JP6085268B2 - Ion concentrator - Google Patents

Description

  The present invention relates to an ion concentration apparatus and an ion concentration method.

  The present invention is used for analysis of natural environment such as analysis of ammonia in the atmosphere, acid gas analysis, water quality inspection of river water, groundwater, etc., or analysis of trace impurities used for industrial and medical purposes. The present invention relates to the concentration of ions necessary for highly sensitive analysis of ions.

The cations to be concentrated here are alkali metal ions such as lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), potassium ions (K ⁺ ), and silver ions (Ag ⁺ ) as typical monovalent monoatomic ions. Metal ions such as copper ions (Cu ⁺ ) and mercury ions (Hg ₂ ²⁺ ), ammonium ions (NH ₄ ⁺ ) as typical polyatomic ions, and divalent magnesium ions as polyvalent monoatomic ions (Mg ²⁺ ), calcium ions (Ca ²⁺ ), strontium ions (Sr ²⁺ ), barium ions (Ba ²⁺ ) and other alkaline earth metal ions, cadmium ions (Cd ²⁺ ), nickel ions (Ni ²⁺ ), zinc ions ( Zn ^2+), copper ions ^{(Cu 2+),} mercury ions ^{(Hg 2+),} iron ions ^{(Fe 2+),} the edge Toion ^{(Co +2),} tin ions ^{(Sn 2+),} lead ions ^{(Pb 2+),} manganese ions ^{(Mn 2+)} and trivalent aluminum ions ^{(Al 3+),} iron ion ^{(Fe 3+),} chromium ions ^(Cr 3+), And metal ions such as tetravalent tin ion (Sn ⁴⁺ ) and lead ion (Pb ⁴⁺ ).

The anions to be concentrated are typical monoatomic ions such as chloride ions (Cl ⁻ ), fluoride ions (F ⁻ ), bromide ions (Br ⁻ ), iodide ions (I ⁻ ), and other halides. As typical polyatomic ions or molecular ions, hypochlorite ion (ClO ⁻ ), chlorite ion (ClO ₂ ⁻ ), chlorate ion (ClO ₃ ⁻ ), perchlorate ion (ClO _4). ^- ) Chlorine oxoanion, bicarbonate ion (HCO ₃ ⁻ ), carbonate ion (CO ₃ ²⁻ ), acetate ion (CH ₃ COO ⁻ ), formate ion (HCOO ⁻ ), methacrylate ion (CH ₂ C) _(CH 3) COO ^-), benzoate ^{_{(C 6 H 5 COO -)}} , permanganate ion (MnO ₄ ^-), cyanide ion (CN ^-), Chioshi Phosphate ion (SCN ^-), nitrate ion (NO ₃ ^-), nitrite (NO ₂ ^-), phosphate ion _(PO ^{4 3-),} dihydrogen phosphate ion _(H 2 PO ₄ ^-), sulfate ion These are ions such as (SO ₄ ²⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), and hydrogen sulfide ion (HS ⁻ ).

Then, when the prior art described in the publicly known literature is examined for means for concentrating the aqueous solution in which ions are dissolved, an electrochemically driven pump is disclosed in Japanese Patent Publication No. 2012-500333. According to the above publication, it is sandwiched between both electrodes and partitioned by an ion exchange membrane to form an anode zone, a cathode zone, and a central generation zone, and a cation aqueous solution or pure water is added to the anode zone. Injects pure water or an anion aqueous solution, energizes both electrodes to produce a cation aqueous solution or an anion aqueous solution, water concentrated in the generation zone, and takes it out from the outlet. The partition membrane installed between the two electrode zones and the generation zone is an ion exchange membrane that prevents the movement of the liquid itself between the two zones, and only ions that are selectively allowed for the polarity of the ion exchange membrane move and the opposite side. Move to the electrode. As a result, the cation or anion and H ions and OH ions generated by electrolysis of water at both electrodes are accumulated in the generation zone to generate a solution having a high ion concentration.
However, although the structure is simple, a by-product oxidized or reduced by the electrode reaction is generated due to direct contact of the ionic aqueous solution with the electrode surface, which may be mixed into the target concentrated ionic solution.
Furthermore, since the entire device configuration is a configuration in which an aqueous ionic solution is partitioned by an ion exchange membrane, it is necessary to increase the voltage applied per unit area in order to pass the required amount of current between the electrodes. For devices that require high currents, devices with improved power efficiency are desired.

Japanese Patent Publication No. 2012-50033

The problem to be solved by the present invention is an apparatus for concentrating ions from a sample solution containing dilute concentrations of ions as a pretreatment for ion analysis, in which the cation to be concentrated or the anion to be concentrated is eluted in an aqueous solution, Alternatively, it is an object to provide a device and a method for concentrating, which favorably recovers an object in which the cation to be concentrated is eluted in the anion source solution, and an object in which the cation anion to be concentrated is eluted in the cation source solution. Furthermore, there is no contamination of by-products that are oxidized or reduced by the electrode reaction during the concentration process, and the energy-saving device is excellent in power efficiency in the operation of the entire concentration device.

In order to solve the above-described problems, the basic apparatus of the present invention
(A) An internal zone consisting of three chambers partitioned by an ion exchange membrane in the container space between both electrodes, and (a1) one end of the zone is a cathode chamber zone, which is in contact with the cathode electrode side and is liquid permeable The cation exchange membrane to which the concentration is applied is partitioned by an anion exchange membrane on the side of the adjacent central concentration chamber, the anion exchange resin is filled in the partitioned space, and the concentration target is installed above the space. (A2) The other end of the zone is an anode chamber zone, which is in contact with the anode electrode side and imparts liquid permeability. The cation exchange membrane and the anion exchange membrane imparted with liquid permeability are overlapped and partitioned by the cation exchange membrane on the adjacent central concentration chamber zone side, and the cation exchange resin is filled in the partitioned space, Deep installed in the upper part of the space (A3) The central portion of the zone is a concentration chamber zone, and the cathode chamber side and an anion exchange membrane are used. An anion exchange resin on the cathode side is filled with a cation exchange resin on the anode side in a space partitioned by the anode chamber side and the cation exchange membrane, with a central longitudinal section sandwiched therebetween, and is installed at the upper or lower part of the space. The inlet 21 for injecting pure water into the anion exchange resin layer side, the inlet 22 for injecting pure water into the cation exchange resin layer side, and the cation exchange resin layer side installed at the lower or upper part of the space. (B) an external zone consisting of two chambers surrounding both electrodes; (B) consisting of a liquid outlet 22 corresponding to the inlet 21 or a liquid outlet 21 corresponding to the inlet 22 on the anion exchange resin layer side; Outside the zone surrounding the cathode electrode A zone, which is partitioned by a cation exchange membrane imparting liquid permeability in contact with the cathode electrode, and comprises an outlet 1 for discharging water and hydrogen gas installed in a part of the space surrounding the electrode (b2) Is an external zone that surrounds the anode electrode, and is partitioned by overlapping the cation exchange membrane imparting liquid permeability and the anion exchange membrane imparting liquid permeability in contact with the anode electrode, in a part of the space surrounding the electrode It proposes an ion concentrator equipped with (c) an external power source connecting the above-mentioned electrodes, which is composed of installed water and an outlet 3 for discharging oxygen gas.

The basic apparatus of the present invention is shown in FIGS.
That is, the outline of the apparatus of the present invention is composed of an ion exchange membrane provided with liquid permeability sandwiched between both electrodes, a main body forming an internal zone composed of three chambers partitioned by a normal ion exchange membrane, and two chambers surrounding both electrodes. An ion concentrator provided with an external power source connecting an external zone and an electrode. The basic form of the apparatus is configured as described above, and as other modifications, only the central concentrating chamber zone described in (a3), which is a part of the basic structure of the apparatus, is changed, and the other constituent elements are changed. Shows five variations of the same ion concentrator.
The details of the present invention will be described later with reference to examples. In order to facilitate understanding of the complicated present invention, the basic form of the present invention will be described first, and an example of cation concentration will be given. The state of progress will be described with reference to the above apparatus, FIG.

A sample solution containing cations, a dilute solution of cesium ions is shown in the examples, but is a representative example of an alkali metal ion solution. This sample solution is injected from the inlet 3 into the anode chamber zone of the apparatus, while pure water is injected from the inlet 1 into the cathode chamber zone of the apparatus. The anode chamber zone is filled with a cation exchange resin, and an ion exchange membrane is used to partition the adjacent zone. The cation exchange membrane is in contact with the central concentrating chamber side, and the anode electrode side is in contact with the electrode. A cation exchange membrane imparted with liquid permeability and an anion exchange membrane further imparted with liquid permeability are overlapped and installed. The cathode chamber zone is filled with an anion exchange resin, and an ion exchange membrane is used to partition the adjacent zone. An anion exchange membrane is provided on the central concentration chamber side, and an electrode is provided on the cathode electrode side. A cation exchange membrane that is in contact with and imparts liquid permeability is installed.
The liquid permeable ion exchange membrane used here is one obtained by adding slits or the like to a normal ion exchange membrane to provide liquid permeability. A normal ion exchange membrane has a small pore size and selective permeability of ions, but has a property of being difficult to permeate liquid, and therefore processing to provide a permeation hole that can permeate liquid such as a slit is necessary. is there.
Also, the cation exchange membrane is used as the liquid permeable ion exchange membrane in contact with the electrode surface. It has excellent acid resistance, base resistance and mechanical strength due to the fluorine-based material, and is sufficient for wear due to electrode reaction. Because it can withstand.
In the central concentration chamber, ion exchange resins having different polarities are filled with a cation exchange resin on the anode side and an anion exchange resin on the cathode side with the central cross section interposed therebetween. And pure water is inject | poured from the inlet_port | entrance 22 in the upper part or the lower part of the cation exchange resin of the said concentration chamber, and as shown in FIG. It is discharged together with the cations gathered in the.

In the cation sample solution injected into the anode chamber zone, cations are adsorbed on the cation exchange resin, and other water and counterion anions pass between the cation exchange resins and pass through the anode electrode. It is discharged to the anode electrode side through a membrane formed by superposing a cation exchange membrane imparted with liquid permeability and an anion exchange membrane imparted with liquid permeability. Oxygen gas and counter ion oxide generated by the electrolytic reaction of water and counter ions at the anode electrode are discharged from the outlet 3 together with water.
In addition, the hydrogen ions generated by this electrode reaction cannot be moved to the concentrator main body side due to electrostatic repulsion from the polarity on the anion exchange membrane side of the membrane superposed on the two-layer structure.
Therefore, there is no room for electrode reaction products and other impurity ions to enter the system from the outside of the partition membrane.
Thus, it has been devised so that impurity ions such as by-products generated in the electrode reaction do not enter the system in the process of concentrating the cation sample solution.
Instead of H ions generated by the electrode reaction, the interface between the anion exchange membrane and the cation exchange resin, which will be referred to as an ion interface, is a H ion due to a deviation from the dissociation equilibrium of water. And OH ions are generated. That is, OH ions derived from water injected into the ion interface are generated on the anion exchange membrane side and H ions are generated on the cation exchange resin side. The OH ions move together with water to the anode electrode side through the anion exchange membrane, and the H ions are ion-adsorbed on the cation exchange resin and move by electrophoresis toward the cathode electrode side by electrophoresis. It passes through the cation exchange membrane toward the central concentration chamber, and further undergoes electrophoresis in the cation exchange resin to reach the central cross section interface.
Furthermore, the cation adsorbed on the cation exchange resin is electrophoresed and moved from both electrodes to the cathode electrode side under the force of an electric field. It passes through the cation exchange membrane toward the central concentrating chamber, and further undergoes electrophoresis in the cation exchange resin to reach the central cross section interface.

On the other hand, in the cathode chamber zone, the injected pure water passes between the anion exchange resins, passes through the cation exchange membrane provided with liquid permeability, and is discharged to the cathode electrode side. And in the cathode electrode which water contacted directly, hydrogen gas and OH ion generate | occur | produce by electrode reaction, and are discharged | emitted from the exit 1 outside with water. OH ions are repelled by the polarity of the cation exchange membrane and cannot enter the system. Instead of the OH ions generated in the electrode reaction, the interface between the cation exchange membrane and anion exchange resin that contacts the cathode electrode, which is called the ion interface, From this deviation, H ions and OH ions are generated. That is, OH ions derived from water injected into the ion interface are generated on the anion exchange resin side and H ions are generated on the cation exchange membrane side. H ions move together with water to the cathode electrode side through the cation exchange membrane, and OH ions are adsorbed on the anion exchange resin and move by electrophoresis toward the anode electrode side by electrophoresis. It passes through the anion exchange membrane toward the central concentration chamber, and further undergoes electrophoresis in the anion exchange resin to reach the central cross section interface.

