TW201311935A - Electrolytic device - Google Patents

Abstract

An opening in the upper part of an electrolysis tank main body is closed by a first cover body with a sealing member sandwiched therebetween. An opening in the first cover body is closed by a second cover body with a sealing member sandwiched therebetween. The opening in the first cover body is smaller than the opening in the electrolysis tank main body. A partition wall that divides the inside of the electrolysis tank main body into a positive electrode chamber and a negative electrode chamber is provided integrally on the lower surface of the second cover body. The positive electrode chamber is disposed in an area on the inside of the sealing member. A positive electrode is attached to the second cover body inside of the positive electrode chamber, and the negative electrode is formed on the inside surface of the electrolysis tank main body. An electrolyte bath inside the electrolysis tank undergoes electrolysis, thereby generating fluorine gas in the positive electrode chamber. A plurality of round through holes may be formed in a liquid partition wall. Each through hole has an upper surface that extends upward at a slant from an end part on the positive electrode chamber side to an end part on the negative electrode chamber side. The diameter of the positive electrode side end of the through holes in the vertical direction is set to a size such that the electrolyte bath can pass through and bubbles of fluorine gas and hydrogen gas cannot pass through. The diameter of the through holes in the vertical direction on the negative electrode side end is larger than the diameter of the through holes on the positive electrode side end.

Description

Electrolytic device

The present invention relates to an electrolysis apparatus comprising an electrolysis cell.

Conventionally, in the manufacturing steps of semiconductors and the like, fluorine gas has been used in various applications such as cleaning of materials and surface modification. In this case, there is a case where fluorine gas itself is used, and NF ₃ (nitrogen trifluoride) gas, NeF (fluorene fluoride) gas, ArF (argon fluoride) gas, etc. synthesized using fluorine gas are also used. The case of various fluorine-based gases.

In order to stably supply the fluorine gas, an electrolysis device that generates fluorine gas by electrolyzing HF (hydrogen fluoride) is usually used. In such an electrolysis apparatus, for example, an electrolytic bath containing a KF-HF (potassium-hydrogen fluoride)-based mixed molten salt is formed in an electrolytic bath. The electrolytic bath in the electrolytic cell generates fluorine gas by electrolysis.

For example, the molten salt electrolysis device described in Patent Document 1 has an electrolytic cell including an electrolytic cell body and an upper lid. The inside of the electrolytic cell is separated by a separator into an anode chamber located at a central portion of the electrolytic cell and a cathode chamber surrounding the anode chamber. An anode is disposed in the anode chamber, and a cathode is disposed in the cathode chamber. At a substantially central portion of the upper cover, an opening for inserting the anode into the electrolytic cell body is formed, and a cover is provided to cover the opening. A gas sealing material is interposed between the cover and the upper cover. A connecting rod for holding the anode is vertically disposed on the cover body.

As described above, fluorine gas and hydrogen gas are generated together in the electrolytic cell. Therefore, a separator for separating the generated fluorine gas from the hydrogen gas is provided in the electrolytic cell. In the electrolytic cell described in Patent Document 2, in order to prevent mixing of gases A separator having a porous or fibrous structure is used. In this case, the electrolytic bath can pass through the separator. Therefore, an increase in the electric resistance between the anode and the cathode disposed in the electrolytic cell is prevented.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-48290

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-104187

In the molten salt electrolysis device described in Patent Document 1, the anode and the upper lid can be easily removed from the electrolytic cell body by removing the lid from the upper lid. Thereby, the anode can be easily replaced even in the case of anode consumption.

However, in the above molten salt electrolysis device, the gas sealing material interposed between the lid body and the upper lid is required to have corrosion resistance to fluorine gas. Further, even a gas sealing material having corrosion resistance to fluorine gas may be corroded by contact with fluorine gas for a long period of time. Therefore, it is necessary to frequently change the gas sealing material. As a result, the cost of maintenance increases. Moreover, since the frequency of replacing the gas sealing material is more than the frequency of replacing the anode, the maintenance work efficiency is poor.

Moreover, the inventors of the present invention found that in the electrolytic cell of Patent Document 2, the generated bubbles block the pores of the separator and hinder the permeation of the electrolytic bath. Thereby, the electrolysis reaction of the electrolytic bath cannot be stably performed.

It is an object of the present invention to provide an electrolysis apparatus which can reduce the cost of maintenance and improve the efficiency of maintenance work.

Another object of the present invention is to provide an electrolysis apparatus which can prevent mixing of gases and can stably perform an electrolysis reaction.

(1) An electrolysis device according to an aspect of the present invention is for generating fluorine gas and other gases by electrolysis of an electrolytic bath, and includes an electrolytic cell for accommodating an electrolytic bath; the electrolytic cell includes: an electrolytic cell body, wherein The upper portion has a first opening; the first cover has a second opening smaller than the first opening, and is provided in the electrolytic cell body so as to close the first opening; and the first sealing member is provided to surround the second opening a first lid body; the second lid body is provided on the first lid body via the first sealing member so as to close the second opening; the first electrode is attached to the second lid body; and the separator is The first chamber that generates fluorine gas in the electrolytic cell body is separated from the second chamber that generates other gas; and the separator is formed such that the first chamber is disposed in the inner region of the first sealing member.

