WO2006062176A1

WO2006062176A1 - Electric deionized liquid production apparatus and process for producing deionized liquid

Info

Publication number: WO2006062176A1
Application number: PCT/JP2005/022600
Authority: WO
Inventors: Hisashi Mizuochi; Koji Yamanaka; Naoyuki Tajima; Hiroshi Inoue; Akira Nakamura
Original assignee: Organo Corporation
Priority date: 2004-12-06
Filing date: 2005-12-02
Publication date: 2006-06-15
Also published as: JP4721323B2; TW200628412A; JP2006159064A

Abstract

An electric deionized liquid production apparatus comprising at least desalting region (1c) filled with an ion exchanger; liquid permeation regions (2a,3b) disposed adjacent to the ion removing sides of the desalting region (1c) and adapted to cause portion of a liquid to be treated to pass therethrough; electrodes (4a,4b) disposed on both sides of the liquid permeation regions and desalting region (1c); liquid to be treated inflow pipe (11) for introducing a liquid to be treated; electrode chambers (6,7) adapted to discharge any liquid having permeated the liquid permeation regions (2a,3b); and desalted liquid outflow pipe (14) for discharging a desalted liquid from the desalting region (1c), wherein the liquid permeation regions (2a,3b) are packed with a porous ion exchanger. Thus, there can be provided an electric deionized liquid production apparatus that without the use of any ion exchange membrane, simplifies the conventional apparatus structure and prevents any occurrence of scale, and provided a relevant process for producing a deionized liquid.

Description

Specification

Technical Field of Electric Deionization Liquid Manufacturing Equipment and Deionization Liquid Manufacturing Method

The present invention uses ion exchange membranes used in various industries such as semiconductor manufacturing industry, pharmaceutical industry, food industry, power plant, laboratory, etc. using deionized liquid or in manufacturing sugar liquid, juice, wine, etc. The present invention relates to an electric deionization liquid production apparatus and a deionization liquid production method with a simplified apparatus structure. Background art

A conventional electric deionized liquid production apparatus basically has a mixed ion exchange resin layer of an anion exchange resin and a cation exchange resin as an ion exchanger in a gap formed by a cation exchange membrane and an anion exchange membrane. Filling it into a deionization chamber, allowing the liquid to be processed to pass through the ion exchange resin layer, and applying a direct current to the flow of the liquid to be processed through the ion exchange membrane in the vertical direction, A deionized liquid is produced while electrically removing ions in the liquid to be treated in the concentrated liquid flowing outside the two ion exchange membranes. In such an electrical deionized liquid production apparatus, it is necessary to arrange a large number of deionization chambers in parallel, and to form separate flow paths separate from the demineralization chambers in each concentration chamber and electrode chamber. The device structure is complicated and increases the manufacturing cost. .

On the other hand, Japanese Patent Application Laid-Open No. 2000-033 3 4 5 60 discloses a deionization chamber filled with a monolithic organic porous ion exchanger (hereinafter, also simply referred to as “monolith”). The deionized water is removed to remove ionic impurities in the water to produce deionized water, and a DC electric field is applied to the deionized chamber to adsorb to the monolith. Electricity to remove ionic impurities out of the system In the gas deionized water production apparatus, the application of the DC electric field is performed in such a way that a number of deionization chambers are arranged in parallel if the ions to be eliminated migrate in the direction opposite to the direction of water flow in the monolith. It is disclosed that the structure of the apparatus can be simplified and material costs, processing costs, and assembly costs can be reduced.

(Patent Document 1) Japanese Patent Laid-Open No. 2 00 3-3 3 4 5 6 0 (Claim 1, Paragraph No. 0 0 3 0)

However, in recent years, without knowing that the demand for rationalization and further reduction in production costs will not stop, further improvements have been desired in the electric deionization liquid production apparatus. In addition, in paragraph number 0 0 30 of Japanese Patent Laid-Open No. 2 03-3-3 3 4 5 60, a monolith having an average diameter of monolith and mesopore of less than 1 μm is used as a monolith filled in the deionization chamber. Although it is described that an ion exchange membrane can be omitted by using in combination, a monolith with an average mesopore diameter of less than 1 μπι can pass ions, but water hardly passes. It had the same effect as the membrane, and it was necessary to supply electrode water or concentrated water separately to the electrode chamber or concentration chamber. That is, conventionally, if a porous ion exchanger having an ion permeation function and a water permeation function is provided on the ion exclusion side of the ion exchanger in the desalination region without using an ion exchange membrane, the device There was no idea that the structure could be simplified and scale could be prevented.

Accordingly, an object of the present invention is to further simplify the structure of the apparatus than the conventional one without using an ion exchange membrane, and to prevent the occurrence of scale, and an apparatus for producing an electric deionized liquid and a deionized liquid. It is to provide a manufacturing method. Disclosure of the invention Under such circumstances, the present inventors have conducted intensive studies, and as a result, a desalting region filled with an ion exchanger and a part of the liquid to be processed disposed adjacent to the ion exclusion side of the desalting region are In an electro-deionized liquid production system equipped with a permeating liquid permeation area, a part of the liquid to be treated introduced into the desalting area is allowed to pass through the liquid permeation area to be electrophoretically excluded. If the structure discharges together with impurities into the electrode chamber or the concentration chamber, the device structure can be further simplified than the conventional one without using an ion exchange membrane. The inventors have found that the generation of scale can be prevented by the diluting effect of the permeate to be treated, and have completed the present invention.

