JP2724772B2 - Electrolysis equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolysis apparatus, and more particularly, to a method in which electrodes are joined to both surfaces of a solid polymer electrolyte membrane such as an ion exchange membrane, and a predetermined voltage is applied to both electrodes. The present invention relates to an electrolysis apparatus for performing electrolysis by feeding a raw material liquid to an electrode contact surface of a polymer electrolyte membrane.

[0002]

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

In an electrolyzer using the above-mentioned solid polymer electrolyte membrane, the electrode interval is only separated by the thickness of the solid polymer electrolyte membrane, and the electrode interval is usually 200 to 700.
Since it is very close to the micron, electrolysis can be performed at a low voltage, and since the voltage is low, each device such as a power supply device can be downsized.

[0004] Further, since the solid polymer electrolyte membrane itself is an electrolyte, ion exchange is carried out smoothly, and high electrolysis can be carried out easily, including a solution having a low solute concentration and pure water. It is known that it has the advantage of gaining efficiency.

[0005]

However, the above-mentioned conventional electrolyzer using the solid polymer electrolyte membrane has a very limited area of the contact angle area of the electrode in contact with the surface of the solid polymer electrolyte membrane. The electrolysis is performed. If some amount of calcium, calcium, etc. is dissolved in the raw material liquid, they tend to precipitate and adhere to the electrolysis generation part, and this precipitate is deposited on the cathode side, such as calcium and sodium. As a result, non-conductive substances such as calcium carbonate and sodium carbonate adhere to the anode side, and eventually the raw material liquid is prevented from coming into contact with the electrolysis-causing site, thereby greatly reducing the efficiency of electrolysis. There is a disadvantage that.

[0006] Further, as the precipitate proceeds, the precipitate penetrates between the solid polymer electrolyte membrane and the electrode, and a sparse precipitate intervenes regardless of conductivity or non-conductivity between the two. This leads to poor physical and electrical contact and has the disadvantage of further inhibiting the occurrence of electrolysis.

That is, although the conventional electrolyzer using a solid polymer electrolyte membrane is efficient, it cannot maintain its efficiency for a long time due to the deposition of dissolved substances in the raw material liquid. It is an issue.

Accordingly, the present invention has been made to solve the above-mentioned drawbacks, and an object of the present invention is to provide an electrolysis apparatus which can stably perform efficient electrolysis and can be maintained for a long period of time.

[0009]

In order to solve the above-mentioned problems, according to the present invention, in order to solve the above-mentioned problems, a solid polymer electrolyte membrane 2 is provided. The first chamber 3 is divided into a first chamber 3 and a second chamber 4, and the first chamber 3 is provided with a first inlet 5 a and a first outlet 6 a of the raw material liquid, and the second chamber 4 is provided with a second inlet 5 b of the raw material liquid. And a second outlet 6b, and a first electrode plate 8 having a large number of openings 7, 7, 7,... On the side of the first chamber 3 of the solid polymer electrolyte membrane 2,
Similarly, a large number of openings 7, 7, 7,.
The first electrode plate 8 and the second electrode plate 9 are provided with a plurality of through holes 7a, 7a,
7a... Are provided in a plurality of rows, and the same number of through holes 7a, 7a, 7a. The first inflow port 5 is provided on both outer sides of the first current collecting electrode 8a and the second current collecting electrode 9b.
a or the first inlet 5b on the inner surface on the side of the second inlet 5b.
a or the second inlet 5b, and the through holes 7a, 7 at the most upstream part of each row of the first current collecting electrode 8a or the second current collecting electrode 9a.
a, 7a... are formed on the inner surface on the first outlet 6a or the second outlet 6b side, and the first outlet 6a or the second outlet 6b and the first current collecting electrode 8a or the Each through hole 7a, 7 at the most downstream portion of each row of the secondary current collecting electrode 9a
a, 7a... and a portion of the inner surface between the diversion recess 15 and the junction depression 16,
.. Are provided to sequentially communicate the adjacent downstream through-holes 7a and upstream through-holes 7a in each row of the first current collecting electrode 8a or the second current collecting electrode 9a. The zigzag flow generating plates 14 and 14 are overlapped with each other, and the first electrode plate 8
And a second electrode plate 9 are connected to a power supply 10 having a power supply reversing device 11 for switching between an anode output terminal and a cathode output terminal at predetermined time intervals.
It takes technical measures that are linked to.