The ions moving to the central concentration chamber as described above are cations derived from the sample solution as well as H ions and OH ions generated at the ion interface by electrophoresis. There is a flow of water presumed to be a flow of associated water molecules generated around ions.
The cations that have been electrophoresed to the interface of the central section of the concentrating chamber stop moving due to the electrostatic repulsion walls of the anion exchange resins of different polarities, desorb from the resin that has adsorbed ions, Is swept away by water injected from the inlet 22 of the concentrating chamber, and a cation-concentrated aqueous solution is discharged from the outlet 21.
Here, it should be noted that even if water is not injected from the inlet 22 of the concentrating chamber, the cation is swept away by the electroosmotic flow described above, and the concentrated aqueous solution of the cation is discharged from the outlet 21. Moreover, it expresses that it elutes with water since the cation is eluted with water at the interface and discharged to the outside. Further, when the anion source solution is used from the inlet 1 instead of pure water, in addition to the above description, the anion in the anion source solution is ion-adsorbed on the anion exchange resin in the cathode chamber zone and is further subjected to electrophoresis. It passes through the anion exchange membrane of the partition membrane, enters the concentration chamber zone, still moves through the anion exchange resin, and moves to the interface of the central section of the concentration chamber. It is presumed that an acid is formed with H ions that have moved from the opposite direction across the interface.
Since the cations are eluted with the acid thus generated, it is expressed as being eluted with an acid for the sake of convenience and distinction from the expression of elution with water. This detail will be described later because it further exhibits an effect specific to the concentration of transition metal ions.
The cations in the sample solution supplied to the anode chamber zone are adsorbed on the filled cation exchange resin, and then almost 100% is recovered, and most of the water in the sample solution is discharged from the outlet provided in the anode chamber zone. Sorted out of the system. Ions adsorbed on the cation exchange resin migrate to the central concentration chamber by electrophoresis, and are eluted with a small amount of electroosmotic flow near the interface or with water injected from the inlet 22 of the concentration chamber. Therefore, mainly by controlling the amount of water injected from the inlet 22 of the concentration chamber, the ions are concentrated by changing the concentration rate.

Although the outline | summary description about the apparatus basic form of this invention is above, it is as follows about the 5 modification of a center part concentration chamber zone.
<Modification 1>
In the ion concentrator according to claim 1, in place of the concentration chamber zone according to (a3), which is a part of the constituent elements,
The central portion of the zone is a concentration chamber zone, and an anion exchange resin is provided on the cathode side in a space partitioned by the cathode chamber side and the anion exchange membrane and by the anode chamber side and the cation exchange membrane. pure cation exchange resin on the side, was charged across the central vertical plane portion comprising a cation-exchange membrane the liquid permeability imparted to the upper or anion exchange resin layer side disposed in the lower part of the space An inlet 22 for injecting pure water or an inlet 22 for injecting pure water into the cation exchange resin layer side, and a liquid discharge port corresponding to the inlet 21 on the cation exchange resin layer side installed below or above the space 22 or an anion exchange resin layer side corresponding to the inlet 22, and an ion concentrator having the same other components as the liquid outlet 21.

Modification 1 of the present invention is shown in FIGS.
This is because the central section of the concentrating chamber is partitioned by a cation exchange membrane imparted with liquid permeability and more firmly supports the interface between the cation exchange resin layer and the anion exchange resin layer.
The cation exchange membrane is given liquid permeability by injecting pure water from the inlet 22 and passing through the central liquid permeable cation exchange membrane and discharging it from the outlet 21 or injecting it from the inlet 21. This is because the water flow indicated by the solid line and the dotted line in FIGS. 7 to 13 is required so as to pass through the central liquid-permeable cation exchange membrane and be discharged from the outlet 22.
A sample solution containing a cation will be described using this modification 1, and a dilute solution of divalent iron ions is shown in the examples, but a typical example of a transition metal ion solution will be described.
Among the metal ions, alkali metals and alkaline earth metals are strongly dissociated into ions and dissolved in the aqueous solution in the presence of OH ions, but many metal ions form hydroxides and precipitate.
Among these hydroxide metal ions having the property of precipitating, transition metal ions that are particularly important industrially are used as the ions to be concentrated in the present invention.

In a system in which such a precipitate is generated, elution with pure water is difficult at the central interface of the central concentration chamber of the present invention. Therefore, an anion source solution is injected from the inlet 1 instead of pure water, and the anion derived from the anion source solution is contacted and reacted with transition metal ions in an acidic atmosphere at the interface. Depending on the type of acid, some metal ions, such as silver ions, lead ions, and monovalent mercury ions, may be insoluble in water when chloride ions in hydrochloric acid act on them. It is sex. Strong acid or weak acid such as hydrochloric acid, nitric acid, sulfuric acid, etc., which includes formic acid and acetic acid except boric acid and carbonic acid, and is injected from the inlet 1 into the cathode chamber zone of the apparatus.
Here, the anion source solution is a solution containing an anion necessary for this purpose, and the anion is the same as that described in paragraph No. 0004 of the present specification excluding OH ions.
Further, the cation source solution produced by the concentration of the anion is a solution containing a cation necessary for this purpose, and the cation is described in the paragraph No. 0003 in the present specification excluding H ions. Is the same as
Accordingly, the anion source solution usually refers to various acidic solutions and various salt aqueous solutions, and the cation source solution refers to various basic solutions and various salt aqueous solutions.

A sample solution containing transition metal ions is injected from the inlet 3, and the transition metal ions adsorbed on the cation exchange resin in the anode chamber zone under the current flowing between the electrodes are transferred to the cathode electrode side by electrophoresis. , Through the cation exchange membrane and carried to the central concentration chamber zone. In addition, an anion, which is a counter ion of an acid that is injected from the inlet 1 and is ion-adsorbed on the anion exchange resin in the cathode chamber zone, is transferred to the anode electrode side by electrophoresis and permeates the anion exchange membrane. To the central concentration chamber zone. Further, pure water is injected from the inlet 22 of the concentration chamber toward the outlet 21 or from the inlet 21 of the concentration chamber toward the outlet 22. In addition, the transition metal ions and the anions described above without injecting pure water passed through the cation exchange resin and the anion exchange resin in the concentrating chamber, respectively. A water-soluble salt is formed at the interface of the ion exchange membrane, and the concentrated ionic liquid is discharged to the outside by electroosmotic flow or injected water.

<Modification 2>
In the ion concentrator according to claim 1, in place of the concentration chamber zone according to (a3), which is a part of the constituent elements,
The central portion of the zone is a concentration chamber zone, and an anion exchange resin is provided on the cathode side in a space partitioned by the cathode chamber side and the anion exchange membrane and by the anode chamber side and the cation exchange membrane. pure cation exchange resin on the side, was charged across the central vertical plane portion consisting of an anion exchange membrane a liquid permeable granted, the upper or anion exchange resin layer side disposed in the lower part of the space An inlet 22 for injecting pure water or an inlet 22 for injecting pure water into the cation exchange resin layer side, and a liquid discharge port corresponding to the inlet 21 on the cation exchange resin layer side installed below or above the space 22 or an anion exchange resin layer side corresponding to the inlet 22, and an ion concentrator having the same other components as the liquid outlet 21.

Modification 2 of the present invention is not shown in the drawings.
This is the same except that the anion exchange membrane provided with liquid permeability is used instead of the cation exchange membrane provided with liquid permeability at the interface in the first modification.

<Modification 3>
In the ion concentrator according to claim 1, in place of the concentration chamber zone according to (a3), which is a part of the constituent elements,
The central portion in the zone is a concentration chamber zone, and an anion exchange resin is provided on the cathode side in a space partitioned by the cathode chamber side and the anion exchange membrane and the anode chamber side and the cation exchange membrane. The anode side is filled with a cation exchange membrane layer laminated at a right angle to the central axis of the concentration chamber zone with a central longitudinal section sandwiched between them, and the anion exchange resin layer installed on the upper or lower side of the space is pure. The inlet 21 for injecting water or the inlet 22 for injecting pure water into the cation exchange membrane layer side, and the drainage of liquid corresponding to the inlet 21 on the cation exchange membrane layer side installed below or above the space This is an ion concentrator in which the other constituent elements are the same as the outlet 22 or the anion exchange resin layer side corresponding to the inlet 22 and having a liquid outlet 21.

A third modification of the present invention is shown in FIGS.
This is the same except that the concentration chamber is filled with a laminated cation exchange membrane instead of the cation exchange resin. The laminated ion exchange membrane is excellent in the selective permeability of ions, and permeates ions of the same polarity well by electrophoresis. Further, it is excellent in the effect of separating the flow of the electroosmotic flow generated in the membrane from the flow of other liquids, and the interface stability is also good. As an ion concentrator, it has the same function as the basic form of the device.

<Modification 4>
In the ion concentrator according to claim 1, in place of the concentration chamber zone according to (a3), which is a part of the constituent elements,
Central portion in said zone is a concentrating chamber zone, the center of the concentrating chamber zone on the cathode side to the cathode chamber side and an anion exchange membrane and in the anode chamber side and the space partitioned by a cation exchange membrane An anion exchange membrane layer laminated at a substantially right angle to the axis is filled with a cation exchange resin on the anode side across the central longitudinal section, and pure anion exchange membrane layer installed on the upper or lower part of the space. The inlet 21 for injecting water or the inlet 22 for injecting pure water into the cation exchange resin layer side, and the drain of the liquid corresponding to the inlet 21 on the cation exchange resin layer side installed at the lower part or upper part of the space. This is an ion concentrator in which other constituent elements are the same as the outlet 22 or the anion exchange membrane layer side corresponding to the inlet 22 and having a liquid outlet 21.

Modification 4 of the present invention is shown in FIGS.
This is the same as the case used in Modification 3 except that the anion exchange membrane laminated in place of the anion exchange resin on the cathode side in the concentration chamber is filled. Its function and utility are the same as in the third modification.

<Modification 5>
In the ion concentrator according to claim 1, in place of the concentration chamber zone according to (a3), which is a part of the constituent elements,
Central portion in said zone is a concentrating chamber zone, the center of the concentrating chamber zone on the cathode side to the cathode chamber side and an anion exchange membrane and in the anode chamber side and the space partitioned by a cation exchange membrane An anion exchange membrane layer laminated at a substantially right angle to the axis is filled with a cation exchange membrane layer laminated at a substantially right angle to the central axis of the cation enrichment zone on the anode side with a central longitudinal section sandwiched therebetween, An inlet 21 for injecting pure water into the anion exchange membrane layer side installed at the top or bottom, or an inlet 22 for injecting pure water into the cation exchange membrane layer side, and a positive electrode installed at the bottom or top of the space An ion concentrator having the same other components as the liquid discharge port 22 corresponding to the inlet 21 on the ion exchange membrane layer side or the liquid discharge port 21 corresponding to the inlet 22 on the anion exchange membrane layer side. It is.

Modification 5 of the present invention is shown in FIGS.
This is the same as the other, except that both the inside of the concentrating chamber are filled with a laminated ion exchange membrane instead of the ion exchange resin. Its function and utility are the same as those described in the third and fourth modifications.

<Concentration method using the apparatus of the present invention>
Concentration methods using the apparatus of the present invention include a continuous method and an intermittent method. The details of each method will be described later, and their representative cases will be described later.

<Continuous concentration method>
When the ion to be concentrated is an anion,
A current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1, pure water is injected from the inlet 3, pure water is injected from the inlet 21, and concentrated ions are included from the outlet 22. 5. Anion continuous ion concentration using the ion concentrating device according to claim 1, wherein the solution containing concentrated ions is discharged from the outlet 22 without discharging the solution or injecting pure water into the inlet 21. Is the method.

Also,
A current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1, pure water is injected from the inlet 3, pure water is injected from the inlet 21, and concentrated ions are included from the outlet 22. The above-mentioned claim, wherein the solution is discharged or injected from the inlet 22 to discharge the solution containing concentrated ions from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or outlet 22 without injecting the pure water. An anion continuous ion concentration method using the ion concentrator according to any one of 5 and 6.

further,
A current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1, a cation source solution is injected from the inlet 3, and pure water is injected from the inlet 21, and concentrated ions are injected from the outlet 22. The solution containing concentrated ions is discharged, or the solution containing concentrated ions is discharged from the inlet 22 and discharged from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. It is an anion continuous ion concentration method using the ion concentration apparatus in any one of Claim 1 to 6.

When the ion to be concentrated is a cation,
A current is passed between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3, pure water is injected from the inlet 1, pure water is injected from the inlet 22, and concentrated ions are included from the outlet 21. The positive ion using the ion concentrator according to any one of claims 1, 2, 3, and 5 wherein the solution containing concentrated ions is discharged from the outlet 21 without discharging the solution or injecting pure water into the inlet 22. It is an ion continuous ion concentration method.

Also,
An electric current is passed between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3, pure water is injected from the inlet 1, pure water is injected from the inlet 21, and concentrated ions are included from the outlet 22. The above-mentioned claim, wherein the solution is discharged or injected from the inlet 22 to discharge the solution containing concentrated ions from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or outlet 22 without injecting the pure water. A cation continuous ion concentration method using the ion concentrator according to any one of 4 and 6.

further,
A current is passed between the electrodes, a solution containing cations as ions to be concentrated is injected from the inlet 3, an anion source solution is injected from the inlet 1, pure water is injected from the inlet 21, and concentrated ions are injected from the outlet 22. The solution containing concentrated ions is discharged, or the solution containing concentrated ions is discharged from the inlet 22 and discharged from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. It is a cation continuous ion concentration method using the ion concentration apparatus in any one of Claim 1 to 6.

When the ion to be concentrated is a transition metal ion, a current is passed between the electrodes, a solution containing the transition metal ion that is the ion to be concentrated is injected from the inlet 3, and a strong acid or a weak acid containing formic acid and acetic acid is removed except for boric acid and carbonic acid. Is injected from the inlet 1 and pure water is injected from the inlet 21 and the solution containing concentrated ions is discharged from the outlet 22, or the solution containing concentrated ions is discharged from the inlet 22 and discharged from the outlet 21. It is a transition metal ion continuous ion concentration method using the ion concentration apparatus according to any one of claims 1 to 6, wherein a solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting pure water.

This continuous concentration method shows a case where anions and cations are concentrated, but the point is in a method of injecting a sample solution while the device is energized and continuously discharging the concentrated ion solution. It is suitable for process monitoring that can always detect variations in dilute sample solutions. Specifically, for water quality monitoring in a plant using ultrapure water.
The details of the ion concentration rate will be described later. In the above-described concentration method, the flow rate adjustment injecting from the pure water inlet 21 or the inlet 22 is mainly used for adjusting the concentration rate. If the injection amount of pure water is small, the concentration rate increases. Conversely, if the injection amount is large, the concentration rate decreases.

