JP6687310B2 - Electric regeneration type ion generation and removal integrated device - Google Patents

Description

The present invention relates to an electric regenerative ion generation / removal integrated device. The present invention relates to an integrated device having both functions mainly used for production of high-purity acid / base chemicals used for analysis such as ion chromatography and removal of impurity ions in a chemical treatment liquid.

Conventionally, an electric regenerative ion generator or an electric regenerative deionizer has been developed as a dedicated device used individually. Ion analyzers such as ion chromatographs require both functions of each device, and they have been used in combination, but a device integrating them has been desired.
That is, an integrated device equipped with an ion generation function for the generation of the eluent and a deionization function for the de-eluent after the separation column is operated with a unified current and operated with a simplified operation. The emergence of a possible integrated device was expected.
Since the ion chromatograph analysis device incorporating such an integrated device is small and portable, it is expected to be expanded in use such as being carried to a measurement site for real-time analysis.

In ion chromatography, which is a method for analyzing trace ions in an aqueous solution, a high-purity eluent is essential for lowering the background of the ion chromatogram (analysis results) and aiming for highly sensitive trace analysis. Must prevent pollution due to the inclusion of impurities in the atmosphere. In particular, even when using a high-purity chemical-level eluent, care must be taken to prevent contamination by carbon dioxide gas, ammonia gas, etc. in the atmosphere that is touched when replenishing it or replacing the container. An apparatus for producing a high-purity eluent has been proposed, which is capable of stably producing an eluent having a required concentration at any time and in a required amount, and has been partially used effectively. For example, the high-purity electrolyte solution generation device disclosed in Japanese Patent No. 49682812 is preferably incorporated and used as an in-line eluent generation device for an ion chromatograph.

In ion chromatography, an eluent containing the ions to be analyzed is injected into the separation column, separated and developed for each component to be analyzed, and eluted outside the separation column. The eluate is subjected to an impurity ion removing device to remove the eluent components other than the component to be analyzed as impurity ions, and then applied to an electric conductivity detector.
Such an impurity ion removing device is another pillar that supports high-sensitivity trace analysis, and is disclosed in Japanese Patent No. 5019663 as a device that pursues the ion selective permeability of the ion exchange membrane to the utmost limit.
In both the impurity ion removing device and the high-purity electrolyte solution producing device described above, an ion-exchange substance is filled between both electrodes and an electric current is passed to selectively move the ions in the solution, while simultaneously regenerating the ion-exchange substance. , Continuous operation is possible.
The ion generation ability and ion removal ability of the above-mentioned device depend on the ion concentration and the magnitude of the current, and it is usual that each device is operated by setting operating conditions according to the purpose of use. On the other hand, the realization of a device that brings about a simple operation by combined use or independent operation by an integrated device which is a completely different concept is what the present invention provides.

We are looking into the prior art showing adjacent structures and elements for the electrically regenerable ion production and removal integrated device of the present invention.
The prior art discloses a electrolyte eluent recycling device, an apparatus and a method of use in Japanese Patent Publication No. 2011-511290.
1 to 8 of the publication are disclosed here, but the basic configuration is common, and a deionization zone in which both electrodes are partitioned by ion exchange membranes and unnecessary ions are moved between them And an ion concentrating zone is formed adjacent to it via an ion exchange membrane. As a method of using ion chromatography, a suppressor and an eluent generating device are connected and used as an integrated device, which is close to the present invention. However, in the prior art, in order to provide recyclability, the ions extracted in the deionization zone are concentrated and used as the eluent ions in the zone adjacent to the deionization zone. They are independent and have different configurations. An eluent generation zone and a deionization zone are arranged adjacent to each other between both electrodes. The relationship between both zones forms a bipolar interface at the boundary and is electrically connected, but blocks the ions to be moved in each zone, supplies regenerated ions with dissociated ions of water, and does not mix with each other. The difference is that they maintain independence.

Special table No. 2011-511290 gazette

The first problem to be solved by the invention is to pass a high current through the entire integrated device, dramatically increase the ion generation capacity and the deionization capacity, and to withstand high-current resistance capable of stably performing highly sensitive ion analysis. Aim to have a structure. In other words, in order to achieve the large deionization that can form a highly pure electrolyte solution and the ultra-dilute background, which are the two main pillars that support high-sensitivity analysis, a device that can stably flow a high current must be used. Required.

Next, the second problem is that the integrated device has a structure in which both the ion generation function and the deionization function are independent of each other and the ions to be generated are not mutually moved.
That is, the ion generation function is a function that can supply an ion generation solution adjusted to a target ion concentration according to its purpose, and it is also possible to operate the integrated device by only ion generation. That is. The deionization function is also the same.

In order to solve the first problem, instead of an ion exchange membrane that forms an electrode interface or a bipolar interface that causes film burn when a high current is applied for a long time between the electrodes of the integrated device, heat resistance The solution is to use a fluorinated cation exchange membrane, which has excellent chemical resistance and chemical stability.

At the electrode interface, a durable fluorine-based cation exchange membrane is used because the deterioration of the material in contact with the electrode occurs due to the so-called electrode reaction oxidation and reduction.
Then, in order to prevent structural problems around the electrode, that is, invasion of hydrogen gas, oxygen gas, and by-products generated by the electrode reaction into the system, the solution is discharged from the system through a membrane with water passage holes to the outside. The solution is to wash it out. Therefore, a fluorine-based cation exchange membrane with water passage holes is preferably used.

Further, among the bipolar interfaces, electrochemical reactions are extremely intense at the interfaces that generate dissociated ions of water, resulting in an environment with strong acidity or strong basicity, and it is required to improve the durability of the ion exchange membrane that constitutes the interface. It A fluorine-based cation exchange membrane is preferably used as the ion exchange membrane.
In addition, various ion exchange membranes and ion exchange resins are used to form a bipolar interface, and a high current is applied to the bipolar interface to perform a comparative experiment of durability.
Further, the maximum current density in the cylinder of the device inner diameter 6mmΦ in experimental examples to be described below is a device having a capacity of 1A / cm ^2, at 700 mA / cm ² for the 70% level, at all times, Comparative Experiment flowing 200mA It is carried out.
However, in the embodiment of the present invention, since the current change is observed, it is set to 0 to 100 mA, but this current can flow up to 250 mA. This means that it has the ability to pass a current as high as about 100 times that of existing equipment.

In order to solve the second problem described above, a bipolar interface is used to connect the ion generation function part and the deionization function part in the integrated device to block the movement of the ions to be generated to the deionization side, and to the deionization side. The structure is such that H ⁺ ions or OH ⁻ ions are supplied for regeneration.
An electric regenerative ion formation / elimination integrated device of the present invention incorporating the above means will be shown below.

<Basic structure 1>
The basic structure of an integrated apparatus for anion chromatography analysis (or abbreviated as an integrated apparatus for anion chromatography), which is an electrically regenerated cation generation / removal integrated apparatus (FIG. 1) of the present invention, will be described with reference to FIG. To do.
An electric regenerative ion generation / removal integrated device comprising: (a) an anode part, and (a1) the anode part is provided with an anode electrode,
(A2) A cathode side of the anode electrode is partitioned by a fluorine-based cation exchange membrane M1 with a water passage in contact therewith (a3) An outlet is provided in the anode part, (b) a cation supply part, and (b1) the above A cation supply section is adjacent to the cathode side of the anode section, is in contact with the fluorine-containing cation exchange membrane M1 with water passage holes, and is filled with a cation exchanger C1; and (b2) the cation exchanger C1. The other end of the filled room is partitioned by a cation exchange membrane M2,
(B3) A cation supply solution inlet is provided in a part of a chamber filled with the cation exchanger C1. (C) a cation generation unit; and (c1) the cation generation unit is a cathode of the cation supply unit. A room adjacent to the cation exchange membrane M2, which is in contact with the cation exchange membrane M2 and is laminated in parallel with the container cross section with the cation exchange membrane, and (c2) a room filled with the anion exchanger A2, and the other end is a fluorine-based cation (C3) A cation-generating solution inlet or a cation-generating solution outlet is provided in a part of the chamber filled with the anion exchanger A2, which is partitioned by the ion exchange membrane M3 (c3),
(C4) A cation-generating solution outlet or a cation-generating solution injection port is provided in a part of the space of the room laminated with the cation-exchange membrane parallel to the container cross-section. An ion removing unit is adjacent to the cathode side of the cation generating unit, is in contact with the fluorine-based cation exchange membrane M3 and is filled with a cation exchanger C3, and (d2) is filled with the cation exchanger C3. The other end of the room is partitioned by a cation exchange membrane M4,
(D3) A cation removing solution inlet is provided in a part of the room filled with the cation exchanger C3, and a cation removing solution outlet is provided in another part of the room. e1) The cation discharge unit is adjacent to the cathode side of the cation removal unit, is provided with a chamber in contact with the cation exchange membrane M4 and filled with a cation exchanger C4, and the other end is a cation exchange unit with a water passage hole. (F) Cathode part and (f1) The cathode, which is partitioned by the membrane M5, (e2) is provided with a cation discharging solution inlet for injecting a cation discharging solution into a part of the chamber filled with the cation exchanger C4. Part has a cathode electrode,
(F2) High-purity basic solution generation and impurity cations that are partitioned by a fluorinated cation exchange membrane M5 with a water passage in contact with the anode side of the cathode electrode, and (f3) have an outlet in the cathode part It is an integrated removal device.

