acetone solvent to dissolve the mixture. Then, 2.5 kg of cellulose acetate is added to 5.6 kg of this solution for dissolution. Then, 3 kg of formamide solvent is added to dissolve and mature.

2. Manufacture of recycled ion exchange resin solution

      50 g of finely ground waste ion exchange resin powder is added to 500 g of water, shaken well, and then mixed into 2 kg of acetone solvent prepared separately. Finally, the waste ion exchange resin was mixed with acetone solution, and then put into a solution in which cellulose acetate was dissolved, as shown in the composition ratio of Table 1 below, shaken well, and aged in a homogeneous state to prepare a recycled ion exchange resin solution. The amount of waste ion exchange resin used above is the same amount of cation exchange resin and anion exchange resin.

                                 TABLE 1

                                                          (Unit: weight%)

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Cellulose Acetate Solution 80 75 70 80 90 95 Ion Exchange Resin Dissolved Acetone Solution 20 25 30 20 10 15

3. Cylindrical Recycling Of ion exchange resin membrane  Produce

     First, the recycled ion exchange resin solution prepared according to the contents of [Table 1] is filled inside the test tube. After a while, the test tube container is upside down to empty the recycled ion exchange resin solution filled inside the test tube container. And when the surface of the recycled ion exchange resin membrane formed attached to the inner wall of the test tube container is dried, soaked for 3 hours in 0 ℃ cooling water and separated from the recycled ion exchange resin cylindrical container in water Example 1 to 3 and Comparative Example 2 , 3 is prepared by heat treatment at 90 ± 1 ℃ and taken out of water to dry the moisture, Comparative Example 1 was prepared without heat treatment.

4. Cylindrical Recycling Ion exchange resin membrane  Desalination Test

       end. Desalination test with brine solution (10 wt% salt)

      A salt solution containing 10 wt% salinity was placed in an 800ml cylindrical recycled ion exchange resin membrane and purified water passed through the recycled ion exchange resin membrane was measured using a gradient salinity meter (25%) to measure the salinity removal rate over time. The results are shown in [Table 2] below.

                                        TABLE 2

division Salinity removal rate (% by weight) over time (hr) 0 One 2 3 4 5 6 7 8 Example 1 10.0 6.7 4.2 2.6 1.7 1.1 0 0 0 Example 2 10.0 6.5 4.0 2.5 1.6 1.0 0 0 0 Example 3 10.0 6.2 3.9 2.4 1.6 1.0 0 0 0 Comparative Example 1 10.0 8.0 7.2 6.8 6.0 5.5 4.9 4.0 3.5 Comparative Example 2 10.0 7.9 5.7 3.8 2.5 1.8 1.2 0.7 0 Comparative Example 3 10.0 7.3 5.3 3.5 2.3 1.4 0.9 0.3 0

       According to the contents of [Table 2], it can be seen that the overall removal and removal rate of salts over time in proportion to the amount of ion exchange resin added. In Examples 1 to 3, after 6 hours, no salinity was detected in the purified water, whereas in Comparative Example 1, the salinity of the recycled ion exchange resin membrane was not compared with that of Examples 1 to 3. It can be seen that the removal rate is much lower, and in Comparative Example 2 and Comparative Example 3, although the heat treatment of the recycled ion exchange resin membrane, the salt removal rate is lower than that of Examples 1 to 3 due to the insufficient amount of the ion exchange resin added. In particular, it can be seen that the salt is not completely removed even after 6 hours.

       I. Desalination test using sea water (salin concentration 3% by weight)

      Seawater with a salt concentration of 3% by weight under the Namhae Bridge was placed in an 800ml cylindrical recycled ion exchange resin membrane, and the purified water passed through this recycled ion exchange resin membrane was subjected to salinity over time using an inclined salinity meter (25%). The results of measuring the removal rate are shown in the following [Table 3].

