JP6473311B2 - Conductive aqueous solution manufacturing apparatus, conductive aqueous solution manufacturing method, and ion exchange device - Google Patents

Description

  The present invention relates to a conductive aqueous solution manufacturing apparatus and manufacturing method, and an ion exchange apparatus used in the manufacturing apparatus.

  In semiconductor and liquid crystal manufacturing processes, semiconductor wafers and glass substrates are cleaned using ultrapure water from which impurities are highly removed.

  In cleaning semiconductor wafers using such ultrapure water, using ultrapure water with a high specific resistance value, static electricity is likely to occur during cleaning, leading to electrostatic breakdown of the insulating film and reattachment of fine particles. It is known that there is a risk. For this reason, in recent years, it has been attempted to adjust the specific resistance value of ultrapure water to a desired level by dissolving a conductivity-imparting substance such as carbon dioxide or ammonia in ultrapure water, thereby suppressing the generation of static electricity. .

  In many cases, a conductive aqueous solution in which a conductivity-imparting substance is dissolved in ultrapure water is manufactured using a device that adds the conductivity-imparting substance to ultrapure water (see, for example, Patent Document 1).

JP 2000-208471 A

  According to the above-described apparatus, the conductive aqueous solution can be stably manufactured with a simple and small configuration, but the concentration (specific resistance value) variation inevitably occurs in the manufactured conductive aqueous solution. Will occur. For example, when the supply flow rate of ultrapure water changes temporarily, it is difficult to adjust the addition amount of the conductivity imparting substance in response to the change in real time. In addition, this concentration variation problem is particularly noticeable due to pump pulsation in an apparatus that adds an aqueous solution in which a conductivity-imparting substance is dissolved at a high concentration to ultrapure water using a reciprocating metering pump or syringe pump. is there.

  Therefore, an object of the present invention is to provide a conductive aqueous solution manufacturing apparatus and a manufacturing method capable of manufacturing a conductive aqueous solution having a stable concentration with a simple and small configuration, and an ion exchange apparatus used in the manufacturing apparatus. Is to provide.

In order to achieve the above-described object, the conductive aqueous solution manufacturing apparatus of the present invention manufactures a conductive aqueous solution in which ammonia or carbon dioxide is dissolved as a conductivity-imparting substance in raw water, and the conductive aqueous solution is used as a point of use. A conductive aqueous solution manufacturing apparatus for supplying a conductive imparting substance adding device that generates a conductive aqueous solution by adding a conductivity imparting substance to raw water, and a conductive aqueous solution generated by the conductivity imparting substance adding device. An ion exchange apparatus having an ion exchange tower configured to circulate and filled with an organic porous ion exchanger, wherein when the conductivity imparting substance is ammonia, the ion exchange tower has an ammonium ion type organic porous material. When the cation exchanger is packed and the conductivity-imparting substance is carbon dioxide, the ion exchange column has a bicarbonate ion type or carbonate ion type organic porous material. Anion exchanger is filled, and a, and an ion exchange device.

The conductive aqueous solution manufacturing method of the present invention is a conductive aqueous solution manufacturing method of manufacturing a conductive aqueous solution in which ammonia or carbon dioxide is dissolved as a conductivity-imparting substance in raw water and supplying the conductive aqueous solution to a use point. A step of generating a conductive aqueous solution by adding a conductivity imparting substance to the raw water, a step of bringing the conductive aqueous solution generated in the step of generating the conductive aqueous solution into contact with the organic porous ion exchanger, The step of bringing the aqueous conductive solution into contact with the organic porous ion exchanger includes the step of bringing the aqueous conductive solution into contact with the ammonium ion-type organic porous cation exchanger to provide conductivity when the conductivity imparting substance is ammonia. When the substance is carbon dioxide, the method includes contacting the aqueous conductive solution with an organic porous anion exchanger in the form of bicarbonate ion or carbonate ion.

The ion exchange apparatus of the present invention is used in a conductive aqueous solution manufacturing apparatus that manufactures a conductive aqueous solution in which ammonia or carbon dioxide is dissolved as a conductivity-imparting substance in raw water and supplies the conductive aqueous solution to a use point. An ion exchange apparatus configured to allow a conductive aqueous solution to flow, and having an ion exchange column filled with an organic porous ion exchanger, and the conductivity imparting substance is ammonia in the ion exchange column. In some cases, an organic porous cation exchanger in the form of ammonium ions is filled, and when the conductivity-imparting substance is carbon dioxide, an organic porous anion exchanger in the form of bicarbonate ions or carbonate ions is filled.

  In such a conductive aqueous solution production apparatus, a conductive aqueous solution production method, and an ion exchange device, when the conductive aqueous solution is circulated (contacted) with the organic porous ion exchanger, the organic porous ion exchanger and the conductive aqueous solution are obtained. An ion exchange reaction is performed with ions derived from the conductivity-imparting substance therein. At this time, even if there is variation in the concentration of the conductive aqueous solution brought into contact with the organic porous ion exchanger (the ion concentration), the ion exchange reaction proceeds so as to maintain an equilibrium state. Therefore, the dispersion of the ion concentration in the liquid phase gradually decreases as the contact with the organic porous ion exchanger proceeds. Since the organic porous ion exchanger has a three-dimensional network structure, the specific surface area is overwhelmingly larger than that of a general granular ion exchange resin. Therefore, the above-described variation in ion concentration can be effectively suppressed with a very small filling amount.

  As described above, according to the present invention, a conductive aqueous solution having a stable concentration can be produced with a simple and small configuration.

It is a schematic block diagram which shows the electrically conductive aqueous solution manufacturing apparatus by one Embodiment of this invention.

  Embodiments of the present invention will be described below with reference to the drawings.

  FIG. 1 is a schematic configuration diagram showing a conductive aqueous solution manufacturing apparatus according to an embodiment of the present invention.

  The conductive aqueous solution manufacturing apparatus 1 of this embodiment manufactures a conductive aqueous solution in which a conductivity imparting substance is dissolved in raw water, and supplies the aqueous solution to the use point 2. And an ion exchange device 4.

