JPH09314145A - Method and apparatus for treating water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve water quality under a high reduction potential to keep the potential over a long period of time. SOLUTION: Three electrolytic cells 20 are arranged in an electolytic bath 10 in which 1% salt water is placed as an electrolyte aqueous solution. Each electrolytic cell 20 is made from porous ceramic consisting mainly of a crystalline clay mineral, and an internal electrode which is formed cylindrically by an aluminum plate and a titanium plate is installed in an electrolytic diaphragm container 21 in which raw water is introduced. Besides, a cylindrical external electrode 23 is arranged opposite to the internal electrode with the container 21 located between the electrodes. High frequency alternating current containing a direct current component is applied between the internal electrode and the external electrode 23 of each electrolytic cell 20 with the polarity inverted time-limitwise.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating ordinary water, that is, water having a strong reducing power, that is, a method for reforming the water so that it has a strong reduction potential, and water used in the treatment method. Regarding a processing device.

[0002]

2. Description of the Related Art Alkaline ionized water and acidic ionized water obtained by electrolyzing water have been widely used in various fields due to their characteristics. Such alkaline ionized water and acidic ionized water are usually placed between the cathode and the anode in a state where the cathode and the anode are arranged in the electrolytic cell and the cathode and the anode are separated by the porous electrolytic diaphragm. A DC voltage is applied.
When a DC voltage is applied between the cathode and the anode, the cathode, and H ⁺ ions are attracted, H ⁺ ions are dissipated becomes H ₂ gas by reaction with electrons in the cathode. As a result, around the cathode, OH ^- ions increase with a decrease in H ⁺ ions, and alkaline ionized water having an alkaline pH value is generated.

[0003] In the vicinity of the anode, OH ^- ions are attracted to the anode, and the OH ^- ions are taken off by the anode to be released as O ₂ gas. As a result, in the neighborhood of the anode, OH ^- with decreasing ion H
⁺ Ions are increased, and acidic ionic water having an acidic pH value is generated.

Alkaline ionized water having an alkaline pH value has a weak oxidizing power and has a reduction potential at which the redox potential (ORP) value becomes negative. The acidic ionized water having an acidic pH value has a strong oxidizing power and has an oxidizing potential with a positive ORP value.

[0005] As described above, the alkaline ionized water and the acidic ionized water obtained by the electrolytic treatment of water have a pH value and O
It is correlated with the RP value and usually cannot be controlled and adjusted separately.

In Japanese Patent Laid-Open No. 5-228474, an alternating current having asymmetric peak values, wave numbers, duty ratios, etc. is applied between the cathode and the anode on the plus side and the minus side of the waveform, Disclosed is a method for modifying the water, in which the ORP value is changed by a direct current generated around each electrode.

Further, in JP-A-6-254567, JP-A-7-31981, and JP-A-8-1166, three electrodes are arranged in water and a high-frequency alternating current is applied between a pair of electrodes. In addition, by passing a direct current between the pair of electrodes and the other electrode, the OR
A method and apparatus for reforming water having a P value with a negative reduction potential is disclosed.

[0008]

It is considered that water having a reduction potential has a large number of freely active electrons, and the energy of the electrons is at a high level. Therefore, as the minus ORP value increases toward the minus side,
The number of active electrons increases, and each electron energy has a high level of strong reducing power. However, in this way, as the ORP value increases toward the negative side, that is, as the reduction potential increases toward the negative side, the electron becomes unstable and tends to release energy and return to a stable state. As a result, the minus ORP value cannot be maintained for a long period of time, and the reduction potential (minus ORP value is
P value) decreases and disappears in a short time.

For this reason, the water modified to have a reduction potential must be used within a short period of time, and its use range is limited, so that there is a problem that it cannot be used over a wide range.

The present invention solves such a problem, and an object thereof is to reform water so that a strong reducing power having a negative ORP value increased to the negative side can be maintained for a long period of time. The object of the present invention is to provide a water treatment method and a treatment device capable of treating the water.

[0011]

According to the method for treating water of the present invention, water to be treated is contained in an electrolytic diaphragm container made of a porous ceramic mainly composed of a crystalline clay mineral, and the electrolytic diaphragm container is filled with an electrolyte. Immersed in an aqueous solution, between the internal electrode containing aluminum placed in the electrolytic diaphragm container, and between the external electrodes placed sandwiching the electrolytic diaphragm container with respect to this internal electrode,
It is characterized in that a high-frequency alternating current containing a direct-current component is applied to bring the water to be treated in the electrolytic diaphragm container to a reducing potential.

It is preferable that the polarities of the internal electrode and the external electrode are reversed in a timed manner, and the internal electrode arranged inside the electrolytic diaphragm container is made of a composite material of aluminum and titanium. It is preferable.

Further, a plurality of electrolytic diaphragm containers are immersed in the electrolytic aqueous solution, and water is stored in each electrolytic diaphragm container.
It is preferable that the reduction potential treatment is performed in order.