That is, the present invention includes a desalting region filled with an ion exchanger, a liquid permeable region through which a part of the liquid to be disposed disposed adjacent to the ion exclusion side of the desalting region, and the desalting region. An electrode disposed on both sides of the salt region and the liquid permeation region, a liquid inflow pipe to be treated for passing the liquid to be treated, an electrode chamber or a concentration chamber for discharging the liquid that has permeated from the liquid permeation region, A desalting solution outlet pipe for discharging desalted solution from the desalting region; and at least a porous ion exchanger in the liquid permeation region. A deionized liquid production apparatus is provided.

The present invention also provides a desalting solution by passing a processing solution through a desalting region filled with an ion exchanger and adsorbing and removing ionic impurities in the processing solution. In an electric deionization liquid production apparatus that removes adsorbed ionic impurities by electrophoretic application by applying an electric field to the desalting region, at least adjacent to the ion exclusion side of the desalting region A part of the liquid to be treated introduced into the desalting region is allowed to pass through the porous ion exchanger, and is discharged into the electrode chamber or the concentration chamber together with the ionic impurities that are electrophoretically excluded. A method for producing a deionized liquid is provided. According to the electric deionization liquid production apparatus and the deionization liquid production method of the present invention, the structure of the apparatus can be further simplified than the conventional one without using an ion exchange membrane, In the liquid permeation region, scale can be prevented from being generated due to the dilution effect of the liquid to be treated. Brief Description of Drawings

FIG. 1 is a schematic diagram showing the structure of an electrical deionized liquid production apparatus according to the first embodiment of the present invention, and FIG. 2 is an electrical diagram of the second embodiment of the present invention. FIG. 3 is a schematic diagram showing the structure of the deionized liquid production apparatus, and FIG. 3 is a schematic diagram showing the structure of the electric deionized liquid production apparatus of the third embodiment of the present invention. FIG. 5 is a schematic diagram showing the structure of an electrical deionized liquid production apparatus according to a fourth embodiment of the present invention, and FIG. 5 shows a desorption used in the electrical deionized liquid production apparatus of FIG. FIG. 6 is a schematic diagram showing the structure of the electrical deionized liquid production apparatus of Example 2, and FIG. 7 is a diagram illustrating the filling state of the ion region and the liquid permeable region. FIG. It is a figure explaining the filling state of the deionization area | region and liquid permeation | transmission area | region used with the electric deionization liquid manufacturing apparatus of this. BEST MODE FOR CARRYING OUT THE INVENTION

In the electric deionization liquid production apparatus of the present invention (hereinafter also simply referred to as “EDI”), the ion exchanger filled in the demineralization zone is not particularly limited, and is filled in the conventional EDI demineralization chamber. Examples of such an ion exchanger include monoliths, granular ion exchange resins, and mixtures of monoliths and granular ion exchange resins. Among these, the monolith is an open cell having a mesopore having an average diameter of 1 to 100 μm, preferably 10 to 100 μm in the wall of the mac mouth pores connected to each other. Structure And the total pore volume is 1 to 50 ml / g, preferably 4 to 20 ml / g, the ion exchange groups are uniformly distributed, and the ion exchange capacity is 0.5 mg equivalent / g dry porous. The thing more than a solid body is mentioned. Further, the flow resistance of the monolith is made smaller than that of the porous ion exchanger loaded in the liquid permeation region. When the porous ion exchanger is a monolith, the average diameter of the mesopore is set to be smaller than the average diameter of the monolith loaded in the desalting region. As a result, it is easy to reduce the fluid flow resistance with respect to the porous ion exchanger loaded in the liquid permeation region, and most of the liquid to be treated is not required to be provided with a separate special channel distribution means. It can flow to the desalting zone. Other physical properties of monolith and methods for producing the same are disclosed in, for example, Japanese Patent Laid-Open No. 2003-334560.

The liquid permeation region is loaded with a porous ion exchanger, and is disposed adjacent to the ion exclusion side of the desalting region. When a part of the liquid to be treated permeates, it is electrophoretically excluded. This is a region through which ionic impurities are transmitted. The porous ion exchanger loaded in the liquid permeation region is particularly limited as long as it retains its shape, electrophoretically excludes ions, and allows a part of the liquid to be treated to permeate. However, examples include monoliths, fibrous porous ion exchangers, and particle agglomerated porous ion exchangers. Of these, monoliths have a uniform distribution of ion exchange groups and prompt ion exclusion. Is preferable.

Examples of the fibrous porous ion exchanger include, for example, single fibers and woven fabrics and non-woven fabrics that are aggregates of single fibers described in JP-A-5-64726, and radiation graft polymerization to these processed products. And an ion-exchange group introduced and processed and molded. Examples of the particle agglomerated porous ion exchanger include thermoplastic polymers and thermosetting resins described in, for example, JP-A Nos. 10-1 9 2 7 1 6 and 10-1 9 27 17. Polymer mixing point Examples include those obtained by bonding ion-exchange resin particles using a remer or a crosslinkable polymer and then processing and molding.

The monolith loaded in the liquid permeation region is the same as the monolith exemplified as the ion exchanger in the desalination region, but no flow rate adjusting means is provided in the permeate flow path as will be described later. The monolith has a smaller mesopore average diameter than the monolith used in the desalination zone. Specifically, the average diameter is 1 to 100 m, preferably 1 to 20 m, in the wall of the macropore and the mac mouth pore that are connected to each other. It has an open cell structure with a smaller mesopore and a total pore volume of: Up to 5 O m 1 / g, preferably 1 to 1 O ml / g, ion exchange groups are uniformly distributed, and the ion exchange capacity is 0.5 mg equivalent / g or more of a dry porous material. It is done. Such a monolith having a small average mesopore diameter can be obtained by a method such as increasing the amount of the surfactant added or increasing the agitation during the production. Examples of the flow rate adjusting means include a flow rate adjusting valve and an orifice.

