JPH11192486A - Frozen body of electrolyzed aqueous solution and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain free ions and hydrogen molecules of a specified content at any time, by electrolyzing an electrolyte solution with an electrolytic device, producing free hydroxy ions at a cathode and free hydrogen ions at an anode and allowing the electrolyzed aq. solution containing these to freeze, keeping as a frozen body and later thawing these. SOLUTION: Either one of the thin electrolyte solution obtd. by dissolving an electrolyte into pure water or city water or the city water is charged into an electrolytic cell provided with the cathode and the anode and a membrane arranged between these, and a direct current-impressed electric current is allowed to flow between the anode and the cathode, then the produced cathode side electrolyzed water solution is frozen with a frozen means.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a frozen body of a cathodic electrolysis aqueous solution generated when a dilute electrolyte solution is electrolyzed by an electrolysis apparatus or the like. The present invention relates to a frozen product of an electrolytically produced aqueous solution using an oxidation-reduction potential when the frozen product is thawed as an index.

[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. In addition, 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, a halogen element, for example, a chlorine ion emits an electron to convert a chlorine atom into a chlorine molecule. 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 as an electrolyte, for example, sodium ion and hydroxyl ion, 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 showed acidity,
On the cathode side, it shows alkalinity.

When a charged membrane is used as a membrane, 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 in the case of an anion exchange membrane, the Only the negative ions move from the cathode side to the anode side.

[0004] The use of an electrolytically produced aqueous solution for living organisms has been known for a long time. When sodium chloride is used as an electrolyte, hypochlorous acid generated at the anode has a strong bactericidal action. Used from disinfectants instead. It is also known that in the above-described electrolysis, hydroxyl radicals are generated on the anode side, and that when used directly on a living body, it has some effect on the biological defense mechanism of the living body, thereby enhancing the immune function. There is also.

On the other hand, as for use on the cathode side, it is possible to suppress abnormal fermentation in the gastrointestinal tract and gastric acid by electrolyzing tap water and drinking the electrolyzed water generated on the cathode side. 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. On the cathode surface, water molecules are reduced, and hydrogen gas is generated. Since the electrolyzed water generated on the cathode side 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 electrolysis apparatus is of a water supply direct connection type, and the electrolysis aqueous solution can be collected from both the cathode side and the anode side with 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.

However, alkali metal hydroxide and hydrogen gas are known as compositions in the above-mentioned cathode-side electrolysis aqueous solution, and as described above, the oxidation-reduction potential and the hydrogen ion concentration are employed as indices. In the cathode side electrolysis aqueous 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, the composition of an acid such as hydrochloric acid, oxygen gas, and hypochlorous acid is known in the anode-side electrolysis aqueous solution, 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.
Furthermore, it was difficult to calculate the oxidation-reduction potential of the aqueous solution of the cathode-side electrolysis product simply by the Nernst equation.

[0008]

SUMMARY OF THE INVENTION 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 freezing ionic species at both electrode sides by electrolyzing an electrolyte solution, that is, a cathode. Then, free hydroxyl ions are generated at the anode and free hydrogen ions are generated at the anode, and the neutralization titration or quantification of the hydroxyl ions forming the alkali and the hydrogen ions forming the acid using Faraday's law. By freezing an aqueous electrolysis solution containing a certain amount of free ions and hydrogen molecules, and then thawing the frozen product, it is possible to always provide a certain amount of free ions and hydrogen molecules.

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 0.1M, the electrolyte is completely dissociated. Is 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 ion species of the opposite sign or only substitution reactions occur, so that a frozen body containing extremely stable free ion species and hydrogen molecules can be provided.

[0010]

In order to solve the above-mentioned problems, a frozen body of the electrolytically produced aqueous solution according to the present invention is provided in an electrolytic cell having a cathode, an anode, and a diaphragm disposed between the cathode and the anode, with pure water or tap water. Either a dilute electrolyte solution obtained by dissolving an electrolyte in water, or tap water was added, a direct current was applied between the cathode and the anode to conduct electrolysis, and the generated cathode-side electrolysis aqueous solution was frozen by a freezing means. It is characterized by being a solid compact.

[0011] Further, a dilute electrolyte solution obtained by dissolving an electrolyte in pure water or tap water or tap water is placed in an electrolytic tank having a cathode and an anode and a diaphragm disposed therebetween, and The frosted body obtained by freezing the generated aqueous solution of the cathode-side electrolysis by refrigeration means and then thawing the frozen body to the same state as the electrolyzed water of the cathode side, It is characterized in that the redox potential when returned is in the range of 0 to 50% with respect to the redox potential of the aqueous solution of the cathode-side electrolysis immediately before freezing.

