JPH05138172A - Electrolytic water purifier - Google Patents

Abstract

PURPOSE:To remove butter ion 111 water being obstructive for pH variation by a ion exchange resin and to easily regenerate efficiency of an ion exchange resin. CONSTITUTION:This purifier anod water paths 15A and 16A connecting with openings of an anode chamber 10A, a cation exchange resin 17A and 18A filled in the anode water paths 15A and 16A, an anode inflow water paths 20A and 21A connected with anode water paths 15A and 16A, and anode outflow water paths 22A and 23A connected with each anode water paths 15A and 16A and valve devices V1, V3, V5 and V7 provided at the anode inflow water paths 20A and 21A and anode outflow water paths 22A and 23A. And a course of inflowing from the anode inflow path 20A through the anode water path 15A to the anode chamber 10A and outflowing followed from the anode water path 16A to the anode outflow water path 23A is mutually exchangable with a course of inflowing from the anode inflow water path 21A through the anode water path 16A to the anode chamber 10A and outflowing followed from the anode water path 15A to the anode outflow water path 22A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic water purifier for obtaining acidic ionized water and alkaline ionized water useful for health and medical purposes.

[0002]

2. Description of the Related Art Conventionally, by electrolyzing water, its pH is changed, that is, water is oxidized on the anode side to generate acidic ionized water, and water is reduced on the cathode side to generate alkaline ionized water. Electrolytic water purifiers are known. However, in the case of obtaining acidic ionized water, for example, if carbonate ions or hydrogen carbonate ions are present in the water to be electrolyzed, there is a problem that the electrolytic efficiency of the conventional electrolytic water purifier decreases. The electrolysis efficiency is the ratio (%) of the actually measured ion generation amount to the theoretical ion generation amount obtained from the flow rate of water and the current value based on Faraday's law.

That is, in H ₂ CO ₃ carbonate, unionized molecules and ions generated by dissociation are in the next dissociation (ionization) equilibrium state in an aqueous solution. H ₂ CO ₃ ⇔ 2H ⁺ + CO ₃ ² -... Also, the equilibrium constant (ionization constant) K at this time is K = [H ⁺ ] ² [CO ₃ ^2- ] / [H ₂ CO ₃ ]. ...

[0004] To this solution, the addition of sodium bicarbonate to completely dissociated, sodium bicarbonate NaHCO ₃ Since the dissociation as ^{_{NaHCO 3 → Na + + H +}} + CO 3 2- ···, CO 3 2 ^- increases the concentration of ions [CO ₃ ^2-] is the concentration of H ₂ CO ₃ equilibrium of the above formula tilted left [H
₂ CO ₃ ] also rises, the equilibrium constant K becomes a constant value, and dissociation is suppressed. Therefore, [H ₂ CO ₃ ] becomes equal to the initial carbon dioxide concentration C _1, and [CO ₃ ²⁻ ] becomes equal to the concentration C ₂ of the added sodium hydrogen carbonate NaHCO ₃ , so that the hydrogen ion concentration [H ⁺ ] ²
Becomes [H ⁺ ] ² = K · C ₁ / C ₂ ... That is, when a common ion (CO ₃ ^{2− in the} above case) is present in the aqueous solution, the concentration of hydrogen ion H ⁺ depends on the concentration of the salt that was initially in the dissociation equilibrium state and that of the added salt. Ratio. Even if a small amount of acid (hydrogen ion H ⁺ ) is added to such an aqueous solution, the pH of the aqueous solution does not change because the H ⁺ ions are combined with CO ₃ ²⁻ present in a large amount in the aqueous solution. Moreover, alkali (hydroxide ion OH ^-) is added, and the OH ^- ions is combine with H ⁺ ions, H
₂ CO ₃ dissociates and releases H ⁺ , so the pH does not change.

[0005]

Therefore, in the conventional electrolytic water purifier, when carbonate ions or hydrogen carbonate ions are present in water, the buffer action as described above suppresses the change in pH due to the anodic electrolytic reaction, and The presence of cations such as Fe ³⁺ , Al ^3+, or organic acids also has a buffering action against pH change due to the cathodic electrolytic reaction, and thus the electrolysis efficiency was low. Further, although such buffering ions can be removed by using an ion exchange resin, there is a problem that the effectiveness of the ion exchange resin deteriorates with time.

The present invention has been made in view of the above problems, and an object of the present invention is to remove a buffer ion in water having a buffering action against a pH change by an ion exchange resin to perform electrolysis. It is to improve the efficiency and to easily regenerate the effect of the ion exchange resin.

[0007]

In order to solve the above-mentioned problems, an electrolytic water purifier according to the first aspect of the present invention electrolyzes water to produce acidic ionized water on the anode side and alkaline ionized water on the cathode side. For producing an electrolytic cell, a pair of anode water passages opened in the anode chamber of the electrolytic cell, a cation exchange resin filled in each anode water passage, a pair of anode water passages connected to each anode water passage, each The configuration includes a pair of anode water outlets connected to the anode water passages and valve devices provided in each of the anode water inlet passage and the anode water outlet passage. Further, the electrolytic water purifier according to the second claim of the present invention, similarly, a pair of cathode water passages opened in the cathode chamber of the electrolytic cell, anion exchange resin filled in each cathode water passage, each cathode The configuration includes a pair of cathode water inlets connected to the water passage, a pair of cathode water outlets connected to each cathode water passage, and a valve device provided in each of the cathode water inlet and the cathode water outlet.

[0008]

According to the electrolytic water purifier of the present invention, on the anode side, the valve device provided in each anode water inlet and each anode water outlet is operated to move water from one anode water inlet to one anode water inlet. To supply to the anode chamber. At this time, the cation components in the water are exchanged with H ⁺ ions in the process of passing through one of the anode water passages, and these H ⁺ ions neutralize the buffer anions that have a buffering effect on the pH decrease to lower the pH. To form a non-buffering salt for. The acidic ionized water produced in the anode chamber is
Water is taken from the other anode water passage through an anode water outlet connected to this anode water passage.

Similarly, on the side of the cathode chamber, the valve device provided in each cathode inlet channel and each cathode outlet channel is operated to move water from one cathode inlet channel through one cathode outlet channel to the cathode. Supply to the room. At this time, the anion component in the water is exchanged with OH ⁻ ion in the process of passing through one of the cathode water passages, and this OH ⁻ ion neutralizes the buffer cation having a buffering effect on pH rise to prevent pH change. This produces a non-buffering salt. The alkaline ionized water produced by the cathodic electrolysis reaction is taken from the other cathode water passage through the cathode water outlet connected to this cathode water passage.

The cation exchange resin is obtained by repeating the above H ⁺ ion exchange reaction, and the anion exchange resin is
By repeating the above-mentioned OH ⁻ ion exchange reaction, the efficiency of each ion exchange decreases with time. Therefore,
After generating acidic ionized water and alkaline ionized water by the above path, by switching each valve device, on the anode side, water is supplied to the anode chamber from the other anode water inlet passage through the other anode water inlet passage, The acidic ionized water generated in the anode chamber is taken from one anode water passage through the anode water outlet connected to this anode water passage, and, on the cathode side, water is taken from the other cathode water inlet to the other cathode water inlet. The water is supplied to the cathode chamber through the water passage, and the alkaline ionized water generated in the cathode chamber is taken from the other anode water passage through the anode water outlet connected to this anode water passage.

At this time, in the same manner as described above, the cation exchange resin is used in the other anode water passage on the water inlet side to the anode chamber, and the anion ions are used in the other cathode water passage on the water inlet side to the cathode chamber. The exchange resins each neutralize the buffer ions in the water. Further, the cation exchange resin in which the ion exchange efficiency in one of the anode water passages on the water outlet side is reduced is regenerated by the reverse reaction of the above ion exchange due to the passage of acidic ion water, and similarly on the water outlet side. The anion exchange resin in one of the cathode water channels is regenerated by the passage of alkaline ionized water.

[0012]

EXAMPLE Next, an electrolytic water purifier of the present invention will be described with reference to an example shown in FIG. 1. Reference numeral 10 denotes an electrolytic cell in which the inside is divided into an anode chamber 10A and a cathode chamber 10B by a diaphragm 11. Is. An anode plate 12 is provided in the anode chamber 10A, and a cathode plate 13 is provided in the cathode chamber 10B. The anode plate 12 and the cathode plate 13 are connected via a rectifier (DC power supply) 14. A porous membrane having innumerable micropores of about 0.1 to 0.5 μm is used for the diaphragm 11, and
The anode plate 12 and the cathode plate 13 are made of stainless steel, titanium,
Platinum, ferrite, carbon or the like is used.

A pair of anode water passages 15A and 16A are opened on both side wall surfaces of the anode chamber 10A.
In the ion exchange tanks 15a and 16a formed in 16A,
H ⁺ type cation exchange resins 17A and 18A are respectively filled. Similarly, a pair of cathode water passages 15B and 16B are opened on both side wall surfaces of the cathode chamber 10B, and the ion exchange tanks 15b and 16 are formed in the cathode water passages 15B and 16B.
b is filled with OH ⁻ type anion exchange resins 17B and 18B, respectively.

Reference numerals 20A and 21A denote a pair of anode water inlet passages, 22
A and 23A are a pair of anode outlets, one of which is an anode inlet 2
0A and the anode water outlet 22A are connected to the ion exchange tank 15a in the one anode water passage 15A, and the other anode water inlet 21A and the anode water outlet 23A are connected to the other anode water passage 16A.
It is connected to the ion exchange tank 16a in A. Further, 20B and 21B are a pair of cathode water channels, 22B and 23B are a pair of cathode water channels, and one cathode water channel 20B and cathode water channel 22B are connected to the ion exchange tank 15b in one cathode water channel 15B, and the other. The cathode water inlet passage 21B and the cathode water outlet passage 23B are connected to the ion exchange tank 16b in the other cathode water passage 16B. Then, one anode water inlet 20A and cathode water inlet 20B, the other anode water inlet 21A and cathode water inlet 21B, and one anode water outlet 22.
Valve devices V _{1 to} V ₈ are provided in A and the cathode water outlet 22B, and in the other anode water outlet 23A and the cathode water outlet 23B, respectively.

One anode water inlet 20A and one cathode water inlet 20
B is a diversion from the first water inflow passage 20, and the other anode water inflow passage 21A and cathode inflow water passage 21B are diverted from the second water inflow passage 21. The water channels 20 and 21 are also branched from the common water supply port 19 on the upstream side. In addition, the anode flood channels 22A and 23A
Joins the acidic ionized water intake 24A on the downstream side,
The cathode water discharge channels 22B and 23B also join the alkali ion water intake port 24B on the downstream side.

In the above construction, for example, first, the valve devices V ₁ of the anode water inlet passage 20A and the cathode water inlet passage 20B are
V ₂ and the other anode outlet 23A and cathode outlet 23B
Valve devices V ₇ and V ₈ of the other are opened, and the other anode inlet channel 21A
And the valve devices V ₃ and V ₄ of the cathode water inlet passage 21B, and the valve devices V ₅ and V of one of the anode water outlet passage 22A and the cathode water outlet passage 22B.
_{When 6} is closed, untreated water W from a water supply source (not shown) is branched from the water supply port 19 through the first water inlet 20 to one of the anode water inlet 20A and the cathode water inlet 20B, It is supplied to the anode chamber 10A and the cathode chamber 10B of the electrolytic cell 10 via the anode water passage 15A and the cathode water passage 15B, respectively. At this time, turn on the rectifier 14 which is a DC power supply.
Then, in the anode chamber 10A, water is oxidized by the anode plate 12, that is, + electrolysis causes the following reaction. 2H ₂ O → 2H ⁺ + 2e ⁻ + O ₂ ········ In addition, in the cathode chamber 10B, water is reduced by the cathode plate 13, that is, by −electrolysis, The reaction takes place. ^{_{2H 2 O + 2e - → 2OH}} - + H 2 ················

Since the hydrogen ion H ⁺ generated in the anode chamber 10A and the hydroxide ion OH ⁻ generated in the cathode chamber 10B by this reaction associate with the water molecule having a strong polarity,
The diaphragm 11 has a size that cannot pass through the diaphragm 11 and is retained in the anode chamber 10A and the cathode chamber 10B, respectively, and water molecules freely pass through the diaphragm 11 to enable continuous electrolysis. Therefore, the concentration of hydrogen ions H ⁺ increases in the anode chamber 10A, the pH decreases, and acidic ion water Wa is generated, while the concentration of hydroxide ions OH ⁻ increases in the cathode chamber 10B. The pH rises and the alkaline water Wb is produced.

Here, untreated water W supplied from the anode water inlet 20A through the anode water passage 15A to the anode chamber 10A.
Is passed through the cation exchange resin 17A in the ion exchange tank 15a, so that the following ion exchange is performed. RH ⁺ + M ⁺ → RM ⁺ + H ⁺ ... (RM ⁺ is H ⁺ type ion exchange resin, M ⁺ is cation in water) Therefore, the hydrogen carbonate ions contained in the water W are neutralized by the subsequent reaction with the H ⁺ ions as described above. _{^{H + + HCO 3 - → H}} 2 CO 3 ······················ Therefore, pH decreased combines with H ⁺ ions generated in the anode chamber 10A Since the hydrogen carbonate ion that inhibits the above is removed, the above anodic electrolysis reaction can be promoted.

Further, from the cathode water inlet 20B to the cathode water passage 1
The untreated water W supplied to the cathode chamber 10B through 5B is
By passing through the anion exchange resin 17B in the ion exchange tank 15b, the following ion exchange is performed. ^{ROH - + A - → RA -} + OH - ···················· (ROH - is OH ^- type ion exchange resin, A ^- in water anions) for this , Fe ³⁺ ions contained in the water W are neutralized by the following reaction with OH ⁻ ions according to the above. 3OH ⁻ + Fe ³⁺ → Fe (OH ⁻ ) ₃ ······· Therefore, the pH rises by combining with OH ⁻ ions generated in the cathode chamber 10B. Since the cation components such as Fe ³⁺ , Al ³⁺ , and organic acid, which hinder the above, are removed, the above-mentioned cathodic electrolysis reaction can be promoted.

Then, the acidic ionized water Wa produced in the anode chamber 10A can be taken in from the water intake port 24A from the other anode water passage 16A including the ion exchange tank 16a and the anode water outlet passage 23A. The alkaline ionized water Wb generated in the cathode chamber 10B can be taken in from the other cathode water passage 16B including the ion exchange tank 16b, the cathode water outlet passage 23B, and the water intake port 24B.

By the way, the cation exchange resin 17A and the anion exchange resin 17B need to be regenerated, because the effect of ion exchange decreases with time by repeating the above reaction. In the water purifier of the present embodiment is therefore, after generating a predetermined amount of acidic ionized water Wa and alkaline ionized water Wb above route, the time of the next electrolyte, contrary to the case described above, the valve device V _3, V ₄ , V
_5, opening the V _6, closes the valve device _{V 1, V 2, V 7} , V 8. Therefore, the untreated water W is branched from the water inlet 19 through the second water inlet 21 to the other anode water inlet 21A and cathode water inlet 21B, and the other anode water inlet 16A and cathode water inlet 16B, respectively. It is supplied to the anode chamber 10A and the cathode chamber 10B of the electrolytic cell 10 via the, and the electrolytic reaction of and is performed.

At this time, the untreated water W supplied to the anode chamber 10A is the cation exchange resin 1 in the ion exchange tank 16a.
The reaction of and is carried out by passing through 8A,
The untreated water W supplied to the cathode chamber 10B passes through the anion exchange resin 18B in the ion exchange tank 16b to undergo the reactions (1) and (2) to neutralize the buffer ions in the water. Then, the acidic ionized water Wa produced in the anode chamber 10A is taken from one of the anode water passages 15A including the ion exchange tank 15a, the anode water outlet passage 22A, and the water intake port 24A.
Water is taken from the ion exchange tank 15a in the process.
The cation exchange resin 17A therein is regenerated by the acidic ionized water Wa passing through the resin and the reverse reaction of and. Similarly, the alkaline ionized water Wb generated in the cathode chamber 10B is taken in from the one cathode water passage 15B including the ion exchange tank 15b, the cathode water outlet 22B, and the water intake port 24B. The anion exchange resin 17B in the tank 15b is regenerated by the reverse reaction of and with the alkaline ionized water Wb passing therethrough.

Therefore, the ion water W produced by supplying water from one of the anode water inlet 20A and the cathode water inlet 20B side is generated.
a, Wb to the other anode water outlet 23A and cathode water outlet 23
A path such as water intake from the B side and the other anode inlet 2
1A and the cathode water inlet 21B side are supplied, and the generated ion water Wa, Wb is taken in from the anode water outlet 22A and the cathode water outlet 22B side, respectively. Water is introduced into the electrolytic cell 10 through the exchange resin, so that the electrolysis efficiency can be improved.

FIG. 2 shows a case where the electrolytic water purifier is used to electrolyze the ion-exchanged water while switching the flow path every 200 liters and alternately regenerating the ion-exchange resin, and the ion-exchange water only on the inlet side. It is an experimental value showing a change in pH in the anode chamber when water is electrolyzed using an electrolytic water purifier provided with a resin. As a result, in the case where the ion exchange resin is provided only on the water inlet side, the change in pH is suppressed by the sharp decrease in the ion exchange effect after the treatment at a constant flow rate, whereas the change of the present invention is suppressed. It was confirmed that in the water purifier, a constant pH as acidic ionized water can always be obtained by regenerating the ion exchange resin.

The present invention is not limited to the above embodiment. For example, instead of the valve devices V _{1 to} V ₈ , a branch connection from the water inlet 19 to the first and second water inlets 20 and 21, the anode water outlets 22A and 23A to the water inlet 2
A switching valve may be provided at the confluence part to 4A and the confluence part from the cathode water discharge channels 22B and 23B to the water intake port 24B, and various other detailed configurations can be changed.

[0026]

As is clear from the above description, according to the electrolytic water purifier of the present invention, the water in which the buffer ion in the water is neutralized by the ion exchange resin on the water inlet side of the electrolytic cell is electrolyzed. Therefore, it is possible to increase the acidic ion concentration of the anode chamber and the alkaline ion concentration of the cathode chamber, and because the acidic ion water and the alkaline ion water are configured to regenerate the ion-exchange resin on the outlet side at the time of water discharge, By alternately switching the water inlet side to the water outlet side and the water outlet side to the water inlet side by the valve device, the effect of the ion exchange resin is constantly regenerated on the water outlet side, and therefore, the ion exchange resin is periodically taken out and regenerated by the regenerator. It has an excellent effect that it does not take time and effort.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a schematic configuration of an embodiment of an electrolytic water purifier of the present invention.

FIG. 2 shows a case where the ion-exchanged water is electrolyzed while the ion-exchange resin is alternately regenerated by alternately switching the direction of the incoming water and the outgoing water by using the electrolytic water purifier of the present invention, and the ion-exchange resin is provided only on the incoming channel side. It is a graph which shows the change of pH in an anode room at the time of electrolyzing water with the electrolytic water purifier provided.

[Explanation of symbols]

10 Electrolyzer 10A Anode chamber 10B Cathode chamber 15A, 16A Anode water passage 15B, 16B Cathode water passage 15a, 15b, 16a, 16b Ion exchange tank 17A, 18A Cation exchange resin 17B, 18B Anion exchange resin 19 Water inlet 20th One inlet 20A, 21A Anode inlet 20B, 21B Cathode inlet 21 Second inlet 22A, 23A Anode outlet 22B, 23B Cathode outlet 24A Acid ion water inlet 24B Alkaline ion water inlet V _1- V ₈ valve device W untreated water Wa acidic ionized water Wb alkaline ionized water

Claims (2)

[Claims] 1. An electrolyzer for electrolyzing water to produce acidic ionized water on the anode side and alkaline ionized water on the cathode side, a pair of anode water passages opened in the anode chamber of the electrolyzer, and each anode water passage. Cation-exchange resin filled in, a pair of anode water inlets connected to each anode water passage, a pair of anode water outlets connected to each anode water passage, and valves provided in each of the anode water inlet and the anode water outlet. An electrolytic water purifier including a device. 2. An electrolytic cell for electrolyzing water to produce acidic ionized water on the anode side and alkaline ionized water on the cathode side, a pair of cathode water passages opened in the cathode chamber of the electrolytic cell, and each cathode water passage. Anion-exchange resin filled in, a pair of cathode water channels connected to each cathode water channel, a pair of cathode water channels connected to each cathode water channel, a valve provided in each of the cathode water channel and cathode water channel An electrolytic water purifier including a device.