In this integrated device, a cation generating portion is provided on the anode side and a cation removing portion is provided on the cathode side, and a bipolar interface (anion exchanger A2 and fluorinated cation exchange membrane M3) is formed at the boundary between both portions. And a durable fluorinated cation exchange membrane is used. Further, both electrode portions are provided with a fluorine-based cation exchange membrane having water passage holes in contact with the electrodes.
In the above (c) cation generation part, (c3) in the case where a part of the chamber filled with the anion exchanger A2 is provided with a cation generation solution injection port, (c4) the cation exchange membrane and the container cross section. The cation-generating solution outlet is provided from a part of the space of the chamber stacked in parallel with the above. (C3) The cation-generating solution outlet is provided in a part of the room filled with the anion exchanger A2. In the case (c4), the cation-generating solution injection port is provided from a part of the space of the room where the cation-exchange membrane is laminated parallel to the container cross section. This is because the flow of the cation-generating solution can have a symmetrical shape through the interface between the two chambers.
Although another cation exchange membrane MM is drawn in the cation removing unit 2 in FIG. 1, it is not essential to the present invention. For example, when a neutral ion exchange membrane that does not affect the flow of ions is attached as a spacer.

<Basic structure 2>
The basic structure of an integrated apparatus for cation chromatography analysis (or abbreviated as an integrated cation chromatography apparatus) which is an electrically regenerated anion generation and removal integrated apparatus (FIG. 2) of the present invention will be described with reference to FIG. .
An electric regeneration-type integrated ion generation / removal device, comprising: (a) a cathode part, and (a1) the cathode part includes a cathode electrode,
(A2) It is partitioned by a fluorine-based cation exchange membrane M1 with a water passage hole which is in contact with the anode side of the cathode electrode, (a3) an outlet is provided in the cathode part, (b) an anion supply part, and (b1) the anion. An ion supply part is adjacent to the anode side of the cathode part, is in contact with the fluorine-containing cation exchange membrane M1 with water passage holes, and is filled with an anion exchanger A1; and (b2) the anion exchanger A1. The other end of the filled room is partitioned by an anion exchange membrane M2,
(B3) Anion supply solution inlet is provided in a part of the room filled with the anion exchanger A1. (C) Anion generation part and (c1) The anion generation part is an anode of the anion supply part. A chamber adjacent to the side, which is in contact with the anion exchange membrane M2 and is laminated in parallel with the container cross section with the anion exchange membrane, and (c2) a chamber filled with the cation exchanger C2, and the other end is a fluorine-based cation. Partitioned by ion exchange membrane M3,
(C3) An anion generating solution injection port or an anion generating solution outlet is provided in a part of the chamber filled with the cation exchanger C2,
(C4) An anion generating solution outlet or an anion generating solution injection port is provided from a part of the space of the room laminated in parallel with the container cross section by the anion exchange membrane. (D) Anion removing section and (d1) the anion. An ion removal section is adjacent to the anion side of the anion generation section, is in contact with the fluorine-based cation exchange membrane M3 and is filled with anion exchanger A3, and (d2) is filled with the anion exchanger A3. The other end of the room is partitioned by an anion exchange membrane M4,
(D3) An anion removing solution inlet is provided in a part of the room filled with the anion exchanger A3, and an anion removing solution outlet is provided in another part of the room. e1) The anion discharging part is adjacent to the anion side of the anion removing part, is provided with a chamber in contact with the anion exchange membrane M4 and filled with the anion exchanger A4, and the other end is a cation exchange with a water passage hole. (E2) An anode part provided with an anion discharging solution inlet for injecting an anion discharging solution into a part of the chamber filled with the anion exchanger A4, which is partitioned by the membrane M5 (e2), and (f1) the anode Part is provided with an anode electrode,
(F2) It is partitioned by a fluorine-based cation exchange membrane M5 with a water passage hole which is in contact with the cathode side of the anode electrode,
(F3) A high-purity acidic solution generation and impurity anion removal integrated apparatus including a discharge port in the anode part.

In this integrated device, an anion generating part is provided on the cathode side and an anion removing part is provided on the anode side, and a bipolar interface (fluorine cation exchange membrane M3 and anion exchanger A3) is formed at the boundary between both parts. And a durable fluorinated cation exchange membrane is used. Further, both electrode portions are provided with a fluorine-based cation exchange membrane having water passage holes in contact with the electrodes.
In the above (c) anion generation part, (c3) in the case where an anion generation solution injection port is provided in a part of the chamber filled with the cation exchanger C2, (c4) the anion exchange membrane is a cross section of the container. Although the anion-producing solution outlet is provided from a part of the space of the chamber stacked in parallel with (c3), the anion-producing solution outlet is provided in a part of the room filled with the cation exchanger C2. In the case (c4), an anion-generating solution injection port is provided from a part of the space of the room where the anion-exchange membrane is laminated parallel to the container cross section. This is because the flow of the anion generating solution can be symmetrical through the interface of both chambers.
Note that, in FIG. 2, another cation exchange membrane MM is drawn in the anion generation part 25, but it is not essential to the present invention. For example, when a neutral ion exchange membrane that does not affect the flow of ions is attached as a spacer.

<Usage mode of basic structure 1 for ion chromatography>
Further, the cation generation / integration type integrated device (FIG. 1) of the basic structure 1 is incorporated and used for generation of a basic eluent and removal of impurity cations in anion chromatography. The ion chromatograph device mainly comprises a cation source, a cation generation / removal integrated device of basic structure 1 (FIG. 1), a separation column, an electric conductivity detector, a pump connecting them and a pipe.

<Usage mode of basic structure 2 for ion chromatography>
Furthermore, the anion generation / removal integrated device of the basic structure 2 (FIG. 2) is incorporated and used for generation of acidic eluent and removal of impurity anions in cation chromatography. The ion chromatograph apparatus mainly comprises an anion source, an anion production and removal integrated apparatus of basic structure 2 (FIG. 1), a separation column, an electric conductivity detector, a pump connecting them, and piping.

<Independent function operation of the device>
Both the cation generation / elimination integrated device of the basic structure 1 (FIG. 1) and the anion generation / elimination integrated device of the basic structure 2 (FIG. 2) both independently operate the ion generation function. At this time, the ion removing device may be operated using pure water as the ion solution to be removed.
Similarly, when the ion removal function is independently operated, pure water may be used as the ion source solution in the ion generator.

It is an electric regeneration type integrated ion generation / removal device that stably exhibits a large ion generation capacity and removal capacity under high current and can be operated by simple operation.

It is a schematic sectional drawing of an electric regeneration type cation production removal integrated device (basic structure 1). In the figure, a symbol + as an anion exchanger and a symbol − as a cation exchanger represent the polarities of the fixed ion exchange groups. It is a schematic sectional drawing of an electric regeneration type anion generation removal integrated device (basic structure 2). In the figure, a symbol + as an anion exchanger and a symbol − as a cation exchanger represent the polarities of the fixed ion exchange groups. It is a flow chart of a NaOH solution generation system. The change in electric conductivity (Na + concentration) of the produced NaOH solution is shown. It is a flowchart of a cation removal system.

The deionization concentration (Na + concentration) for each current value is shown. FIG. 6 is a Na + concentration diagram incorporating FIG. 6 in FIG. 2 shows a flow chart of an anion chromatograph used for measurement. The obtained anion chromatogram is shown. It is a flow chart of an anion chromatograph when Na borate solution is generated in the ion generation part 1.

The obtained anion chromatogram is shown. 1 shows a flowchart of an HCL solution generation system. The change in electric conductivity (Cl ⁻ concentration) of the produced HCL solution is shown. 3 shows a flowchart of an anion removal system. The deionization concentration (Cl ⁻ concentration) for each current value is shown.

FIG. 13 shows the Cl ⁻ concentration incorporating FIG. 2 shows a flow chart of a cation chromatograph used for measurement. The obtained cation chromatogram is shown. The schematic diagram of the apparatus used for the durability test of the electric regenerative deionization apparatus used in the experiment is shown. The schematic sectional drawing of the electric regenerative deionization apparatus used in the experiment is shown. It is a schematic sectional drawing of the apparatus which formed the center bipolar interface by the anion exchanger and the fluorinated cation exchange membrane with a water passage hole.

The schematic sectional drawing of the electric regenerative deionization apparatus used in the experiment is shown. It is a schematic sectional drawing of the apparatus which formed the center bipolar interface by the cation exchanger and the anion exchange membrane with a water passage hole. The schematic sectional drawing of the electric regenerative deionization apparatus used in the experiment is shown. It is a schematic sectional drawing of the apparatus which formed the center bipolar interface with the anion exchanger and the cation exchange membrane with a water passage hole. The schematic sectional drawing of the electric regenerative deionization apparatus used in the experiment is shown. It is a schematic sectional drawing of the apparatus which formed the center bipolar interface by the anion exchanger and the cation exchanger. It represents the change in the measured voltage. It is a durability test result of an electric regeneration type deionization apparatus at an applied current of 200 mA. The symbol x in the figure is the result of a durability test in an apparatus (FIG. 20) formed of an anion exchange resin, which is a bipolar interface in the central portion, and a fluorine-containing cation exchange membrane with water passage holes. The open squares are the results of the durability test in an apparatus (FIG. 22) in which the central bipolar interface was formed with an anion exchanger and a cation exchange membrane with water holes (C66). ◯ is the durability test result in the device (FIG. 21) in which the central bipolar interface was formed with a cation exchanger and an anion exchange membrane with water holes (AHA). Δ indicates the result of the durability test in the device (FIG. 23) in which the central bipolar interface was formed by an anion exchanger and a cation exchanger.

BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be shown, and then Examples and Experimental Examples will be described in detail.
[Embodiment of Basic Structure 1]
An embodiment of the basic structure 1 of the present invention is shown in FIG.
The configuration and operation of an integrated apparatus for anion chromatography analysis, which is an embodiment of the integrated apparatus for electric cation generation / removal of the present invention, will be described with reference to FIG.
An electric regenerative ion generation / removal integrated device comprising: (a) an anode part, and (a1) the anode part is provided with an anode electrode,
(A2) A cathode side of the anode electrode is partitioned by a fluorine-based cation exchange membrane M1 with a water passage in contact therewith (a3) An outlet is provided in the anode part, (b) a cation supply part, and (b1) the above A cation supply unit is adjacent to the cathode side of the anode unit, is in contact with the fluorine-containing cation exchange membrane M1 having water passage holes , and is filled with a cation exchanger C1, preferably a cation exchange resin C1. b2) The other end of the chamber filled with the cation exchanger C1, preferably the cation exchange resin C1, is partitioned by a cation exchange membrane M2,
(B3) A cation supply part is provided in a part of a room filled with the cation exchanger C1, preferably the cation exchange resin C1, (c) a cation generation part, and (c1) the cation generation part. Is adjacent to the cathode side of the cation supply part, is in contact with the cation exchange membrane M2 and is laminated in parallel with the vessel cross section by the cation exchange membrane, and (c2) anion exchanger A2, preferably anion exchange A room filled with the resin A2 is provided, and the other end is partitioned by a fluorinated cation exchange membrane M3 (c3). The anion exchanger A2, preferably a part of the room filled with the anion exchange resin A2 is used as a cation. An ion generating solution inlet or a cation generating solution outlet is provided,
(C4) A cation-generating solution outlet or a cation-generating solution injection port is provided in a part of the space of the room laminated with the cation-exchange membrane parallel to the container cross-section. An ion removing section is adjacent to the cathode side of the cation generating section, is in contact with the fluorine-based cation exchange membrane M3 and is filled with a cation exchanger C3, preferably a cation exchange resin C3, and (d2) the cation. The other end of the chamber filled with the ion exchanger C3, preferably the cation exchange resin C3, is partitioned by a cation exchange membrane M4,
(D3) A cation removing solution inlet is provided in a part of the room filled with the cation exchanger C3, preferably the cation exchange resin C3, and a cation removing solution exit is provided in another part of the room ( e) a cation discharge part and (e1) the cation discharge part is adjacent to the cathode side of the cation removal part, is in contact with the cation exchange membrane M4, and is a cation exchanger C4, preferably a cation exchange resin C4. And a cation exchange membrane M5 with a water passage hole at the other end (e2) The cation exchanger C4, preferably a cation exchange resin C4 A (f) cathode part having a cation-exhausting solution inlet for injecting a working solution, and (f1) the cathode part having a cathode electrode,
(F2) High-purity basic solution generation and impurity cations, which are partitioned by a fluorinated cation exchange membrane M5 with a water passage hole in contact with the anode side of the cathode electrode, and (f3) have an outlet in the cathode part It is an integrated removal device.
The integrated device shown in FIG. 1 is a device having a basic eluent generation device and an impurity cation removal device.

Although the anode is arranged on the left side and the cathode is arranged on the right side of the device, it may be arranged on either the left side or the right side, and this arrangement is only shown for convenience.
The entire device is composed of an anode part, a cation supply part, a cation generation part, a cation removal part, a cation discharge part, and a cathode part according to its function, and is housed in a resin container (not shown). The device is assembled using a cation exchanger packed layer, an anion exchanger packed layer, a cation exchange membrane laminate, a cation exchange membrane, and a fluorine-based cation exchange membrane with water passage holes, sandwiching both electrode plates. Has been. The resin container has, for example, a tubular shape with an inner diameter of 6 mmΦ, the inside communicates with the functional parts, and an inlet and an outlet for injecting a solution from the outside are appropriately provided, and the whole is PEEK (polyether ether ketone). ), PP (polypropylene), or other insulating material.

<Fluorine cation exchange membrane>
Examples include registered trademark Nafion membrane (made by DuPont), which is a fluorinated cation exchange membrane in which tetrafluoroethylene having a sulfone group at the terminal is bonded to polyvinyl fluoride, and registered trademark Selemion CMF membrane (made by Asahi Glass Co., Ltd.). .
In addition, any of NRE-212, 115, 117, 324, 424, and 551 of which several types have been announced as the registered trademark Nafion membrane can be preferably used.
Since the basic skeleton of the polymer is a fluorine-based compound, it has properties such as acid resistance, base resistance, heat resistance, and chemical stability. A cation exchange membrane is obtained by incorporating a sulfone group as an ion exchange group into this. In the present invention, attention is paid to this property, and it is used for the part where the most severe condition is brought.

<Fluorine cation exchange membrane with water holes>
The entire surface of the fluorinated cation exchange membrane is slit, etc., and small water holes are opened. Since the surface of a membrane is usually so dense that it is difficult for a liquid to permeate through it, water passages are provided in the membrane so that an aqueous solution can flow. The gas generated in the electrode plate, the side reaction product, and the like are discharged to the outside of the system, and at the same time, water is passed through in order to prevent the gas from entering the system through the water passage holes.

<Ion exchange membrane>
The anion / cation exchange membrane has a low liquid permeability and a permeability of about 1 / 100-1 / 1000 is used. This is because if the transmittance is at this level, water permeation called electroosmotic flow (water molecules around the ions move together with the ions) is observed along with the movement of the ions by electrophoresis in the lower limit region. That is, in the lower limit region or less, water does not permeate and it becomes difficult for ions to move. Further, it is an upper limit where the selective permeability of ions is expressed in the upper limit region, and an anion exchange membrane allows anions to pass but does not allow cations to pass. Cation exchange membranes have the opposite property. Many types are being developed today and many are available. An ion exchange membrane having excellent oxidation resistance, base resistance and heat resistance is preferable. Examples of anion exchange membranes include Neoceptor (registered trademark) AHA, AMX, ACS, AFN, AFX (manufactured by Tokuyama Corp.), Selemion (registered trademark) AMV, AMT, DS V, AAV, ASV, AHO, AHT, APS4 (Asahi Glass Manufactured by the company) can be used. Further, as the cation exchange membrane, in addition to the above-mentioned fluorine-based cation exchange membrane, styrene type selemion (registered trademark) CMV, CMD, HSF, CSO (manufactured by Asahi Glass Co., Ltd.), Neoceptor (registered trademark) C66 (manufactured by Tokuyama Corporation), etc. Can be used.

<Ion exchanger>
The ion exchanger refers to a substance having an ion exchange function, and includes an ion exchange resin, a monolithic organic porous ion exchanger, and the like, which may be a single substance or a mixture thereof. In addition, it is easy to handle beads, fibers, non-woven fabrics, films, etc., which are formed by processing them. Two or more kinds of ion exchangers may be appropriately stacked alternately or mixed as long as the entire ion exchanger phase has a cation or anion ion exchange ability. The cation exchange resin is not particularly limited, but, for example, Amberlite (registered trademark) IR120B, DOWEX (registered trademark) 50WX2, 50WX4, 50WX8 (manufactured by Dow Chemical Co.) and the like can be used. Among these, Amberlite (registered trademark) IR120B and DOWEX (registered trademark) 50WX8 which are strongly acidic and have an ion exchange group with a high exchange capacity are preferable. As the anion exchange resin, Amberlite (registered trademark) IRA402BL, DOWEX (registered trademark) 1X8, 2X8 and the like having a strongly basic ion exchange group having a high exchange capacity can be used.

<Electrode>
The electrode preferably has a shape in which the electric field is evenly distributed and which does not prevent the passage of the liquid discharged from the water-permeable fluorinated cation exchange membrane that comes into contact with the electrode, and rod-shaped, mesh-shaped or ring-shaped electrodes can be used. The material is not particularly limited, but platinum having corrosion resistance is preferable.
The power source may be incorporated in the apparatus body to be incorporated, an external power source may be used, and a direct current power source is preferable, but an alternating current power source with positive bias conversion may be used. The voltage and current allowed under normal operating conditions are approximately 0.1-150 V and 0.1-250 mA, depending on the size of the equipment.