In addition, an electrolytic cell having a cathode and an anode and a diaphragm interposed therebetween is charged with either a dilute electrolyte solution in which an electrolyte is dissolved in pure water or tap water or tap water. By applying a direct current between the anode and the anode, electrolysis is performed, and the generated cathode-side aqueous electrolysis solution is taken out of the electrolysis tank by the electrolysis method of producing electrolyzed water, which is frozen by refrigeration means and stored and stored as frozen bodies. ,
It is characterized in that the frost is later thawed and used as an aqueous solution of cathodic electrolysis.

Further, the refrigeration means freezes a plurality of frozen bodies, and in thawing, the amount of the aqueous solution of the cathode-side electrolysis can be adjusted by the number of the frozen bodies.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A frozen product of an electrolytically produced aqueous solution according to the present invention is manufactured by an electrolysis apparatus shown in FIG. 1 as an embodiment. That is, as shown in FIG. 1, a cathode 2, an anode 3, and a diaphragm 4 are arranged in an electrolytic cell 1, an electrolyte solution 6 is introduced from an inflow port 6a, a voltage of a DC power supply 5 is applied between both electrodes, and a cathode-side electrolytic generation is performed. The aqueous solution 7 and the anode-side electrolysis aqueous solution 8 flow out of the outlets 7a and 8a, respectively. The cathode-side electrolysis aqueous solution 7 enters the refrigerating device 20 and forms, for example, a spherical frozen body 21 from the outlet of 20 a, and a plurality of the frozen bodies 21 are stored in the tray 22. Therefore, if necessary, the number of frozen bodies 21 can be selected, thawed and used.

The aqueous electrolytic solution containing free ionic species according to the present invention is obtained by electrolytically generating free ions on both electrodes using a platinum electrode as an inactive electrode of the cathode 2 and the anode 3, using sodium chloride as an electrolysis aid. It is.

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 can 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 production of free hydroxyl ions and free hydrogen ions can be performed when the concentration of the electrolyte used is in the range of 10 ^-4 mol / l to a saturated state.
It can be produced in the range of 0 ^-4 to 10 ^-2 mol / l. Free ions can be generated if the DC applied current value is in the range of 10 ^{-1 to} 5A.

In the method for analyzing the electrolytically produced aqueous solution, when an anion exchange membrane is used, on the cathode side, chlorine ions are reduced by the amount moved to the anode side, and sodium hydroxide and sodium hydroxide 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.
Note that hydrochloric acid and hypochlorous acid can be quantified as hydrogen ions on the anode side. The electrode reactions occurring on both sides are shown below.

[0020] The reaction at the cathode side ^{_{H 2 O + e - → 1}} / 2H 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.

[0021] _{^{[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)

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)

[0023] 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, the electrode reactions (5) and (6) proceed at the anode,
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 hydrogen molecules in the aqueous electrolyte solution on the anion side are dissolved as hydrogen gas, and the oxidation-reduction potential can be determined by the Nernst equation. Eh = 0.688 - 0.0885pH + 0.00741og [ O 2] - 0.02951og [H 2] V (11) can be obtained dissolved hydrogen by measuring the amount of dissolved oxygen from the equation (11).

[0026]

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, and platinum electrodes were used as electrodes, and four electrodes were used on the cathode side and the anode side, respectively.
Add 00 ml of 10 ^-1 M sodium chloride solution and add 0.1 ml.
A DC current of 5 A is applied, and electrolysis is performed for 3, 5, 7, 9, and 11 minutes, respectively. Chloride ions and hydroxyl ions generated on the cathode side by neutralization titration and ion chromatography with the generated electrolyte solution Was quantified. In addition, the concentration of chlorine ions and hydrogen ions generated on the anode side is quantified,
The total amount of hydroxyl ions and the amount of hydrogen ions are determined from the Faraday equation, the respective free ions are determined, the electrolyte is separated into water and electrolyte components through a reverse osmosis membrane, the free ions are collected in water, and the free ions are contained. Got water. Tables 1 and 2 show the results.

[0027]

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

[0028]

[Table 2] Free hydrogen ion concentration (concentration unit is 10 ^-3 mole
s / 400ml)

Further, the aqueous solution of the electrolysis generated on the cathode side generated in the electrolysis time of 3, 7, 11 minutes is frozen and thawed one week later.
Table 3 shows the measurement results of the oxidation-reduction potential.

[0030]

[Table 3]

Example 2 The aqueous solution generated by electrolysis on the cathode side was electrolyzed for 7 minutes.
Thaw after 2, 3, 4 and 5 weeks, measure the oxidation-reduction potential,
Each was compared with the oxidation-reduction potential after electrolysis. The results are shown in Table 4.

[0032]

[Table 4]

Example 3 Tap water was electrolyzed using a domestic electrolysis generator, and the obtained aqueous solution of cathode-side electrolysis was frozen and thawed. The oxidation-reduction potential was measured, and the results shown in Table 5 were obtained. Was.