Conventionally, an ion exchange membrane has been attached to the ion rejection side of the desalting zone. Depending on the hardness component concentration in the treated water and the applied current density, there is a problem of scale generation on the ion exchange membrane surface on the concentration chamber side. It was. On the other hand, in the liquid permeation region of the present invention, a part of the liquid to be treated permeates, so that the dilution effect can prevent the generation of scale. In addition, since the liquid that has passed through the liquid-permeable region flows into the electrode chamber or the concentration chamber as it contains ionic impurities, it is not necessary to supply a separate electrode solution or concentrated solution. The ion-exclusion side is the cathode side of the desalting region when removing the cationic impurities, and the anode side of the desalting region when removing the anionic impurities, and the cationic impurities and the anionic impurities are simultaneously removed. When removing, both the cathode side and the anode side. The flow resistance of the porous ion exchanger loaded in the liquid permeation region is larger than the flow resistance of the ion exchanger charged in the desalting region, but without providing a separate special channel distribution means, This is preferable in that most of the liquid to be treated that has flowed into the desalting area flows out of the desalting area as a deionized liquid from the desalting area, and a part of the liquid to be treated permeates into the liquid permeation area. If flow rate adjusting means is provided in the flow path of the effluent permeated from the liquid permeation region, the flow rate of the permeated liquid and the deionized liquid can be adjusted to a desired ratio by the flow rate adjusting means. When the flow rate adjusting means is disposed in the flow path of the effluent permeated from the liquid permeation region, the flow resistance of the porous ion exchanger loaded in the liquid permeation region is the same as that of the ion exchanger filled in the desalination region. It may be the same as the fluid flow resistance. For example, when a monolith is used for both the desalting region and the liquid permeation region, a single monolith processed into a shape extending over the desalting region and the liquid permeation region can be used. This is advantageous in that it is not necessary to separately manufacture the desalination zone monolith and the liquid permeation zone monolith. The flow rate ratio of the permeate passing through the liquid permeation region to the flow rate of the liquid to be treated is, for example, 2 to 30%, preferably 4 to 30%. If this ratio is less than 2%, the diluting effect is reduced and it becomes difficult to prevent the generation of scale, and if it exceeds 30%, it is not preferable because the yield of the desalted solution is reduced.

The form in which the liquid permeation region is disposed adjacent to the ion rejection side of the desalting region is not particularly limited, but the form in which the monoliths are disposed adjacent to each other is preferable in terms of quick ion exclusion. . When the monoliths are arranged adjacent to each other, the monolith for the arrangement desalting region and the monolith for the liquid permeation region are arranged in close contact with each other in the electric field application direction. In addition, the monolith and the ion exchange resin are arranged adjacent to each other, or the mixture of the monolith and the ion exchange resin in the desalination region is a sponge, so the two phases do not mix and the phases are mixed. Can be formed Monkey.

In the electric deionized liquid production apparatus of the present invention, in the case of a gas-on cell or a cation cell, it is arranged adjacent to the side opposite to the ion exclusion side of the desalting region. It may be another liquid permeable region through which a part passes, or a conventional ion exchange membrane. When this liquid permeation region is provided, the liquid that has permeated from this liquid permeation region flows into the electrode chamber or the concentration chamber. This eliminates the need for an ion exchange membrane, thereby simplifying the device structure and reducing the manufacturing cost. Further, when an ion exchange membrane is provided, an electrode solution or a concentrate is separately supplied to the electrode chamber or the concentration chamber adjacent to the ion exchange membrane, as in the case of the conventional EDI. Examples of the porous ion exchanger loaded in the other liquid permeable region include the same porous ion exchangers loaded in the liquid permeable region.

Next, an example of the electric deionized liquid production apparatus according to the first embodiment of the present invention will be described with reference to FIG. Fig. 1 shows a schematic diagram of a two-cell EDI that uses a cation cell ((A) in the figure) and an anion cell ((B)) to remove anionic impurities in the liquid to be treated. FIG.

In FIG. 1, an electric deionized liquid production apparatus 10 is composed of a cation cell 10 a and an anion cell 10 b. The cation cell 10 a is permeated through a weakened thione region 1 a filled with a cation exchanger and a part of the liquid to be treated arranged adjacent to the ion exclusion side (cathode side) of the weakened thione region 1 a. Liquid permeation region 2a, liquid permeation region 3a through which another part of the liquid to be treated disposed adjacent to the anode side of the weakening thione region 1a, and weakness thione region 1a, liquid An anode 4 a and a cathode 4 b disposed on both sides of the permeation region 2 a and the liquid permeation region 3 a, a treatment liquid inflow pipe 11 for passing the treatment liquid to the weakening thione region 1 a, and a liquid permeation The cathode chamber 6 into which the liquid transmitted from the excess region 2a flows, and the liquid transmission region 3a An anode chamber 7 into which the permeated liquid flows and a weak thiol liquid outflow pipe 12 for discharging the weak thiol liquid from the weak thiol region 1a are provided.

The cation cell 10 a is a conventional cation cell in which the ion exchange membranes provided on both sides of the desalting chamber are omitted, and a liquid permeable region in which a cation monolith is loaded is attached to the ion exchange membrane part. . Accordingly, the cation cell 10 a can be formed from a member having a very simple structure in which the weak thione region 1 a, the liquid permeable region 2 a, the liquid permeable region 3 a, and the electrode can be disposed at predetermined positions. In order to form a desalination chamber, a concentration chamber and an electrode chamber by isolation with an ion exchange membrane, compared to conventional electric deionization liquid production equipment that stacks a large number of frames of complicated structure, Assembly costs can be significantly reduced. Furthermore, in the electric deionized liquid production apparatus of this example, the liquid that has permeated through the liquid permeation region 2a and the liquid permeation region 3a becomes a concentrated liquid or an electrode liquid. It is not necessary to provide the liquid inflow path separately from the liquid inflow path to be treated. Therefore, in this example, the electrical deionized liquid production system can reduce the parts and assembly costs from this point as well as the possibility of leakage of the liquid to be processed by eliminating the joints, pipes and joints. In addition, the safety of the equipment and the stability of operation can be improved.