  The conductivity-imparting substance addition device 3 adds a conductivity-imparting substance to raw material water to generate a conductive aqueous solution. The raw material water to be used is not particularly limited as long as impurities are highly removed, but in this embodiment, pure water or ultrapure water is preferably used. Here, “pure water or ultrapure water” refers to treated water obtained by removing ions and nonionic substances from treated water (raw water) using a pure water production apparatus or ultrapure water production apparatus. The treated water having a specific resistance value of 1 MΩ · cm or more is referred to as “pure water”, and the treated water having a specific resistance value of 18 MΩ · cm or more is referred to as “ultra pure water”. Further, the “conductivity-imparting substance” means a substance that generates ions (anions or cations) by dissolving in the raw material water and imparts conductivity to the raw material water by the ions. As such a conductivity imparting substance, many substances can be mentioned, and carbon dioxide and ammonia are particularly preferably used when the produced aqueous conductive solution is used for cleaning a semiconductor wafer.

  The conductivity imparting substance adding device 3 is not particularly limited as long as the conductivity imparting substance can be added to the raw water (pure water or ultrapure water in this embodiment). . For example, when a gaseous conductivity imparting substance is added to and dissolved in the raw water, a method of dissolving using a gas permeable membrane made of hollow fiber, a method of directly bubbling in a pipe, or the like can be used. In addition, when an aqueous solution in which a conductivity-imparting substance is dissolved in pure water or ultrapure water at a high concentration is added to the raw material water for dilution, the aqueous solution stored in the tank is reciprocated using a reciprocating metering pump or syringe pump. A method of adding, a pressure feeding means for pumping the aqueous solution by introducing a pressurized inert gas into the tank, and the like can be used. Note that the use of the pressure feeding means is advantageous in that the pulsation of the pump can be suppressed as compared with the use of a reciprocating metering pump or a syringe pump.

  The ion exchange device 4 is configured such that the conductive aqueous solution generated by the conductivity-imparting substance addition device 3 flows, and has an ion exchange tower filled with an organic porous ion exchanger. The term “organic porous ion exchanger” as used herein means that the skeleton of the organic porous body is a porous body having a skeleton formed of an organic polymer and having a large number of communication holes that serve as a flow path for the reaction solution between the skeletons. Means a porous body introduced so that ion exchange groups are uniformly distributed. The organic porous ion exchanger is a non-particulate ion exchanger. Therefore, the organic porous ion exchanger used here includes a fibrous ion exchanger, but a general granular ion exchanger. Note that ion exchange resins are not included. The organic porous ion exchanger is composed of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is preferably 1 to 100 μm, and the average diameter of the continuous pores is preferably 1 to 1000 μm, The total pore volume is preferably 0.5 to 50 ml / g. Further, the ion exchange capacity per unit weight in a dry state is preferably 0.5 to 10 mg equivalent / g, more preferably 1 to 6 mg equivalent / g, and the ion exchange group is an organic porous ion exchanger. It is preferably distributed uniformly therein.

  Examples of organic porous ion exchangers include organic porous ion exchangers disclosed in JP 2002-355564 A, in which functional groups having an ion exchange function are introduced on the surface of a sintered resin porous body. However, preferred is a monolithic organic porous ion exchanger in which an ion exchange group is introduced into the skeleton of the monolithic organic porous body. Hereinafter, the monolithic organic porous body is also simply referred to as “monolith”, and the monolithic organic porous ion exchanger is also simply referred to as “monolith ion exchanger”. A monolithic organic porous intermediate that is an intermediate (precursor) in the production of a monolith is also simply referred to as a “monolith intermediate”. Specific examples of the monolith ion exchanger will be described later.

When the conductive aqueous solution is supplied to the ion exchange tower and comes into contact with the organic porous ion exchanger, the organic porous ion exchanger performs an ion exchange reaction with ions derived from the conductivity-imparting substance in the conductive aqueous solution. At this time, even if there is a variation in the concentration of the aqueous conductive solution supplied to the ion exchange tower (the above ion concentration), the above ion exchange reaction proceeds so as to maintain an equilibrium state. The variation in the angle gradually decreases from the entrance to the exit of the ion exchange column. Since the organic porous ion exchanger has a three-dimensional network structure, the specific surface area is overwhelmingly larger than that of a general granular ion exchange resin. Therefore, the above-described variation in ion concentration can be effectively suppressed with a very small filling amount. Moreover, although an organic porous ion exchanger is based also on the kind of electroconductive aqueous solution etc., also in the point which can permeate | transmit an electroconductive aqueous solution with the space velocity over 2000 h- ¹ with respect to an organic porous ion exchanger. It is advantageous.

In addition, since the concentration variation of the conductive aqueous solution is suppressed by the mechanism as described above, when the conductivity imparting substance is generated by dissolving in the raw material water and the ion that imparts conductivity to the raw material water is a cation, The ion exchange tower is preferably packed with an organic porous cation exchanger. Moreover, when the said ion is an anion, it is preferable that the ion exchange tower is filled with the organic porous anion exchanger. For example, when the conductivity-imparting substance is ammonia, the ion is a cation, that is, an ammonium ion (NH ₄ ⁺ ). Therefore, the ion exchange column is preferably filled with an organic porous cation exchanger. The ion form of the cation exchanger at this time is not particularly limited, but if it is a salt form such as Na form, salts such as Na are contained in the conductive aqueous solution, thereby contaminating the semiconductor wafer. Therefore, the H form or the ammonium ion form is preferred. When the conductivity-imparting substance is carbon dioxide, the above ions are anions, that is, bicarbonate ions (HCO ₃ ⁻ ) or carbonate ions (CO ₃ ²⁻ ). It is preferable that the exchanger is filled. The ion form of the anion exchanger at this time is not particularly limited, but if it is Cl form or the like, Cl or the like is contained in the conductive aqueous solution, which may contaminate the semiconductor wafer. , OH form, bicarbonate ion form, or carbonate ion form is preferred.

  By the way, in this embodiment, since pure water or ultrapure water is used as a solvent for the conductive aqueous solution, the concentration of the conductive aqueous solution is determined from the amount of the conductive material added in the conductive material adding apparatus 3. It can be generally grasped. However, in order to stably supply a conductive aqueous solution having a desired water quality to the use point 2, it is preferable to continuously monitor the concentration of the conductive aqueous solution.

  For this reason, the electroconductive aqueous solution manufacturing apparatus 1 of this embodiment has the density | concentration measurement means 6 which measures the density | concentration of electroconductive aqueous solution. In the illustrated example, the concentration measuring means 6 is provided in a sampling line branched from a pipe connected to the downstream side of the ion exchange device 4, but may be provided directly in the pipe. The concentration measuring means 6 may be any means that can measure the concentration of the conductive aqueous solution at the outlet of the ion exchange tower. For example, a conductivity meter, a pH meter, a specific resistance meter, an oxidation-reduction potential (ORP) An ion electrode meter or the like can be used. In particular, it is preferable to use a conductivity meter because the concentration can be measured relatively easily and accurately.

