JPH07173663A - Electrolytic device - Google Patents

Abstract

PURPOSE:To continue electrolysis over a long period of time with an excellent electrolytic efficiency at the time of conducting the electrolysis in an electrolytic cell divided into two compartments by a solid polymer electrolyte diaphragm by switching the polarities of the electrodes in the two compartments and the supply of the electrolytes. CONSTITUTION:The inside of an electrolytic cell 1 is divided into a first compartment 3 and a second compartment 4 with a solid polymer electrolyte diaphragm 2, and electrode plates 8 and 9 are bonded to both sides of the diaphragm 2. Water is used as the electrolyte, the water is supplied from a water tank 30 to the compartment 3 by a switching device 12a and circulated between the compartment and tank 30, and the water in the compartment 4 is sealed. A current is applied from a power source 10 with the electrode plate 8 as an anode and the electrode plate 9 as a cathode. The oxygen produced from the anode 8 is dissolved in water as the electrolyte, and the water is circulated through the tank 30 to form an oxygen-enriched water, and hydrogen is generated from the cathode 9. The polarities of the electrodes 8 and 9 are alternately switched at regular time intervals, and the supply of the electrolyte is switched to the compartment 4 from the compartment 3. The deposit on both electrode surfaces are released and removed by the switching of polarities in electrolysis, hence and increase in the electric resistance of the electrode due to the deposit is prevented, and electrolysis is conducted continuously over a long period of time with an excellent current efficiency and productivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyzer, and more specifically, to electrodes on both sides of a solid polymer electrolyte membrane, applying a predetermined voltage to both electrodes, and contacting the solid polymer electrolyte membrane with electrodes. The present invention relates to an electrolyzer that feeds a raw material liquid to a surface to perform electrolysis.

[0002]

2. Description of the Related Art Recently, various electrolyzers utilizing the solid polymer electrolyte membrane as described above have been proposed.

In the electrolyzer using the above solid polymer electrolyte membrane, the electrode interval is very close to the thickness of the solid polymer electrolyte membrane, which is usually 200 to 700 microns.
Electrolysis can be performed at a low voltage, and because it is a low voltage,
It has the advantage that the device can be miniaturized. Further, since the solid polymer electrolyte membrane itself is an electrolyte, ion exchange is smoothly carried out, and high electrolysis efficiency that pure water including a solution having a low solute concentration can be easily electrolyzed is obtained. It has the advantage of

[0004]

However, the above-mentioned conventional electrolysis apparatus utilizing the solid polymer electrolyte membrane has a very limited portion of the contact angle portion of the electrode on the surface of the solid polymer electrolyte membrane. Is electrolyzed. If some form of calcium / calumium is dissolved in the raw material liquid, they tend to deposit and adhere to the electrolysis generation part. As a result, non-conductive substances such as calcium carbonate and sodium carbonate are attached to the anode side, and eventually the contact of the raw material liquid with the electrolysis generation site is blocked to reduce the efficiency of electrolysis.

Further, as the above-mentioned precipitate progresses, the precipitate invades between the solid polymer electrolyte membrane and the electrode, and a sparse precipitate intervenes between the solid polymer electrolyte membrane and the electrode regardless of whether it is conductive or non-conductive. This leads to poor physical and electrical contact, and has the drawback of inhibiting the occurrence of electrolysis.

That is, the conventional electrolysis apparatus using a solid polymer electrolyte membrane is efficient, but the problem is that the efficiency cannot be maintained for a long period of time.

Therefore, the present invention has been made in view of the above, and an object thereof is to provide an electrolysis apparatus capable of stably maintaining efficient electrolysis for a long period of time.