<Intermittent concentration method>
When the ion to be concentrated is an anion, in a state where no current flows between the electrodes, a solution containing the anion that is the ion to be concentrated is injected from the inlet 1 to accumulate a processing target amount, and pure water is supplied to the inlet 3. Then, the anode chamber zone is filled, and then a current is passed between the electrodes, and pure water is continuously injected from the inlets 1 and 3, while pure water is continuously injected from the inlet 21 and concentrated from the outlet 22. The anion using the ion concentrator according to any one of claims 1 to 4, wherein the solution containing ions is discharged or the solution containing concentrated ions is discharged from the outlet 22 without injecting pure water into the inlet 21. This is an intermittent ion concentration method.

Also,
In a state where no current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1 to accumulate a processing target amount, pure water is injected from the inlet 3 to fill the anode chamber zone, and While flowing a current between the electrodes and continuously injecting pure water from the inlets 1 and 3, pure water is injected from the inlet 21 and a solution containing concentrated ions is discharged from the outlet 22, or injected from the inlet 22. 7. The ion concentration according to claim 5, wherein the solution containing concentrated ions is discharged from the outlet 21 or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. This is an anion intermittent ion concentration method using an apparatus.

further,
In a state where no current flows between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1 to accumulate a processing target amount, and a cation source solution is injected from the inlet 3 to fill the anode chamber zone. Then, a current is passed between the electrodes, pure water is continuously injected from the inlet 1, a cation source solution is continuously injected from the inlet 3, pure water is continuously injected from the inlet 21, and concentrated ions are contained from the outlet 22. The solution is discharged or continuously injected from the inlet 22 and the solution containing concentrated ions is discharged from the outlet 21, or the concentrated ions are discharged from the outlet 21 or the outlet 22 without injecting the pure water from the inlet 21 or 22. It is an anion intermittent ion concentration method using the ion concentration apparatus in any one of the said 1 to 6 which discharges the solution containing.

When the ion to be concentrated is a cation, in a state where no current is passed between the electrodes, a solution containing the cation that is the ion to be concentrated is injected from the inlet 3 to accumulate a processing target amount, and pure water is supplied to the inlet 1. Then, the cathode chamber zone is filled, and then a current is passed between the electrodes, and pure water is continuously injected from the inlets 1 and 3, while pure water is continuously injected from the inlet 22 and concentrated from the outlet 21. The ion concentrator according to any one of claims 1, 2, 3, and 5 that discharges a solution containing concentrated ions from the outlet 21 without discharging a solution containing ions or injecting pure water into the inlet 22. This is a cation intermittent ion concentration method to be used.

Also,
In a state in which no current is passed between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3 to accumulate a processing target amount, pure water is injected from the inlet 1 to fill the cathode chamber zone, and then While flowing a current between the electrodes and continuously injecting pure water from the inlets 1 and 3, pure water is injected from the inlet 21 and a solution containing concentrated ions is discharged from the outlet 22, or injected from the inlet 22. 7. The ion concentration according to claim 4, wherein the solution containing concentrated ions is discharged from the outlet 21 or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. It is a cation intermittent ion concentration method using an apparatus.

further,
In a state where no current is flowing between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3 to accumulate a processing target amount, and injected from the anion source solution inlet 1 to fill the cathode chamber zone. Next, an electric current is passed between the electrodes, pure water is continuously injected from the inlet 3, an anion source solution is continuously injected from the inlet 1, pure water is continuously injected from the inlet 21, and a solution containing concentrated ions from the outlet 22. Or the solution containing concentrated ions is discharged from the outlet 21 continuously or the concentrated water is contained from the outlet 21 or the outlet 22 without injecting the pure water from the inlet 21 or 22. It is a cation intermittent ion concentration method using the ion concentration apparatus in any one of said 1 to 6 which discharges | emits a solution.

When the ion to be concentrated is a transition metal ion, a solution containing the transition metal ion that is the ion to be concentrated is injected from the inlet 3 in a state in which no current flows between the electrodes, and strong acid or boric acid and carbonic acid are removed to remove formic acid, A weak acid containing acetic acid is injected from the inlet 1, and then a current is passed between the electrodes, and pure water is injected from the inlet 21 and a solution containing concentrated ions is discharged from the outlet 22, or injected from the inlet 22 and injected from the outlet 21. The ion concentrator according to any one of claims 1 to 6, wherein the solution containing concentrated ions is discharged or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. It is a transition metal ion intermittent ion concentration method.

This intermittent concentration method shows a case where anions and cations are concentrated. However, the point is that the sample solution is injected and the sample solution is stored while the device is not energized, and then energization is started to concentrate. There is a method of discharging the ionic solution. This is because the injection flow rate of the sample solution is very slow and the injection time takes a long time, but the time for discharging the concentrated ions from the apparatus does not take much time. It is easy to make a schedule to concentrate on analysis work. In addition, most of the normal analysis work performed in badge processing is performed by this method.

Using a concentration apparatus of the present invention, a solution containing dilute anions and cations is eluted with pure water, an anion source solution or an acid or base derived from a cation source solution and concentrated by a continuous or intermittent concentration method. This is an effective means for pretreatment to achieve high sensitivity analysis of ion analysis.

Basic ion concentration device that concentrates anions and elutes with pure water Basic type ion concentrator for concentrating anions and eluting from outlet 22 with cation source solution Basic type ion concentrator for concentrating anions and eluting from outlet 21 with cation source solution Basic ion concentration device that concentrates cations and elutes with pure water Basic type ion concentrator for concentrating cations and eluting from outlet 22 with anion source solution Basic ion concentrator that concentrates cations and elutes from outlet 21 with an anion source solution An ion concentrator according to Modification 1 that concentrates anions and elutes them with pure water The ion concentrating device of Modification 1 that concentrates anions and elutes them from the outlet 22 with a cation source solution The ion concentrating device of Modification 1 that concentrates anions and elutes them from the outlet 21 with a cation source solution The ion concentrator of Modification 1 that concentrates cations and elutes them from the outlet 21 with pure water

The ion concentrator of Modification 1 that concentrates cations and elutes with pure water from the outlet 22 It is not preferable to flow pure water along the solid line. The ion concentrator of Modification 1 that concentrates cations and elutes from the outlet 22 with an anion source solution The ion concentrator of Modification 1 for concentrating cations and eluting from the outlet 21 with an anion source solution The ion concentrator of the modification 3 which concentrates an anion and elutes with the pure water from the exit 22 It is not preferable to flow the ion concentrator pure water of Modification 3 that concentrates anions and elutes from the outlet 21 with pure water along the dotted line. The ion concentrator of the modification 3 which concentrates an anion and elutes from the exit 22 with a cation source solution The ion concentrator of the modification 3 which concentrates an anion and elutes from the exit 21 with a cation source solution The ion concentrator of Modification 3 for concentrating cations and eluting from the outlet 21 with pure water The ion concentrator of Modification 3 that concentrates cations and elutes them from the outlet 22 with pure water The ion concentrator of the modification 3 which concentrates a cation and elutes from the exit 22 with an anion source solution

The ion concentrator of Modification 3 for concentrating cations and eluting from the outlet 21 with an anion source solution The ion concentrator of the modification 4 which concentrates an anion and elutes with the pure water from the exit 22 The ion concentrator of the modification 4 which concentrates an anion and elutes with the pure water from the exit 21 The ion concentrator of the modification 4 which concentrates an anion and elutes from the exit 22 with a cation source solution The ion concentrator of the modification 4 which concentrates an anion and elutes from the exit 21 with a cation source solution The ion concentrator of the modification 4 which concentrates a cation and elutes with the pure water from the exit 21 It is not preferable to flow the ion concentrator pure water of Modification 4 that concentrates cations and elutes from the outlet 22 with pure water along the solid line. The ion concentrator of the modification 4 which concentrates a cation and elutes from the exit 22 with an anion source solution The ion concentrator of the modification 4 which concentrates a cation and elutes from the exit 21 with an anion source solution The ion concentrator of the modification 5 which concentrates an anion and elutes with the pure water from the exit 22

The ion concentrator of the modification 5 which concentrates an anion and elutes with the pure water from the exit 21 The ion concentrator of the modification 5 which concentrates an anion and elutes from the exit 22 with a cation source solution The ion concentrator of the modification 5 which concentrates an anion and elutes from the exit 21 with a cation source solution The ion concentrator of the modification 5 which concentrates a cation and elutes with the pure water from the exit 21 The ion concentrator of the modification 5 which concentrates a cation and elutes with the pure water from the exit 22 The ion concentrator of the modification 5 which concentrates a cation and elutes from the exit 22 with an anion source solution The ion concentrator of the modification 5 which concentrates a cation and elutes from the exit 21 with an anion source solution Schematic diagram of analyzer 1 used for measurement Schematic diagram of analyzer 2 used for measurement Schematic diagram of analyzer 3 used for measurement

Flow rate of ion chromatogram pump 2 for cesium ions (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min Relationship between concentration rate of cesium ions and flow rate ratio of pump 1 and pump 2 Flow rate of ion chromatogram pump 2 for cesium ions (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min Relationship between concentration rate of cesium ions and flow rate ratio of pump 1 and pump 2 Flow rate of ion chromatogram pump 2 for cesium ions (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min Relationship between concentration rate of cesium ions and flow rate ratio of pump 1 and pump 2 Flow rate of ion chromatogram pump 2 for cesium ions (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min Flow rate of ion chromatogram pump 2 for cesium ions (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min Relationship between concentration rate of cesium ions and flow rate ratio of pump 1 and pump 2 Relationship between concentration rate of cesium ions and flow rate ratio of pump 1 and pump 2

Flow rate of ion chromatogram pump 2 for cesium ions (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min Relationship between concentration rate of cesium ions and flow rate ratio of pump 1 and pump 2 Increase and decrease of divalent iron ion concentration and absorbance (a) and (c) when pure water was passed through inlet 1, and (b) and (d) when MSA solution was passed through inlet 1 Increase / decrease and concentration of divalent iron ions and absorbance (a) When pure water is flowed along the dotted line to the concentration chamber, (b) When pure water is flowed along the solid line to the concentration chamber Absorbance of divalent iron ions (a) Absorbance of divalent iron ions before being injected into the concentrator, (b) Absorbance of divalent iron ions after passing through the concentrator Current flowing between electrodes changing the absorbance of divalent iron ions (a) 10 mA, (b) 20 mA, (c) 30 mA, (d) 40 mA Schematic diagram of analyzer 4 used for measurement Flow rate of anion ion chromatogram pump 2 (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min, (e) 0.01 mL / Min 1 Fluoro ion, 2 Bromine ion, 3 Phosphate ion, 4 Sulfate ion Relationship between phosphate ion concentration ratio and flow rate ratio of pump 3 and pump 2 Anion ion chromatogram of concentrated solution by intermittent concentration method (1) 2 μM NaF, (2) 2 μM NaBr, (3) 5 μM Na ₂ HPO ₄ , (4) 2 μM Na ₂ SO ₄ ) 9 mL, (b) 18 mL, (c) 36 mL.

Relationship between liquid volume ratio by intermittent concentration method and peak height of Br ion and PO ₄ ion on ion chromatogram Schematic diagram of the analyzer used for measurement The flow rate of the ion chromatogram pump 2 for PO ₄ ions indicates (a) 1 mL / min, (b) 0.1 mL / min, and (c) 0.01 mL / min. Relationship between the concentration rate of PO ₄ ions and the flow rate ratio of pump 3 and pump 2 The flow path of pure water flowing through the ion chromatogram EC of Cs ions shows the flow path of (a) dotted line and (b) solid line. (A) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min at the flow rate of the ion chromatogram pump 2 of Cs ions. Relationship between Cs ion concentration rate and flow rate ratio of pump 1 and pump 2 Schematic diagram of the analyzer used for measurement Flow rate of PO ₄ ion ion chromatogram pump 2 (a) 1 mL / min, (b) 0.1 mL / min, (c) 0.01 mL / min Relationship graph between pump flow rate ratio and PO ₄ ion concentration rate Schematic diagram of the analyzer used for measurement

BEST MODE FOR CARRYING OUT THE INVENTION The best mode of the present invention will be described and described in detail with reference to examples.
7 to 13, Modification 3 shown in FIGS. 14 to 21, Modification 4 shown in FIGS. 22 to 29, and Modification 5 shown in FIGS. 30 to 37. Concentrate cesium ions, divalent iron ions, sample anions, obtain an ion chromatogram by applying to an ion chromatograph, further determine the concentration rate, and whether there is an effect on the flow of pure water injected into the concentrator It is shown in the examples. Moreover, the case where the concentration target ion is eluted with pure water at the interface of the concentration part, as well as the case where it is eluted with a cation source solution or an anion source solution is shown.
In Examples 1 to 3 and 14, it is possible to elute Cs ions with pure water or acid of anion source solution using a modified type 1 type concentrator (FIGS. 10, 11, 12, and 13). Indicates that However, there is a limitation in the sense that the elution time becomes longer when eluting with pure water in the way of flowing pure water (dotted line or solid line) to be injected into the central concentrating part. Indicates no limit.

Cs ions that are electrophoresed on the cation exchange resin toward the interface of the central concentrating portion permeate the cation exchange membrane on the interface and reach the interface with the anion exchange resin having a different polarity. As a result, they are desorbed from the cation exchange resin and become free ions, which are washed away by the flow of pure water surrounding the ions and discharged to the outside. At that time, if pure water flows along the dotted line shown in FIG. 10, Cs ions are discharged and collected almost 100% outside, but if pure water flows along the solid line shown in FIG. The free Cs ions are pushed back to the cation exchange resin side, and a part of the Cs ions are again adsorbed on the cation exchange resin, and it takes a long time to desorb and discharge the Cs ions to the outside. It is.

