WO2015088278A1

WO2015088278A1 - Water softening device and method for regenerating ion exchange resin

Info

Publication number: WO2015088278A1
Application number: PCT/KR2014/012274
Authority: WO
Inventors: 오나리히로토; 미야기게이스케; 오카자키타케시; 야나세사토무
Original assignee: 삼성전자주식회사
Priority date: 2013-12-13
Filing date: 2014-12-12
Publication date: 2015-06-18

Abstract

The present invention relates to a water softening device comprising: a resin chamber which has an ion exchange resin and softens hard water passing through the ion exchange resin; and electrodes which are arranged by placing the resin chamber therebetween and apply voltages to the resin chamber so as to soften the hard water, and which regenerates the ion exchange resin, wherein the ion exchange resin is a slightly acidic cation exchange resin and/or a weakly alkaline anion exchange resin. The present invention provides the water softening device capable of easily regenerating the ion exchange resin and repeating the softening-regenerating without using chemicals or the like while maintaining the performance of softening water, thereby enabling a continuous use thereof.

Description

Regeneration method of water softening device and ion exchange resin

The present invention relates to a softening apparatus and a regeneration method of an ion exchange resin.

The softening device, as disclosed in Patent Literature 1, passes hard water through a cation exchange resin, and at this time, hardness components such as calcium ions and magnesium ions are adsorbed to the cation exchange resin to soften the hard water. A chemical such as sodium chloride is added to the resin to regenerate the cation exchange resin.

In order to regenerate the cation exchange resin of such a softening device, there is a problem in that cost and time are required because drugs must be purchased and put into the softening device on a regular basis.

The softening device disclosed in Patent Document 2 includes a resin chamber having a cation exchange resin and an anion exchange resin, and a pair of electrodes disposed between the resin chambers. Such a softening device allows a voltage to be applied to the resin chamber by an electrode so that the cation exchange resin can be recycled without using a chemical agent or the like.

The principle of regenerating the cation exchange resin in such a softening device will be described.

Since the resin chamber of the softening device has a cation exchange resin and an anion exchange resin, when voltage is applied to the resin chamber by a pair of electrodes, water is decomposed between the cation exchange resin and the anion exchange resin to generate hydrogen ions and hydroxide ions. .

At this time, hydrogen ions are exchanged with hardness components such as calcium ions and magnesium ions adsorbed on the cation exchange resin to regenerate the cation exchange resin.

However, strong acid cation exchange resins or strong alkaline anion exchange resins are used for the ion exchange resin used in the softening device, and thus, the hardness components contained in the water can be adsorbed efficiently. There is a difficult problem.

This is because strong acid cation exchange resins easily adsorb hardness components, but once the hardness components in water are adsorbed, hydrogen ions generated by water decomposition and these hardness components are difficult to exchange.

The strong alkaline anion exchange resin is easy to adsorb anions such as chloride ions in water, but once these anions are adsorbed, the hydroxide ions generated from water decomposition are difficult to exchange with these anions.

[Preceding technical literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 7-232165

[Patent Document 2] Japanese Patent Laid-Open No. 2012-236171

The present invention provides a softening apparatus and a method for regenerating an ion exchange resin to maintain the performance of water softening, to easily regenerate and continuously use the ion exchange resin without the use of drugs.

Softening apparatus according to an aspect of the present invention, after the water softening the water through the resin chamber disposed between the resin chamber and the resin chamber for softening the water passed through the ion exchange resin with the ion exchange resin And an electrode for regenerating the ion exchange resin, wherein the ion exchange resin comprises at least a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin.

Softening here means reducing the hardness component contained in water.

Such a softening device can soften water because the ion exchange resin is at least a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin, and can easily regenerate the ion exchange resin after softening the water.

This is because the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin have the following properties.

The weakly acidic cation exchange resin has the property of easily adsorbing hardness components and hydrogen ions generated by water decomposition compared to the strongly acidic cation exchange resin.

In addition, the weakly alkaline anion exchange resin has the property of easily exchangeable anions in the adsorbed water and hydroxide ions generated by water decomposition as compared with the strongly alkaline anion exchange resin.

Therefore, the softening apparatus according to the present invention can reduce the amount of hydrogen ions and hydroxide ions used for regeneration of ion exchange resins, compared to conventional softening apparatuses using strong acidic cation exchange resins or strong alkaline anion exchange resins. This can shorten the regeneration time of the ion exchange resin and save power.

It is preferable that the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin form particulates, respectively, to be mixed in the resin chamber, and the particle diameters of the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin are respectively 100 µm or more and 500 µm or less.

In addition, when the particle diameters of the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin exceed 500 μm, water decomposition becomes difficult because the sites where the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin contact each other are reduced.

In addition, when the particle diameter of the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin is smaller than 100 µm, water decomposition becomes easier, but pressure loss is more likely to occur during water passage.