[0008]

In order to solve the above-mentioned problems, the structure of the present invention, which is based on the above-mentioned claims and has the above-mentioned object, has a solid polymer electrolyte membrane 2 inside the electrolysis tank 1 in order to solve the above-mentioned problems. Is divided into a first chamber 3 and a second chamber 4, and the first chamber 3 is provided with a first inlet 5a and a first outlet 6a for the raw material liquid, and the second chamber 4 is provided with a second inlet 5b for the raw material liquid. And a second outflow port 6b are provided, a first electrode plate 8 having a large number of openings 7 is provided on the side surface of the first chamber 3 of the solid polymer electrolyte membrane 2, and a large number of the same is provided on the side surface of the second chamber 4. A second electrode plate 9 having an opening 7 is joined, and the first electrode plate 8 and the second electrode plate 9 have a power reversing device 11 for switching between an anode output end and a cathode output end at a predetermined time interval. Connected to the power source 10, and the electrolysis tank 1 has an inlet switching device 12 between the first inlet 5a and the second inlet 5b, and The first outlet port 6a and second outlet 6b
And one or both of the outlet switching devices 13 for connecting the raw material liquid and the raw material liquid pressure feeding devices 12a, 12b for feeding the raw material liquid to the first inflow port 5a and the second inflow port 5b. The inflow switching device 12 and the outflow switching device 13 are interlocked with the power source reversing device 11 to provide a technical means.

[0009]

Therefore, in the electrolyzer of the present invention, the raw material liquid is fed toward the inside of the electrolysis tank 1 by the raw material liquid pressure feeding devices 12a, 12b, and the first electrode plate 8 and the second electrode plate 9 are supplied by the power source 10. A predetermined DC voltage is applied between the two. Then, the first electrode plate 8
The second electrode plate 9 and the second electrode plate 9 are inverted by the power reversing device 11 into an anode and a cathode at predetermined time intervals. That is,
The first electrode plate 8 becomes an anode or a cathode at a predetermined time, and the second electrode plate 9 becomes a cathode or an anode at a predetermined time, contrary to the first electrode plate 8. Further, since the inlet switching device 12 or the outlet switching device 13 is interlocked with the power reversing device 11, it is generated by the raw material liquid electrolyzed by the power reversing device 11 on the anode side or the cathode side or by electrolysis. It acts to select and flush the selected substance.

Further, it is unavoidable that deposits are deposited on the cathode side and the anode side by electrolysis as in the conventional case. However, this precipitate appeared as a colloid in the vicinity of the electrode at the beginning of deposition, and eventually adhered to the electrode and the solid polymer electrolyte membrane 2 to become individualized (solid particles adhered to each other and became solid rather than pure crystals. In this colloidal state, the power source reversing device 11 reverses the anode side to the cathode side to receive an electric repulsive force and further flow with the flow of the raw material liquid. Since it is a monkey, it acts to prevent it from solidifying and being attached.

[0011]

EXAMPLES Next, the present invention is shown in the accompanying drawings. Water was used as a raw material liquid, and this raw material water was electrolyzed to dissolve oxygen generated on the anode side in the raw material water to obtain a high concentration of oxygen. This will be described in detail with reference to an apparatus example for obtaining dissolved high-concentration oxygen water (hereinafter referred to as supersaturated oxygen water).

In the figure, reference numeral 1 is an electrolysis tank, which is divided into a first chamber 3 and a second chamber 4 by a solid polymer electrolyte membrane 2. The electrolysis tank 1 is, of course, made of a water resistant material, and is desirably made of an insulating material in order to cut off electrical connection between the first electrode plate 8 and the second electrode plate 9 to be described later. In addition, since oxygen in the nascent stage generated by electrolysis has a large oxidizing power, a synthetic resin material or the like having excellent corrosion resistance is used. As the solid polymer electrolyte membrane 2, a conventionally known ion exchange resin membrane is used.

The first chamber 3 is provided with a first inlet 5a and a first outlet 6a for the raw material liquid, and the second chamber 4 is provided with a second inlet 5b and a second outlet 6b for the raw material liquid. There is. That is, the electrolysis tank 1 is connected to the first chamber 3 from the first inlet 5a.
The raw material water that has flowed in flows out through the first outflow port 6a, and the raw material water that has flowed into the second chamber 4 through the second inflow port 5b flows out through the second outflow port 6b.