In the cation cell 10 a, the flow resistance of the cation monolith forming the liquid permeation region 2 a and the liquid permeation region 3 a is larger than the flow resistance of the cation exchanger filled in the weak thione region 1 a. . The liquid to be treated is allowed to flow from the vicinity of the cathode side of the weakened thione area 1a, and the liquid to be treated is allowed to flow out from the vicinity of the anode side of the weakened thione area 1a almost diagonally to the inlet of the liquid to be treated. The flow direction of the ions to be treated and the flow direction of the liquid to be treated in the weak thione region 1a are reversed, and a treatment liquid that effectively uses the cation exchanger and does not leak cationic impurities X + can be obtained. Is preferable. In the key cell 10 b of FIG. 1 (B), the cut-off of FIG. The same constituent elements as those of the cancel 10 a are denoted by the same reference numerals, description thereof is omitted, and different points will be described. That is, the difference between the anion cell 10 b and the cation cell 10 a is that the desalination area is filled with an anion exchanger, and the liquid permeation area 2 b and the liquid permeation area 3 b are filled with an anion monolith, The liquid to be treated was introduced from the vicinity of the anode side of the deanion region 1b, and the treatment liquid was caused to flow out from the vicinity of the cathode side of the deanion region 1b on the diagonal line of the inlet of the liquid to be treated. The weak thione liquid outlet pipe 12 of the cation cell 10a is connected to the liquid inlet pipe 13 to be treated of the anion cell 10b. Like the cation cell 10 a, the anion cell 10 b has a very simple structure.

Next, a method for producing a desalted liquid using the electric deionized liquid producing apparatus 10 will be described. The liquid to be treated is caused to flow from the liquid inlet pipe 11 to the weakening thione region 1a. The liquid to be treated which has flowed into the weak thione region 1a has a flow resistance of the cation monolith forming the liquid permeation region 2a and the liquid permeation region 3a. Since it is larger than the liquid resistance, most of the liquid to be treated flows through the weakened thione region 1a, and a part of it passes through the liquid permeable region 2a and the liquid permeable region 3a. The permeate that has permeated the liquid permeation region 2a is discharged as a catholyte into the cathode chamber 6 together with the cationic impurities X + that are electrophoretically excluded. In the liquid permeation zone 2a, a part of the liquid to be treated is always permeating, and scale generation is prevented by the dilution effect. Further, the permeated liquid that has passed through the liquid permeable region 3 a is discharged into the anode chamber 7 as an anolyte. In the figure, the flow path 17 in the weak force thione region 1a is schematically shown, but the actual flow is also generally similar to this.

Next, the liquid to be processed from which the cationic impurities have been removed is caused to flow from the liquid inlet pipe 13 to the de-on region 1 b. The liquid to be treated that has flowed into the deanion region 1 b forms a liquid permeable region 2 b and a liquid permeable region 3 b. Since the liquid flow resistance of the monolith is greater than the liquid flow resistance of the anion exchanger filled in the deionized area 1b, most of the liquid to be treated flows through the deanion area 1b, and part of the liquid is liquid. It passes through the permeation region 2b and the liquid permeation region 3b. The permeated liquid that has passed through the liquid permeable region 2 b is discharged as an anolyte into the anode chamber 7 together with the anionic impurities Y— that are electrophoretically excluded. In the liquid permeation region 2b, like the cation cell 10a, a part of the liquid to be treated is always permeated, and scale generation is prevented by the dilution effect. Further, the permeated liquid that has permeated through the liquid permeable region 3 b is discharged into the cathode chamber 6 as a catholyte. In the figure, the flow path 18 in the deanion region 1 b is schematically shown, but the actual flow is also generally similar to this.

According to the two-cell type electric deionizing liquid production equipment 10 consisting of a cation cell 10 0 a and an anion cell 10 0 b, both the cation cell 1 0 a and the anion cell 1 0 b use an ion exchange membrane at all. Therefore, the device structure can be greatly simplified and the manufacturing cost can be reduced. In addition, in the liquid permeation region 2a on the cathode side of the cation cell 10a and the liquid permeation region 2b on the anode side of the anion cell 10b, the generation of scale that could not be avoided by conventional EDI is transmitted. This can be prevented by the dilution effect of the liquid to be treated.

Next, an example of an electrical deionized liquid production apparatus according to the second embodiment of the present invention will be described with reference to FIG. Fig. 2 shows a cation cell 20 a (in the figure, (A)) that removes cationic impurities in the liquid to be treated and an anion cell 20 b (in the figure, (B)) that removes anionic impurities. It is a schematic diagram of another EDI of the 2-cell type used. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals, description thereof is omitted, and different points are mainly described. That is, FIG. 2 differs from FIG. 1 in that the cation cell 20 a has a cation exchange on the anode side of the weakened thione region 1 a. Membrane 5 is provided to prevent liquid permeation between the weakened thione region 1a and the anode chamber 7. In the anion cell 20b, a cation exchange membrane 5 is provided on the cathode side of the deanion region 1b. However, there is no permeation of liquid between the deanion region 1 b and the cathode chamber 6.

