WO2013001800A1

WO2013001800A1 - Electrolysis device

Info

Publication number: WO2013001800A1
Application number: PCT/JP2012/004145
Authority: WO
Inventors: 昌士児玉; 善夫初代
Original assignee: 東洋炭素株式会社
Priority date: 2011-06-29
Filing date: 2012-06-27
Publication date: 2013-01-03
Also published as: CN103635609A; DE112012002702T8; TW201311935A; KR20140035957A; DE112012002702T5

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

Electrolyzer

The present invention relates to an electrolysis apparatus provided with an electrolytic cell.

Conventionally, fluorine gas has been used in various applications such as material cleaning and surface modification in semiconductor manufacturing processes and the like. In this case, the fluorine gas itself may be used, and various fluorine such as NF3 (nitrogen trifluoride) gas, NeF (neon fluoride) gas, and ArF (argon fluoride) gas synthesized based on the fluorine gas may be used. A system gas may be used.

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

For example, the molten salt electrolysis apparatus described in Patent Document 1 has an electrolytic cell composed of an electrolytic cell main body and an upper lid. The interior of the electrolytic cell is separated by a partition into an anode chamber located at the center of the electrolytic cell and a cathode chamber surrounding the anode chamber. An anode is disposed in the anode chamber, and a cathode is provided in the cathode chamber. An opening for inserting the anode into the electrolytic cell main body is formed in a substantially central portion of the upper lid, and a lid is provided so as to cover the opening. A gas seal material is interposed between the lid and the upper lid. The lid is vertically provided with a connecting rod that holds the anode.

As described above, hydrogen gas is generated along with fluorine gas in the electrolytic cell. Therefore, a partition for separating generated fluorine gas and hydrogen gas is provided in the electrolytic cell. In the electrolytic cell described in Patent Document 2, a separator having a porous or fibrous structure is used in order to prevent gas mixing. In this case, the electrolytic bath can pass through the diaphragm. For this reason, an increase in energization resistance between the anode and the cathode disposed in the electrolytic cell is prevented.
JP 2005-48290 A JP 2000-104187 A

In the molten salt electrolysis apparatus described in Patent Document 1, the anode can be easily removed from the electrolytic cell main body together with the upper lid by removing the lid from the upper lid. Thereby, even when the anode is consumed, the anode can be easily replaced.

However, in the molten salt electrolysis apparatus, the gas seal material interposed between the lid and the upper lid is required to have corrosion resistance against fluorine gas. Further, even a gas seal material having corrosion resistance to fluorine gas is corroded by being in contact with fluorine gas for a long time. Therefore, it is necessary to frequently replace the gas seal material. As a result, maintenance costs increase. Further, since the frequency of replacing the gas seal material is higher than the frequency of replacing the anode, the maintenance work efficiency is poor.

Further, the present inventor has found that in the electrolytic cell of Patent Document 2, the generated gas bubbles block the hole of the partition plate, thereby preventing permeation of the electrolytic bath. As a result, the electrolytic reaction of the electrolytic bath cannot proceed stably.

An object of the present invention is to provide an electrolyzer capable of reducing maintenance costs and improving maintenance work efficiency.

Another object of the present invention is to provide an electrolysis apparatus capable of allowing an electrolytic reaction to proceed stably while preventing gas mixing.

(1) An electrolysis apparatus according to one aspect of the present invention is an electrolysis apparatus for generating fluorine and other gases by electrolyzing an electrolysis bath, and includes an electrolysis tank that accommodates the electrolysis bath. An electrolytic cell main body having a first opening at an upper portion, a first lid body having a second opening smaller than the first opening and provided in the electrolytic cell main body so as to close the first opening; The first seal member provided on the first lid body so as to surround the second opening and the first seal member sandwiched between the first seal member so as to close the second opening are provided on the first lid body. A partition that separates the second lid, a first electrode attached to the second lid, and a first chamber in which fluorine is generated and a second chamber in which other gas is generated in the electrolytic cell body And the partition is formed such that the first chamber is disposed in a region inside the first seal member. It is.