The water treatment apparatus of the present invention is made of a porous ceramic mainly composed of a crystalline clay mineral and contains an electrolytic diaphragm container in which water to be treated is housed, and an aluminum container arranged in the electrolytic diaphragm container. An internal electrode containing, and an electrolytic cell having an external electrode arranged to face the internal electrode with an electrolytic diaphragm container sandwiched between them, and an electrolytic cell containing an electrolytic aqueous solution so that the electrolytic cell is immersed, A means for applying a high frequency alternating current containing a direct current component is provided between the inner electrode and the outer electrode of this electrolytic cell.

It is preferable that the polarities of the internal electrode and the external electrode are reversed in a timely manner, and that the internal electrode is made of a composite material of aluminum and titanium.

Further, it is preferable that a plurality of electrolysis cells are arranged in the electrolysis cell, and the treated water is sequentially supplied into the electrolysis membrane container of each electrolysis cell.

The water treatment apparatus of the present invention is made of a porous ceramic mainly composed of a crystalline clay mineral, and an electrolytic diaphragm container in which water to be treated is contained, and the electrolytic diaphragm container. A plurality of electrolysis cells each having an internal electrode containing aluminum arranged, and each electrolysis cell is arranged inside such that a pair of electrolysis cells become annular in a state of being close to each other, and is arranged inside The electrolytic cell containing the aqueous electrolyte solution so that each electrolyzed cell is immersed, and between each internal electrode of the pair of electrolysis cells arranged close to each other, a high-frequency alternating current containing a direct current component is applied. And means for applying.

Preferably, the internal electrodes of each of the electrolytic cells are made of a composite material of aluminum and titanium.

[0019]

Embodiments of the present invention will be described below in detail with reference to the drawings.

FIG. 1 is a sectional view of a main part showing an example of an embodiment of a water treatment device of the present invention. This processor is
It has an electrolytic cell 10 in which an electrolytic aqueous solution composed of about 1% saline solution is housed, and three electrolytic cells 20 each immersed in the electrolytic aqueous solution in this electrolytic cell 10. Each electrolysis cell 20 is adapted to subject ordinary water to a reduction potential treatment in a state having a strong reduction potential.

FIG. 2 is an exploded perspective view of the electrolytic cell 20. Each electrolytic cell 20 is mainly composed of a crystalline clay mineral and has a porous ceramic (fired product) having an amorphous hydrous oxide.
A bottomed cylindrical electrolytic diaphragm container 21 constituted by
Cylindrical internal electrode 22 arranged in electrolytic diaphragm container 21
And a cylindrical external electrode 23 arranged in a fitted state outside the electrolytic diaphragm container 21.

The electrolytic diaphragm container 21 has a bottomed cylindrical main body 21a having an open upper surface and a closed lower surface, and a horizontal outer peripheral surface of the upper end of the main body 21a so as to project horizontally over the entire circumference. It has the flange part 21b provided. The body portion 21a of the electrolytic diaphragm container 21 has a size of 6 to 8 mm.
It is constructed to a certain thickness.

Each electrolytic diaphragm container 21 is linearly arranged, and the main body 21a of the electrolytic diaphragm container 21 arranged at one end accommodates water to be treated to be subjected to reduction potential treatment. It has become so. Then, the treated water subjected to the strong reduction potential treatment in the electrolytic diaphragm container 21 sequentially receives the main body portion 2 of the electrolytic diaphragm container 21 in the adjacent electrolytic cells 20.
It is supplied to the inside of 1a, and further subjected to strong reduction treatment by each electrolysis cell 20. Then, the treated water subjected to the strong reduction potential treatment is taken out in the electrolytic diaphragm container 21 on the side opposite to the electrolytic diaphragm container 21 in which the water to be treated is first stored.

The cylindrical internal electrode 22 arranged in the main body portion 21a of the electrolytic diaphragm container 21 has a thickness of 1.0 to 1.2.
A titanium plate 22a having a thickness of about mm and an aluminum plate 22b having the same thickness are combined to form a cylindrical shape. The titanium plate 22a is formed in a substantially cylindrical shape with each end being appropriately spaced so as to form about 80% of the peripheral surface of the internal electrode 22, and the aluminum plate 22b is
The titanium plate 22a is curved in an arc shape so as to close the space formed between the respective ends. Each side edge of the aluminum plate 22b is attached to each end of the titanium plate 22a by a plurality of rivets 22c. The titanium plate 22a and the aluminum plate 22b have a large number of through holes 22d each having a diameter of 5 to 8 mm.
Are provided respectively.

The titanium plate 22a and the aluminum plate 2
The 2b is not limited to the structure in which it is joined by a rivet, but may be joined by a bolt and a nut.

The internal electrode 22 as described above is 8 to 10 with respect to the inner peripheral surface of the main body portion 21a of the electrolytic diaphragm container 21.
The diameter is set so that the gap of about mm is opened over the entire circumference, and they are concentrically arranged in the main body portion 21a. Titanium plate 22 in internal electrode 22
One end of the lead wire 27 is attached to the upper end of a.

The internal electrode 22 and the external electrode 23 arranged in a fitted state with the main body portion 21a of the electrolytic diaphragm container 21 sandwiched therebetween.
Is formed by forming a stainless plate having a large number of through holes 23a having a diameter of about 5 to 8 mm into a cylindrical shape. A lead wire 28 is also attached to the upper end of the external electrode 23. The material of the external electrode 23 is not limited to stainless steel, but iron or the like may be used.