In the electrolysis device, the first opening of the upper portion of the electrolytic cell body is closed by the first lid. The second opening of the first cover is closed by the second cover via the first sealing member. The first electrode is attached to the second lid. Since the second opening is smaller than the first opening, the second cover is smaller and lighter than the first cover. Therefore, even when the first electrode is consumed, the first electrode can be easily replaced by removing the second lid from the first lid.

Further, the first chamber is disposed in the inner region of the first sealing member by the partition plate. In this case, since the fluorine gas generated in the first chamber does not contact the first sealing member, corrosion of the first sealing member is prevented. Thereby, the frequency of replacing the first sealing member is reduced.

As a result of this, the cost of maintenance of the electrolysis device is reduced, and the efficiency of maintenance work is improved.

(2) The separator may be integrally provided in such a manner as to surround the periphery of the first electrode Placed in the first cover. In this case, the separator can be easily inspected by removing the second lid from the first lid. Thereby, the cost of maintenance of the electrolysis device is further reduced, and the work efficiency of maintenance is further improved.

(3) The electrolytic cell body can also function as a second electrode. In this case, it is not necessary to separately provide the second electrode. Thereby, the constitution of the electrolysis device can be simplified.

(4) The electrolysis device further includes a second sealing member that is provided in the electrolytic cell body so as to surround the first opening, and the first cover may be provided on the electrolytic cell body via the second sealing member.

In this case, the first lid body can be removed from the electrolytic cell body. Therefore, the inside of the electrolysis device can be inspected by removing the first lid from the electrolytic cell body.

(5) The electrolysis apparatus according to another aspect of the present invention includes: an electrolytic cell that houses an electrolytic bath; and a separator that is disposed in such a manner that the inside of the electrolytic cell is divided into an anode chamber and a cathode chamber and has ions in the electrolytic bath. An opening through which an anode is disposed in an anode chamber of the electrolytic cell; and a cathode disposed in a cathode chamber of the electrolytic cell; the opening of the separator having an upper surface extending obliquely upward toward at least one of the anode chamber and the cathode chamber .

In the electrolysis device, the electrolytic cell is partitioned into an anode chamber and a cathode chamber by a separator. The electrolytic bath in the electrolytic cell is electrolyzed by applying a voltage between the anode disposed in the anode chamber and the cathode disposed in the cathode chamber. Thereby, gas is generated in the anode chamber and the cathode chamber.

An opening through which ions in the electrolytic bath can pass is disposed on the separator. The opening has an upper surface that extends obliquely upward toward at least one of the anode chamber and the cathode chamber surface. Therefore, even if the generated bubble enters the opening from at least one of the anode chamber and the cathode chamber, the bubble returns to the anode chamber or the cathode chamber along the upper surface of the opening. Therefore, by setting the size of the opening in such a manner that the generated bubble cannot pass, the gas generated in the anode chamber can be prevented from being mixed with the gas generated in the cathode chamber, and the opening can be prevented from being clogged by the generated bubble. As a result, mixing of the gas can be prevented, and the electrolytic reaction of the electrolytic bath can be stably performed.

(6) Fluorine gas is generated in the anode chamber, and hydrogen gas is generated in the cathode chamber, and the upper surface of the opening may be disposed to extend obliquely upward toward the cathode chamber side.

Hydrogen is less likely to be dissolved in the electrolytic bath than the fluorine gas, so that the bubbles of hydrogen remain in the opening and easily block the opening. Therefore, by providing the upper surface of the opening to extend obliquely upward toward the cathode chamber side, even if the bubble of hydrogen gas generated in the cathode chamber enters the opening, the bubble returns to the cathode chamber along the upper surface of the opening. Thereby, the opening is prevented from being clogged with hydrogen.

(7) The area of the end of the opening on the anode chamber side may be smaller than the area of the end of the opening on the cathode chamber side.

In this case, the fluorine gas generated in the anode chamber is prevented from entering the opening. Thereby, the fluorine gas is prevented from moving to the cathode chamber, and the fluorine gas is prevented from being mixed with the hydrogen gas.

(8) The separator comprises a liquid separator immersed in an electrolytic bath, and the opening is provided in the liquid separator, and the liquid separator may be formed of a perfluoro resin.

In this case, the liquid separator can be prevented from being corroded by the electrolytic bath. Moreover, the processing of the liquid separator at the time of forming the opening becomes easy. Further, the material cost of the liquid separator is lowered.

(9) Conductive diamond coating can also be applied to the surface of the anode. In this case, since the polarization is less likely to occur in the anode, the gas generation efficiency is improved. Even if the amount of gas generated is increased, the opening of the separator can be prevented from being clogged by the bubbles, so that the electrolytic reaction can be stably performed.

According to the present invention, the cost of maintenance of the electrolysis device can be reduced and the work efficiency of maintenance can be improved.

Further, according to the present invention, mixing of gases can be prevented and the electrolysis reaction can be stably performed.