In this electrolysis apparatus, the first opening at the top of the electrolytic cell main body is closed by the first lid. The second opening of the first lid is closed by the second lid with the first seal member interposed therebetween. The first electrode is attached to the second lid. Since the second opening is smaller than the first opening, the second lid body is smaller and lighter than the first lid body. 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 arranged in a region inside the first seal member by a partition wall. In this case, since fluorine generated in the first chamber does not contact the first seal member, corrosion of the first seal member is prevented. This reduces the frequency of replacing the first seal member.

As a result, the maintenance cost of the electrolyzer is reduced and the work efficiency of the maintenance is improved.

(2) The partition wall may be provided integrally with the first lid so as to surround the periphery of the first electrode. In this case, the partition can be easily inspected by removing the second lid from the first lid. Thereby, the maintenance cost of the electrolyzer is further reduced, and the maintenance work efficiency is further improved.

(3) The electrolytic cell main body may function as the second electrode. In this case, it is not necessary to provide the second electrode separately. Thereby, the structure of the electrolyzer can be simplified.

(4) The electrolysis apparatus further includes a second seal member provided in the electrolytic cell main body so as to surround the first opening, and the first lid body is disposed on the electrolytic cell main body with the second seal member interposed therebetween. It may be provided.

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

(5) An electrolysis apparatus according to another aspect of the present invention is provided so as to partition an electrolytic bath that accommodates an electrolytic bath and an electrolytic chamber into an anode chamber and a cathode chamber, and ions in the electrolytic bath can pass therethrough. A partition having an opening, an anode provided in an anode chamber of the electrolytic cell, and a cathode provided in a cathode chamber of the electrolytic cell, wherein the partition opening extends obliquely upward toward at least one of the anode chamber and the cathode chamber. It has an upper surface.

In the electrolyzer, the electrolytic cell is partitioned into an anode chamber and a cathode chamber by a partition wall. By applying a voltage between the anode provided in the anode chamber and the cathode provided in the cathode chamber, the electrolytic bath in the electrolytic cell is electrolyzed. Thereby, gas is generated in the anode chamber and the cathode chamber.

The partition is provided with an opening through which ions in the electrolytic bath can pass. The opening has an upper surface extending obliquely upward toward at least one of the anode chamber and the cathode chamber. Therefore, even if the generated gas bubbles enter the opening from at least one of the anode chamber and the cathode chamber, the bubbles are returned to the anode chamber or the cathode chamber along the upper surface of the opening. Therefore, by setting the size of the opening so that the generated gas bubbles do not pass, the gas generated in the anode chamber and the gas generated in the cathode chamber are prevented from being mixed. It is possible to prevent the opening from being blocked by the gas bubbles. As a result, the electrolytic reaction of the electrolytic bath can proceed stably while preventing gas mixing.

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

Since hydrogen gas is less soluble in the electrolytic bath than fluorine gas, hydrogen gas bubbles stay in the opening and easily close the opening. Therefore, by providing the upper surface of the opening so as to extend obliquely upward toward the cathode chamber side, even if hydrogen gas bubbles generated in the cathode chamber enter the opening, the bubbles follow the upper surface of the opening. And returned to the cathode chamber. This prevents the opening from being blocked by hydrogen gas.

(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. This prevents the fluorine gas from moving to the cathode chamber and prevents the fluorine gas and the hydrogen gas from being mixed.

(8) The partition may include a liquid partition immersed in the electrolytic bath, the opening may be provided in the liquid partition, and the liquid partition may be formed of a perfluoro resin.

In this case, the electrolytic bath prevents the liquid partition wall from being corroded. In addition, the liquid partition wall can be easily processed when forming the opening. Furthermore, the material cost of the liquid partition is reduced.

(9) A conductive diamond coating may be applied to the surface of the anode. In this case, since the polarization hardly occurs in the anode, the gas generation efficiency is improved. Even if the amount of gas generated increases, the opening of the partition wall is prevented from being blocked by bubbles, so that the electrolytic reaction can proceed stably.

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

In addition, according to the present invention, it is possible to allow the electrolytic reaction to proceed stably while preventing gas mixing.