Therefore, when the acid of the anion source solution is injected from the inlet 1 instead of pure water, the anion derived from this acid migrates by electrophoresis, and passes through the cation exchange membrane to which the liquid permeability of the interface is imparted. It enters the resin side, forms an acidic atmosphere with H ions carried from the opposite side, and elutes the Cs ions adsorbed by ions. Cs ions are discharged and collected almost 100% outside. Therefore, when the acid of the anion source solution is injected from the inlet 1 instead of pure water, it does not depend on the flow of pure water (dotted line or solid line) injected into the central concentration section.
FIG. 15 of the basic type of the present invention, the deformation type 1, and the deformation 3 has a limitation in the case of elution with pure water in the way of flowing pure water (dotted line or solid line) injected into the central concentrating portion described above. Although the concentration device shown in FIG. 27 of the modified example 4 does not have such a limitation in the concentration device of another modified type. This is because the ion exchange membrane laminate is used instead of the ion exchange resin in the concentrating portion, and water does not permeate into the ion exchange membrane laminate via the interface and flows on the surface. Therefore, the Cs ions at the interface are not pushed back and taken into the ion exchange membrane laminate.
In Examples 4 to 10, it is shown that concentration is possible both when the Cs ions are eluted with pure water and with the acid of the anion source solution using the modified type 3 type concentrator.
Furthermore, it shows that anion concentration is also possible.

It also shows that it does not depend on the way of flowing pure water (dotted line or solid line) injected into the central concentration section in Example 13.
Further, when Fe ions are eluted with pure water, precipitation of Fe ions occurs and concentration is insufficient, but when they are eluted with acid in the anion source solution, precipitation is avoided, so that almost 100% outside. Discharged and collected.
Examples 11 to 12 show the case of elution with a salt solution as a cation source solution in the intermittent concentration method and the concentration of anions for the modified type 4 type concentrator.
An embodiment in which a dilute concentration anion sample solution is once stored in the cathode chamber zone by the intermittent concentration method of the present invention and then eluted with pure water after being energized.
In Example 15, it is shown that anion concentration is possible for the modified type 5 type concentrator.
Example 16 shows an experimental example in which the apparatus of the present invention has excellent power efficiency.
The concentration apparatus of the present apparatus will be described in detail below while avoiding duplication with the above description.

<Device body container>
The concentrator main body container is preferably PEEK resin, engineered resin having excellent acid resistance and basicity, mechanical strength and electrical insulation.
<Ion exchange resin>
The cation exchange resin and the anion exchange resin are usually ion exchange resins having an ion exchange group in an insoluble polymer compound, and beads are preferable because of their excellent availability, but they only need to have ion exchange properties, flakes, It may be formed in a fibrous form or a non-woven form. Further, if the ion exchange resin layer as a whole has a cation or anion exchange function, two or more kinds of ion exchange resins may be alternately laminated and mixed as appropriate.

<Ion exchange membrane>
The cation exchange membrane and anion exchange membrane used for the internal partition membrane are usually formed by ion-exchange resin having an ion-exchange group on an insoluble polymer compound, and have selective ion permeability. However, the liquid permeability is small and equal to almost none. Therefore, the ion exchange membrane imparted with liquid permeability is obtained by subjecting the membrane to slit processing or the like to ensure liquid permeability.
In particular, Teflon (registered trademark) -based Nafion (registered trademark) NRE-212, 115, 117, 324, 424, 551 and neoceptor (registered) are used as cation exchange membranes having excellent acid resistance and basicity and excellent mechanical strength. (Trademark) C66 etc. can be used.
As the anion exchange membrane, styrene-based Neoceptor (registered trademark) AHA (trade name: manufactured by Atoms), AMX, ACM, ACS, AFN, AFX, or the like can be used.

<Ion exchange membrane layer>
The ion exchange membrane layer used in the concentrating chamber is usually a membrane-like laminate, but as with the ion exchange resin, it may have ion exchange properties, and may be formed in flakes, fibers, nonwoven fabrics, etc. Good. In addition, if the ion exchange membrane layer as a whole has a cation or anion exchange function, two or more types of ion exchange membranes may be alternately laminated and mixed as appropriate.

<Electrode>
The electrode is preferably platinum or the like having excellent corrosion resistance that can withstand the electrode reaction, but the shape is not particularly limited, and may be a mesh shape, a ring shape, a rod shape, a plate shape, a mesh shape, a fritz shape, or the like.
<Power supply>
Usually, a DC power supply is preferably used as the external power supply, but a positive bias or low-frequency pulse AC power supply may be used.

<Pure water injection / discharge structure in the concentration section>
Concentration part is filled with ion-exchange resin, and the structure in which the inlet is provided in the upper part is provided with the injection hole in the container body part, and the filter is usually mounted inside the injection hole. . Pure water is injected from the external piping into the injection hole, passes through the ion exchange resin through the filter, enters the opposite ion exchange resin packed layer through the interface, or along the interface of the opposite ion exchange membrane layer. Then, it is discharged to the outside through a discharge hole having a structure similar to that of the inlet at the lower part. The upper and lower portions of the inlet and outlet may be reversed. It corresponds to a basic type device and modified examples 1, 2, 3, and 4 type devices.
The structure where the concentrating part is filled with an ion exchange membrane laminate and the inlet is provided at the top is the same around the injection hole and the discharge hole, but the ion exchange is slightly smaller than the inner diameter of the container body. The structure is filled with a membrane laminate, and pure water is injected into the slightly vacant space and is discharged to the outside through the lower gap of the opposite resin filling layer or ion exchange membrane laminate across the interface. The upper and lower portions of the inlet and outlet may be reversed. It corresponds to modification 3, 4, 5 type device.

10 is used under the condition of a constant current of 40 mA, pure water is supplied to the inlet 1, pure water is allowed to flow through the EC inlet 22 as indicated by a dotted line, and the flow rate of the pure water is set to 0. The concentration ratio of Cs ions in the concentrated solution eluted from the outlet 21 when the flow rate was changed at 1 to 1.0 mL / min was measured. A schematic view of the apparatus used for the measurement is shown in FIG. Modification 1 CCPM (manufactured by Tosoh Corporation) is used for pumps 1, 2 and 3 which are supplied to AC (anode chamber), EC (enrichment chamber) and CC (cathode chamber) of the apparatus. The pump 1 sent the sample solution (10 μM CsCl) at 1 mL / min, the pump 2 sent pure water at 0.1 to 1.0 mL / min, and the pump 3 sent pure water at 1.0 mL / min. . The outlet 21 is connected to an injector (20 μL, mounted on ICA-2000, manufactured by Toa) of an ion chromatography system for cation analysis, and the eluate from the outlet 21 is sent to the cation chromatograph without touching the outside air. In the cation chromatograph used for analyzing cations, 2 mM methanesulfonic acid solution was used as an eluent, and TSKgel super IC CR (manufactured by Tosoh Corp.) was used as a separation column. The 2 mM methanesulfonic acid solution was allowed to flow at 0.7 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

In FIG. 41, the modified type 1 type concentrator is used under the condition of a constant current of 40 mA, pure water is supplied to the inlet 1, pure water is supplied to the EC as indicated by the dotted line, and the flow rate of the pump 2 is 0.1, 0,. The ion chromatogram of Cs ion when it changes with 2, 0.5 and 1.0 mL / min is shown.
In the figure, (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, and (d) 0.1 mL / min. From FIG. 41, it was confirmed that the peak of Cs ions was increased and the concentration rate of Cs ions in the concentrate eluted from the outlet 21 was increased by reducing the flow rate of the pump 2.

FIG. 42 shows a variation 1 type concentrator used under the condition of a constant current of 40 mA, supplying pure water to the inlet 1, flowing pure water to the EC as shown by a dotted line, and dividing the flow rate of the pump 1 by the flow rate of the pump 2. The graph of the relationship between the ratio and the concentration rate of Cs ions is shown.
The symbol ■ indicates the concentration ratio obtained from the ratio of the flow rate of the pump 1 divided by the flow rate of the pump 2, and the symbol ● indicates the peak area of the Cs ions in the concentrate eluted from the outlet 21 when the concentrator is not used. It is the concentration rate calculated | required from the ratio divided by the peak area of Cs.

Table 1 shows a variation 1 type concentrator using constant current of 40 mA, supplying pure water to the inlet 1, flowing pure water to the EC as indicated by the dotted line, and dividing the flow rate of the pump 1 by the flow rate of the pump 2. The relationship between the ratio and the concentration ratio obtained from the peak area ratio of Cs ions is shown.

The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak area ratio of Cs ions is the slope of 1.0951, and the correlation coefficient R at that time Was 0.996. From this, the concentration obtained from the flow rate ratio of the pump and the concentration obtained from the measured peak area ratio of Cs ions are almost the same value, and the Cs ions supplied to AC are recovered with a recovery rate of almost 100%. It was a result. It was confirmed that the cation could be easily diluted and concentrated by adjusting the flow rate ratio of the concentrate eluted from the pump 1 and the outlet 21.

13 is used under the condition of a constant current of 40 mA, and when a 100 mM nitric acid solution is supplied as an anion source solution instead of the pure water supplied to the inlet 1, pure water is supplied to the EC inlet 22. The concentration rate of Cs ions in the concentrate eluted from the outlet 21 when the flow rate of the pure water was changed at 0.1 to 1.0 mL / min was measured as indicated by the dotted line. A schematic view of the apparatus used for the measurement is shown in FIG. CCPM (manufactured by Tosoh) is used for the pumps 1, 2, and 3 supplied to the AC, EC, and CC of the apparatus of Modification 1, and the pump 1 sends the sample solution (10 μM CsCl) at 1.0 mL / min. 2 sent pure water at 0.1 to 1.0 mL / min, and pump 3 sent 100 mM nitric acid solution at 0.5 mL / min. A cation chromatograph suppressor is connected between the outlet 21 and the injector of the ion chromatography system for cation analysis (20 μL, mounted on ICA-2000, manufactured by Toa). The ions are removed with a suppressor.
The reason for connecting a cation chromatograph suppressor after the concentrator is that when a nitric acid solution is supplied to the inlet 1, the concentrated liquid eluted from the outlet 21 contains a high concentration of nitrate ions. When ions flow into the cation chromatograph, the elution time of the sample changes greatly, so it was necessary to remove the anions in the concentrate.
The concentrated solution from which the anion has been removed is sent to a cation chromatograph. In the cation chromatograph used for analyzing cations, 2 mM methanesulfonic acid solution was used as an eluent, and TSKgel super IC CR (manufactured by Tosoh Corp.) was used as a separation column. The 2 mM methanesulfonic acid solution was allowed to flow at 0.7 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

In FIG. 43, a modified type 1 type concentrator is used under the condition of a constant current of 40 mA, nitric acid is supplied to the inlet 1 as an anion source solution, pure water is allowed to flow through the EC as indicated by a dotted line, and the flow rate of the pump 2 is set to 0. The ion chromatogram of Cs ion when changing at 1, 0.2, 0.5, and 1.0 mL / min is shown.
In the figure, (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, and (d) 0.1 mL / min.

In FIG. 44, a modified type 1 type concentrator is used under the condition of a constant current of 40 mA, nitric acid is supplied to the inlet 1 as an anion source solution, pure water is allowed to flow through the EC as indicated by a dotted line, and the flow rate of the pump 1 is set to the pump 2 The graph of the relationship between the ratio divided by the flow rate of Cs and the concentration rate of Cs ions is shown. The symbol ■ indicates the concentration ratio obtained from the ratio of the flow rate of the pump 1 divided by the flow rate of the pump 2, and the symbol ● indicates the peak area of the Cs ions in the concentrate eluted from the outlet 21 when the concentrator is not used. It is the concentration rate calculated | required from the ratio divided by the peak area of Cs ion.

Table 2 shows that a modified type 1 type concentrator is used at a constant current of 40 mA, nitric acid is supplied to the inlet 1 as an anion source solution, pure water is allowed to flow through the EC as indicated by the dotted line, and the flow rate of the pump 1 is pump 2 The relationship between the ratio divided by the flow rate of γ and the concentration ratio obtained from the peak area ratio of Cs ions is shown.
The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak area ratio of Cs ions is the slope of 0.9089, and the correlation coefficient R at that time Was 0.999.

41 and FIG. 43, and FIG. 42 and FIG. 44, respectively, show almost the same results. Therefore, in the case of Cs ions, which are alkali metal ions, pure water is supplied to the inlet 1 and acid is supplied. In this case, it was confirmed that there was no difference in the concentration rate of the concentrate eluted from the outlet 21. Although the results are not shown here, similar experimental results were obtained for alkaline earth metal ions. As for transition metal ions, it has been confirmed that a large difference appears between when the acid solution is flowed to the inlet 1 and when pure water is flowed. The transition metal ions are separately described in detail. .

12 is used under the condition of a constant current of 30 mA, and when 100 mM nitric acid solution is supplied as an anion source solution instead of pure water supplied to the inlet 1, pure water is supplied to the EC inlet 21. The concentration rate of Cs ions in the concentrated solution eluted from the outlet 22 when the flow rate of the pure water was changed at 0.1 to 1.0 mL / min was measured as indicated by the solid line. A schematic view of the apparatus used for the measurement is shown in FIG. Modification 1 CCPM (manufactured by Tosoh) is used for the pumps 1, 2, and 3 supplied to the AC, EC, and CC of the type device, the pump 1 sends the sample solution (10 μMCsCl) at 1.0 mL / min, and the pump 2 Sent pure water at 0.1-1.0 mL / min, and pump 3 sent 100 mM nitric acid solution at 0.5 mL / min. A cation chromatograph suppressor is connected between the outlet 22 and the injector of the ion chromatography system for cation analysis (20 μL, mounted on ICA-2000, manufactured by Toa). The ions are removed with a suppressor. The concentrated solution from which the anion has been removed is sent to a cation chromatograph. In the cation chromatograph used for analyzing cations, 2 mM methanesulfonic acid solution was used as an eluent, and TSKgel super IC CR (manufactured by Tosoh Corp.) was used as a separation column. The 2 mM methanesulfonic acid solution was allowed to flow at 0.7 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

In FIG. 45, a variation 1 type concentrator is used under the condition of a constant current of 30 mA, nitric acid is supplied to the inlet 1 as an anion source solution, pure water is allowed to flow through the EC as indicated by a solid line, and the flow rate of the pump 2 is set to 0. The ion chromatogram of Cs ion when changing at 1, 0.2, 0.5, and 1.0 mL / min is shown.
In the figure, (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, and (d) 0.1 mL / min.