  Furthermore, in this embodiment, in order to produce a conductive aqueous solution having a more stable concentration, the amount of conductivity imparting substance added in the conductivity imparting substance adding device 3 is adjusted by feedback control. Is preferred. For this reason, the electroconductive aqueous solution manufacturing apparatus 1 adjusts the addition amount of the electroconductivity imparting substance in the electroconductivity imparting substance adding device 3 based on the concentration of the electroconductive aqueous solution measured by the concentration measuring means 5 ( Control means) 6.

  Although not shown, the conductive aqueous solution production apparatus 1 may be appropriately provided with various filters and valves as necessary.

  Hereinafter, six types of monolith ion exchangers will be described as specific examples of the monolith ion exchanger packed in the ion exchange tower of the present embodiment.

(Configuration of the first monolith ion exchanger)
The first monolith ion exchanger is obtained by introducing an ion exchange group into the first monolith having an open cell structure.

  The first monolith (ie, the first monolith ion exchanger) is an open cell having a common opening (mesopore) having an average diameter of 1 to 1000 μm, preferably 10 to 100 μm, in the walls of the macropores and the macropores connected to each other. It has a structure. That is, in the open cell structure, macropores having an average diameter of 2 to 5000 μm and macropores are overlapped, and the overlapping portions have a common mesopore, and most of them have an open pore structure. In the open pore structure, if water is flowed, the inside of bubbles formed by macropores and mesopores becomes a flow path. The first monolith has a total pore volume of 1-50 ml / g. When the total pore volume is 5 ml / g or less, the common opening becomes small due to the limitation of the manufacturing method, and the average diameter of the opening is substantially less than 20 μm.

  The material constituting the skeleton of the first monolith is an organic polymer material containing 10 to 90 mol% of crosslinked structural units with respect to all the structural units. As such an organic polymer material, there are many materials, and a styrene-divinylbenzene copolymer is preferably used because of the ease of introduction of ion exchange groups and high mechanical strength.

  The ion exchange capacity per unit mass in the dry state of the first monolithic ion exchanger is 0.5 mg equivalent / g or more, preferably 2 mg equivalent / g or more. The ion exchange group introduced into the first monolith ion exchanger is a cation exchange group or an anion exchange group. Examples of the cation exchange group include a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, phosphorus Examples of the anion exchange group include a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a polyethyleneimine, a tertiary sulfonium group, and a phosphonium group.

(Method for producing first monolithic ion exchanger)
First, a first monolith having an open cell structure is manufactured. In addition, the manufacturing method of the 1st monolith shown below is based on the method of Unexamined-Japanese-Patent No. 2002-306976, However, The manufacturing method of a 1st monolith is not limited to this.

  Specifically, first, an oil-soluble monomer containing no ion exchange group, a surfactant, pure water or ultrapure water, and a polymerization initiator as necessary are mixed to form a water-in-oil emulsion. Form. As a mixing method at this time, for example, a method of mixing each component at once, an oil-soluble component (such as an oil-soluble monomer) and a water-soluble component (such as pure water or ultrapure water) are uniformly dissolved separately. Then, a method of mixing the respective components can be used. As for the mixing conditions, the number of stirring revolutions and the stirring time capable of obtaining the target emulsion particle size can be arbitrarily set, and the mixing device is also suitable for obtaining the target emulsion particle size. You can choose.

  The oil-soluble monomer used for the production of the first monolith is a monomer that does not contain any ion-exchange groups, and is a lipophilic monomer that has low solubility in water. Although many things are mentioned as such a monomer, In this embodiment, styrene and divinylbenzene (crosslinkable monomer) are used suitably. In addition, content of divinylbenzene at this time is 10-90 mol% in all oil-soluble monomers, Preferably it is 15-80 mol%.

  As the surfactant used in the production of the first monolith, any oil-in-oil emulsion can be formed when an oil-soluble monomer containing no ion exchange group and pure water or ultrapure water are mixed. Although not particularly limited, sorbitan monooleate is preferably used in the present embodiment. The “water-in-oil emulsion” means an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein.

  As the polymerization initiator used for the production of the first monolith, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. Although many things are mentioned as such a polymerization initiator, In this embodiment, azobisisobutyronitrile is used suitably. In addition, there is a system in which polymerization proceeds only by heating or light irradiation without adding a polymerization initiator, and in such a system, addition of a polymerization initiator is unnecessary.

  Next, the water-in-oil emulsion is allowed to stand in a sealed container under an inert atmosphere and polymerized for a certain period of time at a predetermined temperature. As polymerization conditions at this time, various conditions can be selected depending on the types of monomers and polymerization initiators. For example, when azobisisobutyronitrile is used as the polymerization initiator, the polymerization temperature is 30 to 100 ° C., and the polymerization time is 1 to 48 hours.

  After the completion of the polymerization, the content is taken out and subjected to Soxhlet extraction with a solvent such as isopropanol to remove unreacted monomers and residual surfactant, thereby obtaining a first monolith.

  Then, an ion exchange group is introduce | transduced into the 1st monolith obtained in this way, and a 1st monolith ion exchanger is manufactured. The introduction method at this time is not particularly limited, and for example, known methods such as polymer reaction and graft polymerization can be used.

  As a first method for producing a monolithic ion exchanger, instead of using a monomer not containing an ion exchange group, polymerization is carried out using an oil-soluble monomer containing an ion exchange group to produce a monolith ion exchanger in one step. A method is also mentioned. However, since the control of the porous structure of the monolith ion exchanger is easy and the quantitative introduction of the ion exchange group is possible, the production method described above, that is, after first producing the first monolith, It is preferable to use a method of introducing an ion exchange group into the monolith.

(Second monolith ion exchanger)
The second monolith ion exchanger is obtained by introducing an ion exchange group into the second monolith having a particle aggregation type structure.

  In the second monolith (second monolith ion exchanger), organic polymer particles aggregate to form a three-dimensionally continuous skeleton part, and particle aggregation having three-dimensionally continuous pores between the skeletons Has a mold structure. The material constituting the skeleton is an organic polymer material having a crosslinked structure. That is, this organic polymer material has a structural unit composed of a vinyl monomer and a crosslinker structural unit having two or more vinyl groups in one molecule. There are many organic polymer materials such as this, but styrene-divinylbenzene copolymer is used because of the ease of forming a particle aggregate structure, the ease of introducing ion exchange groups, and the high mechanical strength. Coalescence is preferably used. The second monolith includes, for example, a vinyl monomer not containing an ion exchange group (such as styrene), a specific amount of a crosslinking agent (such as divinylbenzene), an organic solvent (such as alcohols), and a polymerization initiator (2, 2). It can be produced by mixing '-azobis (2,4-dimethylvaleronitrile) and the like and polymerizing it in a stationary state.