Accordingly, the particle diameters of the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin are 100 µm or more and 400 µm or less, and most preferably 250 µm or more and 400 µm or less.

Here, the particle diameter refers to the maximum length from one point to the other at the outer edges of the particulate weakly acidic cation exchange resin and weakly alkaline anion exchange resin.

As an embodiment in which the effect of the present invention is remarkable, it is preferable that the ion exchange capacity of the weakly acidic cation exchange resin is 1 to 9 times the ion exchange capacity of the weakly alkaline anion exchange resin.

If the ion exchange capacity of the weakly acidic cation exchange resin is less than 1 times the ion exchange capacity of the weakly alkaline anion exchange resin, the absolute amount per unit volume of the weakly acidic cation exchange resin in the resin chamber decreases and the performance of the softening device is degraded. Because.

On the other hand, if the ion exchange capacity of the weakly acidic cation exchange resin is greater than 9 times the ion exchange capacity of the weakly alkaline anion exchange resin, the regeneration performance decreases because the locations of the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin are reduced.

If the ion exchange capacity of the weakly acidic cation exchange resin is greater than 9 times that of the weakly alkaline anion exchange resin, the hydroxide ions in the resin chamber are excessive during regeneration, and the regeneration performance is deteriorated due to neutralization reaction with hydrogen ions.

For this reason, the ion exchange capacity of the weakly acidic cation exchange resin is most preferably 3 to 9 times less than that of the weakly alkaline anion exchange resin.

In addition, the resin chamber may be provided in plural, wherein the electrodes may be disposed with a plurality of resin chambers interposed therebetween, and further comprising a conductive member between the plurality of resin chambers so that the ion exchange resin is divided into units separated by the electrode and the conductive member. Can be played.

In addition, the conductive member may be non-ion permeable or non-transmissive.

The resin chamber is formed by being separated by an anion exchange resin membrane disposed on the anode side and a cation exchange resin membrane disposed on the cathode side of the electrodes, and flows from the resin chamber to the anode chamber which is a space between the anode or the conductive member and the anion exchange resin membrane. A flow path and a flow path flowing from the anode chamber to the cathode chamber, which is a space between the conductive member or the cathode and the cation exchange resin film, may be provided.

In addition, the method for regenerating an ion exchange resin according to the present invention provides a voltage between an resin chamber and a resin chamber while applying a voltage to an electrode disposed between a plurality of resin chambers containing an ion exchange resin and a conductive member provided between the plurality of resin chambers. By passing water, the ion exchange resin is regenerated, and the ion exchange resin is regenerated for each unit separated by the electrode and the conductive member.

The resin chamber is formed by being divided by an anion exchange resin membrane provided on the anode side and a cation exchange resin membrane disposed on the cathode side of the electrode, and passed through the resin chamber to regenerate the ion exchange resin, and then from the resin chamber It can pass through the anode chamber which is a space between a member and an anion exchange resin film, and can pass from a cathode chamber into a cathode chamber which is a space between a conductive member or a cathode and a cation exchange resin film.

According to the present invention, it is easy to regenerate the ion exchange resin, and the softening device can be continuously used by repeating the softening-regeneration without using a medicine or the like while maintaining the performance of softening the water.

1 is an exemplary view of a softening device according to an embodiment.

2 is an experimental result showing the relationship between the particle size of the ion exchange resin and the removal rate of the hardness component of the ion exchange resin of the softening apparatus according to an embodiment.

3 is an experimental result showing the relationship between the ion exchange capacity ratio of the softening device according to an embodiment and the removal rate of the hardness component of the ion exchange resin.

4 is an exemplary view of a softening device according to another embodiment.

FIG. 5 is an explanatory diagram of a water circulation path in the softening apparatus shown in FIG. 4.

6 (a) to 6 (b) are diagrams showing the results of Example 1 and Example 2. FIG.

7 is a view showing the results of Example 3 and Comparative Example 1. FIG.

EMBODIMENT OF THE INVENTION Below, embodiment of the softening apparatus which concerns on this invention is described with reference to drawings.

1 is an exemplary view of a softening device according to an embodiment.

As shown in FIG. 1, the water softening device 100 includes a resin chamber 13 in which an introduction port 101 into which water including a hardness component is introduced and a discharge port 102 through which hard water is softened are discharged. And a first electrode and a second electrode which are a pair of electrodes arranged with the resin chamber 13 interposed therebetween.

The first electrode is the anode 21 and the second electrode is the cathode 22.

In the present embodiment, a pair of electrodes, the anode 21 and the cathode 22, are provided to face each other, and by applying a constant voltage, one electrode becomes the anode 21 and the other electrode is the cathode. At this time, a predetermined current flows in the resin chamber 13 from the anode 21 toward the cathode 22.

Here, the positive electrode 21 and the negative electrode 22 may be coated on a surface of a predetermined base made of titanium or the like with an alloy containing platinum, an alloy containing platinum, or a platinum group metal as a main component.