The flange portion 21b of the electrolytic diaphragm container 21 is
It is in a closed state by the disc-shaped lid 24. The lid 24 is pressed against the upper surface of the flange portion 21b via the ring-shaped packing 23. Then, the lid body 24 is fitted to the main body portion 21a of the electrolytic diaphragm container 21 and a plurality of bolts 26 are attached to the ring-shaped stop plate 25 abutted against the lower surface of the flange portion 21b.
And the flange portion 21b of the electrolytic diaphragm container 21 is hermetically sealed by the packing 23.

A lead wire 27 attached to the upper end of the main body portion 22a of the internal electrode 22 is inserted into the lid body 24 in an airtight state. Further, a discharge pipe 31 for discharging the treated water treated in the main body portion 21a of the electrolytic diaphragm container 21 from the main body portion 21a is inserted in an airtight state. An exhaust pipe 32 for discharging hydrogen generated in the main body portion 21a of the electrolytic diaphragm container 21 is connected to the discharge pipe 31.

The water to be treated is supplied in order into the electrolytic diaphragm containers 21 of the three electrolytic cells 20 arranged in the electrolytic cell 10, and the most upstream side in the supply direction. A water injection pipe 33 for injecting water to be treated into the electrolytic diaphragm container 21 is inserted into the electrolytic cell 20 located in the airtight state of the lid body 24. Then, the most upstream electrolysis cell 20
The water treated in the electrolytic diaphragm container 21 is supplied to the electrolytic diaphragm container 21 of the adjacent central electrolytic cell 20 through the water supply pipe 31, and further, the electrolytic diaphragm container of the central electrolytic cell 20. The water treated in 21 passes through the water supply pipe 31 and is supplied into the electrolytic diaphragm container 21 of the adjacent most downstream electrolytic cell 20. Then, the water treated in the electrolytic diaphragm container 21 of the most downstream electrolytic cell 20 is taken out through the water supply pipe 31.

Internal electrodes 22 in three electrolysis cells 20
A high-frequency current containing a DC component is supplied between each lead wire 27 connected to each of the electrolysis cells 20 and each lead wire 28 connected to the external electrode 23 of each electrolysis cell 20.

As the high frequency current supplied between the lead wires 27 and 28, as shown in FIG. 2, a normal 50 Hz or 60 Hz alternating current is supplied to the high frequency alternating current generation circuit 41, and the high frequency current generation circuit 41 causes the high frequency current to be generated. A high frequency alternating current including a direct current component is supplied to the lead wires 27 and 28 via the polarity reversing circuit 42. The high frequency generation circuit 41 first converts an alternating current into a direct current,
Next, this direct current is converted into high-frequency alternating current with a small amount of direct current component left.

The polarity reversing circuit 42 is connected to the lead wire 27.
One of the two and 28 has a positive polarity for a predetermined time, and the other has a negative polarity for that time. And after that predetermined time,
The state in which the positive polarity and the negative polarity are reversed is maintained for a predetermined time. The polarity reversing circuit 42 is provided with a timer 43 that sets a time period during which each polarity is maintained. The high-frequency alternating current including the direct-current component output from the high-frequency alternating-current generation circuit 41 is applied to the lead wires 27 and 28 from the polarity reversing circuit 42, and the inside of each electrolytic cell 20 is passed through the lead wires 27 and 28. It is applied to the electrode 22 and the external electrode 23, respectively.

The high-frequency alternating current containing the direct-current component output from the high-frequency alternating-current generating circuit 41 contains a direct-current component of about 10-40%, the voltage is variable between 0-220V, and about 6-15A. Output of Further, the frequency of the high frequency alternating current may be set to around 30 Hz. In addition, the polarity reversal by the polarity reversing circuit 42 is
It will be carried out on the order of several minutes.

In the water treatment device having such a structure, the three electrolytic cells 20 are immersed in the electrolytic aqueous solution in the electrolytic cell 10 and the electrolytic diaphragm container 21 of each electrolytic cell 20 is
Water to be treated is sequentially added. Then, in a state in which the water to be treated has been poured into one of the electrolytic diaphragm containers 21, the high frequency alternating current including the direct current component has its polarity reversed in a timed manner to the internal electrode 22 and the external electrode 23 of each electrolytic cell 20. Applied in the state.

At this time, if the internal electrode 22 has a positive polarity, the water to be treated in the electrolytic diaphragm container 21 is acidified in proportion to the amount of electricity supplied, and titanium, which is a constituent substance of the internal electrode 22, is also formed. Plate 22a and aluminum plate 22b
From, a trace amount of titanium ions and aluminum ions are eluted. On the contrary, when the internal electrode 22 has a negative polarity, the water to be treated is alkalized in accordance with the amount of electricity applied, and the water to be treated in the electrolytic diaphragm container 21 is made of a porous ceramic mainly composed of a crystalline clay mineral. A small amount of silicon ions is eluted from the electrolytic diaphragm container 21.