Then, on the side surface of the first chamber 3 of the solid polymer electrolyte membrane 2, there is provided a first electrode plate 8 having a large number of openings 7.
A second electrode plate 9 having a large number of openings 7 is also joined to the side surface of the second chamber 4. As the first electrode plate 8 and the second electrode plate 9 having a large number of openings 7, a perforated plate is used in the example of FIG. 1, but a plate having a large number of slits, a wire mesh or the like may be used. 2 and 3, the first electrode plate 8 made of a corrosion-resistant metal mesh and the first collector electrode 8a having a large number of openings 7a joined to the outside of the first electrode plate 8 are provided. Are used in duplicate. The first electrode plate 8 and the second electrode plate 9 (including the first current collecting electrode 8a and the second current collecting electrode (not shown)) are made of stainless steel, nickel, titanium, gold, platinum. Corrosion resistant metal such as is used.

Then, in order to bond the first electrode plate 8 and the second electrode plate 9 to the solid polymer electrolyte membrane 2, the first electrode plate 8, the second electrode plate 9 and the second electrode plate 9 can be formed by various conventionally known means. Each of the solid polymer electrolyte membranes 2 may be fixed or elastically fixed.
In the examples of "Fig. 2" and "Fig. 3", the electrolysis tank 1 is set to the first container 1a.
And a second container 1b in the form of a split container, a first electrode plate 8 made of a metal net having corrosion resistance on one surface of the solid polymer electrolyte membrane 2, and a large number of openings 7a on the outer side of the first electrode plate 8. The first collector electrode 8a having a zigzag flow generating plate 14a is further laid on the outside of the first collector electrode 8a, and the other surface of the solid polymer electrolyte membrane 2 is omitted in FIG. Since the side has substantially the same structure, a second electrode plate (9) made of a corrosion-resistant metal net is provided on the other surface of the solid polymer electrolyte membrane 2, and a large number of openings (7a) are provided outside the second electrode plate (9). ) Having a second collector electrode (9a),
Further, a zigzag flow generation plate (14b) is placed on the outside of the second collector electrode (9a), and these are sandwiched and fixed by the inner surfaces of the first container 1a and the second container 1b (the above reference numerals are parenthesized). The portion is not shown in FIG. 3, and similarly, in the following, this portion has a substantially symmetrical structure with the solid polymer electrolyte membrane 2 at the center, and the description thereof will be omitted.) The first collecting electrode 8a and the second collecting electrode (9a) are formed so as to also serve as electrode holders. Also, although not shown, a packing or the like is interposed as a cushioning material between the outer surface of the zigzag flow generating plate 14a and the inner surface of the first container 1a so that the sandwiching therebetween is stopped by a predetermined force. You may do so.

As shown in FIGS. 2 and 3, the zigzag flow generating plate 14a has an inflow hole 5 communicating with the first inflow port 5a at one end and a first outflow port 6a at the other end. The outflow through hole 6 is opened, and a flow dividing recess 15 communicating with the inflow through hole 5 and a confluent recess 16 communicating with the outflow through hole 6 are provided on the back surface side. Further, the collector electrode 8a is provided with a plurality of vertical columns in which the openings 7a, 7b, 7c, ... Are arranged at predetermined intervals in the vertical direction in FIG. The flow dividing recess 15 and the confluent recess 16 of the zigzag flow generating plate 14a are formed in a horizontally long shape, and the current collecting electrode 8a is formed.
When they are stacked on top of each other, a part of the holes 7a, 7a, 7a ... Or the holes 7f. 7
f. 7f ... (vertical end row in FIG. 2)
Of the opening portions 7a, 7a, 7a ... Or the opening portions 7f. 7f. 7f are communicated with each other by the flow dividing recesses 15 and the flow merging recesses 16, and the adjacent flow apertures 7a, 7b, 7c ... The two recesses 17, 17, 17, ... Which are fitted to the upper side of each of the two and communicate with each other are provided.