In FIG. 46, a modified type 1 type concentrator is used under the condition of a constant current of 30 mA, nitric acid is supplied to the inlet 1 as an anion source solution, pure water is allowed to flow through the EC as indicated by a solid line, and the flow rate of the pump 1 is changed to the pump 2. The graph of the relationship between the ratio divided by the flow rate of Cs and the concentration rate of Cs ions is shown. The symbol ■ indicates the concentration ratio obtained by dividing the flow rate of the pump 1 by the flow rate of the pump 2, and the symbol ● indicates the peak area of Cs ions in the concentrate eluted from the outlet 22 when the concentration device is not used. It is the concentration rate calculated | required from the ratio divided by the peak area of Cs.

Table 3 shows a variation 1 type concentrator using constant current of 30 mA, supplying nitric acid as an anion source solution to the inlet 1, flowing pure water to the EC as shown by a solid line, and the flow rate of the pump 1 to the pump 2. The relationship between the ratio divided by the flow rate of γ and the concentration ratio obtained from the peak area ratio of Cs ions is shown.
The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak area ratio of Cs ions is the slope of 0.9007, and the correlation coefficient R at that time Was 0.998.

43 and 45, and FIGS. 44 and 46 show almost the same results. Therefore, when supplying an acidic solution to the inlet 1, pure water is supplied in either the solid line or the dotted line of EC. Even so, it was confirmed that there was no difference in the concentration rate of the concentrate eluted from the outlet 22.

20 or 21 is used under the condition of a constant current of 30 mA, and when a 100 mM nitric acid solution is supplied as an anion source solution instead of the pure water supplied to the inlet 1, the pure water is converted into EC. Cs ions in the concentrated solution eluted from the outlet 22 or the outlet 21 when flowing as indicated by a solid line by the inlet 21 or a dotted line by the inlet 22 and changing the flow rate of the pure water at 0.1 to 1.0 mL / min. The concentration ratio of was measured. A schematic view of the apparatus used for the measurement is shown in FIG. Modification 3 CCPM (manufactured by Tosoh) is used for pumps 1, 2, and 3 that are supplied to AC, EC, and CC of the type device, and pump 1 sends a sample solution (10 μM CsCl) at 1.0 mL / min. 2 sent pure water at 0.1 to 1.0 mL / min, and pump 3 sent 100 mM nitric acid solution at 0.5 mL / min. A cation chromatograph suppressor is connected between the outlet 22 or 21 and an ion chromatography system injector for cation analysis (20 μL, mounted on ICA-2000, manufactured by Toa) and eluted from the outlet 22 or 21. The anion in the concentrated solution is removed with a suppressor. The concentrated solution from which the anion has been removed is sent to a cation chromatograph. In the cation chromatograph used for analyzing cations, 2 mM methanesulfonic acid solution was used as an eluent, and TSKgel super IC CR (manufactured by Tosoh Corporation) was used as a separation column. The 2 mM methanesulfonic acid solution was allowed to flow at 0.7 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

47, a modified type 3 type concentrator is used under the condition of a constant current of 30 mA, a nitric acid solution is supplied to the inlet 1 as an anion source solution, pure water is allowed to flow through the EC as indicated by a dotted line, and the flow rate of the pump 2 is reduced to 0. The ion chromatogram of Cs ion when changing by 0.1, 0.2, 0.5, and 1.0 mL / min is shown.
In the figure, (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, and (d) 0.1 mL / min.

In FIG. 48, the modified type 3 type concentrator is used under the condition of a constant current of 30 mA, a nitric acid solution is supplied to the inlet 1 as an anion source solution, pure water is allowed to flow through the EC as shown by a solid line, and the flow rate of the pump 2 is set to 0 The ion chromatogram of Cs ion when changing by 0.1, 0.2, 0.5, and 1.0 mL / min is shown.
In the figure, (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, and (d) 0.1 mL / min.

49, a modified type 3 type concentrator is used under the condition of a constant current of 30 mA, a nitric acid solution is supplied to the inlet 1 as an anion source solution, pure water is supplied to the EC as indicated by a dotted line, and the flow rate of the pump 1 is pumped. 2 is a graph showing the relationship between the ratio divided by the flow rate of 2 and the concentration ratio of Cs ions. The symbol ■ indicates the concentration ratio obtained from the ratio of the flow rate of the pump 1 divided by the flow rate of the pump 2, and the symbol ● indicates the peak area of Cs ions in the concentrate eluted from the outlet 21 when the concentrator is not used. It is the concentration rate calculated | required from the ratio divided by the peak area of Cs.

Table 4 shows a variation 3 type concentrator using a constant current of 30 mA, supplying a nitric acid solution as an anion source solution to the inlet 1, flowing pure water to the EC as shown by a dotted line, and pumping the flow rate of the pump 1. 2 shows the relationship between the ratio divided by the flow rate of 2 and the concentration ratio determined from the peak area ratio of Cs ions.
The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak area ratio of Cs ions is the slope of 1.0724, and the correlation coefficient R at that time Was 0.9983.

In FIG. 50, a modified type 3 type concentrator is used under the condition of a constant current of 30 mA, a nitric acid solution is supplied to the inlet 1 as an anion source solution, pure water is supplied to the EC as shown by a solid line, and the flow rate of the pump 1 is pumped. 2 is a graph showing the relationship between the ratio divided by the flow rate of 2 and the concentration ratio of Cs ions. The symbol ■ indicates the concentration ratio obtained from the ratio of the flow rate of the pump 1 divided by the flow rate of the pump 2, and the symbol ● indicates the peak area of the Cs ions in the concentrate eluted from the outlet 22 when the concentrator is not used. It is the concentration rate calculated | required from the ratio divided by the peak area of Cs.

Table 5 shows a variation 3 type concentrator using a constant current of 30 mA, supplying a nitric acid solution as an anion source solution to the inlet 1, flowing pure water to the EC as shown by a solid line, and pumping the flow rate of the pump 1. 2 shows the relationship between the ratio divided by the flow rate of 2 and the concentration ratio determined from the peak area ratio of Cs ions.
The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak area ratio of the Cs ion is a slope of 1.0845, and the correlation coefficient R at that time Was 0.996.

43, 45, 47, 48, 44, 46, 49, and 50 show almost the same results. Therefore, when the acid solution is supplied to the inlet 1, the modified example is obtained. It was confirmed that no difference was observed in the concentration rate of the concentrate eluted from the outlet 21 by using either 1 or Modification 3.

18 is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1, pure water is allowed to flow to the EC inlet 22 as indicated by a dotted line, and the flow rate of the pure water is set to 0. The concentration ratio of Cs ions in the concentrated solution eluted from the outlet 21 when changing at 1 to 1.0 mL / min was measured. A schematic view of the apparatus used for the measurement is shown in FIG. Modified Example 3 CCPM (manufactured by Tosoh) is used for pumps 1, 2, and 3 that are supplied to AC, EC, and CC of the type device, pump 1 sends a sample solution (10 μMCsCl) at 1.0 mL / min, Sent pure water at 0.1-1.0 mL / min, and pump 3 sent pure water at 1.0 mL / min. The outlet 21 is connected to an injector of an ion chromatography system for cation analysis (20 μL, mounted on ICA-2000, manufactured by Toa), and the eluate from the outlet 21 is sent to the cation chromatograph without touching the outside air. The cation chromatograph used for the analysis of the cation was ICA-2000 (manufactured by Toa), a 2 mM methanesulfonic acid solution was used as an eluent, and TSKgel super IC CR (manufactured by Tosoh) was used as a separation column. The 2 mM methanesulfonic acid solution was flowed at 0.7 mL / min, and the separation column was used in a column thermostat set at 40 degrees.

51, a modified type 3 type concentrator is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1, pure water is supplied to the EC as indicated by a dotted line, and the flow rate of the pump 2 is 0.1, 0.00. The ion chromatogram of Cs ion when it changes with 2, 0.5 and 1.0 mL / min is shown.
In the figure, (a) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, and (d) 0.1 mL / min.

In FIG. 52, a modified type 3 concentrator is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1, pure water is supplied to the EC as indicated by a dotted line, and the flow rate of the pump 1 is divided by the flow rate of the pump 2. The graph of the relationship between the ratio and the concentration rate of Cs ions is shown. The symbol ■ indicates the concentration ratio obtained from the ratio of the flow rate of the pump 1 divided by the flow rate of the popump 2, and the symbol ● indicates the peak area of Cs ions in the concentrate eluted from the outlet 21 when the concentrator is not used. It is the concentration rate calculated | required from the ratio divided by the peak area of Cs.

Table 6 shows a variation 3 concentrator using constant current of 30 mA, supplying pure water to the inlet 1, flowing pure water to the EC as indicated by the dotted line, and dividing the flow rate of the pump 1 by the flow rate of the pump 2. The relationship between the ratio and the concentration ratio obtained from the peak area ratio of Cs ions is shown.
The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak area ratio of Cs ions is the slope of 1.246, and the correlation coefficient R at that time Was 0.977.

41 and 51, and FIG. 42 and FIG. 52, almost the same results were obtained. Therefore, when pure water is supplied to the inlet 1, either the first modification or the third modification is used. It was confirmed that there was no difference in the concentration rate of the concentrate eluted from the outlet 21.

A modification 3 type concentrator of FIG. 18 or FIG. 21 is used under the condition of a constant current of 30 mA, pure water is allowed to flow to the EC inlet 22 at 1 mL / min as indicated by a dotted line, and pure water is used to the inlet 1 When MSA (methanesulfonic acid solution) was supplied as the anion source solution, the concentration ratio of divalent Fe ions in the concentrate eluted from the outlet 21 was measured. A schematic view of the apparatus used for the measurement is shown in FIG. Modification 3 CCPM (manufactured by Tosoh) is used for pumps 1, 2 and 3 supplied to AC, EC and CC of the type device, and pump 1 sends a sample solution (10 μM FeCl ₂ ) at 1.0 mL / min. Pump 2 sent pure water at 1.0 mL / min, and pump 3 sent pure water or 100 mM MSA solution at 0.5 mL / min. The outlet 21 is connected to a phenanthrin analysis system capable of measuring divalent Fe ions. Fe ions in the concentrated solution eluted from the outlet 21 are sent to the analysis system without touching the outside air. The detector used for the analysis of Fe ions was UV-8020 (510 nm, manufactured by Tosoh Corporation), and a phenanthroline solution (0.5 mM phenanthroline + 10 mM NH ₂ OH in 100 mM acetate buffer) was used as a carrier solution. The phenanthroline solution was run at 0.5 mL / min.

FIG. 53 shows a modification 3 using a concentrator at 30 mA, flowing pure water to the EC inlet 22 at a rate of 1.0 mL / min as shown by a dotted line, and supplying pure water to the inlet 1 and MSA as an anion source solution. The change of the light absorbency accompanying the increase / decrease in the concentration rate of the divalent Fe ions in the concentrate eluted from the outlet 21 is shown.
In the figure, (a) and (c) are when pure water is flowed to the inlet 1, and (b) and (d) are when MSA solution is flowed to the inlet 1 as an anion source solution.

As shown in FIG. 53, when pure water was supplied to the inlet 1, the absorbance decreased, and when MSA was supplied as an anion source solution, the absorbance increased and was confirmed to be stable. This is because when pure water flows, ions remain adsorbed on the interface between the cation exchanger and anion exchanger in the EC, and divalent Fe ions are not eluted from the outlet 21, and the amount of Fe ions in the concentrate This is because of the decrease. When the acidic solution is supplied, Fe ions at the interface between the cation exchanger and the anion exchanger in the EC are eluted without being adsorbed.

A modification 3 type concentrator of FIG. 20 or FIG. 21 is used under the condition of a constant current of 30 mA, MSA (methane sulfonic acid solution) is supplied to the inlet 1 as an anion source solution, and pure water is connected to the EC inlet 21 by a solid line Or it flowed at 1.0 mL / min to the inlet 22 like a dotted line, and the concentration rate of the bivalent Fe ion in the concentrate eluted from the outlet 22 or the outlet 21 was measured. A schematic view of the apparatus used for the measurement is shown in FIG. CCPM (manufactured by Tosoh) is used for pumps 1, 2, and 3 that supply AC, EC, and CC of type 3 type apparatus, pump 1 sends a sample solution (10 μM FeCl ₂ ) at 1.0 mL / min, Pump 2 sent pure water at 1.0 mL / min, and pump 3 sent 100 mM MSA solution at 0.5 mL / min.
The outlets 21 and 22 are connected to a phenanthrin analysis system capable of measuring divalent Fe ions. Fe ions in the concentrate eluted from the outlets 21 and 22 are sent to the analysis system without touching the outside air. The detector used for the analysis of Fe ions was UV-8020 (510 nm, manufactured by Tosoh Corporation), and a phenanthroline solution (0.5 mM phenanthroline + 10 mM NH 2 OH in 100 mM acetate buffer) was used as a carrier solution. The phenanthroline solution was run at 0.5 mL / min.