  The ion exchange group introduced into the second monolith ion exchanger is the same as the ion exchange group introduced into the first monolith ion exchanger, and the introduction method is also the ion exchange group in the first monolith. It is the same as the method of introducing. As a method for producing the second monolithic ion exchanger, in addition to the method for introducing the ion exchange group into the second monolith after producing the second monolith described above, polymerization is performed using a vinyl monomer containing an ion exchange group. And a method for producing a monolithic ion exchanger in one step.

(Configuration of third monolith ion exchanger)
The third monolith ion exchanger is obtained by introducing an ion exchange group into a third monolith having an open-cell structure with a thick skeleton compared to the first monolith (hereinafter referred to as “bone skeleton structure”). .

  The third monolith has an open cell structure in which bubble-shaped macropores overlap each other, and the overlapping portion forms a common opening (mesopore). The average diameter of the openings is 20 to 200 μm, preferably 20 to 150 μm, particularly 20 It is -100 micrometers, and the inside of the bubble formed with a macropore and opening becomes a flow path. In such a thick skeletal structure, in the SEM (secondary electron image by scanning electron microscope) image of the cut surface of the open cell structure (dry body), the skeleton part area that appears in the cross section is 25-50 in the image region. %, Preferably 25 to 45%. In the third monolith, the thickness of the wall portion constituting the skeleton is approximately 20 to 200 μm. The third monolith has a total pore volume of 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g.

  The material constituting the skeleton of the third monolith is an organic polymer material containing 0.3 to 50 mol%, preferably 0.3 to 5 mol% of a crosslinked structural unit with respect to all the structural units. Many examples of such organic polymer materials include the ease of forming an open-cell structure, the ease of introducing ion-exchange groups, high mechanical strength, and high stability against acids and alkalis. Accordingly, a crosslinked polymer of an aromatic vinyl polymer is preferably used, and a styrene-divinylbenzene copolymer is particularly preferably used.

  In the third monolith ion exchanger, when the ion exchange group is introduced into the third monolith, the entire monolith swells, so that the average diameter of the opening is larger than that of the third monolith, 30 to 300 μm, Preferably it is 30-200 micrometers, especially 35-150 micrometers. Moreover, the thickness of the wall part which comprises frame | skeleton becomes larger than that of a 3rd monolith, and is 30-300 micrometers in general. On the other hand, the total pore volume of the third monolith ion exchanger is the same as the total pore volume of the third monolith because the skeleton part also becomes thick even when the opening diameter increases. Moreover, in the SEM image of the cut surface of the open cell structure (dry body), the skeleton part area appearing in the cross section is the same as that of the third monolith.

  The third monolith ion exchanger has an ion exchange capacity per unit volume of 0.4 mg equivalent / ml or more, preferably 0.4 to 1.8 mg equivalent / ml in a water-wet state, and ions per unit mass. The exchange capacity is, for example, 3 to 5 mg equivalent / g. The ion exchange group introduced into the third monolith ion exchanger is a cation exchange group or an anion exchange group, and examples of the cation exchange group include a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, Examples of the anion exchange group include a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a polyethyleneimine group, a tertiary sulfonium group, and a phosphonium group.

(Method for producing third monolithic ion exchanger)
First, according to the manufacturing method of the first monolith described above, a monolith intermediate (hereinafter referred to as “third monolith intermediate) having an open cell structure similar to that of the first monolith and having a total pore volume of 5 to 16 ml / g. Body)). However, the content of the crosslinkable monomer (divinylbenzene) selected as one component of the oil-soluble monomer is 0.3 to 50 mol%, preferably 0, in the total oil-soluble monomer, unlike the case of the first monolith. 3 to 5 mol%. In addition, 2,2′-azobis (isobutyronitrile) is preferably used as the polymerization initiator.

  Before and after the production of the third monolith intermediate, the vinyl monomer, the crosslinking agent having at least two vinyl groups in one molecule, the vinyl monomer and the crosslinking agent are dissolved, but the vinyl monomer is polymerized. A mixture composed of an organic solvent that does not dissolve the produced polymer and a polymerization initiator is prepared.

  The vinyl monomer used for the preparation of this mixture is not particularly limited as long as it is a lipophilic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. It is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate coexisting in the system. Therefore, in this embodiment, styrene is preferably used. The addition amount of the vinyl monomer is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting at the time of polymerization.

  The crosslinking agent used for the preparation of the mixture preferably contains at least two polymerizable vinyl groups in one molecule and has high solubility in an organic solvent. As such a crosslinking agent, many can be mentioned. In the present embodiment, aromatic polyvinyl compounds such as divinylbenzene are preferably used because of high mechanical strength and stability against hydrolysis. The amount of the crosslinking agent used is preferably 0.3 to 50 mol%, particularly 0.3 to 5 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. In addition, it is preferable to use this crosslinking agent so that it may become substantially equal to the crosslinking density of the monolith intermediate coexisting at the time of vinyl monomer / crosslinking agent polymerization.

  The organic solvent used for the preparation of the above mixture is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, a poor solvent for the polymer formed by polymerization of the vinyl monomer. It is. Such an organic solvent varies greatly depending on the type of vinyl monomer, and thus includes a great number of organic solvents. In the present embodiment, decanol or the like is preferably used. Moreover, when the usage-amount other than a poor solvent is small, a good solvent can also be used as an organic solvent. The amount of the organic solvent used is preferably such that the concentration of the vinyl monomer is 30 to 80% by weight.

  As the polymerization initiator used for the preparation of the mixture, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator is preferably oil-soluble. Although many things are mentioned as such a polymerization initiator, In this embodiment, 2,2'-azobis (2,4-dimethylvaleronitrile) is used suitably. The amount of the polymerization initiator used varies greatly depending on the type of monomer and polymerization temperature, but may range from about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.

  Next, the third monolith intermediate is allowed to stand in a sealed container under an inert atmosphere in a state of being impregnated with the above mixture (solution), and polymerized at a predetermined temperature for a predetermined time. As polymerization conditions at this time, various conditions can be selected depending on the types of monomers and polymerization initiators. For example, when 2,2′-azobis (2,4-dimethylvaleronitrile) is used as the polymerization initiator, the polymerization temperature is 30 to 100 ° C., and the polymerization time is 1 to 48 hours.