According to the two-cell type electric deionizing liquid manufacturing apparatus 20 comprising a cation cell 20 a and an anion cell 20 b, both the caton cell 20 a and the anion cell 20 b are compared with the conventional EDI. Since the ion exchange membrane can be halved, the device structure can be simplified and the manufacturing cost can be reduced. In addition, the liquid permeation region 2 a on the cathode side of the cathode cell 20 a and the liquid permeation region 2 b on the anode side of the anion cell 20 b transmit the generation of scales that could not be avoided by conventional EDI. This can be prevented by the dilution effect of the liquid to be treated. Further, if the anolyte of the cation cell 20a and the catholyte of the anion cell 20b are the permeate that has permeated from the permeation regions 2a and 2b, a separate liquid feed pump or the like can be omitted.

Next, an example of an electrical deionized liquid production apparatus according to the third embodiment of the present invention will be described with reference to FIG. Fig. 3 is a schematic diagram of a single cell type EDI that simultaneously removes force thionic impurities and anionic impurities. In FIG. 3, the same components as those in FIG. 1 are denoted by the same reference numerals, description thereof is omitted, and differences are mainly described. That is, in FIG. 3, the difference from FIG. 1 is that the cell structure is a single-cell cation / anion cell 30. In the desalted region 1c, there are cation exchangers and anion exchangers. At the point where the mixed ion exchanger is filled, the liquid permeation region 2 a on the cathode side of the desalination region 1 c is loaded with a cation monolith, and the liquid permeation region 3 b on the anode side of the desalination region 1 c It is in the point where the anion monolith was loaded.

Next, a method for producing a desalting solution using the cation / anion cell 30 will be described. Processed liquid inflow pipe 1 1 Processed into the desalting zone 1 c through the process 1 Since the liquid resistance of the cation monolith and the anion monolith forming the liquid permeation region 2 a and the liquid permeation region 3 b is larger than that of the mixed ion exchanger filled in the desalting region 1 c, Most of the liquid to be treated flows through the desalting region 1c, and part of the solution passes through the liquid permeation region 2a and the liquid permeation region 3b. The permeate that has permeated the liquid permeation region 2a is discharged as a catholyte into the cathode chamber 6 together with the cationic impurities X + that are electrophoretically excluded. Further, the permeated liquid that has permeated through the liquid permeable region 3 b is discharged into the anode chamber 7 as an anolyte. In the liquid permeation area 2a and the liquid permeation area 3b, a part of the liquid to be treated always permeates, and the dilution effect prevents the generation of scale. In the figure, the flow path 17 in the desalination zone 1 c is schematically shown. The actual flow is also almost the same as this.

According to the one-cell type electric deionized liquid production apparatus 30, the ion exchange membrane can be omitted as compared with the conventional EDI, so that the structure of the apparatus can be simplified and the production cost can be reduced. Further, in the liquid permeation region 2 a on the cathode side and the liquid permeation region 3 b on the anode side of the cation / anion cell ³⁰ , the generation of scale, which could not be avoided by conventional EDI, is reduced. This can be prevented by the dilution effect.

Next, an example of an electrical deionized liquid production apparatus according to the fourth embodiment of the present invention will be described with reference to FIG. Fig. 4 is a schematic diagram of EDI in which a plurality of desalting chambers for removing cationic impurities and anionic impurities simultaneously are arranged in parallel. In FIG. 4, the same components as those in FIG. 1 are denoted by the same reference numerals, description thereof is omitted, and different points are mainly described. That is, FIG. 4 differs from FIG. 1 in that the basic structure of the desalting cell disposed between the electrodes is different. That is, between the anode chamber 7 and the cathode chamber 6, a desalination chamber 1d, 1 partitioned by an anion monolith 2b whose anode side is a liquid permeable region and a cationic monolith 2a whose cathode side is a liquid permeable region d and It is an EDI having a concentrating chamber with the anode side partitioned by a cation monolith which is a liquid permeable region and the cathode side partitioned by an anion monolith which is a liquid permeable region. In the electric deionized liquid production apparatus 40, the number of demineralization chambers ld and Id is not limited to this, and may be one or three or more.

Next, a method for producing a desalting solution using the electric deionizing solution production apparatus 40 will be described. The liquid to be treated is caused to flow into the desalting areas 1 d and 1 d from the liquid to be treated inflow pipe 1 1. The liquid to be treated that has flowed into the desalting areas 1 d and 1 d is filled with the resistance of the monolith that forms the liquid permeation area 2 a and the liquid permeation area 2 b into the desalination areas 1 d and 1 d. Since it is larger than the liquid flow resistance of the mixed ion exchanger, most of the liquid to be treated flows through the desalting regions 1 d and 1 d, and a part thereof passes through the liquid permeation region 2 a and the liquid permeation region 2 b. The permeate that has permeated the liquid permeation region 2 a is discharged as a catholyte and a concentrate into the cathode chamber 6 and the concentration chamber 9 together with the cationic impurities X + that are electrophoretically excluded. Further, the permeated liquid that has permeated through the liquid permeable region 2 b is discharged into the anode chamber 7 and the concentrating chamber 9 as the anolyte and concentrated liquid together with the anionic impurities Y that are electrophoretically excluded. In the liquid permeation region 2a and the liquid permeation region 2b, a part of the liquid to be treated is always permeating, and scale generation is prevented by the dilution effect. In the figure, the flow path 17 in the desalination region 1 d is schematically shown in the figure. The actual flow is almost the same as this.