<Cation supply solution>
Alkali, which is a general term for water-soluble and basic substances such as alkali metal hydroxides, alkaline earth metal hydroxides, and ammonium group (amine group) hydroxides, as well as alkali metal carbonates and alkali metal phosphates , Ammonia, amines, etc.
In addition, pure water is used when only the deionization function of the integrated device is used.
<Cation generating solution>
As the property of the eluent, a buffer solution may be necessary in order to stabilize the pH environment by mitigating the effects of acids and bases unique to the column packing during the elution and development process in the separation column. In that case, a weakly acidic solution such as boric acid or carbonic acid is used in the basic pH range. Pure water is used when no buffer is required.
Furthermore, pure water is used when operating only with the deionization function of this integrated device.
<Cation removal solution>
The ion of interest for deionization is a cation, usually a solution eluted from the separation column using a basic eluent. Further, in the case of operating only with the deionization function of this integrated device, it is the target solution. Furthermore, pure water is used when operating only with the eluent generation function of this integrated device.
<Solution for cation discharge>
Usually, pure water is used, but a process recycle liquid after measuring the electric conductivity may be used.
<Pure water>
Usually, it is pure water with an electric conductivity of 1 μS / cm or less.

(A) Anode part The anode part is partitioned by an anode electrode and a fluorinated cation exchange membrane M1 with a water passage in contact therewith, and a cation supply solution outlet, that is, an anode outlet is provided on the opposite side of the anode electrode. ing.
The anode electrode is connected to a power source, and when energized, a current is transmitted through the cation exchange membrane M1 with a water passage hole to a cation exchanger C1 in an adjacent cation supply unit, preferably a cation exchange resin C1 packed layer, and then the cathode electrode. Until then, it functions as a pivotal source for ion movement and dissociation of water in the device. It is essential that an aqueous solution be present in all of this device before it is energized, and the state in which the aqueous solution is injected from the solution or water inlet provided in the main body and then discharged from the respective outlets through the inside of the main body. Must be made. Since the fluorine-based cation exchange membrane M1 with water passage holes has an ion exchange capacity like other ion exchange resins, it functions as a solid electrolyte in the presence of an aqueous solution and exhibits electrical conductivity. Then, it protects the surrounding ion-exchange resin from the oxidation caused by the electrode reaction, functions as an oxidation-resistant barrier, and also prevents oxygen gas and by-products generated from entering the system. The aqueous solution is discharged from the water via the water passage hole.

(B) Cation supply unit From the outside of the system, the concentration of a cation source, for example, Na ₂ CO ₃ aqueous solution, is adjusted to generate an eluent having a target concentration from the cation supply solution inlet. Inject into C1 packed bed. The cation exchange resin C1 packed layer is partitioned on the anode side by a fluorinated cation exchange membrane M1 with water passage holes and on the cathode side by a cation exchange membrane M2. In the Na ₂ CO ₃ aqueous solution injected from outside the system, Na ⁺ moves while ion-exchanged with the cation-exchange resin C1 packed bed, and water passes through the water-permeable holes of the fluorine-based cation-exchange membrane M1. Is discharged from the system.
On the other hand, H ⁺ generated by the electrode reaction of the anode moves toward the cation exchange resin C1 packed layer via the fluorine-containing cation exchange membrane M1 with water passage holes.
While Na ⁺ is taken in by the ion exchange group of the cation exchange resin C1, it is then replaced by H ⁺ and repeats the movement, and moves toward the cathode by the electrokinetic phenomenon. In this way, the cation exchange resin C2 is automatically regenerated while performing ion exchange.
Then, the cations (Na ⁺ ) pass through the cation exchange membrane M2 and move to the adjacent cation generating part.

(C) The section parallel to the cross section of the container for the cation generation section is a section perpendicular to the axis connecting both electrodes, and the packing layer laminated with the cation exchange membrane in parallel with this is the gap opened up and down as shown in FIG. It has a structure provided.
The cation-generating solution injected into the adjacent anion-exchange resin A2 layer normally flows into this gap, and pure water normally flows into the gap and passes through the stacked packing layer from the upper gap toward the lower cation-generating solution outlet. A solution in which concentrated cations have been washed away flows into the interface between the anion exchange resin A2 layer and the adjacent anion exchange resin A2 layer, and is sent out of the system through the cation generating solution outlet.
The flow of the cation generating solution may be a flow symmetrical to the above flow through the interface. That is, in the cation-generating solution injected into the upper gap, pure water usually passes through the stacked packing layer, and the cation-concentrating solution washed away at the interface with the adjacent cation exchange resin A2 layer is washed out. It is sent out of the system from a cation-generating solution outlet provided under the anion exchange resin A2 layer adjacent to the lower clearance.
Na ⁺ ions that have moved through the cation exchange membrane M2 adjacent to the cation exchange membrane through the adjacent cation exchange membrane M2 are electrophoresed, are blocked by the adjacent anion exchange resin A2 layer, and are concentrated at the interface. To go. The pure water mentioned above flows into it and is washed away. Na ⁺ that has moved to the cation-generating solution outlet is sent out of the system as a basic eluent, and H ⁺ is selectively permeated by the laminated cation-exchange membranes to regenerate while replacing Na ⁺ . However, although the migration to the adjacent anion exchange resin A2 layer is obstructed, water dissociation occurs at the cation exchange membrane M3, which is the boundary between the cation removal portion and the bipolar interface formed in the anion exchange resin A2 layer. The OH ⁻ generated from moves to generate the above H ⁺ and water.
OH ⁻ is responsible for the charge transfer in the anion exchange resin A2 layer.

(D) H ⁺ generated in the cation exchange membrane M3 forming the cation removing portion bipolar interface moves through the cation exchange resin C3 forming the core of the cation removing portion. The cation exchange resin C3 packed bed is a solution containing cations which is a target liquid to be deionized, for example, an aqueous solution of NaOH, and a basic amount in which a trace amount of the anion to be analyzed eluted mainly in the separation column for anion chromatography is mixed. The solution is injected through the cation removing solution inlet.
Na ⁺ is taken in by the ion-exchange group of the cation-exchange resin C3, is replaced by H ⁺ that has moved through the cation-exchange membrane M3 forming the bipolar interface, and is adjacent via the cation-exchange membrane M4. It is moved to the positive ion discharge part by electrokinetic phenomenon. If all Na ⁺ is not transferred to the cation discharge part, Na ⁺ will be mixed into the treated water, and ion chromatographic analysis of highly sensitive trace ions becomes impossible. As a major premise for this, it is necessary to suppress the concentration of the generated eluent described above to be equal to or lower than the deionizing ability.
The treated water (water containing HCl), which has been deionized with cations by flowing through the cation exchange resin C3 packed bed, is provided at the bottom of the packed bed while blocking the way to the cation exchange membranes M3 and M4. It is discharged from the removal solution outlet to the outside of the system.
In the anion chromatographic analysis, the anion in the treated water is applied to an electric conductivity measuring instrument to show the analysis result as an ion chromatogram.

(E) The cations (Na ⁺ ) deionized in the cation discharge part, the cation removal part, move to the cation exchange resin C4 packed layer, and are ion-exchanged and taken into the cation exchange resin C4, and at the same time, at the bipolar interface. Further, it is accumulated in the vicinity of the fluorine-containing cation exchange membrane M7 with water passage holes while being further substituted with H ⁺ derived from it. Pure water was injected from there through a cation discharging solution inlet provided on the upper part of the cation exchange resin C4 packed layer, washed out, and then from the water passage hole of the fluorinated cation exchange membrane M5 with water passage holes to the cathode portion. Is discharged.

(F) Cathode part The cathode part is partitioned by a cathode electrode and a fluorine-based cation exchange membrane M5 with a water passage in contact with the cathode electrode, and a solution outlet for cation discharge, that is, a cathode part discharge port is provided on the opposite side. .
As described above, the role of the fluorine-based cation exchange membrane M5 with water passage holes is that it exhibits electrical conductivity and then protects the surrounding ion exchange resin from the reducing action caused by the electrode reaction, and thus functions as a base-resistant barrier. , In order to prevent hydrogen gas and by-products (NaOH etc.) that are also generated from entering the system, the aqueous solution is discharged from the system through the water passage hole to the outside of the system through the cation discharge solution outlet. .
that's all

[Embodiment of Basic Structure 2]
An embodiment of the basic structure 2 of the present invention is shown in FIG.
With reference to FIG. 2, description will be given of the configuration and action of an integrated apparatus for cation chromatography analysis, which is an embodiment of an electrically regenerated anion integrated removal apparatus of the present invention.
An electric regeneration-type integrated ion generation / removal device, comprising: (a) a cathode part, and (a1) the cathode part includes a cathode electrode,
(A2) It is partitioned by a fluorine-based cation exchange membrane M1 with a water passage hole which is in contact with the anode side of the cathode electrode, (a3) an outlet is provided in the cathode part, (b) an anion supply part, and (b1) the anion. An ion supply unit is adjacent to the anode side of the cathode unit, is in contact with the fluorine-containing cation exchange membrane M1 having water passage holes , and is filled with an anion exchanger A1, preferably an anion exchange resin A1. ) The other end of the chamber filled with the anion exchanger A1, preferably the anion exchange resin A1, is partitioned by an anion exchange membrane M2,
(B3) Anion supply solution inlet is provided in a part of a room filled with the anion exchanger A1, preferably anion exchange resin A1. (C) Anion generator and (c1) Anion generator Is adjacent to the anode side of the anion supply unit, is in contact with the anion exchange membrane M2 and is laminated in parallel with the vessel cross section with the anion exchange membrane, and (c2) a cation exchanger C2, preferably a cation exchange. It is equipped with a room filled with resin C2 and is partitioned by a fluorinated cation exchange membrane M3 at the other end.
(C3) An anion-generating solution injection port or an anion-generating solution outlet is provided in a part of the chamber filled with the cation exchanger C2, preferably the cation exchange resin C2,
(C4) An anion generating solution outlet or an anion generating solution injection port is provided from a part of the space of the room laminated in parallel with the container cross section by the anion exchange membrane. (D) Anion removing section and (d1) the anion. An ion removal section is adjacent to the anode side of the anion generation section, is in contact with the fluorine-based cation exchange membrane M3, and is filled with an anion exchanger A3, preferably an anion exchange resin A3, and (d2) the anion. The other end of the chamber filled with the ion exchanger A3, preferably the anion exchange resin A3, is partitioned by an anion exchange membrane M4,
(D3) A part of the room filled with the anion exchanger A3, preferably the anion exchange resin A3, is provided with an anion removal solution inlet, and another part of the room is provided with an anion removal solution outlet ( e) Anion discharging part and (e1) the anion discharging part is adjacent to the anion side of the anion removing part and is in contact with the anion exchange membrane M4, and is an anion exchanger A4, preferably an anion exchange resin A4. Of the anion exchanger A4, preferably anion exchange resin A4, is anion discharged into a part of the room filled with the anion exchanger A4, preferably anion exchange resin A4. (F) an anode part provided with an anion discharge solution inlet for injecting a solution for use with the solution, and (f1) the anode part provided with an anode electrode,
(F2) It is partitioned by a fluorine-based cation exchange membrane M5 with a water passage hole which is in contact with the cathode side of the anode electrode,
(F3) A high-purity acidic solution generation and impurity anion removal integrated apparatus including a discharge port in the anode part.