In addition, the shape of the anode 21 and the cathode 22 may be a mesh shape and a plate shape.

The softening device of one embodiment can freely change the magnitude of the current flowing into the resin chamber 13 by changing the voltages applied to these electrodes.

The softening apparatus 100 according to the exemplary embodiment includes the anode chamber 11, the resin chamber 13, and the cathode chamber 12 spaced apart along the current direction flowing into the resin chamber 13.

Here, the resin chamber 13 and the anode chamber 11 are spaced apart by the first diaphragm 31, and the resin chamber 13 and the cathode chamber 12 are spaced apart by the second diaphragm 32.

The first diaphragm 31 may be an anion exchange resin membrane, and the second diaphragm 32 may be a cation exchange resin membrane.

In this case, the materials of the anion exchange resin membrane and the cation exchange resin membrane are not particularly limited as long as they have anion exchange function and cation exchange function, respectively.

In this case, when a voltage is applied to the anode 21 and the cathode 22, the first diaphragm 31, which is an anion exchange resin film, selectively transmits anions.

The second diaphragm 32, which is a cation exchange resin film, selectively transmits cations.

The anion exchange resin membrane and the cation exchange resin membrane are preferably 10 µm or more and 300 µm or less, more preferably 50 µm or more and 150 µm or less, in terms of a balance between mechanical strength and ion permeability.

The resin chamber 13 has an ion exchange resin 40 therein. The water introduced into the resin chamber 13 is softened by passing through the ion exchange resin 40 and is led to the generated water.

In more detail, the resin chamber 13 is comprised so that the water which passed through the inside may flow in the direction substantially perpendicular to the electric current direction which flows in the resin chamber 13.

That is, water flows from the introduction port 101 provided in the lower part of the resin chamber 13 toward the discharge port 102 provided in the upper part of the resin chamber 13.

The ion exchange resin 40 is composed of at least one of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42.

In other words, the resin chamber 13 accommodates the weakly acidic cation exchange resin 41 which has a carboxyl group as an exchanger, and the weakly alkaline anion exchange resin 42 which has a tertiary amino group from a primary amino group as an exchanger, for example.

More specifically, the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 each form a particulate form and are mixed and accommodated in the resin chamber 13.

These weakly acidic cation exchange resins 41 and weakly alkaline anion exchange resins 42 are randomly mixed in the resin chamber 13.

More specifically, the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 each have a particle diameter of 100 µm or more and 500 µm or less.

Preferably, the particle size of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 may be 100 μm or more and 400 μm or less.

Most preferably, the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 may have a particle diameter of 250 μm or more and 400 μm or less.

The weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 each have a generally spherical shape, the diameter of which is 100 μm or more and 500 μm or less, and these particle diameters may be provided according to sizes.

In addition, the ratio of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 in the resin chamber 13 is equal to the ion exchange capacity of the weakly acidic cation exchange resin 41. It may be more than one times the exchange capacity.

In addition, in this embodiment, the ratio between the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 is one or more times and nine times or less.

Next, the operation of the water softening device 100 will be described.

First, the softening device receives water prepared at a hardness of 250 mg / L in terms of CaCO ₃ through the introduction port 101 during the softening treatment.

Water introduced into the softening device passes through the ion exchange resin 40 in the resin chamber 13. At this time, no voltage is applied to the positive electrode 21 and the negative electrode 22 which are a pair of electrodes.

As a result, the water can be softened while the hardness components such as calcium ions and magnesium ions contained in the water are adsorbed on the weakly acidic cation exchange resin 41 and reduced.

The softening device applies a predetermined voltage to the pair of electrodes 21, the anode 21 and the cathode 22, at the same time when regenerating the ion exchange resin 40 after the softening treatment is performed once or several times. 101) is provided water prepared at a hardness of 250 mg / L in terms of CaCO ₃ .

At this time, hydrogen ions and hydroxide ions are generated at the interface between the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 by water decomposition.

The hydrogen ions exchange hardness components such as calcium ions and magnesium ions adsorbed to the weakly acidic cation exchange resin 41, and sulfate ions and carbonate ions adsorbed to the weakly alkaline anion exchange resin 42 by hydroxide ions. The ion exchange resin 40 is regenerated by the exchange of the anion component.

However, it is preferable that the length of the flow path in the resin chamber 13 be as short as possible in order to suppress the detached hardness component and the anion component from being resorbed to the ion exchange resin 40.

Next, when the ratio between the weakly acidic cation exchange resin (41) and the weakly alkaline anion exchange resin (42) is 9 times, softening and regeneration are repeated three times, the particle size and hardness of the ion exchange resin (40) are softened. The experimental data showing the relationship with the component removal rate is shown in FIG. 2. The weakly acidic cation exchange resin at the time of softening after repeating the softening-regeneration three times with the particle diameter of the ion exchange resin 40 as 500 μm ( 41) and experimental data showing the removal rate of the hardness component at the ion exchange capacity ratio of the weakly alkaline anion exchange resin 42 are shown in FIG.