Then, in the water to be treated in the electrolytic diaphragm container 21, the dipole arrangement of the non-ionized water molecules is polarized, the eluted silicon compound is monomerized, and water for aluminum ions is added. The coordination of the molecule is changed. That is, the monomerized silicon compound and aluminum ions are surrounded by the electrons migrating from surrounding water molecules. Therefore, the water in the electrolytic diaphragm container 21 has a redox potential (ORP). It will be in a state of becoming larger on the negative side. In this case, in the limited system, the silicon compound and the aluminum ion are not in a stable state, but the electron energy is frequently exchanged between them and the metastable state is slowly changed. Since it is considered that the water in the electrolytic diaphragm container 21 shifts to the stabilized state, the water in the electrolytic diaphragm container 21 can maintain the reduction potential state of the negative ORP value for a long period of time.

Moreover, by sequentially performing such a reduction potential application process in each electrolytic cell 20, the water in each electrolytic diaphragm container 21 has a strong negative ORP value further increased to the negative side. With a reduction potential,
The negative ORP value can also persist for long periods.

Therefore, in order to increase the minus ORP value of the treated water to the minus side, the energization amount of the high frequency alternating current may be increased.

As described above, the direct current component contained in the high frequency alternating current has the polarity of the internal electrode 22 and the external electrode 23 in order to acidify and alkalize the water in the electrolytic diaphragm container 21 depending on the polarity of the internal electrode 22. The water in the electrolytic diaphragm container 21 can be neutralized by reversing the water in a timely manner. In addition, the internal electrode 22 and the external electrode 23
It is also possible to set an arbitrary pH value by appropriately setting the ratio of the time of the positive polarity to the time of the negative polarity. Inversion of the positive polarity and the negative polarity in the internal electrode 22 and the external electrode 23 may not sufficiently elute, diffuse, or react a predetermined component from the internal electrode 22 and the electrolytic diaphragm container 21 in the order of several seconds. Therefore, it is preferable to invert it on the order of several minutes.

The electrolytic diaphragm container 21 is composed of a porous ceramic mainly composed of a crystalline clay mineral in order to elute the silicon compound into the water in the electrolytic diaphragm container 21,
When only the crystalline clay mineral is fired, it becomes a soft state and sufficient mechanical strength cannot be obtained, so alumina is mixed with the crystalline clay mineral to improve the strength of the fired product, It is preferable to adjust the ratio (Cayvan ratio) of the clay minerals silicon (Si) and aluminum (Al).

The internal electrode 22 may contain aluminum so as to elute aluminum ions into the water in the electrolytic diaphragm container 21. As in the above-described embodiment, aluminum and titanium (T
When a composite material with i) is used, the electrolytic diaphragm container 2
Titanium ion (Ti ⁴⁺ ) which is considered to be eluted and remained in the water to be treated in 1 is harmless, and is excited by ultraviolet energy to be frequently converted into Ti ³⁺ and Ti ^4+. As a result, it is considered that the energy is consumed.
Prevents deterioration of the RP value. Therefore, when it is feared that the minus ORP value is deteriorated by the ultraviolet rays of sunlight, such as when the obtained treated water is stored in a transparent container, it is preferable to use a composite material of aluminum and titanium. .

The electrolyte solution and the external electrode 23 contained in the electrolytic cell 10 have an auxiliary function for supplying electricity to the electrolytic diaphragm container 21 and the water to be treated therein. A salt solution of about 1% is sufficient as the electrolyte solution. The material of the external electrode 23 is not particularly limited, and stainless steel, iron, carbon or the like is used. When iron is used as the external electrode 23, iron is eluted into the electrolyte solution and contaminates it. However, by using carbon,
Such contamination can be prevented. In any case, the direct current component applied between the external electrode 23 and the internal electrode 22 is small, and the external electrode 23 and the internal electrode 2 are
Contamination of the electrolyte solution is suppressed because the polarity of 2 is reversed.

The reason why the obtained treated water is made to have a strong reducing potential and the strong reducing potential state is maintained for a long period of time will be described in more detail.

In the electrolysis cell 20, the equilibrium state of water molecules is disturbed by the high-frequency alternating current applied between the internal electrode 22 and the external electrode 23. However, the action of the current disappears at the moment when the direction of the waveform of the high frequency component reverses,
A relaxation phenomenon occurs that tries to return to the equilibrium state. The relaxation time has a difference of several orders of magnitude between a water molecule that functions as a dipole and an ion that coexists with the water molecule. Therefore, in the frequency range of 1 to 30 Hz, the polarization of water has priority. It is thought to occur. As a result, the dipole arrangement of the water molecules, which seems to have a cluster (molecular group) shape, is polarized, and the cohesive force of the clusters of water molecules is relaxed or eliminated, and The balance is disturbed. However, in this case, the pH value changes little.

The disturbance of the electronic equilibrium state becomes larger as the energization amount of the high frequency alternating current becomes larger and the frequency becomes higher, and the ORP value becomes the reduction potential which becomes larger to the negative side.

Since the disturbance of the electronic equilibrium state is resolved and stabilized in about several hours to 24 hours by energizing only the high-frequency alternating current, the minus ORP value also varies from several hours to several hours.
Over the course of 24 hours, the deterioration gradually increases to the positive side.