  By this heat polymerization, the vinyl monomer and the cross-linking agent are adsorbed or distributed on the skeleton of the stationary third monolith intermediate, and the polymerization proceeds in the skeleton, so that the third monolith having a thick skeleton structure is formed. It is formed.

  After the completion of the polymerization, the content is taken out, extracted with a solvent such as acetone, and the unreacted vinyl monomer and the organic solvent are removed to obtain a third monolith.

  Then, an ion exchange group is introduce | transduced into the 3rd monolith obtained in this way, and a 3rd monolith ion exchanger is manufactured. The introduction method at this time is not particularly limited, and for example, known methods such as polymer reaction and graft polymerization can be used. Moreover, the 3rd monolith ion exchanger manufactured swells large 1.4 to 1.9 times of a 3rd monolith as above-mentioned by introduction | transduction of an ion exchange group.

(Configuration of fourth monolith ion exchanger)
The fourth monolith ion exchanger is obtained by introducing an ion exchange group into a fourth monolith having a co-continuous structure.

  The fourth monolith has a three-dimensionally continuous rod-like skeleton having a thickness of 0.8 to 40 μm, preferably 1 to 30 μm, and three-dimensionally continuous pores having a diameter of 8 to 80 μm between the skeletons. Have a co-continuous structure. That is, the co-continuous structure is a structure in which a continuous skeleton phase and a continuous vacancy phase are intertwined and both are three-dimensionally continuous. Since these continuous vacancies are higher in continuity of the vacancies and the size of the vacancies is not biased compared to the monolith described above, it is possible to achieve an extremely uniform ion adsorption behavior. The fourth monolith has a total pore volume of 0.5 to 5 ml / g.

  The material constituting the skeleton of the fourth monolith is a hydrophobic aromatic vinyl polymer containing 0.3 to 5 mol%, preferably 0.3 to 3 mol% of cross-linked structural units based on the total structural units It is. There are many examples of such aromatic vinyl polymers, but it is easy to form a co-continuous structure, to easily introduce ion-exchange groups, to have high mechanical strength, and to be stable against acids and alkalis. From the height, a styrene-divinylbenzene copolymer is particularly preferably used.

  In the fourth monolith ion exchanger, since the whole monolith swells when an ion exchange group is introduced into the fourth monolith, the thickness of the skeleton and the diameter of the pores are larger than those of the fourth monolith. . That is, the thickness of the skeleton is 1 to 60 μm, preferably 3 to 58 μm, and the pore diameter is 10 to 100 μm, preferably 15 to 90 μm, particularly 20 to 80 μm. On the other hand, the total pore volume of the fourth monolith ion exchanger is the same as the total pore volume of the fourth monolith because the skeleton portion also becomes thick even if the opening diameter increases due to the swelling.

  The fourth monolith ion exchanger has an ion exchange capacity per unit volume in a water wet state of 0.3 mg equivalent / ml or more, preferably 0.4 to 1.8 mg equivalent / ml. The ion exchange capacity per mass is, for example, 3 to 5 mg equivalent / g. The ion exchange group introduced into the fourth monolith ion exchanger is a cation exchange group or an anion exchange group. Examples of the cation exchange group include a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, Examples of the anion exchange group include a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a polyethyleneimine group, a tertiary sulfonium group, and a phosphonium group.

(Fourth Monolith Ion Exchanger Production Method)
First, according to the first monolith production method described above, a monolith intermediate (hereinafter referred to as “the monolith intermediate” having an open cell structure similar to that of the first monolith and having a total pore volume of more than 16 ml / g and 30 ml / g or less. A fourth monolith intermediate "). However, the content of the crosslinkable monomer (divinylbenzene) selected as one component of the oil-soluble monomer is 0.3 to 5 mol%, preferably 0, in the total oil-soluble monomer, unlike the case of the first monolith. .3 to 3 mol%. In addition, 2,2′-azobis (isobutyronitrile) is preferably used as the polymerization initiator.

  Before and after the production of the fourth monolith intermediate, the aromatic vinyl monomer, the cross-linking agent having at least two vinyl groups in one molecule, and the aromatic vinyl monomer and the cross-linking agent dissolve but are aromatic. A mixture comprising an organic solvent that does not dissolve the polymer produced by polymerization of the vinyl monomer and a polymerization initiator is prepared.

  The aromatic vinyl monomer used for the preparation of the mixture is not particularly limited as long as it is a lipophilic aromatic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. However, it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate coexisting in the polymerization system. Therefore, in this embodiment, styrene is preferably used. The addition amount of the aromatic vinyl monomer is 5 to 50 times by weight, preferably 5 to 40 times by weight with respect to the monolith intermediate coexisting at the time of polymerization.

  The crosslinking agent used for the preparation of the mixture preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. As such a crosslinking agent, many can be mentioned, but in this embodiment, an aromatic polyvinyl compound is preferably used and divinylbenzene is particularly preferably used because of high mechanical strength and stability against hydrolysis. Used. The amount of the crosslinking agent used is 0.3 to 5 mol%, particularly 0.3 to 3 mol%, based on the total amount of vinyl monomer and crosslinking agent (total oil-soluble monomer). In addition, it is preferable to use this crosslinking agent so that it may become substantially equal to the crosslinking density of the monolith intermediate coexisting at the time of vinyl monomer / crosslinking agent polymerization.

  The organic solvent used for the preparation of the above mixture is an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer, in other words, the aromatic vinyl monomer is polymerized. It is a poor solvent for the polymer produced. Such an organic solvent varies greatly depending on the type of the aromatic vinyl monomer, and thus includes an extremely large number of solvents. In this embodiment, decanol is preferably used. Moreover, when the usage-amount other than a poor solvent is small, a good solvent can also be used as an organic solvent. These organic solvents are preferably used so that the concentration of the aromatic vinyl monomer is 30 to 80% by weight.

  As the polymerization initiator used for the preparation of the mixture, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator is preferably oil-soluble. Although many things are mentioned as such a polymerization initiator, In this embodiment, 2,2'-azobis (2,4-dimethylvaleronitrile) is used suitably. The amount of polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but may be in the range of about 0.01 to 5% with respect to the total amount of aromatic vinyl monomer and crosslinking agent.

