JPH0676672B2 - Electrolytic ozone water production equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to an electrolytic ozone water producing apparatus.

"Prior art" Conventionally, an electrolysis that sandwiches a solid electrolyte membrane between an anode electrode and a cathode electrode, applies a DC voltage between both electrodes, and feeds water to both sides of the solid electrolyte membrane in contact with the anode to generate ozone. A formula ozonizer has been proposed, and the anode contact surface side of the solid electrolyte membrane of this electrolytic ozonizer is used as raw material water in a water tank,
Alternatively, attempts have been made to obtain ozone water by contacting the raw material water in the water channel.

And, as for this type of electrolytic ozone water producing apparatus, various materials and shapes of the solid electrolyte membrane and both electrodes functioning as a catalyst have been proposed, and recently, ozone water having a concentration of 10 ppm or more has been obtained. ing.

[Problems to be Solved by the Invention] However, it was tested that this type of electrolytic ozone water production device does not always exhibit the ozone water production capacity in a predetermined manner when the operation and the rest are sequentially repeated. It turned out.

That is, from the state where ozone water of a predetermined concentration is obtained by the operation, the time until the ozone concentration reaches the predetermined ozone concentration after suspending the temporary operation and restarting the operation is not constant. If it is long, it takes a long time to reach a predetermined ozone concentration after the operation is restarted, and this time tends to be longer as the cumulative total of the rest times becomes longer.

Therefore, the conventional apparatus has a drawback that the time until the desired ozone concentration is reached becomes longer after the operation is restarted as the operation and the rest are repeatedly used.

When the cause of the above phenomenon was clarified, one of the causes was that a turtle vane current flowed between the dissimilar metals of both electrodes when the operation was stopped. It has been confirmed as a result of experiments that this galvanic current is a current in a direction opposite to that at the time of ozone generation, and thus causes wear of the solid electrolyte membrane and inactivation of catalytic functions of both electrodes. It is also said that this galvanic current disturbs the ion clusters of the solid electrolyte membrane, and it is also explained that the electronic behavior is disturbed when the operation is restarted, and the start of the ozone generation ability is delayed.

Further, another cause is that various bacteria sometimes abnormally propagate after the decomposition and elimination of ozone during operation stop, and the generated ozone is initially consumed for the oxidation of the various bacteria. It has been reported that there are many reports that bacteria are more prone to abnormal growth in water that has been once made aseptic than in natural water.If the electrolytic ozonizer is stopped and the ozone water tank is left unattended, The raw material water in the aquarium is sterilized by ozone water, once sterilized, and the sterilizing action disappears when ozone is completely decomposed, so if microorganisms invade from the air in this state, various microorganisms in natural water Although they are balanced and balanced to each other, once aseptic condition is reached, a single or a small number of types of bacteria can be freely propagated. Therefore, if the ozone water of a predetermined concentration is used because a predetermined time has passed since the device was restarted, the generated ozone is water that is consumed only by the oxidation of bacteria and ozone is not dissolved,
Or, there was no danger of using water with residual bacteria.

"Purpose" Therefore, the present invention has been made in view of the above, it is possible to prevent the wear of the solid electrolyte membrane and both electrodes even when the operation is stopped, and there is no risk that abnormal bacteria will propagate abnormally, and after the operation is restarted, the ozone generation ability The object is to provide an electrolysis type ozone water production apparatus whose start is always constant.

[Means for Solving Problems] In order to solve the above-mentioned problems, the structure of the present invention based on the above-mentioned claims is made in accordance with the above-mentioned object by using the solid electrolyte membrane 1 as the anode chamber 13 And the negative electrode chamber 14 and the anode chamber
An anode electrode 3 is housed in 13 and a cathode electrode 4 is housed in a negative electrode chamber 14 in an overlapping manner on the solid electrolytic chamber membrane 1, and a water inlet for circulating raw material water through the anode chamber 13 in the container 10. 11 and outlet 17
And a power supply device 50 for connecting the positive electrode 3 and the negative electrode 4 to each other.
Is a high-voltage output terminal 51 to be applied between the anode electrode 3 and the cathode electrode 4 during normal operation, and one-third to one-half the voltage of the high-voltage output terminal 51. And a low voltage output terminal 52 for applying the voltage of
The anode electrode 3 and the cathode electrode 4 are connected to each other through a changeover switch 54 for switching and connecting the high voltage output terminal 51 side and the low voltage output terminal 52 side.