[1] First embodiment

Hereinafter, an electrolysis device (gas generating device) according to a first embodiment of the present invention will be described with reference to the drawings.

(1) Composition of electrolysis device

Fig. 1 is a schematic cross-sectional view showing an electrolysis apparatus according to a first embodiment of the present invention. The electrolysis device 10 of Fig. 1 is a gas generating device that generates fluorine gas. As shown in FIG. 1, the electrolysis device 10 includes an electrolysis cell 11. The electrolytic cell 11 includes an electrolytic cell body 11a, a first lid 11b, a sealing member 11c, a second lid 11d, and a sealing member 11e. A partition plate 13 is integrally provided on the lower surface of the second lid body 11d so as to surround the space in the center portion of the electrolytic cell body 11a. The electrolytic cell main body 11a, the first lid body 11b, the second lid body 11d, and the separator 13 are formed of a metal or an alloy such as Ni (nickel), monel, pure iron, or stainless steel.

High current power is operated in the electrolytic cell 11. Further, in the case where a gas such as hydrogen is present in the cathode chamber 14b, it is necessary to prevent conduction by static electricity or discharge. The discharge in the cathode chamber 14b is caused. Therefore, the first cover 11b of the cathode chamber 14b is grounded by the ground line E1. Thereby, electric leakage from the electrolytic cell 11 can be prevented to cause electric shock or the like, and gas such as hydrogen gas can be prevented from being exploded.

An electrolytic bath (electrolyte) 12 containing a KF-HF (potassium-hydrogen fluoride) mixed molten salt is formed in the electrolytic cell 11. In the electrolytic cell 11, the anode chamber 14a is formed inside the separator 13, and the cathode chamber 14b is formed on the outer side of the separator 13.

An anode 15a is disposed in the anode chamber 14a. A portion of the separator 13 and the anode 15a are immersed in the electrolytic bath 12. A cathode 15b is formed on the inner surface of the electrolytic cell body 11a. As a material of the cathode 15b, for example, Ni is preferably used.

The HF supply line 18a for supplying HF is connected to the first lid 11b. The HF supply line 18a is covered by the temperature adjustment heater 18b. Thereby, HF can be prevented from being liquefied in the HF supply line 18a. The height of the liquid surface of the electrolytic bath 12 is detected by a liquid level detecting device (not shown). When the height of the liquid surface detected by the liquid level detecting device becomes lower than a specific value, HF is supplied into the electrolytic cell 11 through the HF supply line 18a.

This electrolysis device 10 includes a control unit 23. The electrolytic bath 12 in the electrolytic cell 11 is maintained in a solid state at room temperature and atmospheric pressure. Therefore, in order to perform electrolysis of the electrolytic bath 12, it is necessary to heat the electrolytic bath 12 to 80 to 90 ° C to dissolve it into a liquid state. The control unit 23 controls the temperature control unit (not shown) based on the temperature of the electrolytic bath 12 detected by the temperature sensor (not shown), and maintains the temperature of the electrolytic bath 12 at 80 to 90 °C.

A voltage is applied between the anode 15a and the cathode 15b by the control unit 23. Thereby, the electrolytic bath 12 in the electrolytic cell 11 is electrolyzed. As a result, fluorine gas is mainly generated in the anode chamber 14a. Also, hydrogen is mainly generated in the cathode chamber 14b. gas.

A gas discharge port 16a is provided in the second lid body 11d, and a gas discharge port 16b is provided in the first lid body 11b. An exhaust pipe 17a is connected to the gas discharge port 16a, and an exhaust pipe 17b is connected to the gas discharge port 16b. The gas discharge port 16a communicates with the anode chamber 14a, and the gas discharge port 16b communicates with the cathode chamber 14b. The gas system generated in the anode chamber 14a is discharged from the gas discharge port 16a through the exhaust pipe 17a, and the gas system generated in the cathode chamber 14b is discharged from the gas discharge port 16b through the exhaust pipe 17b.

(2) Details of the electrolytic cell

Figure 2 is an exploded perspective view of the electrolytic cell 11 of Figure 1. Fig. 3 is a bottom view of the second cover 11d.

As shown in Fig. 2, the electrolytic cell body 11a has a bottom surface portion and four side surface portions, and has a rectangular opening H1 at the upper portion. The sealing member 11c is provided on the upper end faces of the four side faces so as to surround the opening H1. The sealing member 11c is, for example, an O-ring including a fluororubber. The first cover 11b has a rectangular shape and has a size larger than the opening H1. The first lid body 11b is disposed on the sealing member 11c so as to close the opening H1 of the electrolytic cell body 11a. Thereby, the electrolytic cell main body 11a and the first lid body 11b are electrically insulated and sealed from each other by the sealing member 11c.

The first lid body 11b has a rectangular opening H2 at a substantially central portion. The sealing member 11e is provided on the upper surface of the first lid body 11b so as to surround the opening H2 along the edge of the first lid body 11b of the opening H2. The sealing member 11e is, for example, an O-ring including a fluororubber. The second cover 11d has a rectangular shape and has a size larger than the opening H2. The second cover 11d is configured to close the opening of the first cover 11b The H2 is disposed on the sealing member 11e. Thereby, the first lid body 11b and the second lid body 11d are electrically insulated from each other by the sealing member 11e and sealed. The HF supply hole 18c inserted into the HF supply line 18a is provided in the first lid body 11b.