As shown in FIG. 2, this device has a cathode on the left side and an anode on the right side, and is an integrated device aiming at generation of anion eluent and deanion.
The entire device comprises a cathode part, an anion supply part, an anion generation part, an anion removal part, an anion discharge part, and an anode part according to its function, and is housed in a resin container (not shown). The device is a cation-exchanger packed layer, an anion-exchanger packed layer, an anion-exchange membrane laminated body, a cation-exchange membrane, an anion-exchange membrane, a fluorine-based cation exchange with water passage holes, sandwiching both electrode plates. It is assembled using a membrane. Details of these members are the same as those described above, and will be omitted.
Compared to the structure of the integrated device for anion chromatographic analysis described above, many ion exchangers and ion exchange membrane laminates are used except for a part of the central part, and those having opposite polarities are used. The behavior is similar.
Therefore, the present apparatus will be briefly described.

<Anion supply solution>
Acids such as hydrochloric acid, nitric acid, nitrous acid, sulfuric acid, phosphoric acid and oxalic acid, and metal halide aqueous solutions such as NaCl, KCl, KI and UF ₄ are used to dissociate anions when made into an aqueous solution. In an aqueous solution containing an anion, when enumerating each ion specifically, it is a halide ion such as a chloride ion, a fluoride ion, a bromide ion, and an iodide ion as monatomic ions. Hypochlorite ion, chlorite ion, chlorate ion, chlorine ion oxo anion or acetate ion, formate ion, methacrylic acid ion, benzoate ion, cyanide ion, as an atomic ion or molecular ion, Thiocyanate ion, nitrate ion, nitrite ion, phosphate ion, dihydrogen phosphate ion, sulfate ion, hydrogen sulfate ion, and hydrogen sulfide ion.
In addition, pure water is used when only the deionization function of the integrated device is used.

<Anion generating solution>
As the property of the eluent, a buffer solution may be necessary in order to stabilize the pH environment by mitigating the effects of acids and bases unique to the column packing during the elution and development process in the separation column. In that case, Na, K, NH ₃ , an amine solution or the like is used in the acidic pH range. Pure water is used when no buffer is required.
In addition, pure water is used when only the deionization function of the integrated device is used.
<Anion removal solution>
The ion of interest for deionization is an anion, usually a solution eluted from the separation column using an acidic eluent. Further, in the case of operating only with the deionization function of this integrated device, it is the target solution.
Furthermore, pure water is used when operating only with the eluent generation function of this integrated device.
<Solution for discharging anions>
Usually, pure water is used, but a process recycle liquid after measuring the electric conductivity may be used.
<Pure water>
Usually, it is pure water with an electric conductivity of 1 μS / cm or less.

As the anion source supplied in the anion supply unit, for example, high-concentration fluoride ion (F ⁻ ), chloride ion (CL ⁻ ), nitrite ion (NO ^{2 −} ), nitrate ion (NO 3 ⁻ ), bromide When an electrolyte solution containing anions such as ions (Br ⁻ ), phosphate ions (PO ₄ ^{3 −} ) and sulfate ions (SO ₄ ²⁻ ) is injected into the anion exchange resin A1 packed layer, the anions are anionic. It is incorporated into the exchange group of the ion exchange resin A1. For example, if an aqueous solution of NaCl is injected, Cl ⁻ is incorporated into the exchange group of the anion exchange resin A1.
On the other hand, the fluorine-based cation exchange membrane M1 with water passage holes forms a bipolar interface with the anion exchange resin A1 layer, and the anions Cl ⁻ in the anion exchange resin A1 packed layer are generated by OH ⁻ generated by dissociation of water. While substituting, the anion Cl ⁻ is electrophoresed toward the anode by electrokinetic phenomenon.
The Na ⁺ released in the packed bed of the anion exchange resin A1 is concentrated along the fluorine-containing cation exchange membrane M1 with water passage holes, but the injected water is washed away and discharged from the water passage holes to the cathode portion. OH ^- NaOH and undissociated fraction NaCl generated in is discharged from the anode section outlet.
After this, the anions pass through the anion exchange membrane M2 and are accumulated in the anion exchange membrane layer.
The anion generation solution injected into the adjacent cation exchange resin C2 layer or injected into the upper gap of the anion exchange membrane layer, usually washed with pure water, is sent out of the system as an acidic eluent.

The cation exchange resin C2 layer, which is the end portion of the anion generation portion, and the anion exchange resin A3 layer, which is the end portion of the anion removal portion, are connected by a fluorine-based cation exchange membrane M3. The interface between the fluorine-based cation exchange membrane M3 and the adjacent packed layer of the anion exchange resin A3 forms a bipolar interface, and by dissociation of water, H ⁺ is added to the cation exchange resin C2 side and OH ^{− is} added to the anion exchange resin A3 side. Cause
These H ⁺ form an acid with the anion accumulated in the anion exchange membrane layer described above. OH ^- it is moves to the anion exchange resin A3 layer of the anion removal unit.
An acidic eluent (for example, an aqueous solution of HCl) containing a small amount of cations is caused to flow through the anion exchange resin A3 packed bed in the anion removal section, and CL ⁻ is taken as an impurity ion while being incorporated into the ion exchange group of the anion exchange resin A3. , And is electrophoresed toward the anode while being replaced with the above-mentioned OH ⁻ . The aqueous solution containing a trace amount of cations is blocked by the anion exchange resin A3 layer by the fluorine-based cation exchange membrane M3 and the anion exchange membrane M4.
It is taken out from the anion removing solution outlet. Then, it is applied to an electric conductivity detector and the analysis result is shown as an ion chromatogram.
Anions move through the anion exchange resin A3 packed layer, pass through the anion exchange membrane M4, and move to the anion exchange resin A4 layer.
An anion discharging solution, usually pure water, is injected into the anion exchange resin A4 layer from the outside, and is discharged to the anode part through the water holes of the fluorine-based cation exchange membrane M5 with water holes.
The interface between the anion exchange resin A4 layer and the fluorine-containing cation exchange membrane M5 with water passage holes forms a bipolar interface, and H ⁺ and OH ⁻ are generated by dissociation of water injected from the outside, and anion exchange is performed. Part of Cl ⁻ that has moved to the resin A4 packed bed reacts with H ⁺ to generate HCl, and is discharged to the anode part through the water passage holes of the fluorine-based cation exchange membrane M5 with water passage holes. It
O ₂ and HCl generated in the anode part are discharged from the discharge part of the anode part.

(1) Confirm the amount of NaOH produced using the cation production function of the integrated device for anion chromatography.
FIG. 3 shows a flowchart of the NaOH solution generation system using the cation supply unit 3 of the anion black integrated device (FIG. 1).
This system has four pumps (Pump1: peristaltic pump, control device manufactured by Nichiri Kogyo, Pump2: LC-10AD, Shimadzu, Pump3: LC-10AD, Shimadzu) in addition to the integrated device for anion chromatography (Fig. 1). , Pump4: Peristaltic pump, using a control unit manufactured by Nichiri Kogyo) and an electric conductivity detector (using only the detector of iSC8010, Nichiri Kogyo).
Pump 1 (0.5 mL / min) is used to supply a 10-100 mM Na ₂ CO ₃ solution to the cation supply part 3. Pump 2 (1 mL / min) is used to supply pure water to the cation generating part 1.
Furthermore, since it is necessary to keep the aqueous solution flowing in the cation removing part and the cation discharging part as well, use Pump3 and Pump4 to deionize the pure water at 1 mL / min and the cation removing solution inlet and the cation discharging solution inlet. Supply to each. The supplied solution is discharged from the cation removing solution outlet and the cation discharging solution outlet.
The cation supply unit supplies 10 mM Na ₂ CO _3, 20 mM Na ₂ CO _3, 50 mM Na ₂ CO _{3, and} 100 mM Na ₂ CO _{3 at} the respective concentrations to generate NaOH, but the magnitude of the current supplied Since the amount of Na ions generated by is different, the amount of Na ions moving from the cation supply part 3 to the cation generation part 1 is further adjusted by adjusting the current applied between the electrodes. The Na ions that have moved to the cation generation part 1 become a NaOH solution with the pure water supplied from Pump 2 and are eluted. The NaOH solution eluted from the cation generating part 1 flows to the electric conductivity detector for detection, and the electric conductivity of the eluate is measured.