FIG. 1 is a schematic cross-sectional view of an electrolysis apparatus according to a first embodiment of the present invention. FIG. 2 is an exploded perspective view of the electrolytic cell of FIG. FIG. 3 is a bottom view of the second lid. FIG. 4 is a schematic cross-sectional view of an electrolysis apparatus according to the second embodiment of the present invention. FIG. 5 is an external perspective view of the liquid partition wall. FIG. 6 is an enlarged view of a through hole formed in the liquid partition wall. FIG. 7 is a view showing another example of the through hole formed in the liquid partition wall. FIG. 8 is a cross-sectional view for explaining another example of the liquid partition wall.

[1] First Embodiment Hereinafter, an electrolysis apparatus (gas generation apparatus) according to a first embodiment of the present invention will be described with reference to the drawings.

(1) Configuration of electrolyzer FIG. 1 is a schematic cross-sectional view of an electrolyzer according to a first embodiment of the present invention. The electrolyzer 10 of FIG. 1 is a gas generator that generates fluorine gas. As shown in FIG. 1, the electrolysis apparatus 10 includes an electrolytic cell 11. The electrolytic cell 11 includes an electrolytic cell main body 11a, a first lid 11b, a seal member 11c, a second lid 11d, and a seal member 11e. A partition wall 13 is integrally provided on the lower surface of the second lid 11d so as to surround the central space in the electrolytic cell main body 11a. The electrolytic cell main body 11a, the first and

second lid bodies

11b and 11d, and the partition wall 13 are made of, for example, a metal or alloy such as Ni (nickel), monel, pure iron, or stainless steel.

In the electrolytic cell 11, high current power is handled. When a gas such as hydrogen is present in the cathode chamber 14b, it is necessary to prevent discharge in the cathode chamber 14b due to static electricity or discharge. Therefore, the first lid 11b of the cathode chamber 14b is grounded by the ground wire E1. Thereby, an electric shock or the like due to electric leakage from the electrolytic cell 11 can be prevented and a gas such as hydrogen can be prevented from exploding.

In the electrolytic cell 11, an electrolytic bath (electrolytic solution) 12 made of a KF-HF (potassium-hydrogen fluoride) mixed molten salt is formed. In the electrolytic cell 11, an anode chamber 14 a is formed inside the partition wall 13, and a cathode chamber 14 b is formed outside the partition wall 13.

The anode 15a is disposed in the anode chamber 14a. A part of the partition wall 13 and the anode 15 a are immersed in the electrolytic bath 12. A cathode 15b is formed on the inner surface of the electrolytic cell main body 11a. For example, Ni is preferably used as the material of the cathode 15b.

HF supply line 18a for supplying HF is connected to the first lid 11b. The HF supply line 18a is covered with a temperature adjusting heater 18b. This prevents HF from being liquefied in the HF supply line 18a. The height of the electrolytic bath 12 is detected by a liquid level detector (not shown). When the height of the liquid level detected by the liquid level detection device becomes lower than a predetermined value, HF is supplied into the electrolytic cell 11 through the HF supply line 18a.

The electrolysis apparatus 10 includes a control unit 23. The electrolytic bath 12 in the electrolytic cell 11 is 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. and dissolve it in a liquid state. The controller 23 controls the temperature controller (not shown) based on the temperature of the electrolytic bath 12 detected by a temperature sensor (not shown), and maintains the temperature of the electrolytic bath 12 at 80 to 90 ° C.

The controller 23 applies a voltage between the anode 15a and the cathode 15b. 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. Further, hydrogen gas is mainly generated in the cathode chamber 14b.

The second lid body 11d is provided with a gas discharge port 16a, and the first lid body 11b is provided with a gas discharge port 16b. An exhaust pipe 17a is connected to the gas exhaust port 16a, and an exhaust pipe 17b is connected to the gas exhaust 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 generated in the anode chamber 14a is discharged from the gas discharge port 16a through the exhaust pipe 17a, and the gas 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 FIG. 2 is an exploded perspective view of the electrolytic cell 11 of FIG. FIG. 3 is a bottom view of the second lid 11d.

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

The first lid 11b has a rectangular opening H2 at a substantially central portion. The seal 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 in the opening H2. The seal member 11e is an O-ring made of, for example, fluorine rubber. The second lid 11d has a rectangular shape and a size larger than the opening H2. The second lid 11d is disposed on the seal member 11e so as to close the opening H2 of the first lid 11b. Thereby, the first lid body 11b and the second lid body 11d are sealed while being electrically insulated from each other by the seal member 11e. The first lid 11b is provided with an HF supply hole 18c into which the HF supply line 18a is inserted.