[0034]

[Table 5]

[0035]

As described above in detail, the frozen body of the electrolytically produced aqueous solution according to the present invention has the following effects. (1) When the number of electrons is the same, the oxidation-reduction potential of the cathode-side electrolysis aqueous solution is the sum of the potentials of dissolved oxygen and dissolved hydrogen, and as long as a negative potential is generated, dissolved hydrogen is present. That is, since the change of the oxidation-reduction potential of the frozen body with time is smaller than that of the solution, the frozen body is most suitable for storing the cathode-side electrolytic aqueous solution. (2) Free ions are present during the electrolysis generation, and freezing and thawing makes it possible to always use electrolyzed water immediately after electrolysis. (3) If there is a refrigeration system for both home and business use, there is the convenience of easily producing frozen water of electrolyzed water, and it can be produced at low cost.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining a process of producing a frozen product of an electrolysis aqueous solution of the present invention by an electrolysis apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolyzer 2 Cathode 3 Anode 4 Diaphragm 5 DC power supply 6 Electrolyte solution, tap water 7 Cathode side electrolysis aqueous solution 8 Anode side electrolysis aqueous solution 20 Refrigerator 21 Iced body 22 Iced container

[Procedure amendment]

[Submission date] June 9, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

In the method for analyzing the electrolytically produced aqueous solution, when an anion exchange membrane is used, on the cathode side, chlorine ions are reduced by the amount moved to the anode side, and sodium hydroxide and sodium hydroxide 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 of sodium hydroxide can be estimated from the product of the current efficiency and the value obtained by dividing the product of current and time by the Faraday constant according to Faraday'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. The sodium hydroxide consumption [OH ⁻ ] _cathod when the subsequent electrolysis solution was neutralized with the same method from the same pH with sodium hydroxide was determined, 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 Faraday constant according to the law of day. 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 at the time of neutralization titration with hydrochloric acid of a certain concentration is set to _zero for free hydrogen ions, and the electrolysis after electrolysis is performed. The consumption [H ⁺ ] _anod of hydrochloric acid when the resulting solution was neutralized with hydrochloric acid from the same pH in the same _manner was determined, and the difference between the former and the latter, [H ⁺ ] _anod- [H ⁺ ] ₀
Free hydrogen ions generated on the anode side by electrolysis can be obtained.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

[Cl ⁻ _(C1) ] − [Cl ⁻ _(C2) ] = [Cl ⁻ _(C3) ] (3) where [Cl ⁻ _(C1) ], [Cl ⁻ _(C2) ], and [C
l ^- _(C3)] indicates the concentration of chlorine ions before the electrolysis, respectively, the chlorine ion concentration after electrolysis, the chloride ion concentration having moved from the cathode side to the anode side. _{^{[OH - (C2)] =}} [Cl - (C3)] (4) free hydroxyl ion content is _{^{[OH -] (C1) ×}} ( current efficiency) - [O
_{^{H - (c2)] = [}} OH -] cathod - [OH -]
It becomes ₀ .

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

The amount of free hydrogen ions is {[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 electrolytic cell having a cathode and an anode and a diaphragm disposed therebetween is charged with either a pure electrolyte solution or a dilute electrolyte solution obtained by dissolving an electrolyte in tap water, or the tap water. A frozen body of an electrolytically produced aqueous solution, characterized in that the electrolytically produced aqueous solution is a solid compact formed by freezing a generated cathode side electrolytically produced aqueous solution by refrigeration means. 2. An electrolytic cell having a cathode and an anode and a diaphragm disposed therebetween is charged with pure water or a dilute electrolyte solution obtained by dissolving an electrolyte in tap water or tap water. The frosted body obtained by freezing the generated aqueous solution of the cathode-side electrolysis by refrigeration means and then thawing the frozen body to the same state as the electrolyzed water of the cathode side, The oxidation-reduction potential at the time of return is compared with the oxidation-reduction potential of the cathode-side electrolytic production aqueous solution immediately before freezing,
A frozen product of the electrolytically produced aqueous solution, which is in the range of 0 to 50%. 3. An electrolytic cell having a cathode and an anode and a diaphragm disposed therebetween is charged with pure water or a dilute electrolyte solution obtained by dissolving an electrolyte in tap water or tap water. By applying a direct current between the anode and the anode, electrolysis is performed, and the generated cathode-side aqueous electrolysis solution is taken out of the electrolysis tank by the electrolysis method of producing electrolyzed water, which is frozen by refrigeration means and stored and stored as frozen bodies. A method of using the frozen product of the electrolytically produced aqueous solution, wherein the frozen product is later thawed and used as a cathode electrolytically produced aqueous solution. 4. The method according to claim 3, wherein the refrigeration unit freezes a plurality of frozen bodies, and at the time of thawing, the amount of the cathode-side electrolysis aqueous solution can be adjusted by the number of the frozen bodies. How to use the frozen matter of the electrolysis aqueous solution.