[0010]

Therefore, the electrolyzer according to the present invention feeds the raw material liquid into the electrolysis tank 1 and applies a predetermined DC voltage between the first electrode plate 8 and the second electrode plate 9 by the power supply 10. Apply.
Then, the first electrode plate 8 and the second electrode plate 9 are respectively inverted by the power supply inversion 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 every predetermined time, and the second electrode plate 9 becomes a cathode or an anode every predetermined time contrary to the first electrode plate 8.

It is inevitable that precipitates are deposited on the cathode side and the anode side by the above-mentioned electrolysis as in the conventional case. However, this precipitate appeared in a colloidal form near the electrode at the beginning of the deposition, and then adhered to the electrode and the solid polymer electrolyte membrane 2 and singulated (solid particles adhered to each other rather than pure crystals, and singulated). In this colloidal state, when the power supply reversing device 11 reverses the anode side to the cathode side, the colloidal state receives an electric repulsion force and further flows along with the flow of the raw material liquid. Therefore, it acts to prevent solidification and adhesion.

The zigzag flow generating plates 14 and 14 have a function of flowing the raw water in a zigzag manner in the direction of contact and separation with respect to the solid polymer electrolyte membrane 2 and a function of sweeping the colloidal deposits. In particular, the water flow in the direction orthogonal to the solid polymer electrolyte membrane 2 is applied to the openings 7 between the first electrode plate 8 and the second electrode plate 9,
Can reach the bottom corners of 7, 7,... And exhibit an efficient sweeping action.

[0013]

Next, the present invention is shown in the accompanying drawings, in which water is used as a raw material liquid, and the raw water is electrolyzed to dissolve the oxygen generated on the anode side into the raw water. This will be described in detail with an example of an apparatus for obtaining dissolved high-concentration oxygen water.

In the figure, reference numeral 1 denotes an electrolysis tank, and the interior of the electrolysis tank 1 is divided into a first chamber 3 and a second chamber 4 by a solid polymer electrolyte membrane 2. Of course, the electrolysis tank 1 is preferably made of a water-resistant material, and is desirably made of an insulating material in order to cut off the electrical connection between the first electrode plate 8 and the second electrode plate 9 and the outside. Since the nascent oxygen generated by the electrolysis has a large oxidizing power, a material having excellent corrosion resistance such as a synthetic resin material is used.

As the solid polymer electrolyte membrane 2, a conventionally known ion exchange resin membrane is used.

The first chamber 3 has a first inlet 5a and a first outlet 6a for the raw material liquid, and the second chamber 4 has a second inlet 5b and a second outlet 6b for the raw liquid. It is provided.

That is, the raw material water flowing into the first chamber 3 through the first inlet 5a is supplied to the first outlet 6a.
The raw water that has flowed out and flowed into the second chamber 4 from the second inlet 5b flows out from the second outlet 6b.

A first electrode plate 8 having a large number of openings 7, 7, 7... On the side of the first chamber 3 of the solid polymer electrolyte membrane 2 A second electrode plate 9 having a large number of openings 7, 7, 7,... Is joined. As the first electrode plate 8 and the second electrode plate 9 having a large number of openings 7, 7, 7,..., A wire mesh is used in the illustrated example, and the mesh of the wire mesh becomes each of the openings 7. In addition, a perforated plate, a plate provided with a large number of slits, or the like can be used. The first electrode plate 8 and the second electrode plate 9 are made of stainless steel, nickel, titanium, gold,
A corrosion-resistant metal such as platinum is used.

The first electrode plate 8 and the second electrode plate 9
Are provided on both outer surface sides of the first through fourth through holes 7a, 7a, 7a,.
Are provided in a plurality of rows, and a second current collecting electrode 9 is provided in a plurality of rows similarly with a large number of through holes 7a, 7a, 7a,.
a is superimposed on each. The first current collecting electrode 8a and the second current collecting electrode 9a are made of stainless steel, nickel, titanium, and the like, like the first electrode plate 8 and the second electrode plate 9.
Corrosion-resistant metals such as gold and platinum are used.