The partition wall 13 includes four

side walls

13a, 13b, 13c, and 13d. As shown in FIG. 3, the partition wall 13 is provided integrally 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 partition wall 13 are made of, for example, Ni or Monel. A rectangular plate-like anode 15a is attached via a mounting member 19 in FIG. 2 in a space surrounded by the four side walls 13a to 13d of the partition wall 13 on the lower surface side of the second lid 11d. As a material of the anode 15a, for example, a low polarizable carbon electrode is used.

(3) Effect In the electrolysis apparatus 10 of FIG. 1 according to the present embodiment, the

seal members

11c and 11e are arranged outside the anode chamber 14a. Therefore, the fluorine gas generated in the anode chamber 14a does not come into contact with the

seal members

11c and 11e. Thereby, corrosion of the sealing

members

11c and 11e can be prevented. As a result, the frequency with which the

seal members

11c and 11e are inspected and replaced is reduced.

Further, by removing the second lid 11d from the first lid 11b, the anode 15a can be easily detached from the electrolytic cell body 11a together with the second lid 11d. Thereby, even when the anode 15a is consumed, the anode 15a can be easily replaced. In particular, when the electrolytic cell 11 is increased in size, the electrolytic cell main body 11a and the first lid 11b are increased in size and weight. Even in such a case, since it is not necessary to increase the size of the second lid 11d, the second lid 11d can be easily detached from the first lid 11b.

Furthermore, when the electrolyzer 10 is used for a long time, it is necessary to check whether or not the partition wall 13 is consumed. Even in such a case, the partition 13 can be removed from the first lid 11b by removing the second lid 11d from the first lid 11b. Thereby, the partition wall 13 can be easily inspected.

As a result, the maintenance cost of the electrolyzer 10 can be reduced and the maintenance work efficiency 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 in the upper portion, but is not limited thereto. For example, the electrolytic cell main body 11a may have a bottom surface portion and a cylindrical side surface portion, and may have a circular opening at the top. In this case, the opening of the electrolytic cell main body 11a is closed by the first lid body 11b having a circular shape.

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

The partition wall 13 includes four side walls 13a to 13d, but is not limited thereto. For example, the partition wall 13 may be constituted by a cylindrical side wall. In addition, the partition wall 13 and the second lid body 11d are preferably provided integrally, and the partition wall 13 and the second lid body 11d formed of separate metal materials are integrally provided by welding. Although it is more preferable, it is not limited to this. The partition wall 13 and the second lid body 11d may be integrally provided by casting.

The partition wall 13 may be provided separately from the second lid body 11d as long as the adhesion with the second lid body 11d is ensured and the airtightness of the anode chamber 14a is maintained. In this case, it is preferable to ensure adhesion by providing a highly corrosion-resistant sealing material such as a metal seal between the partition wall 13 and the second lid 11d.

(5) Correspondence between each component of claim and each part of embodiment The following describes an example of the correspondence between each component of the claim and each part of the embodiment. It is not limited.

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

As the constituent elements of the claims, various other elements having configurations or functions described in the claims can be used.

[2] Second Embodiment Hereinafter, an electrolysis apparatus according to a second embodiment of the present invention will be described with reference to the drawings.

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

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

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

The liquid partition wall 13B is attached to the lower end of the gas partition wall 13A so as to be immersed in the electrolytic bath 12. A plurality of through holes H (FIG. 5 described later) for ensuring the permeability of the electrolytic bath 12 are formed in the liquid partition wall 13B. Details of the liquid partition wall 13B will be described later. As the material of the liquid partition wall 13B, a perfluoro resin such as PTFE (polytetrafluoroethylene) or PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer) is preferably used, and PTFE is particularly preferably used. . In this case, compared with the case where a metal is used as the material of the liquid partition wall 13B, the corrosion of the liquid partition wall 13B by the electrolytic bath 12 is suppressed. Moreover, the process at the time of forming said through-hole H becomes easy. Furthermore, the material cost of the liquid partition wall 13B is reduced.

