JPH01254211A - Substance separator - Google Patents

Abstract

PURPOSE:To obtain a miniaturized deionization equipment by spirally winding a cathode and an anode made of a conductive high molecular layer and interposing a soln. incorporating ions between the electrodes. CONSTITUTION:A substance separator 1 is constituted by interposing a spacer 4 between a cathode 2 and an anode 3 and spirally winding both electrodes 2, 3 and holding them and interposing feed water 10 incorporating ions between both electrodes. The cathode 2 has cation trapping capacity and nickel is used as a conductive supporting material and porous conductive high molecular layers 7 are formed and held to both sides of the supporting material. As the anode, the conductive high molecular layer having anion trapping capacity is utilized. Therefore by such a way, since both electrodes are parallel held and spirally wound and liquid to be treated is allowed to flow between them, pressure drop is made small and deionization can be efficiently performed.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a substance separation device that efficiently separates charged substances (ions) electrochemically from a solution containing them.

(b) Prior Art Conventionally, various methods have been proposed for separating substances.

For example, to separate charged substances, extraction methods, ion exchange methods,
Electrodialysis methods, membrane separation methods, etc. are employed, and if the method is not limited to charged substances, there are adsorption methods and absorption methods using activated carbon, chromatography, etc., and thermal diffusion methods are also included.

This separation of substances includes adsorption, absorption and extraction using pressure differences represented by membranes, differences in concentration and absorption capacity, electrodialysis using potential differences, and thermal diffusion methods using special temperature differences. can be mentioned.

As a method for separating charged substances, methods using ion exchange resins are often used, but there is a limit to the diffusion and movement speed of charged substances in the ion exchange resin, and in order to increase the throughput, ion exchange resins are often used. It is necessary to increase the amount of exchange resin, and as a result, the processing equipment inevitably becomes larger. In particular, in this case, a regeneration system is required, which not only complicates the overall apparatus but also complicates the operation.

In addition, this method requires a large amount of acid or alkali to regenerate the ion exchange resin, making the regeneration process cumbersome. In addition, these acids and alkalis are generally poisonous and deleterious substances and must be handled with great care. In addition, if the ionic substituents in the ion exchange resin strongly adsorb ions in the solution, regeneration becomes difficult and problems such as a shortened life cycle of the ion exchange resin occur. .

(c) Problems to be Solved by the Invention In methods for separating charged substances such as ion exchange and electrodialysis, the separation speed can be infinitely increased due to the concentration drop at the separation surface, the movement of the charged substance, and the limit of the diffusion rate. In addition, ion exchange is packed with particulate matter, and electrodialysis has to be planar due to voltage application. Therefore, in order to increase throughput, it is necessary to increase the flow rate by increasing the separation surface. There are some changes in the system, an increase in the size of the vcrll, and the complexity of the system, including the regeneration process.

The present invention involves winding and holding negative and positive image electrodes in parallel with a predetermined interval between the negative and anode electrodes, and interposing a solution containing ions between the electrodes. By applying a voltage of
The object of the present invention is to provide a substance separation device that can simultaneously and efficiently release anions and cations from each electrode and regenerate the 'I!l electrode.

(e) Means for solving the ff problem In order to solve the above problems, the inventors have attempted to solve the above problem. ! As a result of repeated studies, in order to simplify the regeneration process and simplify the operability, we developed an electrochemical deionization system disclosed in JP-A-62-258741 and JP-A-62-264876. It is preferable to carry out deionization and regeneration using the potential difference between two electrodes, and moreover, with the picture electrodes made of conductive polymer layers held in parallel with a predetermined distance apart. Deionization can be carried out effectively by winding and holding the picture electrode in a spiral shape and applying a predetermined potential while interposing a solution containing ions between the electrodes.In addition, the device can be made more compact. By reversing the polarity of the voltage applied between both electrodes in the regenerating solution, deionization from the picture electrode can be done extremely easily and efficiently, and the electrode can be regenerated. This discovery led to the completion of the present invention.

The present invention will be explained in detail below.

The material separation yIcW1 of the present invention is achieved by interposing a solution containing ions between the anode and anode Ti electrodes and applying a predetermined potential between the two electrodes, thereby increasing the cation trapping ability on the cathode side and the anion extraction ability on the anode side. It uses a conductive polymer layer that exhibits stimulatory properties.

The conductive polymer layer used in the present invention is not particularly limited as long as it is made of a conductive polymer, and specific examples thereof include pyrrole, its nitrogen,
A derivative having a substituent at the 3rd and/or 4th position, 7ran,
Electrolytic oxidation polymerization or chemistry of heterocyclic compound monomers such as derivatives having substituents at the 3- and/or 4-position, and aromatic compound monomers such as 7-niline, phenol, 1,000-ofenol, and their derivatives. Examples include polymers produced by oxidative polymerization. In other words, examples include polypyrrole, polythiophene, polyaniline, poly7rane, etc. Other conductive polymers include polyacetylene, poly(
1,6-hebutadiyne), polyphenylene, polyphenylene, polypa, rough phenylene, polynaphthalene, poly(
(para-phenylene sulfide), poly(meta-722lene sulfite), poly(para-722lene oxide), and the like.