However, the high frequency alternating current applied between the inner electrode 22 and the outer electrode 23 contains a direct current component, and this direct current component suppresses the deterioration of the minus ORP value.

That is, when the internal electrode 22 has a positive polarity, oxygen is generated from the surface of the internal component 22 due to the direct current component contained in the high frequency alternating current, and at the same time, the aluminum plate 22b and the titanium plate 22a forming the internal electrode 22 have A
Ions such as l ³⁺ and Ti ⁴⁺ are eluted. As a result, in the vicinity of the positive polarity internal electrode 22, Al
₂ O ₃ , TiO _2, etc. are mixed. On the contrary, when the internal electrode 22 has a negative polarity, OH ⁻ is generated in the treated water to be alkalized in the periphery of the internal electrode 22, and silicic acid (SiO 2) contained in the crystalline clay material forming the electrolytic diaphragm container 21 is formed. ₄ ) elutes in the treated water that has been made alkaline. Eluted silicic acid particles (crystal)
Is a colloidal size, but the silanol group (-SiOH) covering the surface of the particle has a property of repeating hydrogen bonds with water molecules and is highly hydrophilic. When the amount of OH ⁻ generated in the treated water in the electrolytic diaphragm container 21 increases, the four O atoms surrounding the Si atoms in the polysilicic acid (SiO ₄ ) are replaced by the four OH ⁻ to replace the monosilicic acid (Si (OH) 4). ₄ ) Monomerized ones increase.

At this time, O in (Si (OH) ₄ )
Since H ⁻ is larger than the O atom in SiO ₄ ,
In its three-dimensional structure, there are many gaps, centering on the Si atom,
It is considered that there is also a structure (Si (OH) ₆ ²⁻ ) in which ₆ OH ⁻ are coordinated.

Furthermore, when the polarities of the internal electrode 22 and the external electrode 23 are reversed in a timely manner, Al ³⁺ and Al ₂ O generated by the internal electrode 22 becoming a positive polarity.
₃ is considered to be converted into Al (OH) ₃ and Al ³⁺ by the negative polarity of the internal electrode 22, but the ion diameter of Al ³⁺ is about 0.050 nm and the internal electrode 22 Is slightly larger than the ion diameter of Si ⁴⁺ existing at the center of Si (OH ₆ ) ²⁻ , which is caused by the negative polarity of Si (OH ₆ ) ²⁻ , is slightly larger than that of Al (OH) ₃ structure. in somewhat different forms, four OH around the Al atom ^- is sterically coordinating Al (OH) ₄ ^- states, or six OH ^- is sterically coordinated Al (OH) It is considered that the state of ₆ ³⁻ , in rare cases, 5 OH ⁻ is three-dimensionally coordinated.

Al, if present as Al (OH) ₃ , is an amphoteric element that functions as a base if the reacting environment is acidic, and conversely functions as an acid if the reacting environment is alkaline. For this reason, when the internal electrode 22 has a positive polarity, electrons are likely to be lost in the environment around the internal electrode 22, and conversely, when the internal polarity is negative, electrons are likely to be obtained in the environment around the internal electrode 22. Further, when the internal electrode 22 has a negative polarity, hydrogen bubbles are violently generated in the peripheral portion of the internal electrode 22, so that an environment in which electrons are more easily obtained is created. Therefore, by reversing the polarities of the internal electrode 22 and the external electrode 23, it is considered that four or six, rarely five OH ⁻ are sterically coordinated around the Al atom.

As described above, in the treated water, SiO ₄ becomes S
The treated water has a negative ORP value because it is converted to i (OH) ₆ ²⁻ and Al (OH) ₄ ⁻ , Al (OH) ₆ ^3−, etc. are also generated. A large strong reduction potential state is set on the side. Furthermore, A eluted in the treated water
l (OH) ₄ ⁻ and Al (OH) ₆ ³⁻ are coexisted or converted into hydroxyl ion H ₃ O ₂ ⁻ via a water molecule even when OH ⁻ is unstable. Si (O
By being converted as, ^- OH in H) ₆ ^2-
In a limited system, it is considered to stabilize slowly in a metastable state. Therefore, in the treated water, the minus ORP value remains stable over a long period of time.

The electron energy in the treated water is given to the object, if any, to receive the energy, and exerts a reducing action.
It returns to normal water with a deteriorated P value.

A direct current applied between the inner electrode 22 and the outer electrode 23 elutes a small amount of substance in the treated water, whereby the pH value of the treated water changes. However, the pH of the treated water is controlled by controlling the energization time of the DC component between the inner electrode 22 and the outer electrode 23.
A desired pH value can be obtained by suppressing a change in the value. The value of the treated water is controlled by proportionally distributing the energization time during which the internal electrode 22 has a negative polarity and the energization time during which the internal electrode 22 has a positive polarity.

Further, the pH value of the treated water can be controlled by adjusting the amount of Al ions eluted in the treated water. The amount of Al ions is indirectly determined by adjusting the area ratio of the aluminum plate 22b and the titanium plate 22a with the internal electrode 22 being a composite type of the aluminum plate 22b and the titanium plate 22a, as in the above-described embodiment. The pH value can be adjusted. Aluminum plate 22
The area ratio of b to the titanium plate 22a is 1: 9 to 5: 5.
And it is sufficient.