In the electrolytic cell 11, an anode chamber 14 a is formed inside the partition wall 13, and a cathode chamber 14 b is formed outside the partition wall 13. An anode 15a is disposed so as to be immersed in the electrolytic bath 12 in the anode chamber 14a. As a material of the anode 15a, for example, a low polarizable carbon electrode is preferably used.

It is preferable that a conductive diamond coating is applied to the surface of the anode 15a. Specifically, a diamond having conductivity by using a mixed gas of hydrogen gas and a carbon source as a diamond raw material and adding a small amount of an element (hereinafter referred to as a dopant) having a different valence from carbon to the mixed gas. A coating layer can be formed. As the dopant, boron, phosphorus or nitrogen is preferably used, and boron is particularly preferably used. The weight of the added dopant is preferably 1 ppm or more and 30000 ppm or less, and more preferably 100 ppm or more and 10000 ppm or less with respect to the total weight of the diamond coating layer. By applying a conductive diamond coating to the surface of the anode 15a, polarization hardly occurs in the anode 15a. Therefore, the generation efficiency of fluorine gas is improved. In the present embodiment, the side surface portion of the electrolytic cell main body 11a functions as a cathode.

An 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 with a temperature adjusting heater 18b. This prevents HF from being liquefied in the HF supply line 18a. The height of the electrolytic bath 12 is detected by a liquid level detector (not shown). When the height of the liquid level detected by the liquid level detection device becomes lower than a predetermined value, HF is supplied into the electrolytic cell 11 through the HF supply line 18a.

The upper lid 11f is provided with

gas discharge ports

16a and 16b. An exhaust pipe 17a is connected to the gas exhaust port 16a, and an exhaust pipe 17b is connected to the gas exhaust 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.

When a voltage is applied between the anode 15a and the electrolytic cell body 11a, the electrolytic bath 12 is electrolyzed. 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 main body 11a. Since the upper surface of the bottom surface portion of the electrolytic cell main body 11a is covered with the insulating member 11g, the electrolytic reaction of the electrolytic bath 12 does not proceed 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 guided to the outside of the electrolytic cell 11 from the gas discharge port 16a through the exhaust pipe 17a. Hydrogen gas generated in the cathode chamber 14b is guided to the outside of the electrolytic cell 11 from the gas discharge port 16b through the exhaust pipe 17b.

(2) Details of Liquid Partition Wall FIG. 5 is an external perspective view of the liquid partition wall 13B, and FIG. 6 is an enlarged view of the through hole H formed in the liquid partition wall 13B. 6A is a longitudinal sectional view of the through hole H, FIG. 6B is a side view of the through hole H viewed from the anode chamber 14a, and FIG. 6C is a through view viewed from the cathode chamber 14b. 3 is a side view of a hole H. FIG. FIG. 6A shows a cross section taken along line AA of FIGS. 6B and 6C.

As shown in FIG. 5, a plurality of circular through holes H are formed in the liquid partition wall 13B. In the example of FIG. 5, the plurality of through holes H form two rows along the circumferential direction of the liquid partition wall 13B. In this case, 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, the electrolytic reaction proceeds stably and smoothly in the anode chamber 14a and the cathode chamber 14b.

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 and the hydrogen gas are mixed in the anode chamber 14a or the cathode chamber 14b. Thereby, fluorine gas and hydrogen gas react with each other to reduce the generation efficiency of fluorine gas, and an explosive gas mixture may be generated depending on the ratio of fluorine gas and hydrogen gas.

Therefore, the diameter of each through hole H is set to such a size that the bubbles of fluorine gas and hydrogen gas do not pass. However, this may cause bubbles to stay in the through hole H and close the through hole H. In particular, since hydrogen gas is less soluble in the electrolytic bath 12 than fluorine gas, bubbles of hydrogen gas tend to stay in the through hole H and easily close the through hole H. When the through hole H is blocked, the electrolytic bath 12 cannot move through the through hole H. As a result, the electrolytic reaction cannot proceed stably.