As shown in FIG. 2, when the particle diameters of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 are 100 μm or more and 500 μm, respectively, compared to 500 μm or more and 750 μm or less, which is the size of a general ion exchange resin 40. It can be seen that the removal rate of the hardness component of the ion exchange resin 40 is high.

The reason is that when the particle diameters of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 are in the range of 100 μm or more and 500 μm, respectively, the locations of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 are increased. This is because water decomposition occurs easily.

However, if the particle size is smaller than 100 µm, the pressure loss occurs due to blockage of the

respective ports

101 and 102 and the mesh accompanying them.

In addition, it is preferable to mix | blend the ratio of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 with the ratio of the weakly acidic cation exchange resin 41 as large as possible in consideration of softening performance.

This is because the absolute amount of the weakly acidic cation exchange resin 41 per unit volume is increased. This may be advantageous for softening.

As shown in FIG. 3, it can be seen that the hardness removal performance is excellent when the ion exchange capacity of the weakly acidic cation exchange resin 41 is 1 to 9 times the ion exchange capacity of the weak alkaline anion exchange resin 42. In particular, it can be seen that the hardness removal performance is very excellent when the ion exchange capacity of the weakly acidic cation exchange resin 41 is three to six times the ion exchange capacity of the weak alkaline anion exchange resin 42.

According to the softening device 100, the ion exchange resin 40 may be made of at least one of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 to soften the water flowing into the resin chamber 13, The removal rate of the hardness component adsorbed on the ion exchange resin 40 can be increased, and the water can be easily recycled after the water is softened without the use of a medicament or the like, thereby enabling continuous use.

In addition, the water softening device 100 is not limited to the form shown in FIG.

4 is another exemplary view of the softening device 100.

The softening device 100 of FIG. 4 compares the softening device 100 shown in FIG. 1 with the positive electrode 21 and the negative electrode 22, which are a pair of electrodes disposed with the resin chamber 13 therebetween. It is the same in that it includes.

In addition, the softening apparatus 100 of FIG. 4 has an anode chamber 11 between the anode 21 and the adjacent resin chamber 13, and a cathode between the cathode 22 and the adjacent resin chamber 13. It is the same as the softening device 100 shown in FIG. 1 in that it has a seal 12.

For convenience of explanation, these are shown as the anode chamber 11a and the cathode chamber 12b, respectively.

The softening apparatus 100 of another embodiment differs from the softening apparatus of one embodiment in that a plurality of resin chambers 13 are provided.

4 illustrates the case where two resin chambers 13 are provided as an example.

In FIG. 4, these two resin chambers 13 are shown as the resin chamber 13a and the resin chamber 13b, respectively.

In the softening apparatus 100 according to another embodiment, the conductive member 50, which will be described later, is provided between the plurality of resin chambers 13 as compared with the softening apparatus 100 illustrated in FIG. 1.

The conductive member 50 divides the space between the resin chambers 13 adjacent to each other into the anode chamber 11 and the cathode chamber 12.

In the example shown in FIG. 4, the conductive member 50 divides the space between the resin chamber 13a and the resin chamber 13b.

The conductive member 50 is divided into a cathode chamber 12a which is a space between the resin chamber 13a and the conductive member 50 and an anode chamber 11b which is a space between the conductive member 50 and the resin chamber 13b. do.

The resin chamber 13a is spaced apart from the adjacent space by the first diaphragm 31a and the second diaphragm 32a provided with the resin chamber 13a therebetween.

The resin chamber 13b is spaced apart from the adjacent space by the first diaphragm 31b and the second diaphragm 32b provided with the resin chamber 13b therebetween.

That is, the anode chamber 11a and the resin chamber 13a are separated by the first diaphragm 31a, and the resin chamber 13a and the cathode chamber 12a are spaced apart by the second diaphragm 32a.

In addition, the anode chamber 11b and the resin chamber 13b are separated by the first diaphragm 31b, and the resin chamber 13b and the cathode chamber 12b are spaced apart by the second diaphragm 32b.

Here, the

first diaphragms

31a and 31b may be anion exchange resin membranes, and the

second diaphragms

32a and 32b may be cation exchange resin membranes.

The resin chamber 13a and the resin chamber 13b have ion exchange resin 40 therein.

The ion exchange resin 40 is the same as that of FIG. 1 in that it consists of at least the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42.

In addition, the particle size of the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 and the ratio between the weakly acidic cation exchange resin 41 and the weakly alkaline anion exchange resin 42 in the resin chamber 13 are described in detail. It may be the same as in one case.

The conductive member 50 is a member having conductivity.

The conductive member 50 is conductive, at least non-permeable and non-ionic permeable, and may be resistant to positive and negative polarizations in water.