In order to adjust the pH of the treated water to the neutral range,
Theoretically, OH ⁻ or O ⁺ should be 10 ⁻⁷ mol. Therefore, the presence of Si (OH) ₆ ^2- , which is necessary to adjust the pH of the treated water to around 12, is 10 mg /
About L is sufficient, and the necessary total of Al (OH) ₄ ⁻ and Al (OH) ₆ ³⁻ coexisting with Si (OH) ₆ ²⁻ in the treated water is converted to Al, and is equal to 1 of the Si amount. A minute amount of about / 100 is sufficient.

The silicate minerals eluted in the treated water are colloidal particles having a negative charge on the surface and having a size of about 0.1 to 1.0 μm, and are used for producing Si (OH) ₆ ^2−. Required but surplus is Al (OH) ₄
The presence of ⁻ and Al ³⁺ that does not contribute to the formation of Al (OH) ₆ ³⁻ reduces the negative charge on the surface, promotes collision of colloidal particles, and causes aggregation. When the colloidal particles collide with each other, the SiOH group covering the surface of the colloidal particle is converted into a siloxane bond (SiOH + HOSi = Si-O-).
Si + H ₂ O) is generated, and the particles are bonded to each other. The bound colloidal particles suspend the treated water in a degree of turbidity that exhibits the Tyndall phenomenon. However, in this case, since minerals and organic substances such as Ca and Mg contained in the water to be treated are adsorbed around the surface to grow into cotton-like aggregates and rapidly settle at a speed of about 1 cm / min, No special work is required to separate the colloidal particles by microfiltration, dialysis or the like.

When the colloidal particles are settled, the supernatant water has no colloidal particles, is colorless and transparent, and has a taste that is not uncomfortable, and is suitable for the water quality standard of tap water. The colloidal particles of silicic acid are harmless, and even if they remain in the supernatant water, there is no problem.

The strong reducing potential water obtained by the treatment method and the treating apparatus of the present invention has a reduction potential similar to that of the reducing water obtained by the reducing action over a long period of time in nature, or the ORP value becomes negative. The reduction potential is used. Therefore, like reduced water obtained in the natural world, it has excellent osmotic pressure and is easily taken into the body, so that it can be used as drinking water for improving physical constitution, as well as liquor,
It can be added to tea, juice, etc., or used for cooking. It is also preferably used as a lotion.
Moreover, since the strong reduction potential is maintained for a long time, it is easy to store, and by storing a large amount, a large amount can be used at any time. Further, since the pH value can be set to an arbitrary value, the pH value can be set according to the application, and neutral or acidic strong reducing potential water can be obtained.

Further, in the treatment process of strongly reducing potential water, since the water repeatedly undergoes a strong acidic environment and a strong alkaline environment, the strongly reducing potential water is used for survival of aerobic bacteria, anaerobic bacteria and the like. Is not suitable environment, and it can be expected to have dephosphorization and denitrification effects. Even under normal storage conditions, there is no risk of spoilage over a long period of time.

FIG. 3 is a schematic plan view showing another example of the embodiment of the water treatment apparatus of the present invention. In this water treatment device, for example, four electrolytic cells 20 are used by being immersed in the electrolyte solution in the electrolytic cell 10. Each electrolytic cell 20
It is composed of a bottomed cylindrical electrolytic diaphragm container 21 and a cylindrical internal electrode 22 housed in the electrolytic diaphragm container 21, and no external electrode is provided. The four electrolytic cells 20 are annularly arranged in the electrolytic cell 10 with the pair of electrolytic diaphragm containers 21 being close to each other.

A pair of electrolytic diaphragm containers 21 adjacent to each other in the circumferential direction.
A high-frequency alternating current containing direct-current components having different polarities from each other is applied between the internal electrodes 22 arranged at. Then, the polarities of the pair of internal electrodes 22 to which the high frequency component is applied are inverted in a timely manner.

In this case, the peripheral surfaces of a pair of electrolytic diaphragm containers 21 adjacent to each other in the circumferential direction are positioned between the internal electrodes 22 in each electrolytic diaphragm container 22, and are applied between the internal electrodes 22. By the high-frequency alternating current having the direct current component, the water in each electrolytic diaphragm container 21 is subjected to the reduction potential treatment as in the water treatment device of the above-described embodiment. Then, the water treated in each porous electrolytic diaphragm container 21 is sequentially supplied into the electrolytic diaphragm containers 21 adjacent to each other in the circumferential direction, and in each electrolytic diaphragm container 21, a strong reducing potential is sequentially applied. It is processed.

The number of electrolytic diaphragm containers 21 is not limited to four as described above, but may be six as shown in FIG. 4, for example.