The partition 13 includes four side walls 13a, 13b, 13c, and 13d. As shown in FIG. 3, the partition plate 13 is integrally provided with the second lid body 11d on the lower surface of the second lid body 11d. The four side walls 13a to 13d of the separator 13 include, for example, Ni or a Monel alloy. On the lower surface side of the second lid body 11d, a rectangular plate-shaped anode 15a is attached to a space surrounded by the four side walls 13a to 13d of the separator 13 via the mounting member 19 of Fig. 2 . As a material of the anode 15a, for example, a low-polarity carbon electrode is used.

(3) Effect

In the electrolysis device 10 of Fig. 1 of the present embodiment, the sealing members 11c and 11e are disposed on the outer side of the anode chamber 14a. Therefore, the fluorine gas generated in the anode chamber 14a does not contact the sealing members 11c, 11e. Thereby, corrosion of the sealing members 11c and 11e can be prevented. As a result, the frequency of inspection and replacement of the sealing members 11c and 11e is lowered.

Further, by removing the second lid body 11d from the first lid body 11b, the anode 15a and the second lid body 11d can be easily removed from the electrolytic cell main body 11a. Thereby, even when the anode 15a is consumed, the anode 15a can be easily replaced. In particular, when the electrolytic cell 11 is enlarged, the electrolytic cell main body 11a and the first lid body 11b are increased in size and weight. In this case, since the second lid body 11d does not need to be enlarged, the second lid body 11d can be easily removed from the first lid body 11b.

Further, in the case where the electrolysis device 10 is used for a long period of time, it is necessary to check whether the separator 13 is consumed or not. In this case, the second cover can also be used The body 11d is removed from the first lid body 11b, and the separator 13 is removed from the first lid body 11b. Thereby, the separator 13 can be easily inspected.

As a result of this, the cost of maintenance of the electrolysis device 10 can be reduced, and the efficiency of maintenance work can be improved.

(4) Other embodiments

In the above embodiment, the electrolytic cell main body 11a has a bottom surface portion and four side surface portions, and has a rectangular opening H1 at the upper portion, but is not limited thereto. For example, the electrolytic cell body 11a may have a bottom surface portion and a cylindrical side surface portion, and have a circular opening at the upper portion. In this case, the opening of the electrolytic cell body 11a is closed by the first lid body 11b having a circular shape.

The first lid body 11b has a rectangular opening H2, but is not limited thereto. For example, the first cover 11b may have a circular opening. In this case, the opening of the first lid body 11b is closed by the second lid body 11d having a circular shape.

The partition plate 13 includes four side walls 13a to 13d, but is not limited thereto. For example, the partition 13 may also include a cylindrical side wall. Further, it is preferable that the separator 13 and the second lid 11d are integrally provided, and it is more preferable that the separator 13 and the second lid 11d formed of different metal materials are integrally provided by welding, but are not limited thereto. herein. The partition plate 13 and the second lid body 11d may be integrally provided by casting.

When the adhesion to the second lid 11d is ensured and the airtightness of the anode chamber 14a is maintained, the separator 13 may be provided separately from the second lid 11d. In this case, it is preferable to provide a sealing material having a high corrosion resistance such as a sealing metal between the separator 13 and the second lid 11d to ensure adhesion.

(5) Correspondence between each component of the technical solution and each part of the embodiment relationship

Hereinafter, the respective constituent elements of the technical means and the corresponding examples of the respective portions of the embodiment will be described, but the present invention is not limited to the following examples.

In the above embodiment, the electrolytic bath 12 is an example of an electrolytic bath, the electrolysis device 10 is an electrolysis device, hydrogen is an example of another gas, the electrolytic cell 11 is an example of an electrolytic cell, and the electrolytic cell main body 11a is an example of an electrolytic cell main body. The opening H1 is an example of a first opening, the opening H2 is an example of a second opening, the first lid 11b is an example of a first lid, the second lid 11d is an example of a second lid, and the sealing member 11e is first. In the example of the sealing member, the sealing member 11c is an example of the second sealing member. The anode 15a is an example of a first electrode, the cathode 15b is an example of a second electrode, the anode chamber 14a is an example of a first chamber, the cathode chamber 14b is an example of a second chamber, and the separator 13 is an example of a separator.

As each component of the technical solution, various other elements having the configuration or function described in the claims can be used.

[2] Second embodiment

Hereinafter, an electrolysis device according to a second embodiment of the present invention will be described with reference to the drawings.

(1) Composition of electrolysis device

Fig. 4 is a schematic cross-sectional view showing an electrolysis apparatus according to a second embodiment of the present invention. The electrolysis device 10 of Fig. 4 is an electrolysis device that generates fluorine gas. As shown in FIG. 4, the electrolysis device 10 includes an electrolytic cell 11. The electrolytic cell 11 includes an electrolytic cell body 11a and an upper lid 11f.