In FIG. 54, a modified type 3 type concentrator is used under the condition of a constant current of 30 mA, MSA is supplied to the inlet 1 as an anion source solution, and pure water is supplied to the EC inlet 22 as a solid line or as indicated by a dotted line at the inlet 21. The change of the light absorbency accompanying the increase / decrease in the concentration rate of the bivalent Fe ion in the concentrate eluted from the outlets 21 and 22 is shown by flowing at 0 mL / min.
In the figure, (a) shows the time when pure water is allowed to flow through the EC as indicated by a dotted line, and (b) is the time when pure water is allowed to flow through the EC as indicated by a solid line.
From FIG. 54, (a) and (b) have almost the same absorbance, and the concentrated solution eluted from the outlets 21 and 22 regardless of which direction the pure water is applied to the EC, such as a solid line or a dotted line. It was confirmed that there was no difference in the concentration ratio.

21 is used under the condition of a constant current of 30 mA, MSA (methanesulfonic acid solution) is supplied to the inlet 1 as an anion source solution, and pure water is supplied to the EC inlet 22 as indicated by a dotted line. Measure the recovery rate of divalent Fe ions in the concentrate eluted from the outlet 21 under conditions where the concentration rate of divalent Fe ions in the concentrate eluted from the outlet 21 is 1 at a flow rate of 1 mL / min. did. A schematic view of the apparatus used for the measurement is shown in FIG. Modified Example 3 CCPM (manufactured by Tosoh) is used for pumps 1, 2, and 3 that are supplied to AC, EC, and CC of the type device. Pump 1 sends a sample solution (10 μM FeCl ₂ ) at 1 mL / min, and pump 2 Sent pure water at 1.0 mL / min and pump 3 sent 100 mM MSA solution at 0.5 mL / min.
The outlet 21 is connected to a phenanthrin analysis system capable of measuring divalent Fe ions. Fe ions in the concentrated solution eluted from the outlet 21 are sent to the analysis system without touching the outside air. The detector used for the analysis of Fe ions was UV-8020 (510 nm, manufactured by Tosoh Corporation), and a phenanthroline solution (0.5 mM phenanthroline + 10 mM NH 2 OH in 100 mM acetate buffer) was used as a carrier solution. The phenanthroline solution was run at 0.5 mL / min.

In FIG. 55, the third variation apparatus is used under the condition of a constant current of 30 mA, MSA (methanesulfonic acid solution) is supplied to the inlet 1, pure water is allowed to flow to the EC inlet 22 at 1 mL / min as indicated by the dotted line, The light absorbency accompanying the increase / decrease of the bivalent Fe ion in the concentrate eluting from the exit 21 is shown under the condition that the concentration ratio of the divalent Fe ion in the concentrate eluted from the outlet 21 is 1.
In the figure, (a) is the absorbance of the divalent Fe ion before passing through the modified type 3 type concentrator, and (b) is the divalent Fe ion after passing through the modified type 3 type concentrator under the above-mentioned conditions. Absorbance. From FIG. 55, it can be confirmed that the absorbance values of (a) and (b) are almost the same, and from this, the divalent Fe ions supplied to the AC are 100% in the concentrated solution eluted from the outlet 21. % Recovery was confirmed.

21 is used under the condition of a constant current of 10-40 mA, MSA (methanesulfonic acid solution) is supplied to the inlet 1 as an anion source solution, and pure water is supplied to the EC inlet 22 by a dotted line. The time until the divalent Fe ions supplied to AC were eluted from the outlet 21 was measured. A schematic view of the apparatus used for the measurement is shown in FIG. CCPM (manufactured by Tosoh) is used for pumps 1, 2, and 3 that are supplied to AC, EC, and CC of three types of devices, and pump 1 sends a sample solution (10 μM FeCl ₂ ) at 1 mL / min. Pump 2 sent pure water at 1.0 mL / min, and pump 3 sent 100 mM MSA solution at 0.5 mL / min.
The outlet 21 is connected to a phenanthrin analysis system capable of measuring divalent Fe ions. Fe ions in the concentrated solution eluted from the outlet 21 are sent to the analysis system without touching the outside air. The detector used for the analysis of Fe ions was UV-8020 (510 nm, manufactured by Tosoh Corporation), and a phenanthroline solution (0.5 mM phenanthroline + 10 mM NH 2 OH in 100 mM acetate buffer) was used as a carrier solution. The phenanthroline solution was run at 0.5 mL / min.

In FIG. 56, the modification 3 type concentrator of FIG. 21 is used at 10 to 40 mA, MSA is supplied to the inlet 1, pure water is supplied to the EC inlet 22 at 1 mL / min as indicated by the dotted line, and supplied to AC. Changes in absorbance until divalent Fe ions are eluted from the outlet 21 are shown.
In the figure, (a) 10 mA, (b) 20 mA, (c) 30 mA, (d) 40 mA.
From FIG. 56, it was confirmed that by increasing the current applied between the electrodes, the time until the divalent Fe ions entering AC were eluted from the outlet 21 was confirmed. In addition, it was found that the absorbance after a lapse of a certain time converged around about 60 mV under the current conditions (a) to (d). When concentration is performed using the apparatus of FIG. 40 under the current condition that 100% of the sample ions entering the inlet 3 can be transported to the EC, the concentration rate of the concentrate eluted from the outlet 21 does not depend on the applied current. I was able to confirm.

14 is used under the condition of a constant current of 40 mA, an anion sample solution is supplied to the inlet 1, pure water is supplied to the inlet 3, and pure water is supplied to the EC inlet 21 with a solid line. The concentration rate of F, Br, PO ₄ and SO ₄ ions in the concentrate eluted from the outlet 22 when the flow rate of pure water was changed at 0.1 to 1.0 mL / min was measured. did. A schematic view of the apparatus used for the measurement is shown in FIG. CCPM (manufactured by Tosoh) is used for the pumps 1, 2 and 3 supplied to the AC, EC and CC of the apparatus of the modified example 3, the pump 1 sends pure water at 1.0 mL / min, and the pump 2 is 0 1. Pure water was sent at a rate of 1 to 1.0 mL / min, and pump 3 was sent a sample solution (a mixed solution of ₂ μM NaF, NaBr, Na ₂ SO ₄ and 5 μM Na ₂ HPO ₄ ) at 1.0 mL / min. The outlet 22 is connected to an injector of an ion chromatography system for anion analysis (20 μL, mounted on ICA-2000, manufactured by Toa), and the eluate at the outlet 22 is sent to the anion chromatograph without touching the outside air. The anion chromatograph used for the analysis of the anion used a carbonate solution (12 mM NaHCO ₃ +0.6 mM Na ₂ CO ₃ in H ₂ O) as an eluent and PCI-205 (manufactured by Toa) as a separation column. . The carbonic acid solution was flowed at 1 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

58, a modified type 3 type concentrator is used under the condition of a constant current of 40 mA, pure water is supplied to the inlet 3, pure water is supplied to the EC as shown by a solid line, and the flow rate of the pump 2 is set to 0.01, 0.00. The ion chromatograms of F, Br, PO ₄ and SO ₄ ions when changing at 1, 0.2, 0.5 and 1.0 mL / min are shown. In the figure, 1: F ion, 2: Br ion, 3: PO ₄ ion, 4: SO ₄ ion.
(1) 2 μM NaF, (2) 2 μM NaBr, (3) 5 μM Na ₂ HPO ₄ , (4) 2 μM Na ₂ SO ₄ , (a) 1 mL / min, (b) 0.5 mL / min, (c ) 0.2 mL / min, (d) 0.1 mL / min, (e) 0.01 mL / min.
From FIG. 58, it was confirmed that the peak of each anion increased by decreasing the flow rate of the pump 2, and the concentration rate of each anion in the concentrate eluted from the outlet 22 increased.

59, a modified type 3 type concentrator is used under the condition of a constant current of 40 mA, pure water is supplied to the inlet 3, pure water is supplied to the EC as shown by a solid line, and the flow rate of the pump 3 is divided by the flow rate of the pump 2. The relationship graph of the ratio and the concentration rate of PO ₄ ions is shown. The symbol ■ indicates the concentration ratio obtained from the ratio of the flow rate of the pump 3 divided by the flow rate of the pump 2, and the symbol ● indicates the peak height of PO ₄ ions in the concentrate eluted from the outlet 22 without using a concentrator. It is the concentration ratio obtained from the ratio divided by the peak height of the PO ₄ ion at the time.

Table 7 shows that a modified type 3 concentrator is used at a constant current of 40 mA, pure water is supplied to the inlet 3, pure water is supplied to the EC as shown by a solid line, and the flow rate of the pump 3 is divided by the flow rate of the pump 2. And the concentration ratio obtained from the peak height ratio of PO ₄ ions.
The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1, and the calibration curve when the concentration rate is determined from the peak height ratio of PO ₄ ions is the slope of 1.108. The number R was 0.999. From this, the concentration rate obtained from the flow rate ratio of the pump and the concentration rate obtained from the measured peak height ratio of PO ₄ ions are almost the same value, and PO ₄ supplied to AC with a recovery rate of almost 100%. As a result, ions could be recovered. And it was confirmed that the anion can be easily diluted and concentrated by adjusting the flow rate ratio of the concentrate eluted from the pump 3 and the outlet 22 as in the case of the cation concentration.

22 is used under the condition of a constant current of 160 mA, pure water is supplied to the inlet 3, pure water is supplied to the EC as shown by a solid line, and sample solutions of 9, 18, and 36 mL are supplied to the CC. The concentration rate of F, Br, PO ₄ , and SO ₄ ions in 9 mL of the concentrated solution eluted from the outlet 22 was measured. This example shows an intermittent concentration method. A schematic view of the apparatus used for the measurement is shown in FIG. CCPM (manufactured by Tosoh) is used for the pumps 1, 2, and 3 supplied to the AC, EC, and CC of the apparatus of FIG. 22, and the pump 1 is 1.0 mL / min before energizing between both electrodes of the apparatus. Pure water is sent, and the pump 3 sends a sample solution (mixed solution of ₂ μM NaF, NaBr, Na ₂ SO ₄ and 5 μM Na ₂ HPO ₄ ) at 1.0 to 2.0 mL / min. Supply solution and concentrate. The processing target amount of the sample solution supplied to CC this time is three conditions of 9, 18, and 36 mL. After each sample target amount of sample solution is sent, energization is started between both electrodes, pure water is sent from the pump 2 at 0.1 mL / min, and the pump 3 is switched to pure water at 1.0 mL / min. Then, pure water is continuously sent from the pump 1 and 9 mL of the concentrated liquid is eluted from the EC outlet 22, and the solution is sent to an ion chromatography system injector for anion analysis (20 μL, mounted on ICA-2000, manufactured by Toa). . The anion chromatograph used for the analysis of the anion used a carbonate solution (12 mM NaHCO ₃ +0.6 mM Na ₂ CO ₃ in H ₂ O) as an eluent and PCI-205 (manufactured by Toa) as a separation column. . The carbonic acid solution was flowed at 1 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

FIG. 60 shows a variation 4 type concentrator of FIG. 22 used under the condition of a constant current of 160 mA, supplies pure water to the inlet 3, flows pure water to the EC as shown by a solid line, and passes sample solutions 9 and 18 to CC. The ion chromatograms of F, Br, PO ₄ , and SO ₄ ions in 9 mL of the concentrate eluted from the outlet 22 when 36 mL was supplied are shown. (1) 2 μM NaF, (2) 2 μM NaBr, (3) 5 μM Na ₂ HPO ₄ , (4) 2 μM Na ₂ SO ₄ , (a) 9 mL, (b) 18 mL, (c) 36 mL.
From FIG. 60, it was confirmed that the peak height of each anion in the concentrated solution eluted from the outlet 22 was increased by increasing the amount of the sample solution supplied to the CC.

61, Table 8 shows a sample in which the variation 4 type concentrator in FIG. 22 is used under the condition of a constant current of 160 mA, pure water is supplied to the inlet 3, pure water is supplied to the EC as shown by a solid line, and supplied to the CC. Tables and graphs show the relationship between the ratio of the amount of solution divided by the amount of concentrate eluted from EC and the peak heights of Br ions and PO ₄ ions contained in the EC eluate. The symbol ■ indicates the peak height of Br ions, and the symbol ▲ indicates the peak height of PO4 ions.
The calibration curve for Br ions had a correlation coefficient R of 0.995, and the calibration curve for PO4 ions had a correlation coefficient R of 0.993. From this, it can be seen that linearity is established in the relationship between the concentration ratio obtained from the liquid volume ratio and the peak heights of the measured Br ions and PO ₄ ions.

About the anion concentration in the modification 4 type concentration apparatus shown in FIG. 25, it is confirmed that the anion can be concentrated by supplying a cation source solution to AC.
When the concentrator of FIG. 25 is used under the condition of a constant current of 30 mA and 200 mM sodium carbonate solution is supplied instead of pure water supplied to the inlet 3, pure water is allowed to flow through the EC inlet 22 as shown by a dotted line. The concentration ratio of PO ₄ ions in the concentrate eluted from the outlet 21 when the water flow rate was changed from 0.01 to 1.0 mL / min was measured. A schematic diagram of the apparatus used for the measurement is shown in FIG. The pumps 1, 2, and 3 that supply AC, EC, and CC of the apparatus shown in FIG. 62 use CCPM (manufactured by Tosoh Corporation), and pump 1 sends a sodium carbonate solution (20 mM) at 0.3 mL / min. 2 sent pure water at 0.01 to 1.0 mL / min, and pump 3 sent sample solution (5 μM Na ₂ HPO ₄ ) at 1.0 mL / min. An anion chromatograph suppressor is connected between the outlet 21 and an injector for ion chromatography system for anion analysis (20 μL, mounted on ICA-2000, manufactured by Toa). Cations in the concentrated solution eluted from the outlet 21 Is removed with a suppressor. The concentrated liquid from which the cation has been removed is sent to the anion chromatograph. In the anion chromatograph used for the analysis of anions, a carbonate solution (12 mM NaHCO ₃ +0.6 mM Na ₂ CO ₃ in H ₂ O) was used as an eluent, and PCI-205 (manufactured by Toa) was used as a separation column. . The carbonic acid solution was flowed at 1.0 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

In FIG. 63, a modified type 4 type concentrator of FIG. 25 is used under the condition of a constant current of 30 mA, a cation source solution is supplied to the inlet 3, pure water is allowed to flow through the EC as indicated by a dotted line, and the flow rate of the pump 2 is reduced to 0. The ion chromatogram of PO ₄ ion when changed at 0.01, 0.1, 1.0 mL / min is shown. (A) 1 mL / min, (b) 0.1 mL / min, (c) 0.01 mL / min.