[0066]

【Example】

<Example 1> Water to be treated was treated by the water treatment apparatus shown in FIGS. 1 and 2. As the electrolytic diaphragm container 21 of each electrolytic cell 20 in the treatment apparatus, a clay substance containing leucome clay as a main component mixed with about 10% by weight of alumina powder,
An inner diameter of 110 mm, a depth of 180 mm, and a thickness of 6 mm were used, which was fired at a temperature of about 850 ° C. The internal electrode 22 has a thickness of 1.0 mm and an inner diameter of 8 mm.
Using an aluminum plate 22b and a titanium plate 22a having a large number of mm through holes at an area ratio of 1: 9, the inner diameter of the upper end is 100 mm, the inner diameter of the lower end is 85 mm, and the height is 15
A cylindrical structure having a diameter of 0 mm was used. External electrode 2
For No. 3, a punching plate made of stainless steel (SUS304) having a large number of through holes having a thickness of 1.0 mm and an inner diameter of 8 mm was used in a cylindrical shape having an inner diameter of 170 mm and a height of 180 mm.

The electrolytic cell 10 was filled with a saline solution having a concentration of about 1%, and each electrolytic cell 20 was immersed in the saline solution. Then, in the electrolytic diaphragm container 21 of each electrolytic cell 20,
7.21, well water with ORP value of +256 mV, 8.0
Flow was at a rate of liter / hour. The effective treatment amount in each electrolytic cell 20 was expected to be 1.2 liters.

The internal electrode 22 and the external electrode 23 of each electrolysis cell 20 are supplied with a high-frequency alternating current containing a direct current component.
It was applied at a constant V. This high frequency alternating current is applied to the internal electrode 22.
Is negative polarity, the alternating current is 6.0A (direct current is 1.9A), and the internal electrode 22 is positive polarity, the alternating current is 3.8A (direct current is 1.5A). Met. The polarities of the internal electrode 22 and the external electrode 23 were reversed so that the positive polarity for 5 minutes and the negative polarity for 4 minutes were alternately repeated.

In this way, the water to be treated is sequentially treated by the three electrolysis cells 20 to obtain the final electrolysis cell 20.
The treated water obtained from the discharge pipe 31 of the electrolytic diaphragm container 21 was left for about 30 minutes to sufficiently settle the flocculates and the like, and the supernatant water was collected. The pH was 9.7.
2, treated water having an ORP of -833 mV was obtained.

The treated water obtained was colorless, transparent and odorless, and had a mild drinking sensation.

The pH value and ORP value of the water to be treated and the treated water were measured by a measuring instrument manufactured by Toa Denpa Kogyo Co., Ltd. (trade name "HM-14P type", pH electrode "GST-2419C").
Type ”, and ORP electrode“ PTS-2019C type ”). With treated water, it takes about 3 minutes for the measured value to reach a constant value when measuring the pH value, and 20 minutes or more for the measured value to reach a constant value when measuring the ORP value. Although sometimes required, the measurement time was 3 minutes. OR
The potential of the comparison electrode at the P value is omitted.

The resulting treated water was sealed in a transparent container and stored indoors. After 7 days, the pH was 9.68,
RP is -702 mV, after 15 days, pH is 9.66,
ORP is -322 mV, pH is 9.6 after 30 days.
1, ORP was -159 mV, and after 45 days, pH was 9.
56, ORP +2 mV, pH after 60 days is 9.5
1, ORP was +58 mV.

The treated water thus obtained was sealed in a transparent container and kept refrigerated in a light-shielded state.
H is 9.71, ORP is -760 mV, and after 15 days,
pH is 9.70, ORP is -351 mV, pH is 9.62, ORP is -179 mV after 30 days, pH is 9.59, ORP is -94 mV after 45 days, and pH is 60 days after. The ORP was -55 mV at 9.55.

<Second Embodiment> In the first embodiment, the positive polarity of the internal electrode 22 is changed to AC current 4.2A (DC 1.7).
A) was applied for 10 minutes, and the negative polarity of the internal electrode 22 was applied for 2 minutes with an alternating current of 6.5 A (direct current 2.1 A). Other conditions are the same as in the first embodiment. The treated water thus obtained required 60 minutes in order to sufficiently settle the flocculates and the like. The supernatant water of the treated water has a pH value of 4.64, ORP
The value was -491 mV. The resulting treated water is colorless,
It was transparent and odorless and had a mellow drinking feel.

The treated water obtained was sealed in a transparent container and stored indoors. After 7 days, the pH was 5.08,
RP is -99 mV, pH is 5.10, O after 15 days
RP is +2 mV, pH is 4.97, OR after 30 days
P +103 mV, after 45 days, pH 4.79, O
RP is +211 mV, pH is 4.54 after 60 days,
The ORP was +399 mV.

The treated water obtained was sealed in a transparent container and refrigerated in the light-shielded state.
H is 5.02, ORP is -178 mV, and after 15 days,
pH 5.04, ORP -15 mV, after 30 days,
pH is 4.82, ORP is +88 mV, and after 45 days,
The pH was 4.60, the ORP was +196 mV, and after 60 days, the pH was 4.41 and the ORP was +383 mV.

<Example 3> In Example 1, tap water having a pH value of 7.11 and an ORP value of +421 mV was used as the water to be treated. Other conditions are the same as in the first embodiment. The treated water thus obtained required 30 minutes in order to fully settle the flocculates and the like. The supernatant water of the treated water had a pH value of 9.67 and an ORP value of -766 mV. When the obtained treated water was compared with the tap water used as the water to be treated, it was excellent in color and transparency, had no chlorine odor, and had a mild drinking sensation.