TABLE 3

division Salinity removal rate (% by weight) over time (hr) 0 One 2 3 4 5 6 7 8 Example 1 3.0 2.1 1.4 1.1 0.6 0.3 0 0 0 Example 2 3.0 1.8 1.3 1.0 0.5 0.2 0 0 0 Example 3 3.0 1.6 1.1 0.9 0.4 0.1 0 0 0 Comparative Example 1 3.0 2.7 2.3 1.8 1.4 1.1 0.9 0.6 0.4 Comparative Example 2 3.0 2.4 1.9 1.5 1.1 0.9 0.7 0.3 0 Comparative Example 3 3.0 2.1 1.7 1.4 0.9 0.7 0.5 0.2 0

       According to the contents of [Table 3], it can be seen that even in seawater, salt removal and removal rate is high as time passes in proportion to the amount of ion-exchange resins, such as brine. In Examples 1 to 3, salts were not detected in the purified water after 5 hours. In Comparative Example 1, salts were not compared to Examples 1 to 3 without performing heat treatment of the recycled ion exchange resin membrane. It was found that even after 8 hours have elapsed since the removal rate was far lower, 0.4 wt% of salinity was detected. In Comparative Examples 2 and 3, the recycled ion exchange resin membrane was heat-treated, but due to the insufficient amount of ion exchange resin, It can be seen that the salinity removal rate is lower than that of 1 to 3, and no salinity was detected in the purified water after 8 hours.

Therefore, the recycled ion exchange resin membrane prepared according to the method for producing a recycled ion exchange resin membrane according to the present invention has excellent salt removal ability, so that it can be used for simple water purification by using sea water to solve the drinking water shortage of island people. In addition, the waste cation and anion exchange resin is powdered and mixed with a cellulose acetate solution, which is a high molecular material, to produce a recycled ion exchange resin membrane, which is characterized by an environmentally friendly method of recycling waste resources.

Claims (6)

Preparing an acetone solution in which cellulose acetate is dissolved, And mixing the waste cation exchange resin and the powder of the waste anion exchange resin with the acetone solution to prepare a recycled ion exchange resin solution; Preparing the recycled ion exchange resin membrane using the recycled ion exchange resin solution using a flat plate or a cylindrical container Method for producing a recycled ion exchange resin membrane, characterized in that which is produced through. The method of claim 1, Preparing an acetone solution in which the cellulose acetate is dissolved Iii) adding 15 to 20% by weight of swelling agent to 80 to 85% by weight of water (swelling agent solution preparation step); Ii) 8 to 12% by weight of the swelling agent dissolution solution prepared in step iii) into 88-92% by weight of acetone solution, followed by mixing and dissolving (acetone mixed solution preparation step); Iii) adding 20-25% by weight of cellulose acetate and 25-30% by weight of formamide solution to 45-55% by weight of the acetone mixed solution prepared in step ii) to dissolve and aged (cellulose cellulose solution dissolving step); Method for producing a recycled ion-exchange resin membrane, characterized in that a solution in which cellulose acetate is dissolved is prepared through. The method according to claim 1 or 2, Preparing the recycled ion exchange resin solution Iii) separately adding 8-12% by weight of waste ion exchange resin powder to 88-92% by weight of water (mixing of waste ion-exchange resin solvent); Iii) dissolving 15-25 wt% of the waste ion exchange resin mixed solvent prepared in step iii) in 75-85 wt% of the acetone solution (preparing waste ion exchange resin mixed acetone solution); Iii) mixing 20-30% by weight of the waste ion exchange resin mixed acetone solution prepared in step iii) into 70-80% by weight of a solution of cellulose acetate dissolved in step iii) and aging it in a homogeneous state (recycling) Ion exchange resin solution manufacturing step); Waste ion exchange resin solution is prepared through the method for producing a recycled ion exchange resin membrane. The method of claim 3, wherein Preparing the recycled ion exchange resin film Iii) forming the ion exchange resin membrane using the waste ion exchange resin solution prepared in step iii) using a flat plate or a cylindrical container (recycled ion exchange resin membrane forming step); Iii) when the recycled ion exchange resin membrane is dried, immersing the cooled ion exchange resin membrane in water for 2 to 3 hours to form a recycled ion exchange resin membrane in water (recycled ion exchange resin membrane formation step); Iii) forming a recycled ion exchange resin membrane and separating the membrane from a flat plate or cylindrical vessel and then heat treating at 60 to 100 ° C. (recycled ion exchange resin membrane heat treatment step); Iii) drying the moisture by removing the heat-treated recycled ion exchange resin film from water (recycled ion exchange resin film drying step); Method for producing a recycled ion exchange resin membrane, characterized in that the recycled ion exchange resin membrane is produced through.        The method of claim 2, The swelling agent of step iii) is magnesium perchlorate (Mg (ClO ₄ ) ₂ ) characterized in that the manufacturing method of the recycled ion exchange resin membrane.        The method of claim 3, wherein Waste ion exchange resin powder used in the step iii) is a method for producing a recycled ion exchange resin membrane, characterized in that the mixture of the amount of cation exchange resin and the amount of anion exchange resin is used in the same amount.

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