  Next, the fourth monolith intermediate is allowed to stand in a sealed container under an inert atmosphere in a state of being impregnated with the above mixture (solution), and polymerized at a predetermined temperature for a certain period of time. As polymerization conditions at this time, various conditions can be selected depending on the types of monomers and polymerization initiators. For example, when 2,2′-azobis (2,4-dimethylvaleronitrile) is used as the polymerization initiator, the polymerization temperature is 30 to 100 ° C., and the polymerization time is 1 to 48 hours.

  By this heat polymerization, the aromatic vinyl monomer and the crosslinking agent are adsorbed or distributed on the skeleton of the stationary fourth monolith intermediate, the polymerization proceeds in the skeleton, and the skeleton constituting the monolith structure is two-dimensional. By changing from a wall surface to a one-dimensional rod-like skeleton, a fourth monolith having a co-continuous structure is formed.

  After completion of the polymerization, the contents are taken out, extracted with a solvent such as acetone, and the unreacted vinyl monomer and the organic solvent are removed to obtain a fourth monolith.

  Then, an ion exchange group is introduce | transduced into the 4th monolith obtained in this way, and a 4th monolith ion exchanger is manufactured. The introduction method at this time is not particularly limited, and for example, known methods such as polymer reaction and graft polymerization can be used. Moreover, the 4th monolith ion exchanger manufactured will swell large 1.4 to 1.9 times of a 4th monolith as above-mentioned by introduction | transduction of an ion exchange group.

(Configuration of fifth monolith ion exchanger)
The fifth monolith ion exchanger has an ion exchange group on the fifth monolith in which a large number of particles or protrusions are fixed or formed on the skeleton surface of an organic porous body composed of a continuous skeleton phase and a continuous pore phase. It has been introduced. A preferred structure of the organic porous body of the fifth monolith is a bone skeleton structure similar to the third monolith, or a co-continuous structure similar to the fourth monolith. Hereinafter, the “particle body” and the “projection body” are also collectively referred to as “particle body”.

  The average diameter of the fifth monolith is 8 to 100 μm, preferably 10 to 80 μm. When the fifth monolith has a thick bone skeleton structure, a preferable value of the pore diameter is 10 to 80 μm, and when the fifth monolith has a co-continuous structure, a preferable value of the pore diameter is 10 to 60 μm. The fifth monolith has a total pore volume of 0.5-5 ml / g, preferably 0.8-4 ml / g. A preferable value of the diameter of the particle body and the maximum diameter of the protrusion is 3 to 15 μm, particularly 3 to 10 μm, and the ratio of the particle body of 3 to 5 μm in the total particle body is 70% or more, particularly 80% or more. It is. Further, the particle bodies may be aggregated to form an aggregate. In this case, the diameter of the particle body refers to that of an individual particle. Further, it may be a composite protrusion in which the particle body is fixed to the protrusion. In the case of a composite protrusion, the above-mentioned diameter and maximum diameter refer to values of individual protrusions and particle bodies.

  The material constituting the skeleton of the continuous pore structure of the fifth monolith is an organic polymer containing 0.3 to 10 mol%, preferably 0.3 to 5 mol% of cross-linked structural units with respect to all the structural units. Material. There are many examples of such organic polymer materials, but it is easy to form a continuous pore structure, to easily introduce ion exchange groups, to have high mechanical strength, and to be stable against acids and alkalis. From the height, a cross-linked polymer of an aromatic vinyl polymer is preferably used, and a styrene-divinylbenzene copolymer is particularly preferably used. In addition, examples of the material such as a particle body include the same material in which the same structure is continuous with respect to the material constituting the skeleton, and the different material in which different structures are continuous with each other.

  In the fifth monolith ion exchanger, the entire monolith swells when an ion exchange group is introduced into the fifth monolith. Therefore, when the fifth monolith has a thick skeletal structure, the average diameter of the openings is increased as in the case of the third monolith ion exchanger, and when the fifth monolith has a co-continuous structure, the skeleton thickened. The diameter of the holes and the pores are increased as in the case of the fourth monolith ion exchanger. In addition, the pore diameter of the fifth monolith ion exchanger is similarly increased, the average diameter is 10 to 150 μm, preferably 10 to 120 μm, and when the fifth monolith has a bone skeleton structure, the preferred value of the pore diameter is 10 When the fifth monolith has a co-continuous structure, the preferable value of the pore diameter is 10 to 90 μm. Further, the diameter of the particle body and the maximum diameter of the protrusions are similarly increased, and 4 to 40 μm, preferably 4 to 30 μm, particularly 4 to 20 μm. Among all the particle bodies, 4 to 10 μm particle bodies and the like are included. The occupying ratio is 70% or more, particularly 80% or more. Further, the surface of the skeletal phase is covered with particle bodies or the like for 40% or more, preferably 50% or more. On the other hand, the total pore volume of the fifth monolith ion exchanger is the same as the total pore volume of the fifth monolith because the skeleton part also becomes thick even if the opening diameter increases due to the swelling.

  The fifth monolith ion exchanger has an ion exchange capacity per volume in a water-wet state of 0.2 mg equivalent / ml or more, preferably 0.3 to 1.8 mg equivalent / ml, and a unit mass in a dry state. The per ion exchange capacity is, for example, 3 to 5 mg equivalent / g. The ion exchange group introduced into the fifth monolith ion exchanger is a cation exchange group or an anion exchange group. Examples of the cation exchange group include a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, Examples of the anion exchange group include a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a polyethyleneimine group, a tertiary sulfonium group, and a phosphonium group.

(Fifth Monolith Ion Exchanger Manufacturing Method)
First, a monolith intermediate similar to the third monolith intermediate or the fourth monolith intermediate is produced as the fifth monolith intermediate.

  Before and after the production of the fifth monolith intermediate, the aromatic vinyl monomer, the cross-linking agent having at least two vinyl groups in one molecule, and the aromatic vinyl monomer and the cross-linking agent dissolve but are aromatic. A mixture comprising an organic solvent that does not dissolve the polymer produced by polymerization of the vinyl monomer and a polymerization initiator is prepared.

  As the vinyl monomer used for the preparation of this mixture, the same vinyl monomer as in the case of the third monolith intermediate or the fourth monolith intermediate is used, and styrene is preferably used. The addition amount of the vinyl monomer is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting at the time of polymerization.

As the crosslinking agent used for the preparation of the above mixture, the same crosslinking agent as in the case of the third monolith intermediate or the fourth monolith intermediate is used, and an aromatic polyvinyl compound such as divinylbenzene is preferably used. The amount of the crosslinking agent used is 0.3 to 20 mol%, particularly 0.3 to 10 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. The same organic solvent as in the case of the monolith intermediate or the fourth monolith intermediate is used, and decanol or the like is preferably used. The amount of the organic solvent used is preferably such that the concentration of the vinyl monomer is 10 to 30% by weight.