Example 4 In Example 1, industrial water having a pH value of 7.42 and an ORP value of +712 mV was used as the water to be treated. Other conditions are the same as in the first embodiment. The treated water thus obtained required 30 minutes in order to fully settle the flocculates and the like. The clear water of the treated water is
The pH value was 9.89 and the ORP value was -702 mV.
The amount of the precipitate is slightly larger than that in Example 3, and
The color was slightly brownish, but when compared with the water to be treated, it was superior in color and transparency, had no chlorine odor, and had a mild drinking sensation.

<Example 5> In Example 1, a punching plate made of stainless steel was used as the internal electrode 22. Other conditions are the same as in the first embodiment. The supernatant water of the obtained treated water had a pH value of 9.85 and an ORP value of -622 m.
Although it was V, it was slightly colored in brown.

<Embodiment 6> In the first embodiment, a platinum (P
What was plated with t) was used. Other conditions are the same as in the first embodiment. The supernatant water of the obtained treated water has a pH
Value is 9.49, ORP value is -702 mV, colorless,
It was transparent and odorless.

[0081]

INDUSTRIAL APPLICABILITY As described above, the water treatment method and apparatus of the present invention can easily produce strong reducing potential water having an arbitrary pH value. In addition, since the obtained strong reduced water potential is maintained for a long time, it can be used over a wide range. Moreover, the water to be treated does not need to be subjected to any special pretreatment, and can be always subjected to the strong reducing potential treatment by the small and compact treatment apparatus of the present invention.

[Brief description of drawings]

FIG. 1 is a sectional view of essential parts showing an example of an embodiment of a water treatment apparatus of the present invention.

FIG. 2 is an exploded perspective view of an electrolytic cell used in the water treatment device.

FIG. 3 is a schematic plan view showing another example of the embodiment of the water treatment apparatus of the present invention.

FIG. 4 is a schematic plan view showing still another example of the embodiment of the water treatment apparatus of the present invention.

[Explanation of symbols]

 10 Electrolytic Tank 20 Electrolytic Cell 21 Electrolytic Diaphragm Container 22 Internal Electrode 23 External Electrode

Claims (10)

[Claims] 1. A treated water is contained in an electrolytic diaphragm container made of a porous ceramic mainly composed of a crystalline clay mineral, and the electrolytic diaphragm container is immersed in an aqueous electrolyte solution and placed in the electrolytic diaphragm container. Applying a high-frequency alternating current containing a direct current component between the internal electrode containing aluminum and the external electrode arranged with the electrolytic diaphragm container sandwiched with respect to this internal electrode,
A method for treating water, which comprises subjecting water to be treated in an electrolytic diaphragm container to a reduction potential. 2. The polarities of the internal electrode and the external electrode are
The method for treating water according to claim 1, wherein the water is reversed in a timed manner. 3. The water treatment method according to claim 1, wherein the internal electrode arranged inside the electrolytic diaphragm container is made of a composite material of aluminum and titanium. 4. The method for treating water according to claim 1, wherein a plurality of electrolytic diaphragm containers are immersed in the electrolytic aqueous solution, and water is sequentially subjected to reduction potential treatment in each electrolytic diaphragm container. 5. An electrolytic diaphragm container made of a porous ceramic mainly composed of a crystalline clay mineral and containing water to be treated therein, an internal electrode containing aluminum arranged in the electrolytic diaphragm container, and An electrolytic cell having an external electrode arranged opposite to the internal electrode with an electrolytic diaphragm container interposed therebetween, an electrolytic cell containing an aqueous electrolyte solution so that the electrolytic cell is immersed, an internal electrode of the electrolytic cell and A means for applying a high frequency alternating current containing a direct current component between the external electrodes, and a water treatment device. 6. The water treatment device according to claim 5, wherein the polarities of the inner electrode and the outer electrode are reversed in a timed manner. 7. The water treatment apparatus according to claim 5, wherein the internal electrode is made of a composite material of aluminum and titanium. 8. The treatment of water according to claim 5, wherein a plurality of electrolysis cells are arranged in the electrolysis tank, and treated water is sequentially supplied into the electrolysis diaphragm container of each electrolysis cell. apparatus. 9. An electrolytic diaphragm container made of a porous ceramic mainly composed of a crystalline clay mineral and containing water to be treated, and an internal electrode containing aluminum arranged in the electrolytic diaphragm container. , A plurality of electrolysis cells each having, and each electrolysis cell being arranged inside so that a pair of electrolysis cells are in a state of being close to each other, and each electrolysis cell placed inside is immersed. As described above, and a means for applying a high frequency alternating current containing a direct current component between the internal electrodes of each of a pair of electrolytic cells arranged in close proximity to each other, and an electrolytic cell containing an aqueous electrolyte solution. A water treatment device characterized by: 10. The water treatment apparatus according to claim 9, wherein the internal electrodes of each of the electrolysis cells are each made of a composite material of aluminum and titanium.