"Action" Oxygen is generated when water is electrolyzed in the usual way,
It is known that a part of the generated oxygen exhibits a phenomenon that some ozone is contained. The amount of ozone mixed in is extremely low in normal electrolysis of water, but by changing the materials of the electrodes and applying a voltage three times or more the minimum voltage required for electrolysis of normal water In the present invention, ozone water is obtained by electrolysis as in the conventional case.

The electrolytic ozone water producing apparatus of the present invention is applied with a voltage that is ⅓ to ½ of the voltage during normal operation even after the operation is stopped. Alternatively, oxygen continues to be generated and acts to prevent the growth of bacteria in the raw material water.

And, the current at the time of the above operation suspension is in the same direction as during the operation, so that the electronic behavior of the solid electrolyte membrane and both electrodes due to the reverse current is normally maintained, the wear of the solid electrolyte membrane and the catalytic function of both electrodes are suppressed. It is capable of preventing inactivation and being able to respond instantly when the operation is restarted.

[Example] Next, an example of the present invention will be described below with reference to the accompanying drawings.

In the figure, 100 is an electrolytic ozonizer, which sandwiches the solid electrolyte membrane 1 between an anode electrode 3 and a cathode electrode 4, applies a DC voltage between both electrodes 3 and 4, and contacts the anode electrode 3 of the solid electrolyte membrane 1. As in the conventional case, water is supplied to the surface side to generate electrolytic ozone.

As the solid electrolyte membrane 1, the same fluorine-based cation exchange membrane as the conventional one is used, and the thickness thereof can be appropriately selected, but in the present embodiment, the solid electrolyte membrane 1 has a thickness of 100 to 800 microns. The solid electrolyte membrane 1 usually used has a thickness of less than 100 microns, but the thicker compared to the conventional one is that the resistance value is increased to operate at high potential and small current. However, it is fundamentally different from the conventional idea of increasing the current and increasing the passage of hydrogen ions,
An electric current more than necessary applies stress to the solid electrolyte membrane 1 to stop the function of the ion clusters and further destroys the reticulated ion cluster structure itself. The solid electrolyte membrane 1 is 0.3 amperes at room temperature. / cm and deterioration increases ^more performing continuous energization, it is desirable that the thickness the solid electrolyte membrane 1 be set to a current value of less than 0.3 amps / cm ² in relation to the later direct voltage.

The anode electrode 3 is composed of a corrosion-resistant metal that has air permeability and air permeability and overlaps one surface of the solid electrolyte membrane 1. Specifically, a noble metal such as gold or platinum or lead dioxide is effective as an ozone generation catalyst. It has been confirmed that this is the case, and it is the same as in the prior art that a corrosion resistant metal having a function as an ozone generating catalyst provided with a large number of ventilation portions 2 is used, and the anode electrode 3 is Although a conventionally known one may be used, in the illustrated example, the anode electrode 3 is made of porous corrosion-resistant metal 3a.
And having a large number of contact portions and non-contact portions on the surface of the solid electrolyte membrane 1 interposed between the porous corrosion-resistant metal 3a and the solid electrolyte membrane 1 and electrically connected to the porous corrosion-resistant metal 3a. It is composed of solid solid lead dioxide 3b, and the space portion 5 formed in the non-contact portion of the lead dioxide 3b with the solid electrolyte membrane 1 communicates with the ventilation portion 2 of the porous corrosion-resistant metal 3a.

That is, the porous corrosion-resistant metal 3a is made of a material that is not easily corroded by generated oxygen and ozone, for example, stainless steel, nickel, noble metal or the like is used (composition of these is also possible, and stainless steel is plated with platinum in this embodiment. What has been used is used.) In the illustrated example, the ventilation portion 2 for ensuring air permeability of the porous corrosion-resistant metal 3a is formed by forming the porous corrosion-resistant metal 3a in a lattice shape, in other words, forming a mesh shape, and forming the mesh as the ventilation portion 2. However, in addition to this, a plate provided with a large number of small holes or slits as the ventilation part 2 and a thin porous corrosion-resistant metal 3a juxtaposed in a stripe shape to form the ventilation part 2 in the space between them are not shown. Good.