In detail, the conductive member 50 may be, for example, a plate made of a metal material, and may be coated with a platinum, an alloy containing platinum, or an alloy containing platinum group metal as a main component.

Next, the operation of the softening apparatus 100 of another embodiment will be described.

In the case of the softening treatment in the softening apparatus 100 of another embodiment, the voltage is not applied to the positive electrode 21 and the negative electrode 22 in the same manner as the softening apparatus 100 of FIG. 1.

The water to be treated as soft water of another embodiment is divided into two, and a portion of the water to be treated is introduced into the resin chamber 13a from an introduction port 101a provided in the lower portion of the resin chamber 13a.

The remaining water to be treated is introduced into the resin chamber 13b from an introduction port 101b provided below the resin chamber 13b.

Then, each of the resin chamber 13a and the resin chamber 13b is passed through from the lower side to the upper side, and the introduced treated water can be softened by removing the hardness component by the ion exchange resin 40.

In addition, the softened water is discharged into the generated water through the discharge port 102a provided at the upper portion of the resin chamber 13a and the discharge port 102b provided at the upper portion of the resin chamber 13b, respectively.

When the ion exchange resin 40 is regenerated, a constant voltage is applied to the positive electrode 21 and the negative electrode 22.

As in the case of the softening treatment, the same water as the water to be treated is introduced into the resin chamber 13a from the introduction port 101a and introduced into the resin chamber 13b from the introduction port 101b.

At this time, hydrogen ions and hydroxide ions are generated by water decomposition, and the hardness components adsorbed on the weakly acidic cation exchange resin 41 are exchanged by the hydrogen ions.

In addition, anion components adsorbed on the weakly alkaline anion exchange resin 42 are exchanged by hydroxide ions. The ion exchange resin 40 is then regenerated.

At this time, by applying a constant voltage to the anode 21 and the cathode 22, the conductive member 50 is polarized to become a bipolar electrode.

That is, the anode 21 side of the conductive member 50 forms a cathode, and the cathode 22 side of the conductive member 50 forms a positive electrode.

As the conductive member 50 becomes a bipolar electrode, water decomposition occurs on the surface of the conductive member 50.

In addition, when the second diaphragm 32a is a cation exchange resin membrane, the hardness component such as calcium ions in the resin chamber 13a is easily discharged to the cathode chamber 12a side through the second diaphragm 32a, but the anion component 2 It is difficult to penetrate the diaphragm 32a. That is, the electrodialysis effect occurs.

In addition, when the conductive member 50 is a bipolar electrode, since the second diaphragm 32a side is a cathode, a hardness component that is a cation may be attracted. For this reason, the hardness component can be easily discharged from the resin chamber 13a to the cathode chamber 12a side more efficiently.

That is, the chance of the hardness component being resorbed to the ion exchange resin 40 can be further reduced, thereby improving the regeneration efficiency of the ion exchange resin 40.

When regenerating the ion exchange resin 40 of the softening device of another embodiment, it is preferable that the flow path of water is as follows.

FIG. 5 is a diagram illustrating a flow path of water in the softening apparatus 100 illustrated in FIG. 4.

First, water introduced from the introduction port 101a into the resin chamber 13a and drawn out from the discharge port 102a is then introduced into the lower portion of the anode chamber 11a.

Water introduced into the lower portion of the anode chamber 11a is led out to the upper portion of the anode chamber 11a and then introduced into the lower portion of the cathode chamber 12a.

Water introduced into the lower portion of the cathode chamber 12a is led to the upper portion of the cathode chamber 12a.

In addition, water introduced from the introduction port 101b into the resin chamber 13b and drawn out from the discharge port 102b is then introduced into the upper portion of the anode chamber 11b.

Water introduced into the upper portion of the anode chamber 11b is led out of the lower portion of the anode chamber 11b and introduced into the lower portion of the cathode chamber 12b.

Water introduced into the lower portion of the cathode chamber 12b is led to the upper portion of the cathode chamber 12b.

That is, in the softening device of another embodiment, a flow path flowing from the resin chamber 13a to the anode chamber 11a, which is a space between the anode 21 and the first diaphragm 31a, and the conductive member 50 from the anode chamber 11a. The flow path which flows into the cathode chamber 12a which is a space between and 2nd diaphragm 32a is provided.

Water flows through the resin chamber 13a, regenerates the ion exchange resin, and then flows through the flow path.

In another embodiment, the water softening device includes a flow path flowing from the resin chamber 13b to the anode chamber 11b, which is a space between the conductive member 50 and the first diaphragm 31b, and the cathode 22 from the anode chamber 11b. ) And a flow path flowing into the cathode chamber 12b, which is a space between the second diaphragm 32b.

Water passes through the resin chamber 13b, and after regenerating the ion exchange resin, passes through the flow path.