According to the electric deionization liquid production equipment 40 in parallel with the desalination chamber, all four ion exchange membranes used in the conventional EDI can be omitted, so the equipment structure can be simplified and manufactured. Cost can also be reduced. In addition, in the desalting areas 1 d and I d, the liquid permeation area 2 a on the cathode side and the liquid permeation area 2 b on the anode side allow the generation of scale that could not be avoided by conventional EDI to be treated. This can be prevented by the dilution effect.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Example 1)

(Manufacture of cation monolith for liquid permeation region)

46.3 g of styrene, 2.4 g of dibutenebenzene, 0.3 g of azobissoptironitrile and 3. lg of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene dibutenebenzene / azobisisobutyronitrile / sorbitaci monoleate mixture is added to 1800 m 1 of pure water, and (revolution Z rotation) = ( The mixture was stirred at 1800 rpm / 600 rpm for 5 minutes to obtain a water-in-oil emulsion. After completion of emulsification, the mixture was sufficiently substituted with nitrogen, sealed, and allowed to stand for 24 hours at 60 ° C. After completion of the polymerization, the contents were taken out and subjected to Soxhlet extraction with isopropanol for 12 hours to remove unreacted monomers and sorbitan monooleate. Thereafter, it was dried under reduced pressure at 85 ° C. for a whole day and night. The obtained porous material containing 3.3 mol% of a crosslinking component composed of a styrene / dibutylbenzene copolymer was cut to obtain 16.6 g, and dichloromethane 9 0 Add 0 ml, heat at 35 ° C for 1 hour, cool to 0 ° C with ice, gradually add 8 8. O g of chlorosulfonic acid, and after adding chlorosulfonic acid, raise the temperature to 3 5 The reaction was allowed to proceed for 24 hours at ° C. Thereafter, the reaction product was washed with methanol and washed with water to obtain a porous cation exchanger. The ion exchange capacity of this porous material is 4.5 mg equivalent / g in terms of dry porous material, and sulfonic acid groups are uniformly introduced into the porous material by mating sulfur atoms using EP MA. Confirmed that. As a result of SEM observation, the internal structure of this porous material (cationic monolith for liquid permeation region) has an open-cell structure, and most of the macropores with an average diameter of 30.0 m overlap. When the average value of the diameter of the mesopore formed by the overlap of the macropore and the macropore was determined by the mercury intrusion method, the average diameter was 8.5 ί η! The whole pore The volume was 2.7 ml / g.

(Manufacture of cationic monolith for weak thione region)

19.2 g of styrene, 1.0 g of divinylbenzene, 0.3 g of azobisisobutylonitrile and 1 · l g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene Z divinylbenzene / azobisisobutyronitrile / sonolebitan monooleate mixture was added to 180 ml of pure water, and (revolution rotation) = (1 The mixture was stirred for 2 minutes at 0 00 rpm / 3 30 rpm) to obtain a water-in-oil emulsion. After completion of the emulsification, the gas was sufficiently substituted with nitrogen, sealed, and allowed to stand for polymerization at 60 ° C for 24 hours. After completion of the polymerization, the contents were taken out and Soxhlet extracted with isopropanol for 12 hours to remove unreacted monomers and sorbitan monoleate. Thereafter, it was dried under reduced pressure at 85 ° C. for a whole day and night. The porous body containing 3.3 mol% of the cross-linking component made of styrene / divinylbenzene copolymer was cut and 7.9 g was sampled, and 90 ml of dichloromethane was added. 3 After heating at 5 ° C for 1 hour, ice-cool to 0 ° C, slowly add 42.0 g of chlorosulfonic acid, warm up after addition of chlorosulfonic acid, and react at 35 ° C for 24 hours. It was. Thereafter, the reaction product was washed with methanol and washed with water to obtain a porous cation exchanger. The ion exchange capacity of this porous material was 4.6 mg equivalent / g in terms of dry porous material. As a result of SEM observation, the internal structure of the porous body had an open-cell structure, and most of the macropores with an average diameter of 100 / m overlapped. The average diameter of the mesopores formed by the overlap of the mac mouth pores and the macropores was determined by the mercury intrusion method, and the average diameter was 29.0 ^ πι, and the total pore volume was 8.6 ml / g.

(Manufacture of anion monolith for liquid permeation area)

Styrene 4 6.3 g instead of p-chloromethylol styrene 2 7 · 4 Using g, 1.6 g of dibutenebenzene, 0.3 g of azobissopuchi-tolyl, and 2.0 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the p-chloromethylstyrene Z dibierbensen / azobisi soptyronitrile Z sorbitan monooleate mixture was added to 1 80 ml of pure water, and (revolution Z rotation) = (1 800 r pm / 600 r pm) for 5 minutes to obtain a water-in-oil emulsion. After completion of the emulsification, it was sufficiently substituted with nitrogen, sealed, and allowed to stand for polymerization at 60 ° C for 24 hours. After the polymerization was completed, the contents were taken out and Soxhlet extracted with isopropanol for 12 hours to remove unreacted monomers and sorbitan monooleate. Thereafter, it was dried under reduced pressure at 85 ° C. for a whole day and night. The porous body containing 5.0 mol% of the cross-linking component consisting of p_chloromethylstyrene / divinylbenzene copolymer obtained in this way was cut to obtain 10.7 g, and 900 g of tetrahydrofuran was collected. After heating at 60 ° C for 1 hour, cool to room temperature, gradually add 58.8 g of trimethylamine (30%) aqueous solution, heat up after addition of trimethylamine aqueous solution, and heat at 60 ° C for 6 hours. Reacted. After completion of the reaction, the porous body was taken out, washed with methanol, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 3.6 mg equivalent Zg in terms of dry porous material, and it was confirmed by S IMS that trimethylammonium groups were uniformly introduced into the porous material. As a result of SEM observation, the internal structure of this porous body had an open-cell structure, and most of the macropores with an average diameter of 30 m overlapped. The average diameter of the mesopore formed by the overlap of the mac mouth pore and the mac mouth pore was determined by the mercury intrusion method, and the mean diameter was 7.8 μm and the total pore volume was 4. Oml / g. Met.