These conductive polymers can be used without any particular manufacturing method.

More specifically, a layer of a p-type conductive polymer having a cation-trapping ability is used as a conductive polymer having a cation-trapping ability through a reduction reaction, and the conductive polymer does not easily diffuse through the conductive polymer. Examples include those formed by doping with a polyanion that cannot be obtained.

Specific examples of such polyanions include polyvinyl sulfuric acid, polyvinyl sulfonic acid, polystyrene sulfonic acid, sulfonated styrene-butanoene copolymer, polyallylsulfonic acid, polymethallylsulfonic acid, poly-2
-acrylic 7mido-2-methylpropanesulfonic acid and the like.

That is, a conductive polymer doped with a polyanion has a cation-trapping ability due to its reduction.

On the other hand, conductive polymers with anion-trapping ability are doped with low-molecular-weight anions such as perchlorate ions, chloride ions, borohydrofluoride ions, sulfate ions, and alkylsulfonate ions through oxidation reactions. It is itself a cationic polymer. Such conductive polymers are also electrochemically redoxed in a plastic manner. In other words, it has a redox function and functions as a redox polymer.

When such a conductive polymer is reduced in a solution, it releases anions and becomes neutral, and upon reoxidation, it captures the anions again as a dopant.

That is, a p-type thick conductive organic polymer doped with a low molecular weight anion has an anion fall promoting ability.

In other words, a conductive polymer with anion-trapping ability refers to a conductive polymer doped with a low molecular weight anion that can easily diffuse through the conductive polymer. Specific examples of such low molecular weight anions include, for example. , inorganic and organic anions such as the above-mentioned chlorine ion, borohydrofuride ion, and ethyl sulfate ion.

In this way, as is already known, a conductive polymer consisting of a composite of a conductive polymer and an anion (as a dopane) can be prepared by forming a conductive polymer in a solution of a monomer capable of forming a conductive polymer. molecule! It can be obtained by dissolving an anion or a polyanion and oxidatively polymerizing the above monomer in this solution (for example, J, Chew, Soc, Ch.
ew, Common, 1979.635, and Japanese Patent Application Laid-Open No. 1988-98165).

This oxidative polymerization method is not particularly limited,
It is appropriately selected from electrolytic oxidative polymerization, chemical oxidative polymerization, and photooxidative polymerization.

In this case, the p-type conductive polymer with anion-trapping ability is
In order to capture a large amount of anions in the solution, the conductive polymer is partially reduced in advance, and some of the low molecular weight anions electrostatically bound to the conductive polymer are dedoped. In this case, generally conductive polymers transition from conductivity to insulating properties by dedoping, so in the present invention, the above partial dedoping amount is determined depending on the conductive polymer used and in the solution. Although it is appropriately selected depending on the type of ion to be targeted, it is usually preferable that the conductive polymer has a conductivity of 10-'S/am or more.

The conductive polymer is reduced in order to perform this dedoping, but the reduction method is not limited in any way (either electrolytic reduction or chemical reduction can be used, but the amount of dedoping can be easily reduced). It is preferable to use electrolytic reduction which can be controlled in a controlled manner.

Then, in the substance separation device of the present invention, the above-mentioned two poles are wound in a helical shape and held in a state where the two poles are held in parallel with a predetermined interval between them. 1.7. It has the greatest characteristics.

That is, the picture electrodes made of conductive polymer layers are held parallel to each other with a predetermined spacing between them, and the two electrodes are wound and held in a spiral shape, and a solution containing ions is interposed between the electrodes. However, by applying a predetermined voltage, the device can be made smaller and deionization can be performed effectively.
Thereafter, by reversing the polarity of the voltage applied between the two electrodes in the regenerating solution, the picture electrode can be deionized very easily and efficiently, and the electrode can be regenerated.

In addition, in order to wind and hold both poles in a spiral shape, for example, the poles are wound around a porous hollow body, and the base r of the negative and anode is
What is necessary is to configure the solution outflow part in part a to open into the porous hollow body.

Since both electrodes are held in parallel and wound in a helical shape in this way, an increase in pressure loss is suppressed even when the flow rate of the processing liquid is increased, and a decrease in substance concentration on the reaction surface is also suppressed. Further, unlike these ordinary spiral membrane modules, since a permeate flow path is not required, the structure can be simplified, and the volumetric efficiency can be improved by forming the module in a helical shape. Furthermore, deionization is performed while the processing liquid flows along the electrode between the negative and Fi electrodes, which is extremely efficient.

In the substance separation device of the present invention, by using both electrodes formed by holding a conductive polymer layer on a conductive support, leads from the electrodes can be easily made, and the conductive polymer layer is Molecules can be held securely, and the strength of the entire electrode can be significantly improved. As a result, the electrode can be easily wound in a spiral shape.

Examples of the conductive support include metals such as platinum, gold, stainless steel, and nickel, or conductive gold R oxides such as ink oxide, tin oxide, and ITO, or carbon,
Examples include Graph 7 Phyto.

In the material separation device of the present invention, by using a porous conductive polymer layer, its surface area is significantly increased, which improves the efficiency of deionizing a solution containing ions and improves the efficiency of deionizing a solution containing ions by reversing the electrodes. can be regenerated quickly and easily.

In order to form a porous electrode in this way, it is sufficient to make the conductive support porous and hold a conductive polymer layer on the surface of the conductive support, thereby increasing the surface area, that is, the reaction surface. This allows deionization and regeneration to be achieved more efficiently.

In this case, the porosity can be arbitrarily selected depending on the application, but from the viewpoint of increasing the reaction area and strength of the electrode,
It is desirable that the area be in the range of 10 to 80% of the total area of each electrode.

In the present invention, the method for holding the conductive polymer on the conductive support is not particularly limited, but for example, if the conductive polymer itself is soluble, it may be coated after dissolving to make it porous. If it is insoluble, a method such as adding a filler such as a binder and molding it is preferably adopted.

・In the substance separation device of the present invention, a conductive polymer layer with cation trapping ability and 6 conductive polymer layers with anion trapping ability are used, and a solution containing ions is interposed between these two electrodes. While applying a potential load to the negative and positive electrodes, yIcr! 1 and applying a voltage between these electrodes,
The ions in the solution are reversibly captured and released by the electrode, and in this way the ions are processed and the electrode is electrochemically regenerated.

That is, according to the substance separation device of the present invention, a solution containing ions is interposed between both electrodes, a conductive polymer layer having a cation trapping ability is used as a cathode, and a conductive polymer layer having an anion trapping ability is used as a cathode. By applying a voltage that acts as an anode to oxidize this conductive polymer layer with anion extraction ability, and reducing the conductive polymer layer with cation trapping ability, the anions in the solution become an anode. On the other hand, cations in solution are trapped at the cathode.

The load voltage applied between the negative and positive electrodes is appropriately selected depending on the redox potential of each conductive polymer layer on the electrode, but is usually rlLv.

Next, in the substance separation device of the present invention, the polarity of the applied voltage is reversed, and the anion-trapping electrode is used as the cathode, while the cation-trapping electrode is used as the anode, so that the conductive polymer layer with anion-trapping ability is formed. By reducing and oxidizing the conductive polymer layer with cation trapping ability, the anions and cations trapped by each electrode are released into the solution, and in this way, each electrode Regenerated electrochemically.

The medium of the ion-containing solution used in the present invention may be water, an organic solvent, or a mixture thereof, and the medium is not limited in any way.

(e) Function The substance separation device of the present invention has the above-mentioned configuration and uses a conductive polymer layer. 4 [While holding I in parallel with a predetermined interval, wind the two poles in a spiral shape,
This method applies a predetermined potential while interposing a solution containing ions between the electrodes, making it possible to miniaturize the device and improve volumetric efficiency, while also being effective. 1) Deionization can be performed. After that, by reversing the polarity of the voltage applied between the two electrodes in the regenerating solution, deionization from the picture electrode can be done extremely easily and efficiently, and 7. The polarity can be regenerated. It has an effect.

Also, hold the picture electrodes in parallel in this way, wind them in a helical shape, and apply the Fl! Because it is something that drains liquid, it is a place J! l! Even if the flow rate of the solution is increased, the increase in pressure loss is suppressed, and the decrease in the concentration of substance '11 at the reaction surface is also suppressed.Furthermore, the processing solution is deionized while flowing between the anode and the anode along the electrode. The deionization efficiency is extremely high.

(f) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

FIG. 1 is a perspective view showing the substance separation device of the present invention, and FIG. 2 is an enlarged cross-sectional view of the portion marked A.

In FIG. 1, (1) is a material separation device, and the material separation device (1) separates cathode/anode (2), (3) and connecting electrodes (2), (3) at a predetermined interval ( A spacer (4) which separates and holds the image electrodes (2) and (3) in parallel.
It consists of potential application terminals (5a) and (5b) for electrically connecting to an external power source (not shown).

A spacer (4) is provided between the picture electrodes (2) and (3).
), thereby making these two poles (2) and (3)
The picture electrodes (2) and (3
) is wound in a spiral shape and held, and the picture electrodes (2) and (3
) is configured such that supply water (10) containing ions can be interposed and circulated between the two.