To the integrated device for anion chromatography in Fig. 1, supply 10 mM Na ₂ CO _3, 20 mM Na ₂ CO _3, 50 mM Na ₂ CO _{3, and} 100 mM Na ₂ CO ₃ from the cation supply unit and apply. FIG. 4 shows changes in the electrical conductivity (Na + concentration) of the produced NaOH solution when the applied current was changed to 20 mA, 40 mA, 60 mA, 80 mA, and 100 mA.
The symbols shown in FIG. 4 are as follows.
◆: 10 mM Na ₂ CO ₃ is supplied to the cation supply part 3,
●: 20 mM Na ₂ CO ₃ is supplied to the cation supply part 3,
▲: 50 mM Na ₂ CO ₃ was supplied to the cation supply part 3,
×: supplying 100 mM Na ₂ CO ₃ to the cation supply part 3,

(2) Confirming the removal capacity of the NaOH solution using the decationization function of the integrated device for anion chromatography.
FIG. 5 shows a flowchart of the cation removal system using the cation removal portion 2 of the integrated device for anion chromatography (FIG. 1).
This system uses four pumps (Pump1: Peristaltic pump, controller from Nichiri Kogyo, Pump2: LC-10AD, Shimadzu, Pump3: Peristaltic pump, Japanese) It uses a control device made by Riko Kogyo, Pump4: peristaltic pump, a control device made by Nichiri Kogyo Co., Ltd.) and an electric conductivity detector (only the DX120 detector is used, Dionex).
Pumps 1, 3 and 4 (1 mL / min) are used to supply pure water to the cation supply part 3, the cation generation part 1 and the cation discharge part 4. Using Pump2 (1 mL / min), supply 50 mM NaOH solution to cation removal part 2. In the cation removing portion 2, cations are moving from the cation removing portion 2 to the cation discharging portion 4 under an electric field. Therefore, the cations contained in the NaOH solution flowing into the cation removal portion 2 move to the cation discharge portion 4 and are removed. Therefore, the eluate from the cation-removed portion 2 becomes decationized water. The eluate from the cation removing portion 2 flows to an electric conductivity detector for detection, and the electric conductivity of the eluate is measured. Determine the Na ⁺ concentration from this electrical conductivity, change the current, and
Using the difference from the Na ⁺ concentration as the deionization capacity, the deionization concentration for each current value (
Na ⁺ concentration) is shown in FIG.

(3) An ion chromatograph device incorporating an anion chromatography integrated device (Fig. 1) for the production of a basic eluent and removal of impurity cations in anion chromatography.
It is essential that the concentration of NaOH produced in the anion black integrated device (FIG. 1) of the above (1) is lower than the amount of Na ⁺ that can be removed by the anionic black integrated device of the above (2) (FIG. 1). This is clear from the principle of ion chromatography in which most of the ions in the eluent are separated by the column and then the ions to be inspected remaining after being removed by the deionization device are measured by electric conductivity.
Therefore, referring to FIG. 7 in which FIG. 6 is incorporated into FIG. 4, the production amount of the NaOH solution of the integrated device for anion chromatography (FIG. 1) is lower than the concentration of the Na ₂ CO ₃ solution supplied to the cation supply unit 3. By doing so, it can be seen that the amount of Na ions that can be removed by the cation removal portion 2 is lower than that.
The symbols added to FIG. 7 are shown below.
◯: Na ion removal concentration in the cation removal portion 2, that is, the integrated device for anion chromatography (FIG. 1) adjusts the concentration of the Na ₂ CO ₃ solution supplied to the cation supply portion 3 and the applied current. , Can be used as a device for anion chromatography.

(4) The integrated device for anion chromatography is incorporated into an anion chromatograph to obtain an ion chromatogram using a standard anion sample.
By adjusting the current applied to the anion black integrated device (Fig. 1) and the concentration of the Na ₂ CO ₃ solution supplied to the cation supply part 3, the amount of NaOH solution produced by the anion black integrated device in Fig. 1 Is less than the amount of cations removed in the cation removal portion 2, and the Na ions in the NaOH solution produced in the cation production portion 1 of the integrated unit for anion chromatography in FIG. It was confirmed that the negative ions could be detected with high sensitivity using an electric conductivity detector. The flow chart of the anion chromatograph used for the measurement is shown in FIG.
A 15 mM Na ₂ CO ₃ solution (0.5 mL / min) is supplied to the cation supply part of the integrated device for anion chromatography in FIG. The applied current was set to 100 mA (40 V) in order to stably generate about 2800 μS / cm (about 12.5 mM) NaOH solution.
The approximately 2800 μS / cm NaOH solution generated in the cation generation part 1 was injected into the separation column together with the standard anion sample as the eluent, and the eluate was put into the cation removal part 2 to remove Na ions, The electric conductivity of the eluate from the ion removal part 2 was 4 μS / cm or less. This means that the Na ions in the NaOH solution produced in the cation producing part 1 were almost completely removed.
Further, the obtained anion chromatogram is shown in FIG.
As can be seen from the anion chromatogram shown in FIG. 9, it was confirmed that the baseline was very stable and that highly sensitive detection of anions was possible.
The samples used are shown below.
1: water dip, 2: F (0.5 mg / L), 3: Cl (1 mg / L), 4: NO ₂ (1.5 mg / L), 5: Br (1 mg / L), 6: NO ₃ (3 mg / L), 7: CO ₃ (unknown), 8: SO ₄ (4 mg / L), 9: PO ₄ (3 mg / L), sample injection volume (20 μL).

A sodium borate solution is generated as an eluent using an integrated apparatus for anion chromatography (FIG. 1), and is also incorporated into an anion chromatograph apparatus to obtain an ion chromatogram using a standard anion sample.
FIG. 10 shows a flow chart of the anion chromatograph when the Na borate solution is produced in the ion producing part 1 using the anion chromatography integrated device (FIG. 1).
In addition to the anion black integrated device (Fig. 1), this system uses two pumps (Pump1: peristaltic pump, control device manufactured by Nichiri Kogyo, Pump2: LC-10AD, Shimadzu) and an injector (20 uL, RHeodyne ), A separation column (Shim-Pack IC-SA2, Shimadzu), and an electric conductivity detector (ICA2000, Toa DKK).
Using Pump 1 (0.5 mL / min), supply a 15 mM Na ₂ CO ₃ solution to the cation supply part 3. Pump 2 (1 mL / min) is used to supply a 20 mM boric acid solution to the cation generating part 1.
Also, since it is necessary to start up the deionization section at the same time, inject 1 mL of pure water from each injection port of the cation removal section and the cation ejection section.
By applying a voltage between the electrodes, Na ions move from the cation supply part 3 toward the cation generation part 1. The Na ions that have moved to the cation generating portion 1 become a Na borate solution together with the boric acid solution supplied from Pump 2 and are eluted. Under an applied current of 100 mA (about 41 V), the optimal about 1050 μS / cm Na borate solution of the separation column used was produced in the cation generating part 1.
The generated Na borate solution flows into the injector. The sample anions injected by the injector together with the sodium borate solution flow into the separation column. The sample anion is separated and eluted by the sodium borate solution in the separation column, and flows into the cation removal part 2. In the cation removing portion 2, cations are moving from the cation removing portion 2 to the cation discharging portion 4 under an electric field. Therefore, the cations contained in the eluate of the separation column flowing into the cation removal portion 2 move to the cation discharge portion 4 and are removed. Therefore, the eluate from the cation removal portion 2 becomes boric acid and acid-type sample anions.
The eluate from the cation removing portion 2 flows to an electric conductivity detector for detection, and the electric conductivity of the eluate is measured. The electric conductivity of the eluate from the cation-removed part 2 was 4 μS / cm or less. This means that the Na ions in the Na borate solution generated in the cation generating part 1 were almost completely removed.

Furthermore, the obtained anion chromatogram is shown in FIG.
As can be seen from the anion chromatogram shown in FIG. 11, it was confirmed that the baseline was very stable, and highly sensitive detection of anions was possible.
The sample used is shown below.
1: water dip, 2: F (0.5 mg / L), 3: Cl (1 mg / L), 4: NO ₂ (1.5 mg / L), 5: Br (1 mg / L), 6: NO ₃ (3 mg / L), 7: PO ₄ (3 mg / L), 8: SO ₄ (4 mg / L), sample injection volume (20 μL).