(Manufacture of anion monoliths for detachment areas)

P-Chloromethylstyrene 19.2 instead of styrene 19.2g g was mixed with 1.0 g of dibutenebenzene, 0.3 g of azobisoxy mouth-tolyl and 2.0 g of sorbitan monoleate, and dissolved uniformly. Next, add the p-chloromethylstyrene / dibutenebenzene / azobisi soptite-tolyl Z sorbitan monooleate mixture to 180 ml pure water (revolution / spinning) using a planetary stirrer = (, 1 00 rpm / 3 30 rpm) for 2 minutes to obtain a water-in-oil emulsion. After completion of the emulsification, the gas was sufficiently substituted with nitrogen, sealed, and allowed to stand for polymerization at 60 ° C for 24 hours. After the completion of the polymerization, the contents were taken out and extracted with Sopropanol for 12 hours to remove unreacted monomers and sorbitan monoleate. Thereafter, it was dried under reduced pressure at 85 ° C. for a whole day and night. 6.8 g of a porous material containing 5.0 mol% of a cross-linking component composed of p-chloromethylstyrene Z divinylbenzene copolymer obtained in this manner was cut and collected, and 900 g of tetrahydrofuran was collected. After heating at 60 ° C for 1 hour, cool to room temperature, gradually add trimethylamine (30%) aqueous solution 4 3. lg, and after adding the trimethylamine aqueous solution, raise the temperature to 60 ° C. The reaction was performed at ° C for 6 hours. After completion of the reaction, the porous body was taken out, washed with methanol, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 3.7 mg equivalent Zg in terms of dry porous material. As a result of SEM observation, the internal structure of this porous body had an open-cell structure, and most of the macropores with an average diameter of 70 xm overlapped. When the average value of the diameter of the mesopore formed by the overlap of the mac mouth pore was determined by the mercury intrusion method, the mean diameter was 2 1.0 μm and the total pore volume was 8.4 ml. / g.

(Preparation of cation cell)

In order to produce the electric deionized liquid production apparatus 20 as shown in FIG. 2, a cation cell 20a as shown in FIG. 5 was first produced. Obtained liquid permeability From the cation monolith for the excess region and the cation monolith for the weak force thione region, in the pure water wet state, the length (H) 50 mm, width (W) 4 Omm, thickness (L 20 mm, two rectangular parallelepiped 2 a, 1 1 a was cut out to obtain a filler that was stacked and filled in the weak thione chamber, and then in the cell container 2 0 1, in order from the cathode chamber (left side in the figure), the cation monolith for liquid permeation region 2 a and Cationic monolith for weakness cation region 1 1 a is closely packed, and cation monolith for weakness thione region 1 1 a is placed in the adjacent space on the anode side of cation exchange resin 1 2 a (Amberlite IR 1 20 B, Rohm and (Made by Haas) Filled with a volume of 80 m 1. The cell container 20 1 has a cation monolith for weakening thione region 1 1 in the figure. Treatment resin outflow pipe 1 2 is placed on the anode side upper surface where exchange resin 1 2 a is located Next, a cathode chamber was formed on the cathode side of the cell container 20 1, and a cathode made of SUS 3 04 was disposed on the outer surface of the cathode chamber, and the cation exchange resin 1 2 a A cation exchange membrane (Nafion 350; manufactured by DuPont) is placed in close contact with the anode side, and an anode made of a platinum-coated titanium substrate is placed on the outer surface of the cation exchange membrane. A cation cell 20 a was prepared by providing a take-out port, for the sake of simplicity, the description of the cation exchange membrane, the electrode chamber, and the electrode was omitted in FIG.

(Preparation of anion cell)

From the obtained anion monolith for the liquid permeation region and the anion monolith for the deanion region, in a pure water wet state, each of the two rectangular parallelepipeds 2 (H) 5 Omm, width (W) 40 mm, thickness (Lj 20 mm) 2 b and lib were cut out to obtain a filler to be stacked and filled in the deanion chamber, and then into the cell container 20 2, in order from the anode chamber (left side in FIG. 5), the anion monolith for liquid permeation region 2 b and the union monolith for the union region 1 1 b are intimately packed and placed in the adjacent space on the cathode side of the union region monolith for the deanion region 1 1 b. Anion exchange resin 1 2 b (Amberlite IRA 40 2 BL, manufactured by Romand Haas) 80 ml volume was filled. The cell container 20 2 is provided with an inflow pipe 13 for the liquid to be treated (depressurized thione liquid) on the bottom surface where the union area monolith for deanion area 1 1 b is located, and the anion replacement resin 1 2 b is A desalting solution outflow pipe 14 is attached to the upper surface on the cathode side. Next, an anode chamber was formed on the anode side of the cell container 202, and an anode made of a platinum-coated titanium substrate was further arranged on the outer surface of the anode chamber. In addition, a cation exchange membrane (Naf ion 350; manufactured by DuPont) is placed in close contact with the cathode side of the anion exchange resin 12 b, and the outer surface of the cation exchange membrane is made of SUS 304. An anion cell 20 b was prepared by disposing a cathode and appropriately providing a nozzle and a lead wire outlet.

(Production of electric deionization liquid production equipment 20)

The resulting cation cell 20 a treated liquid outflow pipe 12 is connected to the gas-on cell 20 b treated liquid inflow pipe 13, and the two electrode chambers are permeated through the other two electrode chambers. A part of the liquid was supplied.

, (Manufacture of deionized liquid)

The obtained electric deionized liquid production apparatus 20 was continuously supplied at a flow rate of 15 1 / h with water having a conductivity of 1305 to 111 as a liquid to be treated, and a DC current of 2.5 A was applied. When a current was applied in series from the thione cell to the anion cell, an operating voltage was 110 V and a treatment liquid having an electrical conductivity of 1 / i S / cm was obtained at a flow rate of 10 / h. The flow rate of the permeate (catholyte) permeated through the force thione cell 20a and the flow rate of the permeate (anolyte) permeated through the gas cell 2Ob were 2.5 1 / h, respectively. .