  As the polymerization initiator used for the preparation of the above mixture, the same polymerization initiator as in the case of the third monolith intermediate or the fourth monolith intermediate is used, and 2,2′-azobis (2,4-dimethylvalero) is used. Nitrile) is preferably used. The amount of the polymerization initiator used is also in the range of about 0.01 to 5% based on the total amount of the vinyl monomer and the crosslinking agent, as in the case of the third monolith intermediate or the fourth monolith intermediate. Good.

  Next, the fifth monolith intermediate is impregnated in the above-mentioned mixture (solution) in a sealed container under an inert atmosphere and polymerized at a predetermined temperature for a predetermined time. As polymerization conditions at this time, various conditions can be selected depending on the types of monomers and polymerization initiators. For example, when 2,2′-azobis (2,4-dimethylvaleronitrile) is used as the polymerization initiator, the polymerization temperature is 20 to 100 ° C., and the polymerization time is 1 to 48 hours.

  By this heat polymerization, when the fifth monolith intermediate is the same as the third monolith intermediate, an organic porous body having a thick skeleton structure is formed, and the fifth monolith intermediate becomes the fourth monolith intermediate. When it is the same as the body, a co-continuous organic porous body is formed.

At this time, in the above-described process, by selecting at least one of the following conditions (1) to (5), the particle body having the characteristic structure of the fifth monolith is converted into the skeleton surface of the organic porous body. As a result, a fifth monolith can be formed.
(1) The polymerization temperature is at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator.
(2) The mol% of the crosslinking agent used for the preparation of the mixture is at least twice the mol% of the crosslinking agent used for the production of the fifth monolith intermediate.
(3) The vinyl monomer used for the preparation of the mixture is a vinyl monomer having a structure different from that of the oil-soluble monomer used for the production of the fifth monolith intermediate.
(4) The organic solvent used for adjusting the mixture is a polyether having a molecular weight of 200 or more.
(5) The density | concentration of the vinyl monomer used for adjustment of a mixture is 30 weight% or less in the said mixture.

  For the principle of formation of particle bodies and the like, refer to Japanese Patent Application Laid-Open No. 2009-108294.

  After the completion of the polymerization, the content is taken out, extracted with a solvent such as acetone, and the unreacted vinyl monomer and the organic solvent are removed to obtain a fifth monolith.

  Then, an ion exchange group is introduce | transduced into the 5th monolith obtained in this way, and a 5th monolith ion exchanger is manufactured. The introduction method at this time is not particularly limited, and for example, known methods such as polymer reaction and graft polymerization can be used.

(Sixth monolith ion exchanger)
The sixth monolith ion exchanger has a bone skeleton structure similar to that of the third monolith, and an ion exchange group is introduced into the sixth monolith in which a porous structure is introduced on the surface of the skeleton part. is there.

  The porous structure of the sixth monolith is a structure similar to a so-called honeycomb in which innumerable pores exist in the surface layer portion. Many pores include those that are independent from each other and those that are adjacent to each other. The material constituting the skeleton of the sixth monolith is an organic polymer material having a cross-linked structure, which is preferable because of the ease of forming an open cell structure, the ease of introducing ion exchange groups, the high mechanical strength, and the like. Is a styrene-divinylbenzene copolymer.

  The sixth monolith is, for example, a monolith intermediate similar to the third monolith intermediate, a vinyl monomer (such as styrene), and a crosslinking agent having at least two or more vinyl groups in one molecule (such as divinylbenzene). In a state of being impregnated with a mixture of an aliphatic alcohol having 3 to 9 carbon atoms (such as 1-octanol) and a polymerization initiator (such as 2,2′-azobis (2,4-dimethylvaleronitrile)) It can be produced by standing in a sealed container under an inert atmosphere and polymerizing at a predetermined temperature for a certain period of time.

  The ion exchange group introduced into the sixth monolith ion exchanger is the same as the ion exchange group introduced into the above-described monolith ion exchanger, and the introduction method also introduces the ion exchange group into the above monolith. It is the same as the method to do.

  For details of the sixth monolith ion exchanger, refer to JP-A-2009-191148.

  Hereinafter, the present invention will be described in detail with reference to specific examples. However, this is merely an example and does not limit the present invention.

Example 1
Diluted ammonia water was produced as a conductive aqueous solution using the conductive aqueous solution production apparatus shown in FIG. 1, and the conductivity of diluted ammonia water at the inlet and outlet of the ion exchange device (ion exchange tower) was measured.

  An organic porous cation exchanger is used as the ion exchanger packed in the ion exchange tower. Specifically, a fourth monolith ion (cation) exchange having a co-continuous structure whose skeleton is made of a styrene-divinylbenzene copolymer. Using the body. This fourth monolith ion (cation) exchanger is cylindrical, has an outer diameter of 90 mm, a height of 40 mm, and a capacity of 250 mL. The ionic form of the fourth monolith ion (cation) exchanger is the H form.

As raw material water, ultrapure water having a specific resistance of 18 MΩ · cm or more and TOC of 1.0 ppb or less is used, and ammonia water stored in a PFA chemical solution tank is used as a conductivity-imparting substance addition device. “DDA” (manufactured by Grundfos) was added to the raw water. As the ammonia water stored in the chemical solution tank, 29 wt% ammonia water (for electronics industry, manufactured by Kanto Chemical Co., Inc.) diluted 200 times was used. Moreover, the diluted ammonia water from the electroconductivity imparting substance adding device was passed through the ion exchange tower at a flow rate of 10 L / min (space velocity 2400 h ⁻¹ ) and brought into contact with the organic porous ion exchanger.

  The amount of ammonia water added to the raw water is adjusted so that the conductivity of the diluted ammonia water supplied to the use point is 10 μS / cm, and the conductivity at the inlet and outlet of the ion exchange tower at that time is adjusted. The conductivity was measured using a conductivity meter (product number “M300”, manufactured by METTLER TOLEDO).

(Example 2)
As a conductivity imparting substance adding device, by introducing pressurized nitrogen gas whose pressure is adjusted by a regulator (product number “EVD-1500”, manufactured by CKD) into the chemical tank, the ammonia water stored in the chemical tank is Measurement was performed under the same conditions as in Example 1 except that the method of pumping and adding to raw material water was used. As the ammonia water stored in the chemical tank, the 29 wt% ammonia water described above was used.