Therefore, the zigzag flow generating plate 14a is formed.
As is most clearly shown in FIG. 3, the raw material liquid flows from the inside of the flow dividing recess 15 of the zigzag flow generating plate 14a to the confluent recess 1
6 to the inside of each recess 17 and each of the apertures 7a, 7b, 7c ...
It is designed to be a zigzag flow as indicated by.

The first electrode plate 8 and the second electrode plate 9 are connected to a power supply 10 having a power supply reversing device 11 which inverts the anode output end and the cathode output end at a predetermined time interval.
The power source 10 is a conventionally known transformer / rectifier circuit 11a for converting a commercial power source into a predetermined DC voltage (8V in the embodiment),
It comprises a conventionally known power supply inverting circuit 11 in which a timer circuit is built-in or externally attached and the anode output terminal and the cathode output terminal are inverted at every set time, and a control circuit 11c which works in conjunction with the power supply inverting circuit 11b.

In the electrolysis tank 1, an inlet switching device 12 between the first inlet 5a and the second inlet 5b or an outlet switching device 1 between the first outlet 6a and the second outlet 6b.
3, one or both of them are connected, and further raw material liquid pressure feeding devices 12a and 12b for pressure feeding the raw material liquid are connected to the first inflow port 5a and the second inflow port 5b, and the inflow port switching device 12 and The outlet switching device 13 is interlocked with the power reversing device 11.

A pump may be used as the material liquid pressure feeding device 12, but in the example shown in FIG. 1, the pumps 12a and 12b are used.
Are respectively connected to the first inflow port 5a and the second inflow port 5b, and the pumps 12a and 12b also serve as the inflow port switching device 12. That is, both pumps 12a and 12b are controlled so that when one is operating, the other is stopped.
Controlled by 1c, the raw material water is pumped only to the anode side or the cathode side. The inlet switching device 12 is a 3-port 2-position switching valve 12 shown in FIG.
b is used (although not shown in the figure, the raw material liquid pressure feeding devices 12a, 1
It is needless to say that 2b is separately provided. In this case, one pump is usually used unlike the example shown in FIG. 1, and the flow path is branched into two on the downstream side of the pump. ) May be used, and the 3-port 2-position switching 12c is connected to the first outlet 6a and the second outlet 6b.
It may be arranged on the side, that is, on the downstream side of the electrolysis tank 1.
However, when an inlet switching device (herein referred to as an outlet switching device 13) is provided on the downstream side of the electrolysis tank 1, when the raw material water is supplied to one of the anode side and the cathode side and the other is stopped, It should be noted that oxygen or hydrogen generated on the non-use side is pushed back to the upstream side, and this oxygen or hydrogen may be mixed on the use side.

Further, the inlet switching device 12 and the outlet switching device 13 can have various embodiments. In the case of FIG. 5, a 4-port 2-position switching valve is used for the outlet switching device 13, The 4-port 2-position switching valve connects both outflow ports, but this is used to obtain supersaturated oxygen water described later, and it goes without saying that each of the outflow ports may be connected to a separate place of use. is there. Further, the 4-port 2-position switching valve may be connected to the first outlet 6a and the second outlet 6b side (both outlet ports are connected to the first outlet 6a and the second outlet 6b, respectively). . In this “FIG. 5” example, the raw material water flows on both the anode side and the cathode side.

Further, in the example of FIG. 6, the inlet switching device 1 is shown.
In the example in which both 2 and the outlet switching device 13 are provided, the inlet switching device 12 uses a 3-port 2-position switching valve, and the outlet switching device 13 uses a 4-port 2-position switching valve. . Then, the inlet switching device 12 causes the raw material water to flow only to one of the anode side and the cathode side (in the example, the anode side),
The other is configured so that raw material water does not flow, one outflow port of the outlet switching device 13 communicates with a water tank 30 described later, and the other port communicates with a hydrogen exhaust port or a hydrogen treatment unit not shown. .

In the embodiment shown in FIG. 1, the first outlet 6
a and the second outlet 6b are respectively connected to the raw material liquid pressure feeding devices 12a and 1a.
The water tank 30 is provided with the inflow passages 31a and 31b that intervene 2b.
Communicating with the raw material water of the first outlet 6a and the second outlet 6b
Are connected to the water tank 30 through circulation paths 32a and 32b, respectively.

Then, a voltage is applied by the power source 10 in a state where the first electrode plate 8 is the anode and the second electrode plate 9 is the cathode, and the control circuit 11c operates one raw material liquid pressure feeding device 12a to operate the other raw material liquid. The pressure feeding device 12b is in a stopped state. Then, the raw material water passes through the first chamber 3 and circulates in the water tank 30, and the raw material water in the second chamber 4 does not flow in a sealed state. Therefore, the raw material water is electrolyzed in the electrolysis tank 1 in this state, and oxygen is generated in the first chamber 3 and hydrogen is generated in the second chamber 4. Then, the oxygen generated in the first chamber 3 is accompanied by the raw material water and is dissolved in the raw material water. This oxygen dissolution is generally known to have a saturated concentration with respect to the water temperature, but when oxygen immediately after electrolysis is brought into contact with raw material water, oxygen can be dissolved at a concentration higher than the conventionally known saturated concentration. The main one is that nascent oxygen has a high dissolving power. Moreover, the hydrogen generated in the second chamber 4 becomes a gas and stays.

When operated for a certain period of time (1 minute in the embodiment) in the above state, this time the first electrode plate 8 is reversed so that a voltage is applied to the cathode and the second electrode plate 9 is an anode, Further, one raw material liquid pressure feeding device 12a is stopped and the other raw material liquid pressure feeding device 12b is in a state of being operated. Then, the raw material water passes through the second chamber 4 and circulates in the water tank 30,
The raw material water in the first chamber 3 does not flow in a sealed state. Therefore, the raw water is electrolyzed in the electrolysis tank 1 in this state, and oxygen is generated in the second chamber 4 and hydrogen is generated in the first chamber 3. Then, the oxygen generated in the second chamber 4 is accompanied with the raw material water and is dissolved in the raw material water. By repeating this process, the dissolved oxygen concentration in the water tank 30 is sequentially increased. With respect to hydrogen, since it is generated in the stagnant raw material water and becomes a large gas bubble, the contact frequency with the raw material water is low, so it hardly dissolves in the water, and when it is next injected into the water tank 30 by the water flow, the water surface immediately increases. The hydrogen can also be directly collected from the electrolysis tank 1 or exhausted as in the example of FIG.

Although the example of utilizing oxygen by electrolysis of water has been described above, it goes without saying that hydrogen may be utilized and chlorine gas generated by electrolysis using seawater as a raw material liquid is utilized. You may do so.

In the figure, 18 is a lead of the collecting electrode 8a,
19 is a packing, and 20 is a screwing screw hole.

[0028]

The present invention is as described above, and since the first electrode plate 8 and the second electrode plate 9 are alternately used without the anode and the cathode being divided, the cathode side is used. When the cations are continuously attracted to the used first electrode plate 8 and the cations are eventually saturated, the cations are precipitated and solidify. If reversed, the cations will be repelled from the first electrode plate 8 by receiving an electric repulsive force, and will be separated from the first electrode plate along with the water flow. It is possible to provide an electrolysis device that can stably perform electrolysis.

In addition, specifically, artificial seawater is used as the first electrode plate 8.
Was used as the anode and the second electrode plate 9 was exclusively used as the cathode, and continuous operation was performed with a porous stainless electrode having a length and width of 30 cm in the example of "Fig. 1". White deposits could be visually observed on the second electrode plate 9 in about 5 minutes. When a DC voltage of 8 V was applied, a current of 3 amps flowed in the initial stage, but after 5 minutes, the current value was 0.5 amperes or less. In this state, the electrode was disassembled and washed with water having a jet pressure of 5K, but no peeling of adhered substances was observed, and the electrode was reassembled in the original state, and a DC voltage of 8V was applied in the same manner. A current of about 1 amp flowed, but the current value thereafter remained at 0.5 amp or less. Therefore, in this device example (new electrode is used), when the power source and the inlet switching device 12 are switched every one minute, it is the same that a current of 3 amps flows in the initial stage. Gradually decreased, and became stable when it decreased to 1.5 amps. Then, when the dissolved oxygen content of the "Fig. 1" device was measured, it was 25 at a water temperature of 15 degrees Celsius.
The dissolved oxygen concentration could be increased to ppm, and when the saturated oxygen concentration was measured by continuously aerating the oxygen in the cylinder to this artificial seawater, it was 8 ppm, so electrolysis was clearly continued efficiently. When the measurement was repeated, a current of about 1.7 amperes might flow for several minutes when the power was turned on after being left for several hours, but after that, the above stable current value was obtained and repeat continuity was confirmed. .

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of the electrolyzer of the present invention.

FIG. 2 is a front view of an electrolysis tank showing another embodiment.

FIG. 3 is a central vertical cross-sectional view of “FIG. 2”.

FIG. 4 is a fluid circuit diagram showing an embodiment.

FIG. 5 is a fluid circuit diagram showing another embodiment.

FIG. 6 is a fluid circuit diagram showing still another embodiment.

[Explanation of symbols]

 1 Electrolysis Tank 2 Solid Polymer Electrolyte Membrane 3 First Chamber 4 Second Chamber 5a First Inlet 5b Second Inlet 6a First Outlet 6b Second Outlet 7 Opening 8 First Electrode Plate 9 Second Electrode Plate 10 Power source 11 Power reversing device 12 Inlet switching device 12a, 12b Raw material liquid pressure feeding device 13 Outlet switching device

Claims (2)

[Claims] 1. The inside of the electrolysis tank is divided into a first chamber and a second chamber by a solid polymer electrolyte membrane, and the first chamber is provided with a first inlet and a first outlet of a raw material liquid.
The second chamber is provided with a second inflow port and a second outflow port for the raw material liquid, and the first electrode plate having a large number of openings on the side face of the first chamber of the solid polymer electrolyte membrane, the second chamber A second electrode plate having a large number of openings is also joined to the side surface, and the first electrode plate and the second electrode plate are a power reversing device that switches an anode output end and a cathode output end at predetermined time intervals. The electrolysis tank is connected to a power source, and the electrolysis tank has one of an inlet switching device for the first inlet and the second inlet, or an outlet switching device for the first outlet and the second outlet. Alternatively, both are connected, and further, a raw material liquid pumping device for pumping the raw material liquid is connected to the first inlet and the second inlet, and the inlet switching device and the outlet switching device are interlocked with the power reversing device. An electrolyzer characterized in that 2. The inside of the electrolysis tank is partitioned into a first chamber and a second chamber by a solid polymer electrolyte membrane, and the first chamber has a first inlet and a first outlet for a raw material liquid.
The second chamber is provided with a second inflow port and a second outflow port for the raw material liquid, and the first electrode made of a corrosion-resistant metal net having a large number of openings on the side face of the first chamber of the solid polymer electrolyte membrane. A plate and a first collector electrode having a large number of openings joined to the outside of the first electrode plate, and a second electrode made of a corrosion-resistant metal net also having a large number of openings on the side surface of the second chamber A plate and a second collector electrode having a large number of openings joined to the outside of the second electrode plate are joined together, and the first electrode plate and the second electrode plate are an anode output end and a cathode output end. Is connected to a power source having a power reversing device for switching at a predetermined time interval, and the electrolysis tank has an inlet switching device between the first inlet and the second inlet, or a first outlet and a second outlet. And one or both of the outlet switching devices, and the raw material is connected to the first inlet and the second inlet. Connecting the raw liquid pumping device for pumping, electrolyzer, characterized in that the inlet switching device and the outlet port switching device was linked to the power inverter.