(Example 2)

(Preparation of anion and cation simultaneous treatment type cell)

Cation and anion using a monolith prepared in the same manner as in Example 1. A simultaneous processing type cell was produced. In order to produce an electric deionized liquid production apparatus 30a as shown in Fig. 6, the liquid permeation region cation monolith and the liquid permeation region anion monolith and the weak force thione region catholyte obtained in Example 1 were used. Cut out a rectangular parallelepiped of length (H) 50 mm, width (W) 40 mm, and thickness (L j 20 mm) in pure water wet state from the union monolith and the union monolith for the weakness thione region. The liquid permeation zone force thione monolith 2a, the weak force thione zone cation monolith 1 1a, the deionized 2-on zone anion monolith 1 1b, and the liquid permeation zone anion monolith 3b. In the cell container 20 3 as shown in Fig. 7, the cathode chamber (left side in the figure) was loaded in close contact with 2a, lla, lib, 3b in this order. Cation monolith 1 1 Outflow pipe to be treated 1 1 is attached, and the treatment liquid outflow pipe 1 4 is attached to the upper surface on the anode side where the anion monolith 1 1 b is located, and from the liquid permeation areas 2 a and 3 b as shown in FIG. A flow rate adjusting valve 15 was attached to the flow path of the effluent that flowed out, and then a cathode chamber was formed on the cathode side of the cell container 20 3, and a SUS cathode was further arranged on the outer surface of the cathode chamber. In addition, an anode chamber is formed on the anode side, and an anode of a platinum-coated titanium substrate is arranged on the outer surface of the anode chamber, and an appropriate nozzle or lead wire outlet is provided to provide an electrical deionized liquid production apparatus. 30 a was prepared Note that, for the sake of simplicity, the description of the electrode chamber and the electrode was omitted in FIG.

(Manufacture of deionized liquid)

Water with a conductivity of 130 μSZcm was continuously passed at 15 L / h as the liquid to be processed into the obtained electrical deionized liquid production apparatus 30a, and the cation monolith for the liquid permeation region was flown through the flow control valve 15. When the flow rate of the catholyte and anolyte that passed through squirrel 2a and liquid anion monolith 3b was 2 L / h respectively, and a 2.5 A DC power supply was applied, the operating voltage was 1 0 0 V With conductivity 1 μS / A cm treatment solution was obtained at a flow rate of 11 L / h. Industrial applicability

According to the present invention, without using an ion exchange membrane, the apparatus structure can be further simplified than the conventional one, and the generation of scale can be prevented and the method for producing the deionized liquid can be prevented. Can be provided.

Claims

The scope of the claims

1. a desalting zone filled with an ion exchanger;

A liquid permeable region through which a part of the liquid to be treated is disposed adjacent to the ion exclusion side of the desalting region;

Electrodes disposed on both sides of the desalting region and the liquid-permeable region;

A treatment liquid inlet pipe for passing the treatment liquid;

An electrode chamber or a concentrating chamber for discharging the liquid permeated from the liquid permeation region, and a desalting liquid outflow pipe for discharging the desalted liquid from the desalting region. Is equipped with a porous ion exchanger.

2. The apparatus for producing an electrical deionized liquid according to claim 1, wherein the flow resistance of the porous ion exchanger is larger than the resistance of the ion exchanger filled in the desalting region.

3. The porous ion exchanger has an open cell structure with mesopores having an average diameter of 1 to 100 / m in the walls of macropores and macropores connected to each other, and the total pore volume is 1 It is a monolithic organic porous ion exchanger that has an ion exchange group of uniformly distributed and an ion exchange capacity of 0.5 mg equivalent / g or more of a dry porous material. The electric deionized liquid production apparatus according to claim 1 or 2.

4. The ion exchanger filled in the desalting region is partly or wholly connected to each other and has an average diameter of 1 to 1000 μηι in the wall of the mac mouth pore and the mac mouth pore, And the monolithic organic porous ion-exchanger mesopore loaded in the liquid permeation region has an open cell structure having a mesopore larger than the average diameter, and has a total pore volume of 1 to 5 Om 1 / g, The ion exchange groups are uniformly distributed, and the ion exchange capacity is 0.5 mg equivalent / g dry porous material or more. 4. The apparatus for producing an electrical deionized liquid according to claim 3, wherein the apparatus is a Norris organic porous ion exchanger.

5. The electric deionized liquid according to any one of claims 1 to 4, wherein a flow rate adjusting means is disposed in a part or all of the flow path of the effluent permeated from the liquid permeable region. Manufacturing equipment.

6. A solution to be treated is passed through a desalting zone filled with an ion exchanger to adsorb and remove ionic impurities in the treating solution to obtain a desalting solution, and the desalting zone In an electric deionization liquid production apparatus that removes adsorbed ionic impurities by electrophoretic application by applying an electric field to the deionization region, it is arranged adjacent to at least the ion exclusion side of the desalting region A part of the liquid to be treated introduced into the desalting region is passed through a porous ion exchanger, and discharged to the electrode chamber or the concentration chamber together with the ionic impurities that are electrophoretically excluded. A method for producing a deionized liquid.

7. The method for producing a deionized liquid according to claim 6, wherein the flow resistance of the porous ion exchanger is larger than the resistance of the ion exchanger filled in the desalting region.

8. The porous ion exchanger has an open cell structure with mesopores having an average diameter of 1 to 1.0 μm in the walls of macropores and macropores connected to each other, and has a total pore volume. Is a monolithic organic porous ion exchanger in which the ion exchange group is uniformly distributed and the ion exchange capacity is 0.5 mg equivalent / g or more of the dry porous body. The method for producing a deionized liquid according to claim 6 or 7, wherein: