JPH11192485A - Production of free hydroxide ion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably produce free hydroxide ion water containing free hydroxide ion by electrolyzing an electrolytic solution in an electrolyzer to form free hydroxide ions on the cathode side, and collecting the electrolytically produced liquid from the electrolyzer to remove the electrolyte by a distillation method, a reverse osmosis method, or the like. SOLUTION: The electrolytically formed produced liquid containing free ion seeds is electrolized by using an electrolyzer 1. That is, an electrolytic solution 6 is allowed to flow into the electrolyzer 1 from an inflow port 6a, and it is passed between a cathode 2, an anode 3, and a diaphragm 4 to allow it to flow out as produced liquids 7, 8 on the cathode and anode sides from outflow ports 7a, 7b on the cathode and anode sides, respectively. The cathode 2 and the anode 3 each consist of inert electrodes, and as the inert electrodes, platinum electrodes are used, and as an electrolytic aid of the electrolytic solution 6, sodium chloride is used. An electric current is applied to between both the electrodes 2, 3 from DC power supply 5 to electrolytically form free ions on both the electrodes 2, 3. The electrolytically produced liquid 7 is distilled by a distillation device 9 to form free hydroxide ion water 10 from which electrolyte has been removed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolysis solution containing free ions using an electrolysis apparatus in which an electrolytic solution is placed in an electrolytic cell having a cathode and an anode, and a direct current voltage is applied between the two electrodes to perform electrolysis. More particularly, the present invention relates to a method for producing free ions in an electrolytic solution in which free hydroxyl ions are collected on the cathode side and free hydrogen ions are collected on the anode side.

[0002]

2. Description of the Related Art Conventionally, electrolysis of water has been carried out using an electrolyte such as sodium chloride or potassium chloride as an electrolysis aid. Also, electrolysis of water has been performed using a supporting electrolyte that does not actually participate in the reaction, such as sulfuric acid. When a halide is used as in the former case, sufficient ion dissociation is performed, and the electrolyte is completely ionized.
Therefore, in the electrolytic solution, the anions diffuse and move to the anode and the cations diffuse to the cathode, and the charged ions in the solution play a role of moving. Therefore, at the anode, the halogen element,
For example, chlorine ions emit electrons to convert chlorine atoms into chlorine molecules. In addition, water molecules emit electrons at the anode to generate hydrogen ions and oxygen molecules, and react with chlorine ions diffused and moved from the cathode to form hydrochloric acid. When hydrochloric acid is formed, the hydrogen ion concentration decreases, and chlorine gas partially becomes hypochlorous acid. On the anode side, hydrochloric acid and hypochlorous acid form an acidic solution, and the gas-liquid equilibrium is maintained between chlorine gas and oxygen gas under a constant partial pressure.

On the other hand, at the cathode, sodium hydroxide is generated by an alkali metal, for example, sodium ion and hydroxide ion, which are electrolytes, and hydrogen gas is generated by electrolysis of water. Therefore, on the cathode side, the result shows alkalinity by sodium hydroxide. As a result, the anode side shows acidity and the cathode side shows alkalinity. Further, when a charged membrane is used as a diaphragm disposed between the cathode and the anode, for example, in the case of a cation exchange membrane, only cations in the electrolyte solution move from the anode side to the cathode side, and the anion exchange membrane In this case, only the anions in the electrolyte solution move from the cathode side to the anode side.

[0004] The use of an electrolyzed product formed by electrolysis by applying a direct current between a cathode and an anode to a living body has been known for a long time. When sodium chloride is used as an electrolyte, the following solution is generated at the anode. Chlorous acid is used instead of a disinfectant because of its strong bactericidal action. In addition, in the above-described electrolysis, it is already known that when a sulfate group is present, a hydroxyl radical is generated on the anode side, and when used directly on a living body, by exerting some influence on a biological defense mechanism of the living body, Some say that it enhances immune function.

On the other hand, as for use on the cathode side, it is possible to suppress abnormal fermentation in the gastrointestinal tract and suppress gastric acid by electrolyzing tap water and drinking the electrolytic water generated on the cathode side. Therefore, it is widely used. The alkaline electrolyzed water generated on the cathode side is a hydroxide of an alkali metal, and particularly in the case of calcium, is dissolved in water as calcium hydroxide. Further, water molecules are reduced on the cathode surface, and hydrogen gas is generated. Since the cathode-side generated electrolyzed water contains a large amount of hydrogen gas, the oxidation-reduction potential is lowered due to the concentration ratio with water, and may reach as high as -300 mV. For these purposes, the electrolyzer is directly connected to the water supply, and the electrolysis product can be collected from both the cathode side and the anode side by a simple operation. The oxidation-reduction potential of the solution and the hydrogen ion concentration are used as indices to indicate the characteristics of the electrolytically generated solution.

[0006]

However, in the above-mentioned cathodic electrolysis solution, alkali metal hydroxide and hydrogen gas are known as compositions, and as described above, the indicators are the oxidation-reduction potential and the hydrogen ion concentration. Has been adopted. In the cathodic electrolysis solution, the oxidation-reduction potential is used as an index of reducibility, but the oxidation-reduction potential in the solution is determined by the concentration correlation between hydrogen gas and water and the hydrogen ion concentration according to the Nernst equation, It cannot always be an indicator of reducibility. Furthermore, it cannot be a scavenger having a function of eliminating superoxide anion radicals, which are free radicals, by hydroxide and hydrogen gas. Similarly, in the anode-side electrolysis solution, an acid such as hydrochloric acid, oxygen gas, and hypochlorous acid are known as compositions, but it is obvious that hypochlorous acid plays a role in disinfecting action. It is. However, phenomena such as promotion of granulation are difficult to explain with these compositions, and it is necessary to find an independent system for the healing system.

In vivo, mitochondria in the cells undergo oxygen electron reduction, and H ₂ in a four-electron reduced state is converted from a superoxide anion radical which is a one-electron reduction of oxygen.
The reaction proceeds continuously to O, and hydrogen ions and hydroxyl ions are consumed in the process. Of these ionic species,
Hydroxide ions are said to be involved in the electron transport system.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to solve the above problem by electrolyzing an electrolyte solution to form free ionic species at both poles, ie, free hydroxyl ions at a cathode. This is to generate free hydrogen ions at the anode, and the neutralization titration or ion quantification of the hydroxyl ions constituting the alkali and the hydrogen ions constituting the acid is performed by Faraday's law. It is an object of the present invention to provide water containing free hydroxyl ions by a distillation method or a reverse osmosis method, or a combination of both, of a catholyte electrolysis solution produced on the cathode side.

In general, an electrolyte such as sodium chloride dissolves in water and becomes sodium ion as a cation and chloride ion as an anion. At a concentration of about 0.1 M, the electrolyte is completely dissociated at the same time. Since the activity coefficient can be approximated to 1, the concentrations of both ions are the same. Similarly, in the case of sodium hydroxide or hydrochloric acid, the concentrations of cations and anions are also the same.The former reacts with the acid and the latter reacts with the base, but the free ionic species free hydroxyl ion and free Hydrogen ions do not react with acids or bases, and only free ionic species of the opposite sign or only substitution reactions occur, so that free hydroxyl ionized water containing extremely stable free hydroxyl ionic species can be provided.

[0010]

In order to solve the above-mentioned problems, a method for producing free hydroxyl ions according to the present invention comprises: placing an electrolytic solution in an electrolytic cell having a cathode and an anode of an inert electrode; A direct current is applied between the anode electrodes to electrolyze the electrolyte solution to generate free hydroxyl ions on the cathode side. Then, the electrolysis solution is collected from the electrolytic cell and distilled by a distillation method. Removing the electrolyte by either purifying by reverse osmosis or combining distillation and reverse osmosis to produce free hydroxyl ionized water containing free hydroxyl ions. It is characterized by.

Further, an electrolyte solution is put into an electrolytic cell having a cathode and an anode of an inert electrode and a diaphragm disposed therebetween, and a direct current is applied between the cathode and the anode electrode to cause the electrolyte solution to flow. To produce free hydroxyl ions on the cathode side, and then the electrolytic product is collected from the electrolytic cell and distilled by a distillation method, or purified by a reverse osmosis method, or The method is characterized in that the electrolyte is removed by any one of a combination of a distillation method and a reverse osmosis method to produce free hydroxyl ionized water containing free hydroxyl ions.

[0012] Further, the invention is characterized in that the membrane is either a charged membrane or an uncharged membrane.

Further, the concentration of the electrolyte solution is 10 ⁻⁴ mo.
from 1 / l to the saturated state, the concentration of anion and cation is 10
^-4 to 10 ^-6 mol / l, and the DC applied current value is 1
It is in the range of 0 ^{-1 to} 5A.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION One embodiment of the method for producing free hydroxyl ions of the present invention will be described below. First, the electrolysis solution containing free ionic species is electrolyzed using an electrolytic cell 1 as shown in FIG. The electrolyte solution 6 enters the electrolytic cell 1 from the inlet 6a, passes between the cathode 2, the anode 3, and the diaphragm 4, and becomes the cathode-side and anode-side generated liquids 7 and 8, respectively, which are the cathode-side outlet 7a and the anode, respectively. It flows out from the side outlet 8a. The cathode 2 and the anode 3 are composed of inert electrodes, a platinum electrode is used as the inert electrode, sodium chloride is used as an electrolytic aid for the electrolyte solution 6, and a DC power source 5 is connected between the cathode 2 and the anode 3.
, And free ions are electrolytically generated at both electrodes. Next, the electrolysis product liquid 7 is distilled by the distillation apparatus 9 to generate free hydroxyl ionized water from which the electrolyte has been removed.

Here, as the electrolysis assistant, in addition to sodium chloride which is a monovalent monovalent electrolyte, potassium chloride or sodium chloride is used.
It may be calcium chloride, magnesium chloride, or the like, which is a monovalent monovalent electrolyte, or sulfuric acid, which is a supporting electrolyte. The inert electrode may be any electrode as long as it is a platinum-based electrode, and it is an absolute condition that it is an irreversible electrode. The diaphragm 4 may employ either an anion exchange membrane or a cation exchange membrane. Further, although a neutral membrane which is an uncharged membrane can be employed, a charged membrane is more preferable than a neutral membrane because a charged membrane can further enhance ion selectivity.
A neutral membrane may be used as long as the pores of the membrane are small.

The formation of free hydroxyl ions and free hydroxyl ions can be performed when the concentration of the electrolyte used is in the range of 10 ^-4 mol / l to a saturated state, and the free ion concentration of the anion and cation is 10 ^-4 to 10. ^It can be produced in the range of ^-2 mol / l.
Free ions can be generated if the DC applied current value is in the range of 10 ^{-1 to} 5A.

According to the method for analyzing the electrolytic product, when an anion exchange membrane is used, the amount of chlorine ions on the cathode side decreases by the amount moved to the anode side, and sodium hydroxide and sodium ions form sodium hydroxide. The amount of hydroxyl ions can be determined by neutralization titration. Alternatively, the reduced amount of chloride ions may be quantified by ion chromatography. Neutralization titration and ion chromatography can be quantified with almost the same precision. The total amount of free hydroxide ion and sodium hydroxide can be estimated by dividing the product of current and time by Faraday's constant according to Faraday's law. Free hydroxyl ions can be determined from the difference between the total amount of hydroxyl ions and the amount determined by neutralization titration or ion chromatography. On the anode side
Free hydrogen ions are determined from the difference between the total amount of hydrogen ions determined by Faraday's law and the amount of hydrogen ions determined by neutralization titration or ion chromatography. On the anode side, hydrochloric acid and hypochlorous acid can be quantified as hydrogen ions. The electrode reactions occurring on both sides are shown below.

Reaction on the cathode side H ₂ O + e ⁻ → 1/2 H ₂ + OH ⁻ _(C1) (1) Na ⁺ + OH ⁻ _(C2) → NaOH (2) where [OH ⁻ _(C1) ], [OH ⁻ _{( C2)} ] indicate the total hydroxide ion concentration and the hydroxide ion concentration of sodium hydroxide, respectively.

[0019] _{^{[Cl - (C1)] -}} [Cl (C2)] = [Cl - (C3)] (3) _{^{where, [Cl - (C1)]}} , [Cl (C2)], [Cl - (C3 ₎ ]
Indicates the chloride ion concentration before electrolysis, the chloride ion concentration after electrolysis, and the chloride ion concentration moved from the cathode side to the anode side, respectively. _{^{[OH - (C2)] =}} [Cl - (C3)] (4)

[0020] The reaction at the anode side _{1 / 2H 2 O → 1 /} 4O 2 + H + (a1) + e - (5) Cl - (al) → 1 / 2Cl 2 + e - (6) 1 / 2Cl 2 + H 2 O → ^{_{HOCl + H + (a2) +}} e - (7) H + (a2) + Cl - (a2) → HCl (8)

[0021] Since the amount of chlorine ions diffused moves from the cathode side to the anode side is a bipolar-side the same amount _{^{[Cl - (a1)] +}} [Cl (a2)] = [Cl - (C3)] (9) Therefore At the anode, the electrode reactions (5) and (6) proceed,
Hydrochloric acid is generated by (5) and (8).

The amount of free hydrogen ions is [H ⁺ _(a1) ] + [H ⁺ _(a2) ]-[HOCl]-[HCl] (10) [H ⁺ _(a1) ] + [H ⁺ _(a2) ] Is the value obtained by dividing the product of current and electrolysis time by the Faraday constant according to Faraday's law.

The electrolysis solution produced by the above method may be distilled by a distillation apparatus, purified by a reverse osmosis method, or a combination of the distillation method and the reverse osmosis method. Free hydroxyl ionized water containing only Since free hydroxyl ion water is incorporated into the water network and undergoes hydrogen bonding and exists in the water, it cannot be analyzed by general analytical methods, so after neutralization with ascorbic acid, the ability to scavenge superoxide radicals Is analyzed by electron spin resonance. Compare and confirm using pure water of the same quality as a control.

[0024]

The present invention will be described in more detail by way of examples. The present invention is not limited to these examples. Example 1 An anion exchange membrane was used in a rigid vinyl chloride electrolytic cell, a platinum electrode was used as an electrode, and 400 ml of a 10 ^-1 M sodium chloride solution was placed on each of a cathode side and an anode side.
A 0.5 A direct current is applied, and electrolysis is performed for 3, 5, 7, 9, and 11 minutes, respectively. The generated electrolyte is subjected to neutralization titration and ion chromatography to chlorine ion and water generated on the cathode side. The concentration of acid ions was quantified to determine free hydroxyl ions. Table 1 shows the results.

[0025]

[Table 1] Free hydroxyl ion concentration (concentration unit is 10 ^-3 mole
s / 400ml)

400 ml of a cathodic electrolysis solution electrolyzed for 9 minutes
Was placed in a distillation apparatus and distilled, and the distillation was completed when 200 ml had been distilled. After cooling, quantitative analysis of sodium ions and chlorine ions was performed by ion chromatography. As a result, the value was the same as that of the pure water used for the control, and it was confirmed that ions other than free hydroxyl ions were removed.

In order to further confirm free hydroxyl ions, 5 ml of L-ascorbic acid was added to 100 ml of distilled cathodic electrolysis water to generate free protons, followed by elimination of superoxide produced by the hypoxanthine-xanthine oxidase system. The performance was measured with an electron spin resonance apparatus. The control used was pure water of the same quality. Table 2
Shows the results.

[0028]

[Table 2] Superoxide erasing ability (unit is unit / g)

EXAMPLE 2 Cathodic electrolysis solution 40 generated in Example 1 for an electrolysis time of 7 minutes
After treating 00 ml by a reverse osmosis method, quantitative analysis of sodium ion and chloride ion was performed by ion chromatography. As a result, it becomes the same value as pure water used for control,
It was confirmed that ions other than free hydroxyl ions were removed. After 5 ml of L-ascorbic acid was added to 100 ml of cathodic electrolysis water treated by the reverse osmosis method to generate free protons, the elimination ability of superoxide produced by the hypoxanthine-xanthine oxidase system was measured by an electron spin resonance apparatus. In addition, the same pure water was used for the control. Table 3 shows the results.

[0030]

[Table 3] Elimination ability of superoxide (unit is unit / g)

Example 3 Cathode electrolysis solution 4 generated in Example 1 for an electrolysis time of 11 minutes
After distilling 000 ml and treating by reverse osmosis,
Quantitative analysis of sodium ion and chlorine ion was performed by ion chromatography. As a result, the value was the same as that of the pure water used for the control, and it was confirmed that ions other than free hydroxyl ions were removed. After 5 ml of L-ascorbic acid was added to 100 ml of the cathodic electrolyzed water treated by the reverse osmosis method to generate free protons, the elimination ability of superoxide by the hypoxanthine-xanthine oxidase system was measured by electron spin resonance. It was measured by the device. The control used was pure water of the same quality. Table 4 shows the results.

[0032]

[Table 4] Elimination ability of superoxide (unit is unit / g)

[0033]

As described above, the method for producing free hydroxyl ions according to the present invention has the following effects. 1) By electrolyzing the electrolyte solution under certain conditions, free ions are generated at the cathode and the anode. The free ions do not react with the electrolyte solution composed of cations and anions, acids or bases, and are extremely stable. When the cathodic electrolysis product is taken into a living body, it easily reaches a site where active oxygen containing free radicals is localized, as long as there is no free ion of the opposite sign, and plays a role as a scavenger. . In addition, when ascorbic acid is present in the living body, it displaces the hydrogen of the hydroxyl group at the 3rd and 2nd position of ascorbic acid, releases hydrogen ions, and reacts with hydrogen ions and superoxide anion to cause disproportionation. It produces hydrogen peroxide. Thus, the free hydroxide ion exhibits a superoxide dismutase-like action. As a result, a cell-level repair action can be promoted, and the disease can be improved. Further, since the anodic electrolysis solution contains free hydroxyl ions, it promotes collagen production and exerts an effect on wound healing.

2) The free ions are transported as water molecules, which are slightly dissociated with the diffusion transfer of the ions by electrolysis, and are transported as electrons, whereby an energy balance is established. Is generated as In addition, since the reaction proceeds electrochemically, it can be handled stoichiometrically and can be performed extremely easily, and can be produced and manufactured at low cost, so that it can be easily performed on an industrial scale. It works.

3) Contaminants such as an electrolytic aid in the electrolysis solution are removed by a distillation method or a reverse osmosis method, and free ion water in which free ions are efficiently retained can be easily produced. Further, the free ion-containing electrolytic product solution produced by the method for producing free hydroxyl ions of the present invention has a remarkable effect such that it can be used as a drug by increasing the accuracy.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a configuration of an electrolytic device according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolyzer 2 Cathode 3 Anode 4 Diaphragm 5 DC power supply 6 Electrolyte solution 7 Cathode side electrolysis solution 8 Anode side electrolysis solution 9 Distillation apparatus 10 Free hydroxyl ion water

[Procedure amendment]

[Submission date] June 9, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

According to the method for analyzing the electrolytic product, when an anion exchange membrane is used, the amount of chlorine ions on the cathode side decreases by the amount moved to the anode side, and sodium hydroxide and sodium ions form sodium hydroxide. The amount of hydroxyl ions can be determined by neutralization titration. Alternatively, the reduced amount of chloride ions may be quantified by ion chromatography. Neutralization titration and ion chromatography can be quantified with almost the same precision. Further, the total amount of free hydroxyl ions and sodium hydroxide ions of sodium hydroxide can be estimated from the product of the current efficiency and the value obtained by dividing the product of the current and the time by the Farady constant according to Farady's law. Further, the electrolyte solution before electrolysis is acidified with a certain concentration of hydrochloric acid, and the consumption amount of sodium hydroxide [OH ⁻ ] ₀ when neutralization titration is performed with a certain concentration of sodium hydroxide is set to ₀ for free hydroxyl ions. Consumption of sodium hydroxide when the subsequent electrolysis solution is neutralized with sodium hydroxide from the same pH in the same manner [O
H ⁻ ] _catod is _calculated , and the difference between the former and the latter, [O
From H ⁻ ] _cathod − [OH ⁻ ] ₀ , free hydroxyl ions generated on the cathode side by electrolysis can be determined. The total amount of hydrogen ions on the anode side is Fara
It can be estimated from the product of the current efficiency and the value obtained by dividing the product of the current and the time by the Farady constant according to dy's law. In addition, the electrolyte solution before electrolysis is made alkaline with sodium hydroxide of a certain concentration, and the consumption amount of hydrochloric acid [H ⁺ ] ₀ when neutralized and titrated with a certain concentration of hydrochloric acid is set to ₀ for free hydrogen ions. The consumption amount of hydrochloric acid [H ⁺ ] _anod when the resulting solution was neutralized with hydrochloric acid from the same pH by the same method was determined, and the difference between the former and the latter [H ⁺ ] _anod- [H ⁺ ] ₀ was used to determine the anode by electrolysis. The free hydrogen ions generated on the side can be determined.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

[0019] ^{_{[Cl - (C1)] -}} [Cl (C2)] = [Cl - (C3)] (3) ^{_{where, [Cl - (C1)]}} , [Cl (C2)], [Cl
^- _(C3) ] respectively indicate the chloride ion concentration before electrolysis, the chloride ion concentration after electrolysis, and the chloride ion concentration moved from the cathode side to the anode side. ^{_{[OH - (C2)] =}} [Cl - (C3)] (4) hydroxyl ions of the free is _{^{[OH -] (C1) ×}} ( current _{^{efficiency) - [OH -] (C2}} ) = [OH +] _cathod −
[OH ⁻ ] becomes ₀ .

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

Free hydrogen ion amount {[H ⁺ _(a1) ] + [H ⁺ _(a2) ]} × (current efficiency)-[HOCl]-[HCl] = [H ⁺ _anod ]-[H ⁺ ] ₀ (10)

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takayoshi Hanaoka 1041 Ueda, Oaza, Ueda City, Nagano Prefecture

Claims (4)

[Claims] 1. An electrolyte solution is placed in an electrolytic cell provided with a cathode and an anode of an inert electrode, and a direct current is applied between the cathode and the anode electrode to electrolyze the electrolyte solution. Generating acid ions, and then collecting the electrolytic product from the electrolytic cell and distilling it by a distillation method,
Alternatively, it is characterized in that it is purified by a reverse osmosis method, or the electrolyte is removed by either of a distillation method and a reverse osmosis method, to produce free hydroxyl ion water containing free hydroxide ions. Method for producing free hydroxyl ions. 2. An electrolyte solution is placed in an electrolytic cell having a cathode and an anode of an inactive electrode and a diaphragm disposed therebetween, and a direct current is applied between the cathode and the anode to cause the electrolyte solution to flow. To produce free hydroxyl ions on the cathode side, and then the electrolytic product is collected from the electrolytic cell and distilled by a distillation method, or purified by a reverse osmosis method, or A method for producing free hydroxyl ions, comprising removing an electrolyte by one of a combination of a distillation method and a reverse osmosis method, and producing free hydroxyl ion water containing free hydroxyl ions. 3. The method for producing free hydroxyl ions according to claim 2, wherein said diaphragm is either a charged membrane or an uncharged membrane. 4. The concentration of the electrolyte solution is 10 ⁻⁴ mol /.
1 to a saturated state, and the concentration of the anion and cation is 10 ⁻⁴ to
10 ^-6 mol / l, and the DC applied current value is 10 ^-1
The method for producing free hydroxyl ions according to claim 1, 2 or 3, wherein the concentration is in the range of 5 to 5A.