Further, on both sides of the first current collecting electrode 8a and the second current collecting electrode 9b, on the inner surface on the side of the first inlet 5a or the second inlet 5b, the first inlet 5a or the second current Inlet 5b, first current collecting electrode 8a or second current collecting electrode 9a
Are formed in the inner surface on the side of the first outlet 6a or the second outlet 6b so as to communicate with the through holes 7a, 7a, 7a,. The converging recess 16 communicating the outflow port 6b with the through holes 7a, 7a, 7a,... At the most downstream portion of each row of the first current collecting electrode 8a or the second current collecting electrode 9a, In a portion between the concave portion 15 and the converging concave portion 16, a downstream through hole 7a adjacent to each row of the first current collecting electrode 8a or the second current collecting electrode 9a is provided.
17, 1, which sequentially communicate with the upstream through hole 7 a
The zigzag flow generating plates 14 provided with 7, 17,...

The zigzag flow generating plate 14 has an inflow hole 5 communicating with the first inlet 5a at one end and an outflow hole 6 communicating with the first outlet 6a at the other end. A diverging recess 15 communicating with the inflow through hole 5 and a merging recess 16 communicating with the outflow through hole 6 are provided.

When the zigzag flow generating plate 14 has the diverging concave portion 15 and the merging concave portion 16 formed in a horizontally long shape and overlaps with the first current collecting electrode 8a, a part thereof is located above and below the current collecting electrode 8a. .. (In FIG. 2, the upper and lower ends of the rows) are positioned so as to be commonly fitted to a part of the upper side (in FIG. 2, the near side), and these through holes 7 a, 7 a, 7 a. Holes 7a, 7
are connected to each other by a diversion concave part 15 and a merge concave part 16. Further, the zigzag flow generating plate 14 is provided at a portion between the branch concave portion 15 and the merge concave portion 16.
Are placed on the collecting electrode 8a, the recesses 17, 17, 17, 17,... Which fit over two adjacent through holes 7a, 7a, 7a,.・ It is arranged.

Therefore, as shown most clearly in FIG. 3, the zigzag flow generating plate 14 has various recesses 17 from the inside of the diversion recess 15 of the zigzag flow generating plate 14 to the inside of the merging recess 16. , 17, 17... And the insides of the through holes 7a, 7a, 7a... Of the collecting electrode 8a alternately, so as to form a zigzag flow as shown by an arrow P.

Although it is a matter of course that the zigzag flow generating plate 14 is also overlapped on the outer surface side of the second current collecting electrode 9a, its structure is symmetrical with the solid polymer electrolyte membrane 2 as a center. Then, the description is omitted.

To join 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, What is necessary is just to fix or stop each of the solid polymer electrolyte membranes 2.

In the illustrated example, the electrolysis tank 1 is connected to the first container 1a.
And a second container 1b. The first electrode plate 8 of a corrosion-resistant wire mesh is formed on one surface of the solid polymer electrolyte membrane 2 and a large number of openings 7a, 7a, 7a
Since the zigzag flow generating plate 14 is further stacked on the outside of the first current collecting electrode 8a having the... And the other surface side of the solid polymer electrolyte membrane 2 has substantially the same structure, On the other surface of the solid polymer electrolyte membrane 2, a corrosion-resistant wire mesh second electrode plate 9 is provided.
A second current collecting electrode 9a having a large number of openings 7a outside the second electrode plate 9 and a zigzag flow generating plate 14b outside the second current collecting electrode 9a are further stacked.
And the second container 1b are sandwiched and fixed between the inner surfaces thereof.

The first current collecting electrode 8a and the second current collecting electrode 9a also serve as electrode holders. Also, although not shown in the drawing, packing or the like is interposed between the outer surface of the zigzag flow generating plate 14 and the inner surface of the first container 1a as a cushion material, and the sandwiching thereof is stopped by a predetermined force. You may make it so.

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 for reversing an anode output terminal and a cathode output terminal at predetermined time intervals.

The power supply 10 includes a conventional well-known transformer / rectifier circuit 11a for converting a commercial power supply into a predetermined DC voltage (8V in the embodiment), and a built-in or external timer circuit, and an anode output terminal for each set time. It comprises a conventionally known power supply reversing device 11 whose cathode output terminal is reversed, and a control circuit 11b interlocked with the power supply reversing device 11.

The electrolytic cell 1 has 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 is connected to the first inlet 5a and the second inlet 5b, and raw material pumping devices 12a and 12b for pumping the raw material liquid are connected to the first inlet 5a and the second inlet 5b. The outlet switching device 13 is linked to the power reversing device 11.