(1) Confirmation of the amount of HCl produced using the integrated device for cationic chromatography (Fig. 2) Fig. 12 shows a flowchart of the HCl solution production system using the integrated device for cationic chromatography (Fig. 2).
This system uses an integrated device for cation chromatography (Fig. 2) and four pumps (Pump1: peristaltic pump, control device manufactured by Nichiri Kogyo, Pump2: LC-10AD, Shimadzu, Pump3: LC-10AD, Shimadzu Pump4). : Peristaltic pump, using a control device manufactured by Nichikogyo Co., Ltd.) and an electric conductivity detector (using only the detector of iSC8010, Nichiri Kogyo).
Pump 1 (0.5 mL / min) is used to supply a 10-100 mM NaCl solution to the anion supply part 27. Pump 2 (1 mL / min) is used to supply pure water to the anion generation part 25.
In addition, it is necessary to keep the aqueous solution flowing in the anion removal part and the anion discharge part, so use Pump3 and Pump4 at 1 mL / min of pure water to remove the anion solution and the anion discharge solution. Supply to each. Then, the supplied solution is discharged from the anion removing solution outlet and the anion discharging solution outlet.
The integrated device for cationic chromatography shown in FIG. 2 was supplied from the anion supply unit at each concentration of 10 mM NaCl _, 20 mM NaCl _, 50 mM NaCl _{, and} 100 mM NaCl, and the applied current was 20 mA, 40 mA, 60 mA, 80 mA, FIG. 13 shows the change in electric conductivity (Cl ⁻ concentration) of the HCL solution produced when the current was changed to 100 mA.
The symbols shown in FIG. 13 are as follows.
◆: 10 mM NaCl is supplied to the anion supply part 27,
■: 20 mM NaCl is supplied to the anion supply part 27,
▲: 50 mM NaCl was supplied to the anion supply part 27,
×: 100 mM NaCl was supplied to the anion supply part 27,

(2) Confirm the removal ability of the HCl solution using the deanion function of the integrated device for cationic chromatography.
A flow chart of the anion removal system using the anion removal portion 26 of the integrated device for cation chromatography (FIG. 2) is shown in FIG.
This system has four pumps (Pump1: peristaltic pump, control device manufactured by Nichiri Kogyo, Pump2: LC-10AD, Shimadzu, Pump3: peristaltic pump) in addition to an integrated device for cation black (Fig. 2). It consists of a control unit manufactured by Nichiri Kogyo, Pump4: peristaltic pump, a control unit manufactured by Nichiri Kogyo), and an electric conductivity detector (using only DX120 detector, Dionex).
Pure water is supplied to the anion supply part 27, the anion generation part 25, and the anion discharge part 20 by using Pumps 1, 3 and 4 (1 mL / min). Pump 2 (1 mL / min) is used to supply 50 mM HCl solution to the anion removal portion 26. In the anion-removing portion 26, anions move from the anion-removing portion 26 to the anion-extracting portion 20 under an electric field. Therefore, the anions contained in the HCl solution that has flowed into the anion removal portion 26 move to the anion discharge portion 20 and are removed. Therefore, the eluate from the anion-removed portion 26 becomes deanionized water. The eluate from the anion-removed portion 26 flows to an electric conductivity detector for detection, and the electric conductivity of the eluate is measured. Determine the concentration, Cl when the current 0 by varying the current ^{- -} Cl from the electrical conductivity indicating the ^- (Concentration Cl) in FIG. 15 as deionized ability difference from the concentration, deionized concentration for each current value .

(3) An ion chromatograph device in which an apparatus integrated with cation chromatography (FIG. 2) is incorporated for generation of an acidic eluent and removal of impurity anions in cation chromatography.
It is essential that the concentration of HCl generated in the device (1) of integrated cation black (FIG. 2) is lower than the amount of Cl ⁻ that can be removed by the device (1) of integrated cation black (2). This is clear from the principle of ion chromatography in which most of the ions in the eluent are separated by the column and then the ions to be inspected remaining after being removed by the deionization device are measured by electric conductivity.
Therefore, referring to FIG. 16 in which FIG. 15 is incorporated into FIG. 13, the amount of HCl solution produced by the integrated device for cation chromatography (FIG. 2) should be such that the concentration of HCl solution supplied to the anion supply unit 27 is low. Thus, it is understood that the amount is less than the amount of Cl ions removed by the anion removal portion 26.
The symbols added to FIG. 16 are shown below.
◯: Cl ion removal concentration of the anion removal portion 26, that is, the cation black integrated device (FIG. 2) adjusts the concentration of the HCl solution supplied to the anion supply portion 27 and the applied current to obtain the cation. It can be used as a chromatograph device.

(4) An integrated device for cation chromatography is incorporated into a cation chromatograph device to obtain an ion chromatogram using a standard cation sample.
By adjusting the current applied to the integrated device for cation chromatography (FIG. 2) and the concentration of the NaCl solution supplied to the anion supply part 27, the amount of HCl solution produced by the integrated device for cation chromatography in FIG. The amount of the anions removed by the anion removing portion 26 is smaller than that of the anion removing portion 26, and the Cl ions in the HCl solution produced in the anion producing portion 25 of the integrated device for cation chromatography in FIG. It was confirmed that the cations could be detected with high sensitivity by the conductivity detector. The flow chart of the cation chromatograph used for the measurement is shown in FIG.
A 20 mM NaCl solution (0.5 mL / min) is supplied to the anion supply part of the integrated device for cation chromatography in Fig. 2. The applied current was set to 100 mA (43.7 V) in order to stably generate about 3300 μS / cm (about 8.5 mM) HCl solution.
The about 3300 μS / cm HCl solution generated in the anion generation part 25 was injected into the separation column together with the standard cation sample as an eluent, and the eluate was injected into the anion removal part 26 to remove Cl ions, The electric conductivity of the eluate from the ion removal portion 26 was 0.37 μS / cm or less. This means that the Cl ions in the HCl solution produced in the anion producing portion 26 were almost completely removed.
Further, the obtained cation chromatogram is shown in FIG.
As can be seen from the cation chromatogram shown in FIG. 18, it was confirmed that the baseline was very stable and that highly sensitive detection of cations was possible.
The sample used is shown below.
1: Li (50 μg / L), 2: Na (200 μg / L), 3: NH ₃ (200 μg / L), 4: K (500 μg / L), 5: Mg (500 μg / L) , 6: Ca (500 μg / L), sample injection volume (20 μL).
[Experimental example]

A comparative experiment was conducted to show the high current durability of the bipolar interface formed by various ion exchange membranes using an electric regeneration type deionization device.
A schematic diagram of the electric regenerative deionization apparatus used in the experiment is shown in FIG.
The devices used were pumps 1 and 3 (peristaltic pump, flow control at 1 mL / min), pump 2 (1 mL / min, DP-8020, Tosoh, Tokyo, Japan), ion removal device (200 mA, Nichiri, Chiba, Japan, which shows the equipment used in Figures 20-23).
Cation exchange resin as the cation exchanger, anion exchange resin as the anion exchanger, and a bipolar interface of the deionization chamber in the apparatus of FIG. 20 are the anion exchange resin and the fluorinated cation exchange membrane (CMF) with water passage holes. , Anion exchange membrane (AHA) with water passage and cation exchange resin in the device of Fig. 21,
In the device of FIG. 22, a cation exchange membrane (C66) with a water passage hole and an anion exchange resin,
The apparatus of FIG. 23 was composed of an anion exchange resin and a cation exchange resin.

Terms and symbols used in the drawings of FIGS. 20 to 23 are as follows.
Anion exchange membrane (AHA, Astom Co., Ltd.),
Cation exchange membrane with water passage hole (C66, Astom Co., Ltd.),
Fluorine cation exchange membrane (CMF, Asahi Glass),
Fluorine-based cation exchange membrane with water passage holes (CMF, Asahi Glass),
D _OH ; OH ⁻ , Ions generated by water dissociation, D _H ; H ⁺ , ions generated by water dissociation, anion exchange resin (registered trademark Amberlite, IRA402BL, 0.6−0.8 mm, L, 0.6 meq / mL, Organo, Tokyo, Japan ),
Cation exchange resin (registered trademark Amberlite, IR120BL, 0.6-0.8 mm, 2.0 meq / mL or more, Organo, Tokyo, Japan).

As shown in FIG. 19, the pure aqueous solution containing a trace amount of ions is sent to the ion removing device by the pump 2. Cations are removed in the deionization chamber 2 filled with the cation exchange resin, and anions are removed in the deionization chamber 1 filled with the anion exchange resin. Pure water (electrical conductivity of 1 μS / cm or less) is sent to the ion removal device by pumps 1 and 3 as process water. Bubbles generated at the electrode are also discharged out of the system along with the process water.

Using the device shown in FIG. 20, the durability test of the ion removing device was conducted at an applied current of 200 mA. The apparatus shown in FIGS. 20 to 23 is a cylinder having an inner diameter of 6 mmΦ, and the applied current density is 700 mA / cm ² . Since the maximum permissible current is 1000 mA / cm ² , the operation was performed at the 70% level. A current of 200 mA was applied to the devices of FIGS. 20 to 23, and changes in the measured voltage at that time are shown in FIG.

In the symbol in FIG. 24, x indicates a device formed of an anion exchange resin which is a bipolar interface in the central portion and a fluorine-based cation exchange membrane with water passage holes,
□ is an anion exchange resin that is a bipolar interface in the central part and a cation exchange membrane (C66) (13) with a water passage hole.
◯ is a cation exchange resin which is a bipolar interface in the central part and an anion exchange membrane (AHA) (12) with a water passage hole.
The symbol Δ is a device formed of an anion exchange resin and a cation exchange resin, which is a bipolar interface in the central portion.