The solid solid lead dioxide 3b interposed between the porous corrosion-resistant metal 3a and the solid electrolyte membrane 1 is in the form of particles or pellets having a diameter of several tens of microns to several millimeters in the illustrated example. A large number of particles of lead dioxide 3b are held by a porous corrosion-resistant metal 3a having a mesh size smaller than that of the particles. That is, in order to manufacture this anode electrode 3, first, the solid electrolyte membrane 1 is laid flat, and the particles of lead dioxide 3b are laid on it so as to be spread to a predetermined thickness. Porous corrosion resistant metal consisting of
Encapsulate with 3a. When particles of lead dioxide 3b are piled up in this way, it depends on the diameter of the particles of lead dioxide 3b, but there is a comparison between the particles and the contact area between the particles and the through hole 2 of the porous corrosion-resistant metal 3a. A large number of wide passages (average cross-sectional diameter of more than a dozen microns or more) can be secured, and as shown in Fig. 1, the particles of lead dioxide 3b are dispersed in a single layer with some space between them. If this is done, this passage can be secured more widely, and this passage is set so that the water to be fed can smoothly penetrate into one surface of the solid electrolyte membrane 1. In addition to the above-mentioned embodiment, the porous corrosion-resistant metal 3a having the through hole 2 is plated with the lead dioxide 3b (this plating is performed on the entire surface including the front and back of the porous corrosion-resistant metal 3a or on at least one surface). Also, the lead dioxide 3b can be interposed between the porous corrosion-resistant metal 3a and the solid electrolyte membrane 1, and if the ventilation part 1 is not blocked by this plating, the solid electrolyte membrane 1 will have a It has a large number of contact parts and contacted parts, is electrically connected to the porous corrosion-resistant metal 3a, and is formed in the non-contact part of the lead dioxide 3b with the solid electrolyte membrane 1 and the porous corrosion-resistant metal. It is possible to communicate with the ventilation part 2 of 3a, and further, the porous corrosion-resistant metal 3a having the through hole 2 is plated with lead dioxide 3b so as to retain the particulate lead dioxide. Good.

The cathode electrode 4 stacked on the other surface side of the solid electrolyte membrane 1 is also made of conventionally known stainless steel, titanium, noble metal or the like, and may be formed like a wire mesh like the porous corrosion-resistant metal 3a, but may have small holes. You may use what opened 4'or many slits.

The present invention obtains ozone water by utilizing the principle of the electrolysis type ozonizer 100 as described above. As shown in FIG. 2 and below, the container 10 is made of the solid electrolyte membrane 1 and is divided into the anode chamber 13 and the anode chamber 14. Partitioning, the anode electrode 13 is accommodated in the anode chamber 13 and the cathode electrode 4 is accommodated in the negative electrode chamber 14 by superposing them on the solid electrolyte membrane 1, respectively. A water inlet 11 and a water outlet 17 are provided.

In the present embodiment, the container 10 is composed of two halves, and the anode chamber 13 has a plurality of longitudinal holding ribs 13a, 1 on the one-side container portion 10a.
3a, 13 ... are provided, and the valley portion 13 between each retaining rib 13a in the vertical direction is provided.
b and a recess 13c that surrounds the four groups of the vertical holding ribs 13a and communicates with each valley 13b. Further, the negative electrode chamber 14 is provided with a plurality of lateral holding ribs 14a, 14a, 14a, ... on the other side container portion 10b, and a trough portion 14b between the lateral holding ribs 14a and four sides of the lateral holding ribs 14a group are formed. It is configured by a concave portion 14c that communicates with each valley portion 14b surrounding the enclosure.

The solid electrolyte membrane 1 may be sandwiched between the vertical ribs 13a and the horizontal ribs 14a when the one side container portion 10a and the other side container portion 10b are stacked to form the container 10. At that time, in the solid electrolyte membrane 1, particles of lead dioxide 3b are interposed between the solid electrolyte membrane 1 and the porous corrosion-resistant metal 3a on the surface side of the anode chamber 13 (although not shown in FIG. 3). Also in this embodiment, similarly to FIG. 1, the anode electrode 3 having lead dioxide 3b interposed therein is overlapped with the cathode electrode 4 on the side of the negative electrode chamber 14 so that they are sandwiched together.

Further, in this embodiment, a method of immersing the container 10 in the water tank 20 is adopted, the water inlet 11 is provided below the container 10 so as to communicate with the anode chamber 13, and the outlet 17 is provided. The upper part of the container 10 is also provided so as to communicate with the anode chamber 13 so that the tip is opened below the water surface. That is, the anode chamber 13
Is communicated with the outside through a water inlet 11 and an outlet 17, and the water in the water tank 20 flows into the anode chamber 13. In the illustrated example, the outlet 17 is connected to an ejector 23 which is connected to a discharge port of a submersible pump 22 which is rotated by a motor 21, so that water in which ozone and oxygen in the anode chamber 13 are mixed in a bubble form is sucked. In this way, the water in the water tank 20 is forcedly circulated through the anode chamber 13 by the action of the ejector 23.