Therefore, in the present embodiment, as shown in FIG. 6, each through hole H has an upper surface L1 that extends obliquely upward from the end on the anode chamber 14a side to the end on the cathode chamber 14b side. Hereinafter, the end of the through hole H on the anode chamber 14a side is referred to as the anode side end, and the end of the through hole H on the cathode chamber 14b side is referred to as the cathode side end. The lower surface L2 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 facing downward in the inner peripheral surface of the through hole H, and the lower surface of the through hole H refers to a region facing upward in the inner peripheral surface of the through hole H. Say.

The diameter D1 in the vertical direction of the anode side end of the through hole H is set to a size that allows the electrolytic bath to pass therethrough and does not allow the bubbles of fluorine gas and hydrogen gas to pass through. The diameter D1 is, for example, 1 mm or more and 3 mm or less, and preferably 1 mm or more and 2 mm or less. The diameter D2 in the vertical direction of the cathode side end of the through hole H is larger than the diameter D1. The diameter D2 is, for example, 5 mm to 10 mm, and preferably 5 mm to 8 mm. The thickness TH of the liquid partition wall 13B is, for example, 5 mm or more and 10 mm or less, and preferably 5 mm or more and 8 mm or less.

In the electrolysis apparatus 10 according to the present embodiment, even if hydrogen gas bubbles 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 the liquid Surface. Therefore, hydrogen gas bubbles that have entered the through hole H from the cathode chamber 14 b are prevented from blocking the through hole H.

The vertical diameter of the through hole H on the anode chamber 14a side is smaller than the vertical diameter of the through hole H on the cathode chamber 14b side. Furthermore, as described above, the fluorine gas is more easily dissolved in the electrolytic bath 12 than the hydrogen gas. This prevents fluorine gas bubbles from entering the through hole H from the anode chamber 14a.

Thus, the bubbles of fluorine gas and hydrogen gas are prevented from moving through the through hole H, and the bubbles of fluorine gas and hydrogen gas are prevented from blocking the through hole H. As a result, the electrolytic reaction can proceed stably and smoothly without reducing the generation efficiency of the fluorine gas.

(3) Other examples of through holes (3-1)
The shape of the through hole H of the liquid partition wall 13B is not limited to the examples of FIGS. FIG. 7 is a diagram illustrating another example of the through hole H formed in the liquid partition wall 13B. Differences of the example of FIGS. 7A and 7B from the example of FIGS. 5 and 6 will be described.

In the example of FIG. 7A, 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 end. . Also in this case, hydrogen gas bubbles entering the through hole H from the cathode chamber 14b are prevented from blocking the through hole H, and fluorine gas bubbles can enter the through hole H from the anode chamber 14a. Is prevented.

In the example of FIG. 7B, 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. Also in this case, hydrogen gas bubbles that have entered the through hole H from the cathode chamber 14 b are prevented from blocking the through hole H. Further, even if a fluorine gas bubble 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 on the liquid surface. Accordingly, it is possible to prevent the fluorine gas bubbles that have entered the through hole H from the anode chamber 14a from blocking 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 vertical cross section of another shape such as an oval shape, a triangle, or a quadrangle.

(3-3)
In the above example, the upper surface L1 of the through hole H is provided so as to linearly extend obliquely upward toward the cathode side end. However, the present invention is not limited thereto, and for example, the upper surface L1 of the through hole H is directed toward the cathode side end. It may be provided so as to bend and extend obliquely upward.

(4) Another Example of Liquid Partition Wall FIG. 8 is a cross-sectional view for explaining another example of the liquid partition wall 13B. FIG. 8 shows a lower end portion of the gas partition wall 13A and an upper end portion of the liquid partition wall 13B. The example of FIG. 8 will be described while referring to differences from the examples of FIGS.

In the example of FIG. 8, the upper end portion of the liquid partition wall 13B is provided so as to cover the lower end portion of the outer peripheral surface (surface on the cathode chamber 14b side) of the gas partition wall 13A. When the electrolytic reaction of the electrolytic bath 12 proceeds while the lower end of the gas partition wall 13A is immersed in the electrolytic bath 12, the gas partition wall 13A is polarized in the electrolytic bath 12, and the outer peripheral surface of the gas partition wall 13A has a positive charge. . In this case, the metal is ionized from the outer peripheral surface of the positive gas partition wall 13A and is eluted into the electrolytic bath 12, and the outer peripheral surface of the gas partition wall 13A is easily corroded. Therefore, in this example, the outer peripheral surface portion of the gas partition wall 13A immersed in the electrolytic bath 12 is covered with the liquid surface partition wall 13B. This prevents the electrolytic bath 12 from coming into contact with the outer peripheral surface of the gas partition wall 13A, and prevents the portion of the outer peripheral surface of the gas partition wall 13A immersed in the electrolytic bath 12 from corroding.