In FIG. 64, the modified type 4 type concentrator of FIG. 25 is used under the condition of a constant current of 30 mA, the cation source solution is supplied to the inlet 3, pure water is allowed to flow through the EC as indicated by the dotted line, and the flow rate of the pump 3 is pumped. 2 is a graph showing the relationship between the ratio divided by the flow rate of 2 and the concentration ratio of PO ₄ ions. The symbol ◆ indicates the concentration ratio obtained by dividing the flow rate of the pump 1 by the flow rate of the pump 2, and the symbol ▲ indicates the peak height of PO ₄ ions in the concentrate eluted from the outlet 21 without using a concentrator. It is the concentration rate obtained from the ratio divided by the peak height of PO ₄ at the time. The calibration curve when the concentration rate is obtained from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is obtained from the peak height ratio is a slope of 1.0244, and the correlation coefficient R at that time is 0. .996.

This result is almost the same as the result of FIGS. 60 and 61 obtained by the concentration of the anion using the concentrator of FIG. 22 as shown in Example 11. Therefore, in the anion, at the inlet 3 It was confirmed that there was no difference in the concentration rate of the concentrate eluted from the outlet 21 when pure water was supplied and when the cation source was supplied.
In addition, the reason for connecting the suppressor for anion chromatography after the concentrator is as follows.
When a salt solution is supplied to the inlet 3, the concentrated solution eluted from the outlet 21 contains a high concentration of cations. When the high concentration of cations flows into the anion chromatograph, the elution time of the sample As a result, the cation in the concentrate must be removed.

Table 9 shows the variation 4 type concentrator of FIG. 25 used under the condition of a constant current of 30 mA, the cation source solution is supplied to the inlet 3, pure water is supplied to the EC as indicated by the dotted line, and the flow rate of the pump 3 is pumped. 2 represents the relationship between the ratio divided by the flow rate of 2 and the concentration of PO ₄ ions.

In the concentration of the cation in which the membrane of the modified example 3 was laminated, an experiment was conducted to confirm that there was no problem whether pure water flowing to the EC flowed to either the solid line or the dotted line. In Example 5, since a concentration experiment in which pure water flowing through the EC is performed along the dotted line in the same manner as in the variation 3 type concentration device shown in FIG. 18 is performed, the variation 3 type concentration device shown in FIG. 19 is used here. It was used to create data when pure water was allowed to flow at the EC inlet 21 as shown by a solid line.
19 is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1, pure water is allowed to flow to the EC inlet 21 as shown by a solid line, and the flow rate of the pure water is 0.1-1 mL / The concentration ratio of Cs ions in the concentrated solution eluted from the outlet 22 when changed in minutes was measured. A schematic view of the apparatus used for the measurement is shown in FIG. CCPM (manufactured by Tosoh) is used for pumps 1, 2, and 3 supplied to AC, EC, and CC of the apparatus of FIG. 19, pump 1 sends a sample solution (10 μMCsCl) at 1 mL / min, and pump 2 is 0 .Pure water was sent at a rate of 1 to 1.0 mL / min, and pump 3 sent pure water at a rate of 0.1 mL / min. The outlet 2 is connected to an injector of an ion chromatography system for cation analysis (20 μL, mounted on ICA-2000, manufactured by Toa), and the eluate from the outlet 2 is sent to the cation chromatograph without touching the outside air. The cation chromatograph used for the analysis of the cation was ICA-2000 (manufactured by Toa), a 2.5 mM methanesulfonic acid solution was used as an eluent, and Shim pack IC-C4 (manufactured by Shimadzu) was used as a separation column. The 2.5 mM methanesulfonic acid solution was flowed at 1 mL / min, and the separation column was used in a column thermostat set at 40 degrees.

In FIG. 66, the concentrator of FIG. 19 is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1, pure water is supplied to the EC as shown by the solid line, and the flow rate of the pump 2 is 0.1, 0.2 , 0.5, and 1.0 mL / min, Cs ion ion chromatograms are shown. (A) 1 mL / min, (b) 0.5 mL / min, (c) 0.2 mL / min, (d) 0.1 mL / min.

Table 10 shows a variation 3 type concentrator of FIG. 19 used under the condition of a constant current of 30 mA, supplying pure water to the inlet 1, flowing pure water to the EC as shown by a solid line, and changing the flow rate of the pump 1 to that of the pump 2. The relationship between the ratio divided by the flow rate and the concentration rate of Cs ions is shown.

In FIG. 67, the concentrator of FIG. 19 is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1, pure water is supplied to the EC as shown by a solid line, and the flow rate of the pump 1 is divided by the flow rate of the pump 2. The relationship graph of ratio and the concentration rate of Cs ion is shown. The symbol ■ indicates the concentration ratio obtained by dividing the flow rate of the pump 1 by the flow rate of the pump 2, and the symbol ◆ indicates the peak height of Cs ions in the concentrate eluted from the outlet 22 without using a concentrator. It is the concentration ratio obtained from the ratio divided by the peak height of Cs at the time. The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak height ratio is the slope of 1.0883, and the correlation coefficient R at that time is 0. .998.

66 and 67, almost the same result is obtained. Therefore, in the type in which the membrane of the modification 3 is laminated, the pure water flowing to the EC is flowed to either the solid line or the dotted line. It was confirmed that there was no difference in the concentration rate.

When the modified type 1 type concentrator in FIG. 10 or 11 is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1 and pure water is allowed to flow to the EC inlet 21 or 22 as shown by a solid line and a dotted line, The concentration ratio of Cs ions in the concentrate eluted from the outlet 22 or 21 was measured. A schematic view of the apparatus used for the measurement is shown in FIG. 10 or 11 CCPM (manufactured by Tosoh) is used for pumps 1, 2, and 3 that supply AC, EC, and CC of the type concentrator, and pump 1 receives a sample solution (10 μMCsCl) at 1 mL / min. The pump 2 sent pure water at 1 mL / min, and the pump 3 sent pure water at 1 mL / min. The outlet 2 is connected to an injector of an ion chromatography system for cation analysis (20 μL, mounted on ICA-2000, manufactured by Toa), and the eluate from the outlet 2 is sent to the cation chromatograph without touching the outside air. The cation chromatograph used for the analysis of the cation was ICA-2000 (manufactured by Toa), a 2.5 mM methanesulfonic acid solution was used as an eluent, and Shim pack IC-C4 (manufactured by Shimadzu) was used as a separation column. The 2.5 mM methanesulfonic acid solution was flowed at 1 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

FIG. 65 shows the Cs ion when the modified type 1 type concentrator of FIG. 10 or 11 is used under the condition of a constant current of 30 mA, pure water is supplied to the inlet 1 and pure water is allowed to flow through the EC as indicated by the dotted line and the solid line. The ion chromatogram of is shown. (A) dotted line, (b) solid line.
From this result, it was found that when the cation was concentrated, the location of the EC outlet was important and could not be provided on the cation exchange resin. On the other hand, when the anion is concentrated, the EC outlet cannot be provided on the anion exchange resin.

In the modified example 5 membrane lamination type concentrator of FIG. 30, an experiment was conducted to confirm that anion concentration was possible.
When the type 5 concentrator of the modified example 5 in FIG. 30 is used under the condition of a constant current of 40 mA and pure water is supplied to the inlet 3, pure water is allowed to flow through the EC inlet 21, and the flow rate of the pure water is 0.01-1 mL. The concentration ratio of PO ₄ ions in the concentrate eluted from the outlet 22 when changed at 1 / min was measured. A schematic view of the apparatus used for the measurement is shown in FIG. 68. CCPM (manufactured by Tosoh) is used for the pumps 1, 2, and 3 supplied to the AC, EC, and CC of the apparatus of FIG. 68, the pump 1 sends pure water at 1 mL / min, and the pump 2 is 0.01 to Pure water was sent at 1.0 mL / min, and pump 3 sent the sample solution (5 μM Na ₂ HPO ₄ ) at 1.0 mL / min. The outlet 2 is connected to an injector of an ion chromatography system for anion analysis (20 μL, mounted on ICA-2000, manufactured by Toa), and the eluate at the outlet 22 is sent to the anion chromatograph without touching the outside air. In the anion chromatograph used for the analysis of anions, a carbonate solution (12 mM NaHCO ₃ +0.6 mM Na ₂ CO ₃ in H ₂ O) was used as an eluent, and PCI-205 (manufactured by Toa) was used as a separation column. . The carbonic acid solution was flowed at 1.0 mL / min, and the separation column was used in a column thermostat set at 40 ° C.

In FIG. 69, the modified type 5 concentrator of FIG. 30 is used under the condition of a constant current of 40 mA, pure water is supplied to the inlet 3, pure water is supplied to EC, and the flow rate of the pump 2 is set to 0.01, 0.1. , Shows an ion chromatogram of PO ₄ ion when changed at 1.0 mL / min. (A) 1 mL / min, (b) 0.1 mL / min, (c) 0.01 mL / min.

Table 11 shows that a modified type 5 type concentrator of FIG. 30 is used under the condition of a constant current of 40 mA, pure water is supplied to the inlet 3, pure water is supplied to EC, and the flow rate of the pump 3 is divided by the flow rate of the pump 2. The relationship between the ratio and the concentration ratio of PO ₄ ions is shown.

In FIG. 70, the modified type 5 type concentrator of FIG. 30 is used under the condition of a constant current of 40 mA, pure water is supplied to the inlet 3, pure water is supplied to EC, and the flow rate of the pump 3 is divided by the flow rate of the pump 2. It shows the relationship graph of the ratio and PO ₄ ions concentration rate. The symbol ◆ indicates the concentration ratio obtained from the ratio of the flow rate of the pump 1 divided by the flow rate of the pump 2, and the symbol ■ indicates the peak height of PO ₄ ions in the concentrate eluted from the outlet 2 without using a concentrator. It is the concentration rate obtained from the ratio divided by the peak height of PO ₄ at the time. The calibration curve when the concentration rate is determined from the pump flow rate ratio is a straight line with a slope of 1. The calibration curve when the concentration rate is determined from the peak height ratio is a slope of 0.84, and the correlation coefficient R at that time is 0. .996.
This result is almost the same as the result of FIGS. 60 and 61 in which the anion concentration is performed using the variation 4 type concentrator of FIG. 22 as shown in Example 11, and therefore, in the apparatus of FIG. It was also confirmed that anions can be concentrated. From this result, the apparatus of FIG. 30 can also be used for cation concentration.

An experiment was conducted to show that the concentration device of the present invention is superior in terms of power efficiency as compared with a device having a structure in which an ion solution is simply sandwiched between electrodes using an ion exchange membrane. In order to confirm that the interface formed by the cation exchange resin and the anion exchange membrane laminate in the EC in the modified 4-type concentrator in FIG. 22 is necessary to operate at a low current, the modified 4 in FIG. The difference in electrical resistance between the electrodes with and without the cation exchange resin packed in the EC of the type concentrator was measured.
When the cation exchange resin was present, the current was 20 mA, the voltage was 100 V, and the electrical resistance was 5 kohm, and when there was no cation exchange resin, the current was 0.3 mA, the voltage was 100 V, and the electrical resistance was 333 kohm. Thus, it has been confirmed that by having the cation exchanger layer in the EC, it is possible to lower the electrical resistance between the electrodes as compared with the structure in which the ion solution simply exists.
Therefore, it shows that the concentrating device of the present invention is excellent in terms of power efficiency.

The ion concentrator of the present invention is used for groundwater, river, lake water quality inspection and acid rain, natural environmental analysis such as radioactive cesium, etc., as well as water quality management of pure water, and other industrial, medical, etc. medicines, agricultural chemicals, food additives, etc. It can be used to improve the sensitivity of analytical instruments by collecting and analyzing trace ions.
Furthermore, it can be used as a reprocessing apparatus utilizing high concentration for reprocessing after use of industrial high-concentration strong acids and bases for industrial cleaning, regeneration, separation and dissolution.