As can be seen from FIG. 24, the change in the voltage of the device formed of the anion-exchange resin, which is the central bipolar interface, and the fluorine-based cation-exchange membrane with water holes is constant, and the device is not broken. However, in the other three devices, the central bipolar interface has an anion exchange resin and a cation exchange membrane with water passage holes (C66), an anion exchange membrane with water passage holes (AHA) with cation exchange resin and anion exchange membrane. It is composed of resin and cation exchange resin, and it can be seen that the voltage rises and the device breaks. In addition, the failure of the interface portion is disassembled after the test and visually confirmed. The cation-exchange membrane with water passage holes (C66) turned black, and the anion-exchange membrane with water passage holes (AHA) had cation-exchange resin adhered to the surface of the membrane. The anion exchange resin and the cation exchange resin were tightly attached. It is presumed that the tissue is broken and the ion exchange function is impaired in all cases.
The results revealed that the bipolar interface in the central part was formed of an anion exchange resin and a fluorinated cation exchange membrane with water passage holes, which was superior. Also, in the above experiment, the type with water passage holes was confirmed, but since the above results are comparisons of the durability of the materials, it is assumed that the same durability is exhibited even without water passage holes. It is regarded.

The electric regenerative ion generation / removal integrated device of the present invention, when using a single function, pollutes the high-purity acid or basic solution in an amount required for chemical analysis, chemical synthesis, or chemical treatment. It is used as a handy generator without any. Also, it is widely used in the field for deionization treatment such as pretreatment and posttreatment of pure water.
Furthermore, when both functions are used in combination, it can be carried as a simple ion chromatograph device to a chemical analysis site and brought in for use as a convenient analyzer device.

1. Cation generating part
2. Cation removal part
3. Cation supply part
Four. Cation emission part
Five. Cathode part
6. Anode part
7. Fluorine-based cation exchange membrane with water passage holes
8. Cation exchange membrane laminate
9. Bipole interface (interface consisting of fluorinated cation exchange membrane and anion exchange resin, water dissociation part)
Ten. Bipole interface (interface consisting of cation exchange membrane and anion exchange resin, ion concentrated portion)

11. Cation exchange membrane
12. anode
13. cathode
14. Anion exchanger, anion exchange resin
15. Cation exchanger, Cation exchange resin
16. Anion exchange membrane laminate
17. Anion exchange membrane
18. Bipole interface (interface consisting of anion exchange resin and fluorinated cation exchange membrane, water dissociation part)
19. Bipole interface (an interface consisting of cation exchange resin and anion exchange membrane, ion concentrated part)
20. Anion discharge part

twenty one. Anion discharge solution inlet
twenty two. Solution inlet for cation discharge
twenty three. Solution outlet for anion discharge
twenty four. Solution outlet for cation discharge
twenty five. Anion generation part
26. Anion removal part
27. Anion supply part
28. Solution inlet or outlet for cation generation
29. Solution outlet or inlet for cation generation
30. Solution inlet for cation removal

31. Solution outlet for cation removal
32. Solution inlet for cation supply
33. Solution outlet for cation supply
34. Anion generation solution inlet or outlet
35. Solution outlet or inlet for anion generation
36. Anion removal solution inlet
37. Anion removal solution outlet
38. Anion supply solution inlet
39. Solution outlet for anion supply

M1. Fluorine-based cation exchange membrane with water passage M2. Cation exchange membrane or anion exchange membrane M3. Fluorine-based cation exchange membrane M4. Cation exchange membrane or anion exchange membrane M5. Fluorine-based cation exchange membrane with water passage holes MM. Ion exchange membrane for spacer A1. Anion exchanger, anion exchange resin A2. Anion exchanger, anion exchange resin A3. Anion exchanger, anion exchange resin A4. Anion exchanger, anion exchange resin C1. Cation exchanger, cation exchange resin C2. Cation exchanger, cation exchange resin C3. Cation exchanger, cation exchange resin C4. Cation exchanger, Cation exchange resin

Claims (4)

An electric regenerative ion generation / removal integrated device comprising: (a) an anode part, and (a1) the anode part is provided with an anode electrode,
(A2) A cathode side of the anode electrode is partitioned by a fluorine-based cation exchange membrane M1 with a water passage in contact therewith (a3) An outlet is provided in the anode part, (b) a cation supply part, and (b1) the above A cation supply section is adjacent to the cathode side of the anode section, is in contact with the fluorine-containing cation exchange membrane M1 with water passage holes, and is filled with a cation exchanger C1; and (b2) the cation exchanger C1. The other end of the filled room is partitioned by a cation exchange membrane M2,
(B3) A cation supply solution inlet is provided in a part of a chamber filled with the cation exchanger C1. (C) a cation generation unit; and (c1) the cation generation unit is a cathode of the cation supply unit. A room adjacent to the cation exchange membrane M2, which is in contact with the cation exchange membrane M2 and is laminated in parallel with the container cross section with the cation exchange membrane, and (c2) a room filled with the anion exchanger A2, and the other end is a fluorine-based cation (C3) A cation-generating solution inlet or a cation-generating solution outlet is provided in a part of the chamber filled with the anion exchanger A2, which is partitioned by the ion exchange membrane M3 (c3),
(C4) A cation-generating solution outlet or a cation-generating solution injection port is provided in a part of the space of the room laminated with the cation-exchange membrane parallel to the container cross-section. An ion removing unit is adjacent to the cathode side of the cation generating unit, is in contact with the fluorine-based cation exchange membrane M3 and is filled with a cation exchanger C3, and (d2) is filled with the cation exchanger C3. The other end of the room is partitioned by a cation exchange membrane M4,
(D3) A cation removing solution inlet is provided in a part of the room filled with the cation exchanger C3, and a cation removing solution outlet is provided in another part of the room. e1) The cation discharge part is adjacent to the cathode side of the cation removal part, is provided with a chamber in contact with the cation exchange membrane M4 and filled with a cation exchanger C4, and the other end is provided with fluorine with a water passage hole. (E2) provided with a cation discharge solution inlet for injecting a cation discharge solution into a part of the chamber filled with the cation exchanger C4, which is partitioned by a system cation exchange membrane M5 (f) a cathode part ( f1) the cathode part includes a cathode electrode,
(F2) High-purity basic solution generation and impurity cations that are partitioned by a fluorinated cation exchange membrane M5 with a water passage in contact with the anode side of the cathode electrode, and (f3) have an outlet in the cathode part Removal integrated device. An electric regeneration-type integrated ion generation / removal device, comprising: (a) a cathode part, and (a1) the cathode part includes a cathode electrode,
(A2) It is partitioned by a fluorine-based cation exchange membrane M1 with a water passage hole which is in contact with the anode side of the cathode electrode, (a3) an outlet is provided in the cathode part, (b) an anion supply part, and (b1) the anion. An ion supply unit is adjacent to the anode side of the cathode unit, is in contact with the fluorine-containing cation exchange membrane M1 with water passage holes , and is filled with an anion exchanger A1; and (b2) the anion exchanger A1. The other end of the filled room is partitioned by an anion exchange membrane M2,
(B3) Anion supply solution inlet is provided in a part of the room filled with the anion exchanger A1. (C) Anion generation part and (c1) The anion generation part is an anode of the anion supply part. A chamber adjacent to the side, which is in contact with the anion exchange membrane M2 and is laminated in parallel with the container cross section with the anion exchange membrane, and (c2) a chamber filled with the cation exchanger C2, and the other end is a fluorine-based cation. Partitioned by ion exchange membrane M3,
(C3) An anion generating solution injection port or an anion generating solution outlet is provided in a part of the chamber filled with the cation exchanger C2,
(C4) An anion generating solution outlet or an anion generating solution injection port is provided from a part of the space of the room laminated in parallel with the container cross section by the anion exchange membrane. (D) Anion removing section and (d1) the anion. An ion removal section is adjacent to the anion side of the anion generation section, is in contact with the fluorine-based cation exchange membrane M3 and is filled with anion exchanger A3, and (d2) is filled with the anion exchanger A3. The other end of the room is partitioned by an anion exchange membrane M4,
(D3) An anion removing solution inlet is provided in a part of the room filled with the anion exchanger A3, and an anion removing solution outlet is provided in another part of the room. e1) The anion discharging part is adjacent to the anion side of the anion removing part, is provided with a chamber in contact with the anion exchange membrane M4 and filled with the anion exchanger A4, and the other end is a cation exchange with a water passage hole. (E2) An anode part provided with an anion discharging solution inlet for injecting an anion discharging solution into a part of the chamber filled with the anion exchanger A4, which is partitioned by the membrane M5 (e2), and (f1) the anode Part is provided with an anode electrode,
(F2) It is partitioned by a fluorine-based cation exchange membrane M5 with a water passage hole which is in contact with the cathode side of the anode electrode,
(F3) A high-purity acidic solution production and impurity anion removal integrated device comprising a discharge port in the anode part. An ion chromatograph apparatus incorporating the electric regeneration type ion generation / removal integrated apparatus according to claim 1 for generating a basic eluent and removing impurity cations in anion chromatography. An ion chromatograph apparatus incorporating the electric regeneration type ion generation / removal integrated apparatus according to claim 2 for generating an acidic eluent and removing anions of impurities in cation chromatography.