Further, the container 10 is connected with a hydrogen discharge port 19 which communicates with the negative electrode chamber 14 and has a tip opening outside the water surface. This hydrogen outlet
19 is for releasing hydrogen generated by electrolysis to the atmosphere, and hydrogen may be released directly, but when used in a narrow closed space, the hydrogen concentration in the used space becomes high and there is a danger. In such a case, it is needless to say that the hydrogen decomposition catalyst 26 is arranged at the hydrogen outlet 19.

Reference numeral 50 is a power supply device connected to the anode electrode 3 and the cathode electrode 4, and the power supply device 50 has a high voltage output terminal 51 for applying between the anode electrode 3 and the cathode electrode 4 during normal operation.
And a low-voltage output terminal 52 for applying a voltage of one third to one-half the voltage of the high-voltage output terminal 51 with the same polarity.

The power supply device 50 may be a conventionally known circuit that applies a DC voltage between the anode electrode 3 and the cathode electrode 4, and has one cathode terminal 53 and a high voltage output terminal 51 (see 5.
5V) and a low voltage output terminal 52.

The power supply device 50 is connected to the anode electrode 3 and the cathode electrode 4 via a changeover switch 54 for switching and connecting the high voltage output terminal 51 side and the low voltage output terminal 52 side. That is, the cathode electrode 4 is connected to the cathode terminal 53, and the anode electrode 3 is connected to either one of the high voltage output terminal 51 and the low voltage output terminal 52 through the changeover switch 54. A high voltage (5.5 V) is applied between the anode electrode 3 and the cathode electrode 4 during operation, and a low voltage (2 V) is applied during operation stop.

In order to electrolyze water to obtain ozone, a voltage three times or more the voltage required for electrolyzing water is usually applied. Therefore, some electrolysis occurs even if the voltage is reduced to one third. The reason why this voltage is set to ⅓ or more and ½ or less is that if it is set to ½ or more, electric energy is economically wasted.

In the figure, 27 is a mixing chamber, 28 is an air intake pipe having one end exposed outside the water surface and the other end communicating with the negative electrode chamber 14, and these are provided as necessary. Then, if the blower 28 is connected to one end of the air intake pipe 28 to cool the cathode electrode 14, the electrolysis efficiency can be improved. Further, 30 is a strainer, and a water intake hole 33 is provided at one end.
It has a communication port connected to the water inlet 11 of the container 10 at the other end, and contains the filter medium 32, the ion exchange resin 31, etc., and this strainer 30 is also arranged as necessary. Is.

[Advantages of the Invention] Since the present invention is as described above, it is possible to prevent a small amount of ozone or oxygen or ozone-mixed oxygen from being generated even when the operation is stopped, and to prevent bacteria from growing in the raw material water. Since the current flow is in the same direction as during operation, an electrolytic ozone that maintains the normal electronic behavior of the solid electrolyte membrane and both electrodes due to reverse current, prevents wear of the solid electrolyte membrane, and deactivation of the catalytic function of both electrodes A water production device can be provided.

And, the current when the operation is stopped is one tenth of that during normal operation.
Below (when 5A in normal operation of 5.5V, if 2.5V, 0.4.
It was 0.2 A at 1.5 V. ), The power consumption was negligible.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a main part of an electrolytic ozone water producing apparatus of the present invention,
FIG. 2 is an overall front view, and FIG. 3 is an enlarged sectional view taken along the line AA. 1-solid electrolyte membrane, 2-lead dioxide particle layer, 3-anode electrode, 4-cathode electrode, 50-power supply device, 51-anode output terminal,
52 ~ Anode output terminal, 53 ~ Cathode terminal, 54 ~ Changeover switch, 100 ~ Electrolytic ozonizer

Claims (1)

[Claims] 1. A container 10 is partitioned into a positive electrode chamber 13 and a negative electrode chamber 14 by a solid electrolyte membrane 1, and an anode electrode 3 and a negative electrode chamber 14 are provided in the anode chamber 13.
Each of the cathode electrodes 4 is housed in a superposed manner on the solid electrolyte membrane 1, and the container 10 is provided with a water inflow port 11 and an outflow port 17 through which the raw material water passes and circulates in the anode chamber 13. Power supply device 50 that is connected to 3 and the cathode electrode 4
Is a high-voltage output terminal 51 to be applied between the anode electrode 3 and the cathode electrode 4 during normal operation, and one-third to one-half the voltage of the high-voltage output terminal 51. And a low-voltage output terminal 52 for applying the voltage of 5., and a switching switch 54 for switching and connecting the high-voltage output terminal 51 side and the low-voltage output terminal 52 side with the power supply device 50 and the anode electrode 3 and the cathode electrode 4. Electrolytic ozone water production device connected via the.