The electrolytic cell body 11a and the upper lid body 11f are formed of a metal or an alloy such as Ni (nickel), monel, pure iron or stainless steel. The electrolytic cell body 11a has a bottom surface portion and a side surface portion, and has an opening at the upper portion. Cover the bottom The insulating member 11g is disposed in such a manner as to face the upper surface of the face. An insulating member (sealing member) 11h is attached to the upper end surface of the side surface portion. The insulating members 11g and 11h contain an insulating material such as a resin. The upper cover 11f is placed on the insulating member 11h so as to close the opening of the electrolytic cell body 11a. Thereby, the electrolytic cell main body 11a and the upper cover body 11f are electrically insulated from each other by the insulating member 11h.

An electrolytic bath 12 containing a KF-HF (potassium-hydrogen fluoride) mixed molten salt is accommodated in the electrolytic cell 11. A cylindrical partition plate 13 is provided to extend downward from the lower surface of the upper cover 11f. The separator 13 includes a cylindrical gas separator 13A and a cylindrical liquid separator 13B. The gas separator 13A is integrally provided to the upper lid body 11f. The height of the lower end portion of the gas separator 13A is set to be substantially equal to the height of the liquid surface of the electrolytic bath 12. As the material of the gas separator 13A, a metal or an alloy such as Ni (nickel), a Ni alloy, a Monel alloy, pure iron or stainless steel is preferably used. In this case, the corrosion of the gas separator 13A caused by the fluorine gas and the hydrogen fluoride vapor is suppressed. The gas partition 13A may also be provided to be detachable from the upper cover 11f.

The liquid separator 13B is attached to the lower end portion of the gas separator 13A so as to be immersed in the electrolytic bath 12. A plurality of through holes H (FIG. 5 described below) for ensuring the permeability of the electrolytic bath 12 are formed in the liquid separator 13B. Details of the liquid separator 13B will be described below. As the material of the liquid separator 13B, a perfluoro resin such as PTFE (polytetrafluoroethylene) or PFA (polyfluoroalkoxy) is preferably used, and PTFE is particularly preferably used. . In this case, the corrosion of the liquid separator 13B caused by the electrolytic bath 12 is suppressed as compared with the case where metal is used as the material of the liquid separator 13B. Also, forming the above-mentioned through Processing at the hole H becomes easy. Further, the material cost of the liquid separator 13B is lowered.

In the electrolytic cell 11, the anode chamber 14a is formed inside the separator 13, and the cathode chamber 14b is formed on the outer side of the separator 13. The anode 15a is disposed in the anode chamber 14a so as to be immersed in the electrolytic bath 12. As a material of the anode 15a, for example, a low-polarity carbon electrode is preferably used.

Preferably, conductive diamond coating is applied to the surface of the anode 15a. Specifically, a mixed gas of hydrogen gas and a carbon source is used as a diamond raw material, and an element (hereinafter referred to as a dopant) having a small atomic valence different from carbon is added to the mixed gas, whereby a conductive diamond coating can be formed. Cloth layer. As the dopant, boron, phosphorus or nitrogen is preferably used, and boron is particularly preferably used. The weight of the dopant to be added is preferably 1 ppm or more and 30,000 ppm or less, more preferably 100 ppm or more and 10,000 ppm or less, based on the total weight of the diamond coating layer. Polarization is less likely to occur in the anode 15a by applying conductive diamond coating to the surface of the anode 15a. Therefore, the fluorine gas generation efficiency is improved. In the present embodiment, the side surface portion of the electrolytic cell main body 11a functions as a cathode.

The HF supply line 18a for supplying HF into the electrolytic cell 11 is connected to the upper lid 11f. The HF supply line 18a is covered by the temperature adjustment heater 18b. Thereby, HF is prevented from being liquefied in the HF supply line 18a. The height of the liquid level of the electrolytic bath 12 is detected by a liquid level detecting device (not shown). When the height of the liquid surface detected by the liquid level detecting device becomes lower than a specific value, HF is supplied into the electrolytic cell 11 through the HF supply line 18a.

Gas discharge ports 16a and 16b are provided in the upper lid body 11f. Gas row An exhaust pipe 17a is connected to the outlet 16a, and an exhaust pipe 17b is connected to the gas discharge port 16b. The gas discharge port 16a communicates with the anode chamber 14a, and the gas discharge port 16b communicates with the cathode chamber 14b.

The electrolytic bath 12 is electrolyzed by applying a voltage between the anode 15a and the electrolytic cell body 11a. In this case, fluorine gas is generated on the surface of the anode 15a, and hydrogen gas is generated on the inner surface of the side surface portion of the electrolytic cell body 11a. Since the upper surface of the bottom surface portion of the electrolytic cell body 11a is covered with the insulating member 11g, the electrolytic reaction of the electrolytic bath 12 cannot be performed on the upper surface of the bottom surface portion, and hydrogen gas is not generated.

The fluorine gas generated in the anode chamber 14a is introduced from the gas discharge port 16a to the outside of the electrolytic cell 11 through the exhaust pipe 17a. The hydrogen gas generated in the cathode chamber 14b is introduced from the gas discharge port 16b to the outside of the electrolytic cell 11 through the exhaust pipe 17b.

(2) Details of liquid separator

Fig. 5 is an external perspective view of the liquid separator 13B, and Fig. 6 is an enlarged view of the through hole H formed in the liquid separator 13B. Fig. 6(a) is a longitudinal cross-sectional view of the through hole H, Fig. 6(b) is a side view showing the through hole H from the anode chamber 14a, and Fig. 6(c) is a side view showing the through hole H from the cathode chamber 14b. Fig. 6(a) is a cross-sectional view taken along line A-A of Fig. 6(b) and Fig. 6(c).

As shown in FIG. 5, a plurality of circular through holes H are formed in the liquid separator 13B. In the example of Fig. 5, a plurality of through holes H are formed in two rows along the circumferential direction of the liquid separator 13B. In this case, the ions in the electrolytic bath 12 can move between the anode chamber 14a and the cathode chamber 14b through the plurality of through holes H. Thereby, in the anode chamber 14a and the cathode chamber 14b, the electrolysis reaction proceeds stably and smoothly.

In this case, when the fluorine gas and the hydrogen gas generated by the electrolytic reaction move through the through hole H, the fluorine gas is mixed with the hydrogen gas in the anode chamber 14a or the cathode chamber 14b. Thereby, the fluorine gas reacts with the hydrogen gas to cause a decrease in the generation efficiency of the fluorine gas, and it is also considered that an explosive mixed gas may be generated from the ratio of the fluorine gas to the hydrogen gas.

Therefore, the diameter of each through hole H is set to such a size that bubbles of fluorine gas and hydrogen gas cannot pass. However, there is a case where the air bubbles are retained in the through hole H and the through hole H is blocked. In particular, since hydrogen gas is less likely to be dissolved in the electrolytic bath 12 than the fluorine gas, bubbles of hydrogen gas are likely to remain in the through holes H, and the through holes H are easily blocked. When the through hole H is clogged, the electrolytic bath 12 cannot move through the through hole H. Thereby, the electrolysis reaction cannot be stably performed.

Therefore, in the present embodiment, as shown in FIG. 6, each of the through holes H has an upper surface L1 extending obliquely upward from the end portion on the anode chamber 14a side to the end portion on the cathode chamber 14b side. Hereinafter, the end portion of the through hole H on the anode chamber 14a side is referred to as an anode side end, and the end portion of the through hole H on the cathode chamber 14b side is referred to as a cathode side end. The lower surface H2 of the through hole H extends horizontally from the anode side end to the cathode side end. Here, the upper surface of the through hole H refers to a region in the inner circumferential surface of the through hole H that faces downward, and the lower surface of the through hole H refers to a region in the inner circumferential surface of the through hole H that faces upward.

The diameter D1 of the upper and lower sides of the anode side end of the through hole H is set to such a size that the electrolytic bath can pass and the bubbles of fluorine gas and hydrogen cannot pass. The diameter D1 is, for example, 1 mm or more and 3 mm or less, preferably 1 mm or more and 2 mm or less. The diameter D2 of the upper side of the cathode side end of the through hole H is larger than the diameter D1. The diameter D2 is, for example, 5 mm or more and 10 mm or less, preferably 5 mm or more and 8 Below mm. The thickness TH of the liquid separator 13B is, for example, 5 mm or more and 10 mm or less, preferably 5 mm or more and 8 mm or less.

In the electrolysis device 10 of the present embodiment, even if bubbles of hydrogen gas enter the through hole H from the cathode chamber 14b, the bubbles return to the cathode chamber 14b along the upper surface of the through hole H and float up to the liquid surface. Therefore, the air bubbles of the hydrogen gas entering the through hole H from the cathode chamber 14b are prevented from clogging the through hole H. Further, the diameter of the through hole H on the anode chamber 14a side in the vertical direction is smaller than the diameter of the through hole H on the cathode chamber 14b side. Further, as described above, the fluorine gas is easily dissolved in the electrolytic bath 12 as compared with the hydrogen gas. Therefore, the bubble of the fluorine gas is prevented from entering the through hole H from the anode chamber 14a.

In this manner, the bubbles of the fluorine gas and the hydrogen gas are prevented from moving through the through holes H, and the bubbles of the fluorine gas and the hydrogen gas are prevented from clogging the through holes H. Thereby, the electrolytic reaction can be stably and smoothly performed without lowering the production efficiency of the fluorine gas.

(3) Other examples of through holes (3-1)

The shape of the through hole H of the liquid separator 13B is not limited to the examples of FIGS. 5 and 6. Fig. 7 is a view showing another example of the through hole H formed in the liquid separator 13B. 7(a) and 7(b), differences from the examples of FIGS. 5 and 6 will be described.

In the example of Fig. 7(a), the upper surface L1 of the through hole H extends horizontally from the anode side end to the intermediate point P1 between the anode side end and the cathode side end, and extends obliquely upward from the intermediate point P1 to the cathode side. So far. In this case as well, the bubbles of hydrogen gas entering the through hole H from the cathode chamber 14b block the through hole H, and the bubbles of the fluorine gas are prevented from entering the through hole H from the anode chamber 14a.

In the example of Fig. 7(b), the upper surface L1 of the through hole H extends obliquely downward from the anode side end to the intermediate point P1, and extends obliquely upward from the intermediate point P1 to the cathode side end. In this case as well, the gas bubbles of hydrogen gas entering the through hole H from the cathode chamber 14b are prevented from clogging the through hole H. Further, even if the bubble of the fluorine gas enters the through hole H from the anode chamber 14a, the bubble returns to the anode chamber 14a along the upper surface L1 of the through hole H, and floats up to the liquid surface. Therefore, the air bubbles of the fluorine gas entering the through hole H from the anode chamber 14a are prevented from clogging the through hole H.

(3-2)

In the above example, the through hole H has a circular vertical cross section, but the through hole H may have a longitudinal cross section of another shape such as an elliptical shape, a triangular shape, or a quadrangular shape.

(3-3)

In the above-described example, the upper surface L1 of the through hole H is provided to extend linearly obliquely upward toward the cathode end. However, the surface L1 is not limited thereto. For example, the upper surface L1 of the through hole H may be directed toward the cathode side. The end is arranged to extend obliquely upward obliquely.

(4) Other examples of liquid separators

Fig. 8 is a cross-sectional view for explaining another example of the liquid separator 13B. Fig. 8 shows the lower end portion of the gas partition 13A and the upper end portion of the liquid partition 13B. Regarding the example of Fig. 8, differences from the examples of Figs. 5 and 6 will be described.

In the example of Fig. 8, the upper end portion of the liquid separator 13B is provided so as to cover the lower end portion of the outer peripheral surface (the surface on the cathode chamber 14b side) of the gas separator 13A. When the electrolytic reaction of the electrolytic bath 12 is performed in a state where the lower end of the gas separator 13A is immersed in the electrolytic bath 12, the gas separator 13A in the electrolytic bath 12 Polarization occurs, and the outer surface of the gas separator 13A has a positive charge. In this case, the metal is ionized from the outer peripheral surface of the positively-charged gas separator 13A and eluted in the electrolytic bath 12, and the outer peripheral surface of the gas separator 13A is easily corroded. Therefore, in this example, the portion of the outer peripheral surface of the gas separator 13A immersed in the electrolytic bath 12 is covered by the liquid-surface separator 13B. Thereby, the electrolytic bath 12 is prevented from coming into contact with the outer peripheral surface of the gas separator 13A, and corrosion of a portion of the outer peripheral surface of the gas separator 13A immersed in the electrolytic bath 12 is prevented.

Further, the upper end portion of the liquid level separator 13B preferably extends above the liquid surface of the electrolytic bath 12. In this case, it is possible to surely prevent the electrolytic bath 12 from contacting the outer peripheral surface of the gas separator 13A. Further, since the upper end portion of the liquid level separator 13B is located on the side of the cathode chamber 14b, the fluorine gas and the hydrogen fluoride vapor do not contact the liquid surface even if the upper end portion of the liquid surface partition plate 13B extends above the liquid surface of the electrolytic bath 12. Separator 13B. Therefore, corrosion of the liquid level partition 13B is prevented.

(5) Other embodiments (5-1)

In the above embodiment, the gas separator 13A and the liquid separator 13B are provided as separate bodies, but corrosion of the gas separator 13A and the liquid separator 13B is prevented or corrosion of the gas separator 13A and the liquid separator 13B is prevented. When it is not a problem, the gas separator 13A and the liquid separator 13B may be integrally provided.

(5-2)

In the above embodiment, the gas separator 13A and the liquid separator 13B are each cylindrical. However, the gas separator 13A and the liquid separator 13B may have other shapes such as an angular column shape or a flat plate shape. .

(5-3)

The above embodiment is an example in which the present invention is applied to an electrolysis device that generates fluorine gas, but the present invention can also be applied to an electrolysis device that generates other gases such as oxygen.

(6) Correspondence between each component of the technical solution and each part of the embodiment

Hereinafter, the respective constituent elements of the technical means and the corresponding examples of the respective portions of the embodiment will be described, but the present invention is not limited to the following examples.

In the above embodiment, the electrolytic bath 12 is an example of an electrolytic bath, the electrolytic cell 11 is an example of an electrolytic cell, the through hole H is an opening, the upper surface L1 is an upper surface, and the separator 13 is an example of a separator. The anode chamber 14a is an example of an anode chamber, the anode 15a is an anode, the cathode chamber 14b is a cathode chamber, the cathode 15b is a cathode, and the liquid separator 13B is a liquid separator.

As each component of the technical solution, various other elements having the configuration or function described in the claims can be used.

[Industrial availability]

The present invention can be effectively utilized in various electrolysis devices such as gas generating devices.

10‧‧‧Electrolytic device

11‧‧‧ Electrolyzer

11a‧‧‧ Electrolytic cell body

11b‧‧‧1st cover

11c‧‧‧ Sealing member

11d‧‧‧2nd cover

11e‧‧‧ Sealing member

11f‧‧‧Upper cover

11g‧‧‧Insulating components

11h‧‧‧Insulating components

12‧‧Electrical bath

13‧‧‧Baffle

13A‧‧‧ gas partition

13a, 13b, 13c, 13d‧‧‧ side walls

13B‧‧‧Liquid partition

14a‧‧‧Anode chamber

14b‧‧‧Cathode chamber

15a‧‧‧Anode

15b‧‧‧ cathode

16a‧‧‧ gas discharge

16b‧‧‧ gas discharge

17a‧‧‧Exhaust pipe

17b‧‧‧Exhaust pipe

18a‧‧‧Supply pipeline

18b‧‧‧heating heater

18c‧‧‧HF supply hole

19‧‧‧Installation components

23‧‧‧Control Department

D1‧‧‧ diameter

D2‧‧‧ diameter

E1‧‧‧ Grounding wire

F ₂ ‧‧‧Fluorine

H‧‧‧through hole

H ₂ ‧‧‧hydrogen

H1‧‧‧ openings

H2‧‧‧ openings

L1‧‧‧ upper surface

L2‧‧‧ lower surface

P1‧‧‧ intermediate point

TH‧‧‧ thickness

Fig. 1 is a schematic cross-sectional view showing an electrolysis apparatus according to a first embodiment of the present invention.

Figure 2 is an exploded perspective view of the electrolytic cell of Figure 1.

Fig. 3 is a bottom view of the second cover.

Fig. 4 is a schematic cross-sectional view showing an electrolysis apparatus according to a second embodiment of the present invention.

Figure 5 is a perspective view showing the appearance of a liquid separator.

6(a) to 6(c) are enlarged views of the through holes formed in the liquid separator.

7(a) and 7(b) are views showing another example of a through hole formed in a liquid separator.

Fig. 8 is a cross-sectional view for explaining another example of the liquid separator.

10‧‧‧Electrolytic device

11‧‧‧ Electrolyzer

11a‧‧‧ Electrolytic cell body

11b‧‧‧1st cover

11c‧‧‧ Sealing member

11d‧‧‧2nd cover

11e‧‧‧ Sealing member

12‧‧Electrical bath

13‧‧‧Baffle

14a‧‧‧Anode chamber

14b‧‧‧Cathode chamber

15a‧‧‧Anode

15b‧‧‧ cathode

16a‧‧‧ gas discharge

16b‧‧‧ gas discharge

17a‧‧‧Exhaust pipe

17b‧‧‧Exhaust pipe

18a‧‧‧Supply pipeline

18b‧‧‧heating heater

18c‧‧‧HF supply hole

19‧‧‧Installation components

23‧‧‧Control Department

E1‧‧‧ Grounding wire

H1‧‧‧ openings

H2‧‧‧ openings

Claims (9)

An electrolysis device for generating fluorine gas and other gases by electrolysis of an electrolytic bath; and comprising an electrolytic cell for accommodating an electrolytic bath; the electrolytic cell comprising: an electrolytic cell body having a first opening at an upper portion; The first cover has a second opening smaller than the first opening, and is provided in the electrolytic cell body so as to close the first opening; and the first sealing member is provided on the second opening so as to surround the second opening a first lid body; the second lid body is provided on the first lid body via the first sealing member so as to close the second opening; and the first electrode is attached to the second lid body; and a separator that separates the inside of the electrolytic cell body into a first chamber that generates fluorine gas and a second chamber that generates another gas; and the partition plate is disposed in a manner that the first chamber is disposed in an inner region of the first sealing member And formed. The electrolysis device according to claim 1, wherein the separator is integrally provided to the first lid so as to surround the periphery of the first electrode. The electrolysis apparatus according to claim 1 or 2, wherein the electrolysis cell system functions as a second electrode. The electrolysis device according to claim 1 or 2, further comprising: a second sealing member provided in the electrolytic cell body so as to surround the first opening; wherein the first cap system is provided on the electric device via the second sealing member Unsink the body. An electrolysis device comprising: an electrolysis cell for accommodating an electrolysis bath; a separator disposed to divide the inside of the electrolysis cell into an anode chamber and a cathode chamber, and having an opening through which ions in the electrolysis bath can pass; The cathode chamber is disposed in the anode chamber of the electrolytic cell; and the cathode is disposed in the cathode chamber of the electrolytic cell; the opening of the separator has an obliquely upwardly extending toward at least one of the anode chamber and the cathode chamber Above the surface. The electrolysis apparatus according to claim 5, wherein the fluorine gas is generated in the anode chamber, and hydrogen gas is generated in the cathode chamber; and the upper surface of the opening is provided to extend obliquely upward toward the cathode chamber side. The electrolysis device according to claim 6, wherein an area of the end portion of the opening on the anode chamber side is smaller than an area of an end portion of the opening on the cathode chamber side. The electrolysis device according to any one of claims 5 to 7, wherein the separator comprises a liquid separator immersed in the electrolytic bath; the opening is provided in the liquid separator; and the liquid separator is formed of a perfluoro resin. The electrolysis device according to any one of claims 5 to 7, wherein the surface of the anode is coated with a conductive diamond.