In this case, the cathode (2) has a cation fall-promoting ability, has a conductive support (6a) made of nickel, and has polyvinyl sulfate doped on both sides of the support (6a).
A porous conductive polymer N (7) made of 2g of polypyrrole was formed and held thereon, while the anode (3) had an anion trapping ability and nickel was used as a conductive support (6b).
0.2 g of a porous conductive polymer layer (8) made of reduced polypyrrole was formed and held on both sides of the support (61+).

In Figure 1, (9) has demineralized water (20) in the middle.
A support pipe with an inlet (not shown).

With this configuration, while supplying water (10) containing ions into the substance separation device (1), in other words, yin and yang ff
1 (2'I, (3) 1 ml: [IF water (10) total intervention,
By applying a predetermined potential between the negative and positive electrodes 71 (2) and (3) while circulating, cations are captured on the cathode (2) side, while anions are captured on the anode (3) side. Ru.

In this case, the above feed water (10) is 3,3X10-"
Using 55 ml of a mol/1 potassium chloride aqueous solution, when this feed water (10) is circulated and energized for 90 minutes at a current density of 0.22 ml to /c-2, the concentration of potassium chloride becomes 2,0XIO-comoi/c-2. Desalinated water reduced to 1 (
20) was obtained, and deionization was confirmed.

In addition, when the above solution is poured, a predetermined reverse voltage is applied between both electrodes, and electricity is passed while circulating for 90 minutes at a current density of 0.22 wA/c, the concentration of potassium chloride becomes 3.2 x 10
- It was confirmed that it was possible to reproduce it by increasing the level to 01/1.

(g) Effects of the invention In the substance ayl device of the present invention, a conductive polymer layer that exhibits cation trapping ability on the cathode side and anion trapping ability on the anode side is used, and ions are contained between the negative and anode electrodes. A device that separates charged substances by interposing a solution and applying a predetermined voltage between the negative and positive electrodes. Yuin・
By winding and holding the anode in a helical shape, the device can be made smaller and the volumetric efficiency can be improved, and moreover, it has the effect of effectively deionizing the device.

In addition, since the picture electrodes are held in parallel and wound in a spiral shape, and the processing solution is flowed between them, an increase in pressure loss is suppressed even when the flow rate of the processing solution is increased, and the reaction This also suppresses a decrease in substance concentration on the surface, and furthermore, since deionization is performed while the processing liquid flows between the two electrodes and along the electrodes, the deionization efficiency is extremely improved.

Furthermore, as a result of these, the separation process of charged substances is simplified and the regeneration operation is also simplified, so the entire separation system becomes energy-saving and process-saving, which has the effect of reducing separation costs.

In the substance separation device of the present invention, by applying a predetermined reverse voltage between the two electrodes after capturing ions, the polarity of the voltage applied between the two electrodes is reversed in the regenerating solution after deionization. This has the effect that the electrode can be deionized very easily and efficiently, allowing the electrode to be regenerated.

In the substance separation device of the present invention, by using negative and positive electrodes formed by holding a conductive polymer layer on a conductive support, leads from the electrodes can be easily made, and the conductive The polymer can be held securely, and the strength of the entire electrode can be significantly improved.As a result, the electrode can be easily wound in a spiral shape, reducing manufacturing costs. It has an effect.

In the substance M separation device of the present invention, by using a porous conductive polymer layer, the surface area is significantly increased, that is, the reaction surface is increased, and a solution containing ions is removed. This has the effect of improving deionization efficiency and regenerating the electrode by reversing the electrode.

[Brief explanation of the drawing]

No. ill is a perspective view showing the substance separation device of the present invention, FA2
The figure is an enlarged cross-sectional view of the part marked A. (1)...Matter jflIgltr! ! , (2)・1
131, (3)・[, (4)...Spacer, (6m
) = (6b)... conductive support, (7), (8').
... Porous conductive polymer layer, (9) ... Support pipe,
(10)...Supplied water, (20)...Demineralized water, (1)
···interval.

Claims (4)

[Claims] (1) Using a conductive polymer layer that exhibits cation-trapping ability on the cathode side and anion-trapping ability on the anode side, a solution containing ions is interposed between the negative and anode electrodes, and a predetermined amount of A device for separating charged substances by applying a voltage of A substance separation device featuring: (2) The substance separation device according to claim 1, wherein after capturing the ions, both electrodes are regenerated by applying a predetermined reverse voltage between the two electrodes. (3) The substance separation device according to claim 1 or 2, wherein the negative and positive electrodes are formed by holding a conductive polymer layer on a conductive support. (4) The substance separation device according to any one of claims 1 to 3, wherein the conductive polymer layer is porous.