A pump may be used for the raw material liquid feeders 12a and 12b. In the example shown in FIG. 1, the raw material liquid feeders 12a and 12b are connected to the first inlet 5a and the second inlet 5b.
The raw material liquid feeding devices 12a and 12b also serve as the inlet switching device 12. That is, both the raw material liquid pressure feeding devices 12a and 12b are controlled by the control circuit 11b so that when one is operated, the other is stopped.
Raw water is pumped only to the anode side or the cathode side.

The inflow switching device 12 is shown in FIG.
(The illustration is omitted in the figure, but it is needless to say that the raw material liquid pumping devices 12a and 12b are separately provided. In this case, one pump is usually used unlike the example in FIG. 1) Then, the flow path is branched into two at the downstream side of the pump.) Or the three-port second-place switching 12c may be connected to the first outlet 6a and the second outlet 6b, that is, of the electrolysis tank 1. It may be arranged on the downstream side. However, when an inflow switching device (hereinafter referred to as an outflow switching device 13) is provided on the downstream side of the electrolysis tank 1, when the raw material water is flown 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 unused side is pushed back to the upstream side, and this oxygen or hydrogen may be mixed into the used side.

Further, the inflow switching device 12 and the outflow switching device 13 can be implemented in various embodiments. In the case of FIG. 5, a 4-port 2-position switching valve is used for the outflow switching device 13. The four-port two-way switching valve connects the two outflow ports, but this is used for obtaining oxygen water described later, and it goes without saying that each of the two outflow ports may be separately connected to the place of use. . Further, the four-port second-position switching valve may be connected to the first outlet 6a and the second outlet 6b (both outlet ports may be connected to the first outlet 6a and the second outlet 6b, respectively). . In the example of FIG. 5, the raw water flows on both the anode side and the cathode side.

Further, the example shown in FIG.
In the example in which both the outlet 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 inflow switching device 12 feeds the raw water only to one of the anode side and the cathode side (in the embodiment, the anode side),
The other is configured so that the raw water does not flow, one outlet port of the outlet switching device 13 communicates with a water tank 30 or the like described later, and the other port communicates with a hydrogen exhaust port or a hydrogen processing unit (not shown). .

The embodiment shown in FIG.
a and the second outlet 6b are connected to the raw material liquid pressure feeders 12a and 12a, respectively.
The water tank 30 is formed by the inflow passages 31a and 31b intervening the 2b.
The first outlet 6a and the second outlet 6b
Are connected to the water tank 30 by circulation paths 32a and 32b, respectively.

Then, a voltage is applied by the power supply 10 in a state where the first electrode plate 8 is an anode and the second electrode plate 9 is a cathode. The pumping device 12b is in a stopped state. Then, the raw water passes through the first chamber 3 and circulates to the water tank 30, and the raw water in the second chamber 4 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 first chamber 3 and hydrogen is generated in the second chamber 4.

After operating for a certain period of time (one minute in the embodiment) in the above state, the operation is reversed so that a voltage is applied to a state where the first electrode plate 8 is a cathode and the second electrode plate 9 is an anode. Further, one raw material liquid feeding device 12a is stopped, and the other raw material liquid feeding device 12b is operated. Then, the raw water passes through the second chamber 4 and circulates to the water tank 30,
The raw material water in the first chamber 3 does not flow in a sealed state. Accordingly, 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.

The oxygen generated in the second chamber 4 is accompanied by the raw water and is dissolved in the raw water. This process is repeated to sequentially increase the dissolved oxygen concentration in the water tank 30. In addition, hydrogen is generated in the retained raw water and becomes a large gas bubble, so that it hardly dissolves in the water because the frequency of contact with the raw water is low. The hydrogen can be directly collected or exhausted from the electrolysis tank 1 if it is dissipated into the atmosphere from the gas and as shown in the example of FIG.

In the above, an example in which oxygen is used by electrolysis of water has been described. Of course, hydrogen may be used, or chlorine gas generated by electrolysis using seawater as a raw material liquid may be used. You may do it.

In the figure, reference numeral 18 denotes a lead of the current collecting electrode 8a;
Reference numeral 19 denotes a packing, and 20 denotes a screw screw hole.