(Comparative example)
The measurement was performed under the same conditions as in Example 1 except that a granular cation exchange resin having the same capacity as that of the organic porous cation exchanger in Example 1 was used as the ion exchanger packed in the ion exchange tower. As the cation exchange resin, “Amberlite (registered trademark) IR-124” manufactured by Dow Chemical Company was used.

  Table 1 shows the measurement results of the conductivity at the inlet and outlet of the ion exchange tower in Example 1, Example 2, and Comparative Example.

  In Example 1 and Example 2, it was confirmed that the variation in conductivity at the outlet of the ion exchange tower was greatly improved as compared with the comparative example. This is due to the difference in the configuration of the ion exchanger packed in the ion exchange tower, and is considered to be an effect of the organic porous cation exchanger. In the comparative example, a cation exchange resin with a capacity of 5 L was required to suppress the variation in conductivity to the same extent as in Example 1. Also in this respect, the superiority of the organic porous ion exchanger was confirmed.

  On the other hand, when Example 1 and Example 2 are compared, the variation in conductivity at the outlet of the ion exchange column is improved more in Example 2, which is the conductivity at the inlet of the ion exchange column. Therefore, it is considered that the variation in conductivity caused by the pulsation of the pump is suppressed.

DESCRIPTION OF SYMBOLS 1 Conductive aqueous solution manufacturing apparatus 2 Use point 3 Conductivity imparting substance addition apparatus 4 Ion exchange apparatus 5 Concentration measuring means 6 Control part

Claims (11)

A conductive aqueous solution manufacturing apparatus for manufacturing a conductive aqueous solution in which ammonia or carbon dioxide is dissolved in a raw material water as a conductivity imparting substance , and supplying the conductive aqueous solution to a use point,
A conductivity-imparting substance adding device for adding the conductivity-imparting substance to the raw water to generate the conductive aqueous solution;
An ion exchange apparatus having an ion exchange tower configured to circulate the conductive aqueous solution generated by the conductivity imparting substance addition apparatus and filled with an organic porous ion exchanger, the conductivity imparting substance Is an ammonia ion-type organic porous cation exchanger, and when the conductivity-imparting substance is carbon dioxide, the ion-exchange tower contains bicarbonate ions or carbonates. An ion exchange device filled with an ionic organic porous anion exchanger;
A conductive aqueous solution manufacturing apparatus having: Measures the concentration of ions contained in the conductive aqueous solution that has circulated through the ion exchange device and generated when the conductivity-imparting substance is dissolved in the raw water and imparts conductivity to the raw water. Concentration measuring means;
Control means for adjusting the addition amount of the conductivity-imparting substance in the conductivity-imparting substance addition device based on the concentration measured by the concentration measurement means;
The electrically conductive aqueous solution manufacturing apparatus of Claim 1 which has these.   The conductivity-imparting substance addition device stores the aqueous solution in which the conductivity-imparting substance is dissolved at a high concentration in pure water or ultrapure water, and introduces a pressurized inert gas into the tank. The conductive aqueous solution manufacturing apparatus according to claim 1, further comprising: a pumping unit that pumps the aqueous solution stored in the tank and adds the solution to the raw water. The raw material water is pure water or ultrapure water, the conductivity-imparting substance is ammonia, and the ion exchange column is filled with an organic porous cation exchanger in the form of ammonium ions. The electrically conductive aqueous solution manufacturing apparatus of any one of these. The raw water is pure water or ultrapure water, the conductivity-imparting substance is carbon dioxide, and the ion exchange tower is filled with an organic porous anion exchanger of bicarbonate ion type or carbonate ion type. The electrically conductive aqueous solution manufacturing apparatus of any one of Claim 1 to 3. A method for producing a conductive aqueous solution in which ammonia or carbon dioxide is dissolved in a raw material water as a conductivity imparting substance , and the conductive aqueous solution is supplied to a use point,
Adding the conductivity-imparting substance to the raw water to produce the conductive aqueous solution;
Contacting the conductive aqueous solution generated in the step of generating the conductive aqueous solution with an organic porous ion exchanger;
Including
In the step of bringing the conductive aqueous solution into contact with the organic porous ion exchanger, when the conductivity-imparting substance is ammonia, the conductive aqueous solution is brought into contact with an ammonium ion-type organic porous cation exchanger, and the conductive When the imparting substance is carbon dioxide, contacting the aqueous conductive solution with an organic porous anion exchanger in the form of bicarbonate ion or carbonate ion,
A method for producing a conductive aqueous solution. Ions contained in the aqueous conductive solution brought into contact with the organic porous ion exchanger, the ions that are generated by dissolving the conductivity-imparting substance in the raw water and impart conductivity to the raw water Measuring the concentration;
Adjusting the amount of the conductivity-imparting substance added to the raw water based on the concentration measured in the step of measuring the concentration of the ions;
The electrically conductive aqueous solution manufacturing method of Claim 6 containing this.   The step of generating the conductive aqueous solution introduces a pressurized inert gas into a tank that stores an aqueous solution in which the conductivity-imparting substance is dissolved at a high concentration in pure water or ultrapure water. The method for producing a conductive aqueous solution according to claim 6, comprising pumping the stored aqueous solution and adding it to the raw water. The raw water is pure water or ultrapure water, the conductivity-imparting substance is ammonia, and the step of bringing the conductive aqueous solution into contact with the organic porous ion exchanger comprises converting the conductive aqueous solution into an ammonium ion-type organic material. The method for producing a conductive aqueous solution according to claim 6, comprising contacting with a porous cation exchanger. The raw water is pure water or ultrapure water, the conductivity-imparting substance is carbon dioxide, and the step of bringing the conductive aqueous solution into contact with the organic porous ion exchanger comprises converting the conductive aqueous solution into a bicarbonate ion form. Alternatively, the method for producing a conductive aqueous solution according to any one of claims 6 to 8, comprising contacting with a carbonate ion type organic porous anion exchanger. A conductive aqueous solution in which ammonia or carbon dioxide is dissolved as a conductivity imparting substance in raw material water is manufactured and used in a conductive aqueous solution manufacturing apparatus that supplies the conductive aqueous solution to a use point so that the conductive aqueous solution circulates. The ion exchange apparatus is configured to have an ion exchange column filled with an organic porous ion exchanger, and the ion exchange column has an ammonium ion form when the conductivity-imparting substance is ammonia. An ion exchange apparatus in which an organic porous cation exchanger is filled, and when the conductivity-imparting substance is carbon dioxide, a bicarbonate ion type or a carbonate ion type organic porous anion exchanger is filled.

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