As a result, the ion exchange resin is regenerated for each unit (block) separated by the positive electrode 21, the negative electrode 22, and the conductive member 50, which are electrodes.

5 may also be applied to the softening apparatus 100 described with reference to FIG. 1.

In this case, for example, water is first introduced from the introduction port 101 into the resin chamber 13 to be led to the discharge port 102.

Next, water is introduced into the lower part of the anode chamber 11.

Then, water is extracted from the upper portion of the anode chamber 11 and introduced again to the lower portion of the cathode chamber 12. And water is drawn out to the upper part of the cathode chamber 12.

In this case, the upper and lower portions of each chamber are designated in the introduction and derivation of water, but the upper and lower portions may be reversed.

In addition, this invention is not limited to the said embodiment.

For example, the resin chamber of the embodiment has at least one of a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin, but has a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin as a main component, and further has a strong acid cation exchange resin or a strongly alkaline anion exchange resin. It is also possible.

The weakly acidic cation exchange resin and the weakly alkaline anion exchange resin are generally spherical in the embodiment, but may be in the form of a flat plate, a gel or an amorphous form.

In the embodiment, the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin are randomly contained in the resin chamber, but may be regularly contained in the resin chamber.

The weakly acidic cation exchange resin preferably has exchange groups other than carboxyl groups, and the weakly alkaline anion exchange resin may have exchange groups other than primary to tertiary amino groups.

In addition, it is preferable that the particle diameters of all ion exchange resins do not need to be the same, and the average particle diameter of the ion exchange resin accommodated in a resin chamber is 100 micrometers or more and 500 micrometers or less.

In the embodiment, the water containing the hardness component is configured to flow from the lower portion of the resin chamber to the upper portion, but may be configured to flow from the upper portion to the lower portion, or may be rotated to flow in the horizontal direction.

In addition, although the flow direction of the above-mentioned water was substantially perpendicular to the direction of the current which flows through the inside of a resin chamber in the Example, it does not necessarily need to be perpendicular and may be parallel or inclined at a predetermined angle.

In the said embodiment, although an electrode is comprised so that it may become a pair, it may be comprised so that it may be a plurality of pairs, and it may be a soluble electrode or an insoluble electrode.

The positive electrode and the negative electrode may be the same or different.

When regenerating the ion exchange resin, the embodiment introduces water prepared at a hardness of 250 mg / L in terms of CaCO ₃ from the inlet port, but it is not necessary to introduce water of such hardness. You may introduce | transduce or may introduce the water which does not contain the hardness component.

The first diaphragm and the second diaphragm may be a membrane having a pass selectivity such as an ion exchange resin membrane, or a membrane having no pass selectivity such as a porous membrane.

The first diaphragm and the second diaphragm may be the same or different.

Besides, needless to say, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit thereof.

Hereinafter will be described in more detail using an embodiment of the present invention. The present invention is not limited by these Examples unless the gist of the present invention is departed.

(Example 1)

Embodiment 1 is the softening apparatus 100 shown in FIG.

The ion exchange resin 40 is uniformly so that the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin whose particle diameters in the hydrous state are adjusted to 300 μm to 425 μm are 3: 1 with an ion exchange capacity (meq / ml), respectively. It is a mixture.

The anode 21 and the cathode 22 are mesh-shaped electrodes in which platinum is coated on titanium, which is a substrate, and has an electrode size of 5 cm x 10 cm.

The first diaphragm 31 is a strong alkaline anion exchange resin film having a thickness of 100 μm, and the second diaphragm 32 is a strong acid cation exchange resin film having a thickness of 100 μm.

That is, the water softening device 100 includes a transparent polyvinyl chloride cartridge, and 80 mL of the ion exchange resin 40, the positive electrode 21, the negative electrode 22, the first diaphragm 31, the second diaphragm 32 Set to.

The water to be treated is hard water having a hardness of 250 mg / L in terms of calcium carbonate (CaCO ₃ ).

This treated water was introduced from the inlet port 101 into the resin chamber 13 at a rate of 120 mL / min and discharged from the discharge port 102 to obtain soft water (softening).

The same treated water was then introduced as regeneration water into the resin chamber 13 from the inlet of the introduction port 101 at a rate of 10 mL / min and at the same time a current density of 2 A / dm 2 between the anode 21 and the cathode 22. 30 minutes (electrical regeneration).

At this time, the regeneration water discharged from the resin chamber 13 outlet passes through the anode chamber 11 and the regeneration liquid discharged therefrom passes through the cathode chamber 12 again and is discharged out of the apparatus. This softening-electric regeneration process is repeated eight times.

(Example 2)

Embodiment 2 is the softening apparatus 100 shown in FIG.

The positive electrode 21, the negative electrode 22, and the conductive member 50 are mesh-shaped electrodes in which platinum is coated on titanium, which is a substrate, and has an electrode size of 5 cm x 10 cm.