[0041]

The present invention is as described above. Since the first electrode plate 8 and the second electrode plate 9 are alternately used without sharing the roles of the anode and the cathode, the cathode side is used. When the cations continue to be attracted to the used first electrode plate 8 and the cations are eventually saturated, the cations are then precipitated and solidified. When inverted, the cations receive an electric repulsion and separate from the first electrode plate 8 and separate from the first electrode plate with the flow of water, and the cathode side is substantially the same. It is possible to provide an electrolyzer capable of performing electrolysis stably.

Specifically, artificial seawater is applied to the first electrode plate 8.
Is used as the anode and the second electrode plate 9 is dedicated to the cathode. In the example shown in FIG. 1, continuous operation was performed with a 30 cm-long porous stainless steel electrode. When a DC voltage of 8 V was applied, a current of 3 amps initially flowed, but after 5 minutes, the current value became 0.5 amps or less. In this state, the electrode was disassembled and washed with water sprayed at a spray pressure of 5K, but no detachment of the deposit was observed. The assembly was reassembled to the original state, and a DC voltage of 8 V was applied in the same manner. A current of about 1 amp flowed, but the current thereafter remained below 0.5 amp. Therefore, when the power supply and the inlet / outlet switching device 12 are switched every other minute in this device example (a new electrode is used), it is the same that a current of 3 amps flows at the initial stage. Gradually decreased and became stable when it decreased to 1.5 amperes.

Then, when the dissolved oxygen content of the apparatus shown in FIG. 1 was measured, the dissolved oxygen concentration could be increased to 25 ppm at a water temperature of 15 ° C. by using a commercially available dissolved oxygen meter (this oxygen concentration decreases the saturation amount). The reason why the value exceeded the saturation amount was not determined, but it is clear that the saturation has been reached.) The oxygen in the cylinder was continuously aerated in this artificial seawater to measure the saturated oxygen concentration. 7.5
ppm, the electrolysis is clearly continued efficiently. This measurement was repeated, and when the power was turned on after standing for several hours, a current of about 1.7 amps flowed for several minutes. However, after that, the stable current value was obtained and the repetition continuity was confirmed.

[Brief description of the drawings]

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

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

FIG. 3 is a central longitudinal 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]

 Reference Signs List 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 7a through hole 8 first electrode plate 8a first Current collecting electrode 9 Second electrode plate 9a Second current collecting electrode 10 Power supply 11 Power supply reversing device 12 Inlet switching device 12a Raw material liquid pumping device 12b Raw material liquid pumping device 13 Outlet switching device 14 Zigzag flow generating plate

Claims (1)

(57) [Claims] 1. An electrolysis tank (1) is partitioned into a first chamber (3) and a second chamber (4) by a solid polymer electrolyte membrane (2), and the first chamber (3) contains raw materials. A first inlet (5a) and a first outlet (6a) for the liquid; a second inlet (5b) and a second outlet (6b) for the raw material liquid in the second chamber (4); A first electrode plate (8) having a large number of openings (7, 7, 7,...) Is provided on the side of the first chamber (3) of the polymer electrolyte membrane (2). Is connected to a second electrode plate (9) also having a large number of openings (7, 7, 7,...), And both of the first electrode plate (8) and the second electrode plate (9) are joined. On the outer surface side, a first current collecting electrode (8a) provided with a plurality of rows of a large number of through holes (7a, 7a, 7a.
a, 7a, 7a...) are provided in a plurality of rows, respectively, and the first current collecting electrode (8a) and the second current collecting electrode (9
b), on the inner surface on the side of the first inlet (5a) or the second inlet (5b), the first inlet (5a) or the second inlet (5b), and the first current collecting electrode (8a) or each through-hole (7) at the most upstream part of each row of the second collecting electrode (9a).
a, 7a, 7a,...)
Is provided on the inner surface on the first outlet (6a) or second outlet (6b) side, with the first outlet (6a) or the second outlet (6).
b) and the first collecting electrode (8a) or the second collecting electrode (9)
a) Each through hole (7a, 7a, 7a
..), and a portion of the inner surface between the junction recess (15) and the junction recess (16) at the first current collecting electrode (8a) or the second electrode. Collector electrode (9
a) a recessed portion (17, 17, 1) that sequentially communicates an adjacent downstream through-hole (7a) and an upstream through-hole (7a) in each row;
7) are provided, and the first electrode plate (8) and the second electrode plate (9) have an anode output terminal and a cathode output terminal at predetermined positions. An electrolyzer connected to a power supply (10) having a power supply reversing device (11) that switches at time intervals.