1 Anion exchange resin, indicated by plus ion exchange group fixing group polarity.
2 Cation exchange resin, indicated by minus of ion exchange group fixing group polarity.
3 Anion Exchange Membrane 4 Cation Exchange Membrane 5 Cation Exchange Membrane with Liquid Permeability 6 Anion Exchange Membrane with Liquid Permeability 7 Cation Exchange Membrane with Liquid Permeability 8 Cathode Electrode 9 Anode Electrode

Claims (20)

(A) An internal zone consisting of three chambers partitioned by an ion exchange membrane in the container space between both electrodes, and (a1) one end of the internal zone is a cathode chamber zone, which is in contact with the cathode electrode side and transmits liquid An anion exchange resin is filled in the cathode chamber zone partitioned by an anion exchange membrane on the adjacent central concentration chamber zone side, and installed at the upper part of the cathode chamber zone. (A2) The other end of the inner zone is the anode chamber zone, and is in contact with the anode electrode side to transmit liquid. Cation exchange resin in the anode chamber zone divided by the cation exchange membrane on the side of the adjacent central concentration chamber zone by overlapping the cation exchange membrane imparted with the property and the anion exchange membrane imparted with the liquid permeability filled with, the anode chamber zone The solution or pure water including installation enriching target cations part consists inlet 3 for injecting a cation source solution (a3) central portion in the inner zone is a concentrating chamber zone, said cathode chamber zone side And an anion exchange membrane and in the concentration chamber zone partitioned by the anode chamber zone side and the cation exchange membrane, an anion exchange resin on the cathode side and a cation exchange resin on the anode side, and the center of the concentration chamber zone An inlet 21 for injecting pure water into the anion exchange resin layer side, or an inlet 22 for injecting pure water into the cation exchange resin layer side, which is filled in across the longitudinal section and installed in the upper or lower part of the concentration chamber zone ; Further, a liquid discharge port 22 corresponding to the inlet 21 on the cation exchange resin layer side installed in the lower part or upper part of the concentration chamber zone or a liquid discharge port corresponding to the inlet 22 on the anion exchange resin layer side Consisting of 21 ( B) an external zone consisting of two chambers surrounding each electrode separately
(b1 ) The external zone is an external zone surrounding the cathode electrode, and is partitioned by a cation exchange membrane imparting liquid permeability in contact with the cathode electrode, and water and hydrogen gas installed in a part of the space surrounding the electrode Consisting of outlet 1 for discharging
(b2) ) The external zone is an external zone surrounding the anode electrode, and is partitioned by overlapping a liquid permeable cation exchange membrane in contact with the anode electrode and a liquid permeable anion exchange membrane. Consists of an outlet 3 for discharging water and oxygen gas installed in a part of the space surrounding
(C) An ion concentrator provided with an external power source connecting the electrodes. In the ion concentrator according to claim 1, in place of the concentrating chamber zone according to (a3), which is a part of the constituent elements,
The central part of the inner zone is a concentration chamber zone, and is located on the cathode side in the concentration chamber zone partitioned by the cathode chamber zone side and the anion exchange membrane and by the anode chamber zone side and the cation exchange membrane. An anion exchange resin is filled on the anode side with a cation exchange resin, and a central longitudinal section made of a cation exchange membrane having a liquid permeability is provided in the central longitudinal section of the concentration chamber zone . An inlet 21 for injecting pure water into the anion exchange resin layer side installed at the upper part or the lower part, an inlet 22 for injecting pure water into the cation exchange resin layer side, and a lower part or an upper part of the concentration chamber zone. The other cation exchange resin layer side corresponding to the inlet 21 and the liquid discharge port 22 corresponding to the inlet 21 or the anion exchange resin layer side corresponding to the inlet 22 and the liquid discharge port 21 corresponding to the other components are the same. concentrated Location. In the ion concentrator according to claim 1, in place of the concentrating chamber zone according to (a3), which is a part of the constituent elements,
The central part of the inner zone is a concentration chamber zone, and is located on the cathode side in the concentration chamber zone partitioned by the cathode chamber zone side and the anion exchange membrane and by the anode chamber zone side and the cation exchange membrane. An anion exchange resin is filled on the anode side with a cation exchange resin, and a central longitudinal section made of an anion exchange membrane imparted with liquid permeability is filled in the central longitudinal section of the concentration chamber zone , and the concentration chamber zone An inlet 21 for injecting pure water into the anion exchange resin layer side installed at the upper part or the lower part, an inlet 22 for injecting pure water into the cation exchange resin layer side, and a lower part or an upper part of the concentration chamber zone. The other cation exchange resin layer side corresponding to the inlet 21 and the liquid discharge port 22 corresponding to the inlet 21 or the anion exchange resin layer side corresponding to the inlet 22 and the liquid discharge port 21 corresponding to the other components are the same. concentrated Location. In the ion concentrator according to claim 1, in place of the concentrating chamber zone according to (a3), which is a part of the constituent elements,
The central part of the inner zone is a concentration chamber zone, and is located on the cathode side in the concentration chamber zone partitioned by the cathode chamber zone side and the anion exchange membrane and by the anode chamber zone side and the cation exchange membrane. A cation exchange membrane layer in which an anion exchange resin is laminated on the anode side at a substantially right angle to the central axis of the concentration chamber zone is filled with a central longitudinal section of the concentration chamber zone interposed therebetween, and an upper portion of the concentration chamber zone or An inlet 21 for injecting pure water into the anion exchange resin layer side installed in the lower part, an inlet 22 for injecting pure water into the cation exchange membrane layer side, and a positive part installed in the lower part or upper part of the concentration chamber zone. An ion concentrator having the same other components as the liquid discharge port 22 corresponding to the inlet 21 on the ion exchange membrane layer side or the liquid discharge port 21 corresponding to the inlet 22 on the anion exchange resin layer side. . In the ion concentrator according to claim 1, in place of the concentrating chamber zone according to (a3), which is a part of the constituent elements,
The central part of the inner zone is a concentration chamber zone, and is located on the cathode side in the concentration chamber zone partitioned by the cathode chamber zone side and the anion exchange membrane and by the anode chamber zone side and the cation exchange membrane. An anion exchange membrane layer laminated at a substantially right angle to the central axis of the concentration chamber zone is filled with a cation exchange resin on the anode side across the central longitudinal section of the concentration chamber zone , and the upper portion of the concentration chamber zone or An inlet 21 for injecting pure water into the anion exchange membrane layer side installed in the lower part, an inlet 22 for injecting pure water into the cation exchange resin layer side, and a positive part installed in the lower or upper part of the concentration chamber zone. An ion concentrating device having the same other constituent elements as the liquid discharge port 22 corresponding to the inlet 21 on the ion exchange resin layer side or the liquid discharge port 21 corresponding to the inlet 22 on the anion exchange membrane layer side. . In the ion concentrator according to claim 1, in place of the concentrating chamber zone according to (a3), which is a part of the constituent elements,
The central part of the inner zone is a concentration chamber zone, and is located on the cathode side in the concentration chamber zone partitioned by the cathode chamber zone side and the anion exchange membrane and by the anode chamber zone side and the cation exchange membrane. An anion exchange membrane layer laminated at a substantially right angle to the central axis of the concentration chamber zone, and a cation exchange membrane layer laminated at a substantially right angle to the central axis of the concentration chamber zone on the anode side, the central longitudinal section of the concentration chamber zone An inlet 21 for injecting pure water into the anion exchange membrane layer side, or an inlet 22 for injecting pure water into the cation exchange membrane layer side, which is filled across the surface and installed at the upper or lower part of the concentration chamber zone ; Further, a liquid discharge port 22 corresponding to the inlet 21 on the cation exchange membrane layer side installed in the lower or upper part of the concentration chamber zone or a liquid discharge port 21 corresponding to the inlet 22 on the anion exchange membrane layer side. Other configuration requirements as First and ion concentrator. A current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1, pure water is injected from the inlet 3, pure water is injected from the inlet 21, and concentrated ions are included from the outlet 22. 5. Anion continuous ion concentration using the ion concentrating device according to claim 1, wherein the solution containing concentrated ions is discharged from the outlet 22 without discharging the solution or injecting pure water into the inlet 21. Method. A current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1, pure water is injected from the inlet 3, pure water is injected from the inlet 21, and concentrated ions are included from the outlet 22. The above-mentioned claim, wherein the solution is discharged or injected from the inlet 22 to discharge the solution containing concentrated ions from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or outlet 22 without injecting the pure water. An anion continuous ion concentration method using the ion concentrator according to any one of 5 and 6. A current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1, a cation source solution is injected from the inlet 3, and pure water is injected from the inlet 21, and concentrated ions are injected from the outlet 22. The solution containing concentrated ions is discharged, or the solution containing concentrated ions is discharged from the inlet 22 and discharged from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. An anion continuous ion concentration method using the ion concentrator according to any one of claims 1 to 6. A current is passed between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3, pure water is injected from the inlet 1, pure water is injected from the inlet 22, and concentrated ions are included from the outlet 21. The positive ion using the ion concentrator according to any one of claims 1, 2, 3, and 5 wherein the solution containing concentrated ions is discharged from the outlet 21 without discharging the solution or injecting pure water into the inlet 22. Ion continuous ion concentration method. An electric current is passed between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3, pure water is injected from the inlet 1, pure water is injected from the inlet 21, and concentrated ions are included from the outlet 22. The above-mentioned claim, wherein the solution is discharged or injected from the inlet 22 to discharge the solution containing concentrated ions from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or outlet 22 without injecting the pure water. A cation continuous ion concentration method using the ion concentrator according to any one of 4 and 6. A current is passed between the electrodes, a solution containing cations as ions to be concentrated is injected from the inlet 3, an anion source solution is injected from the inlet 1, pure water is injected from the inlet 21, and concentrated ions are injected from the outlet 22. The solution containing concentrated ions is discharged, or the solution containing concentrated ions is discharged from the inlet 22 and discharged from the outlet 21, or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. A cation continuous ion concentration method using the ion concentrator according to claim 1. In a state where no current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1 to accumulate a processing target amount, pure water is injected from the inlet 3 to fill the anode chamber zone, and While supplying a current between the electrodes and continuously injecting pure water from the inlets 1 and 3, pure water is continuously injected from the inlet 21 and a solution containing concentrated ions is discharged from the outlet 22 or pure water. A method of intermittent anion ion concentration using the ion concentrator according to any one of claims 1 to 4, wherein the solution containing concentrated ions is discharged from the outlet 22 without injecting into the inlet 21. In a state where no current is passed between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1 to accumulate a processing target amount, pure water is injected from the inlet 3 to fill the anode chamber zone, and While flowing a current between the electrodes and continuously injecting pure water from the inlets 1 and 3, pure water is injected from the inlet 21 and a solution containing concentrated ions is discharged from the outlet 22, or injected from the inlet 22. 7. The ion concentration according to claim 5, wherein the solution containing concentrated ions is discharged from the outlet 21 or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. Anion intermittent ion concentration method using an apparatus. In a state where no current flows between the electrodes, a solution containing anions, which are ions to be concentrated, is injected from the inlet 1 to accumulate a processing target amount, and a cation source solution is injected from the inlet 3 to fill the anode chamber zone. Then, a current is passed between the electrodes, pure water is continuously injected from the inlet 1, a cation source solution is continuously injected from the inlet 3, pure water is continuously injected from the inlet 21, and concentrated ions are contained from the outlet 22. The solution is discharged or continuously injected from the inlet 22 and the solution containing concentrated ions is discharged from the outlet 21, or the concentrated ions are discharged from the outlet 21 or the outlet 22 without injecting the pure water from the inlet 21 or 22. An anion intermittent ion concentration method using the ion concentrator according to any one of claims 1 to 6 which discharges the solution which contains it. In a state in which no current is passed between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3 to accumulate a processing target amount, pure water is injected from the inlet 1 to fill the cathode chamber zone, and then While supplying a current between the electrodes and continuously injecting pure water from the inlets 1 and 3, pure water is continuously injected from the inlet 22 and a solution containing concentrated ions is discharged from the outlet 21 or pure water. A method for intermittent cation ion concentration using the ion concentrator according to claim 1, wherein the solution containing concentrated ions is discharged from the outlet 21 without injecting into the inlet 22. In a state in which no current is passed between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3 to accumulate a processing target amount, pure water is injected from the inlet 1 to fill the cathode chamber zone, and then While flowing a current between the electrodes and continuously injecting pure water from the inlets 1 and 3, pure water is injected from the inlet 21 and a solution containing concentrated ions is discharged from the outlet 22, or injected from the inlet 22. 7. The ion concentration according to claim 4, wherein the solution containing concentrated ions is discharged from the outlet 21 or the solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. Cation intermittent ion concentration method using an apparatus. In a state where no current is flowing between the electrodes, a solution containing cations that are ions to be concentrated is injected from the inlet 3 to accumulate a processing target amount, and injected from the anion source solution inlet 1 to fill the cathode chamber zone. Next, an electric current is passed between the electrodes, pure water is continuously injected from the inlet 3, an anion source solution is continuously injected from the inlet 1, pure water is continuously injected from the inlet 21, and a solution containing concentrated ions from the outlet 22. Or the solution containing concentrated ions is discharged from the outlet 21 continuously or the concentrated water is contained from the outlet 21 or the outlet 22 without injecting the pure water from the inlet 21 or 22. A cation intermittent ion concentration method using the ion concentrator according to any one of claims 1 to 6, wherein the solution is discharged. An electric current is passed between the electrodes, a solution containing transition metal ions, which are ions to be concentrated, is injected from the inlet 3, and a strong acid is injected from the inlet 1, or boric acid and carbonic acid are not contained, and formic acid and acetic acid are added. Injecting the weak acid contained therein and injecting pure water from the inlet 21 and discharging the solution containing concentrated ions from the outlet 22, or discharging from the inlet 22 and discharging the solution containing concentrated ions from the outlet 21; The transition metal ion continuous ion concentration method using the ion concentration apparatus according to any one of claims 1 to 6, wherein a solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. In a state where no current is passed between the electrodes, a solution containing transition metal ions, which are ions to be concentrated, is injected from the inlet 3, a strong acid is injected from the inlet 1, or no boric acid and carbonic acid are contained, and A weak acid containing formic acid and acetic acid is injected, and then an electric current is passed between the electrodes, and pure water is injected from the inlet 21 and a solution containing concentrated ions is discharged from the outlet 22 or injected from the inlet 22 and discharged. The ion concentrator according to any one of claims 1 to 6, wherein a solution containing concentrated ions is discharged from the outlet 21 or a solution containing concentrated ions is discharged from the outlet 21 or the outlet 22 without injecting the pure water. Transition metal ion intermittent ion concentration method to be used.