The

first diaphragms

31a and 31b are strongly alkaline anion exchange resin membranes having a thickness of 100 µm, and the

second diaphragms

32a and 32b are strongly acidic cation exchange resin membranes having a thickness of 100 µm.

That is, the water softening device 100 includes a transparent polyvinyl chloride cartridge, and 160 mL (80 mL × 2) of the ion exchange resin 40, the positive electrode 21, the negative electrode 22, and the

first diaphragms

31a and 31b.

2nd diaphragm

32a, 32b is set.

This treated water was introduced into the

resin chambers

13a and 13b from the

introduction ports

101a and 101b at a rate of 120 mL / min and discharged from the

discharge ports

102a and 102b to obtain soft water (softening).

The same treated water was then introduced as reclaimed water from the inlet of the

introduction ports

101a and 101b into the

resin chambers

13a and 13b at a rate of 10 mL / min and at the same time 2A / between the anode 21 and the cathode 22. Allow 30 minutes to flow at a current density of dm2 (electrical regeneration).

When the voltage is applied, the conductive member 50 becomes a bipolar electrode, and the anode 21 side of the conductive member 50 forms a cathode and the cathode 22 side forms a positive electrode. At this time, the water passage is as shown in FIG. 5.

This softening-electric regeneration process is repeated eight times.

6 (a) and 6 (b) are experimental results of Example 1 and Example 2. FIG.

6 (a) shows the relationship between the treatment flow rate and the hardness component removal rate in Examples 1 and 2. FIG.

Here, the horizontal axis represents the integrated value of the treatment flow rate, and the vertical axis represents the hardness component removal rate.

In Fig. 6 (a), the relationship between the treatment flow rate and the hardness component removal rate is shown for each of the water softening-electric regeneration in Example 1 and Example 2.

6 (b) shows the removal rate of the hardness components of Examples 1 and 2 as the average value calculated from the results of FIG. 1.

6 (b), the current flowing through the ion exchange resin 40 is shown per unit volume.

As shown, it can be seen that Example 1 and Example 2 together achieve a high hardness component removal rate.

In addition, Example 2 has a higher hardness component removal rate than Example 1 although the current flowing per unit volume in the ion exchange resin 40 is smaller.

This is an effect of installing the conductive member 50.

(Example 3)

Embodiment 3 is the water softening device 100 shown in FIG.

The device configuration of the water softening device 100 is the same as that of the first embodiment.

This treated water was introduced into the resin chamber 13 from the introduction port 101 at a rate of 320 mL / min (SV = 4 min-1) and discharged from the discharge port 102 to obtain soft water (softening).

The same treated water was then introduced as reclaimed water from the inlet 101 to the resin chamber 13 at a rate of 10 mL / min and at the same time a current density of 1 A / dm 2 between the anode 21 and the cathode 22. 30 minutes (electrical regeneration).

At this time, the regeneration water discharged from the resin chamber 13 outlet was passed to the anode chamber 11, and the regeneration liquid discharged therefrom was passed to the cathode chamber 12 again and discharged out of the apparatus. The process of softening-electric regeneration is repeated 10 times.

(Comparative Example 1)

The softening device 100 shown in FIG.

The device configuration of the softening device 100 is the same as that in Example 3 except that the ion exchange resin 40 is changed from a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin to a strongly acidic cation exchange resin and a strong alkaline anion exchange resin. .

And the same as Example 3, the to-be-processed water was processed.

7 shows the results of Example 3 and Comparative Example 1. FIG.

7 shows the relationship between the treatment flow rate and the hardness component removal rate for Example 3 and Comparative Example 1. FIG.

In FIG. 7, the relationship between the processing flow rate and the hardness component removal rate is shown for each time of water softening-electrical regeneration for Example 3 and Comparative Example 1. FIG.

As shown in Example 3, the removal rate of the hardness component at the time of repeating the softening-electric regeneration process ten times was stabilized at about 66%.

On the contrary, in Comparative Example 1, the hardness component removal rate was lower than about 50%.

As a result, the use of the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin is easier to regenerate the ion exchange resin 40 and the exchange of the ion exchange resin 40 than that of the strong acid cation exchange resin and the strong alkaline anion exchange resin. It can be seen that the frequency is less.

Claims

A pair of electrodes;

A plurality of resin chambers spaced apart from each other between the pair of electrodes;

At least one conductive member disposed between the plurality of resin chambers; And

Each of the plurality of resin chambers is provided with at least one of a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin and includes a plurality of ion exchange resins to soften the water and to perform regeneration when a voltage is applied to the pair of electrodes Water softening device.
The method of claim 1, wherein the conductive member,

A softening device that is non-ion permeable or non-permeable.
The method of claim 1,

And a water softening device for regenerating the plurality of ion exchange resins for each unit separated by the conductive member.
The method of claim 1,

A plurality of first diaphragms disposed adjacent to the plurality of ion exchange resins and transmitting anions during regeneration of the ion exchange resins; And

And a plurality of second diaphragms disposed adjacent to each of the plurality of ion exchange resins and allowing a cation to pass through during the regeneration of the ion exchange resins.
The method of claim 1,

A flow path formed between the pair of electrodes and the plurality of ion exchange resins, respectively;

And a flow path formed between the conductive member and the plurality of ion exchange resins.
The method of claim 1, wherein the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin,

A softening device which forms a particulate form, is mixed and accommodated in the inside of the resin chamber, and has a particle size of 100 µm or more and 500 µm or less, respectively.
The method of claim 1,

A softening device, wherein the ion exchange capacity of the weakly acidic cation exchange resin is 1 to 9 times less than the ion exchange capacity of the weakly alkaline anion exchange resin.
The method of claim 1,

The first diaphragm is a strong alkaline anion exchange resin membrane,

The second diaphragm is a soft acidic cation exchange resin membrane.
A pair of electrodes;

A resin chamber disposed between the pair of electrodes; And

A water softening device comprising an ion exchange resin provided in the resin chamber and made of at least one of a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin to soften water and regenerate when a voltage is applied to the pair of electrodes. .
The method of claim 9,

A first diaphragm disposed adjacent to the ion exchange resin and spaced apart from an anode of the pair of electrodes and transmitting anions during regeneration of the ion exchange resin; And

And a second diaphragm disposed adjacent to the ion exchange resin, spaced apart from a cathode of the pair of electrodes, and transmitting a cation during regeneration of the ion exchange resin.
The method of claim 9, wherein the weakly acidic cation exchange resin and weakly alkaline anion exchange resin,

A softening device which forms a particulate form and is mixed and accommodated inside the resin chamber.
The method of claim 11, wherein the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin,

A water softening device having a particle diameter of 100 μm or more and 500 μm or less, respectively.
The method of claim 9,

A softening device, wherein the ion exchange capacity of the weakly acidic cation exchange resin is 1 to 9 times less than the ion exchange capacity of the weakly alkaline anion exchange resin.
When regenerating a plurality of ion exchange resins in a plurality of resin chambers disposed between the pair of electrodes, a voltage is applied to the pair of electrodes,

Water is introduced into each of the plurality of resin chambers,

When the water introduced into each of the plurality of resin chambers passes through the ion exchange resin, respectively, the passed water is discharged to the outside,

The regeneration of the plurality of ion exchange resins includes selectively regenerating the plurality of ion exchange resins based on a flow path of water flowing through the plurality of resin chambers.
The method of claim 14,

The plurality of resin chambers are separated by units by a conductive member spaced apart from the plurality of ion exchange resins,

Selectively regenerating the plurality of ion exchange resins may include a plurality of first diaphragms disposed on both sides of the plurality of ion exchange resins and disposed on the anode side of the electrodes, and a plurality of second diaphragms disposed on the cathode side; And selecting a plurality of flow paths formed between the conductive members.
The method of claim 15, wherein the distribution channel of water,

A path moving in the order of at least one ion exchange resin, an anode chamber adjacent to the at least one ion exchange resin, and a cathode chamber adjacent to the at least one ion exchange resin,

The anode chamber is a space adjacent to the anode of the flow path formed adjacent to the at least one ion exchange resin,

And the cathode chamber is a space adjacent to the cathode of the flow path formed adjacent to the at least one ion exchange resin.
The method of claim 14, wherein the water is introduced into the plurality of resin chambers, respectively,

Recycling method of the ion exchange resin comprising a portion of the water to be introduced into the plurality of resin chambers are introduced into at least one resin chamber, and the remaining water is introduced into the other resin chamber.
The method of claim 14, wherein the plurality of ion exchange resin,

A method for regenerating an ion exchange resin comprising a weakly acidic cation exchange resin and a weakly alkaline anion exchange resin mixed and accommodated.
In the regeneration method of the ion exchange resin provided in the softening device,

During the softening treatment, water is introduced into the resin chamber containing the ion exchange resin, and when the introduced water passes through the ion exchange resin, the water is discharged to the outside.

When the ion exchange resin is regenerated, a voltage is applied to electrodes disposed on both sides of the resin chamber, and water flows into the resin chamber, and when water introduced into the resin chamber passes through the ion exchange resin, Regeneration method of the ion exchange resin to be discharged to.
The method of claim 19,

The ion exchange resin includes a weak acid cation exchange resin and a weak alkaline anion exchange resin,

Regeneration of the ion exchange resin,

When hydrogen ions and hydroxide ions are formed at the interface between the weakly acidic cation exchange resin and the weakly alkaline anion exchange resin by water decomposition, the hardness components of the ions adsorbed to the weakly acidic cation exchange resin are exchanged by the hydrogen ions, and the hydroxide ions A method of regenerating an ion exchange resin comprising causing an anion component adsorbed on the weakly alkaline anion exchange resin to be exchanged.