Further, it is preferable that the upper end portion of the liquid surface partition 13B extends to above the liquid surface of the electrolytic bath 12. In this case, it is possible to reliably prevent the electrolytic bath 12 from contacting the outer peripheral surface of the gas partition wall 13A. Since the upper end portion of the liquid level partition wall 13B is located on the cathode chamber 14b side, even if the upper end portion of the liquid level partition wall 13B extends above the liquid surface of the electrolytic bath 12, fluorine gas and fluorine are added to the liquid level partition wall 13B. There is no contact with hydrogen fluoride vapor. Therefore, corrosion of the liquid level partition wall 13B is prevented.

(5) Other embodiments (5-1)
In the above embodiment, the gas partition wall 13A and the liquid partition wall 13B are provided as separate bodies. However, the corrosion of the gas partition wall 13A and the liquid partition wall 13B is prevented, or the corrosion of the gas partition wall 13A and the liquid partition wall 13B does not matter. In this case, the gas partition wall 13A and the liquid partition wall 13B may be provided integrally.

(5-2)
In the above embodiment, the gas partition wall 13A and the liquid partition wall 13B are each cylindrical. However, the present invention is not limited to this, and the gas partition wall 13A and the liquid partition wall 13B may have other shapes such as a rectangular tube shape or a flat plate shape. Good.

(5-3)
The above embodiment is an example in which the present invention is applied to an electrolysis apparatus that generates fluorine gas. However, the present invention can be similarly applied to an electrolysis apparatus that generates other gas such as oxygen gas.

(6) Correspondence between each component of claim and each part of embodiment The following describes an example of a correspondence between each component of the claim and each part of the embodiment. It is not limited.

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

The present invention can be effectively used for various electrolyzers such as gas generators.

Claims

An electrolyzer for generating fluorine and other gases by electrolyzing an electrolytic bath, comprising:
It has an electrolytic cell that houses an electrolytic bath,
The electrolytic cell is
An electrolytic cell body having a first opening at the top;
A first lid provided on the electrolytic cell main body so as to have a second opening smaller than the first opening and close the first opening;
A first seal member provided on the first lid so as to surround the second opening;
A second lid provided on the first lid with the first seal member sandwiched so as to close the second opening;
A first electrode attached to the second lid;
A partition that separates the inside of the electrolytic cell main body into a first chamber in which fluorine is generated and a second chamber in which another gas is generated;
The partition wall is an electrolysis apparatus, wherein the first chamber is formed in a region inside the first seal member.
The electrolytic apparatus according to claim 1, wherein the partition wall is provided integrally with the first lid body so as to surround a periphery of the first electrode.
The electrolyzer according to claim 1, wherein the electrolytic cell main body functions as a second electrode.
A second seal member provided on the electrolytic cell main body so as to surround the first opening;
The electrolysis apparatus according to any one of claims 1 to 3, wherein the first lid is provided on the electrolytic cell main body with the second seal member interposed therebetween.
An electrolytic cell containing an electrolytic bath;
A partition wall provided to partition the inside of the electrolytic cell into an anode chamber and a cathode chamber, and having an opening through which ions in the electrolytic bath can pass;
An anode provided in the anode chamber of the electrolytic cell;
A cathode provided in the cathode chamber of the electrolytic cell,
The opening of the partition has an upper surface extending obliquely upward toward at least one of the anode chamber and the cathode chamber.
Fluorine gas is generated in the anode chamber, hydrogen gas is generated in the cathode chamber,
The electrolytic apparatus according to claim 5, wherein the upper surface of the opening is provided so as to extend obliquely upward toward the cathode chamber side.
The electrolysis apparatus according to claim 6, wherein an area of an 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 partition includes a liquid partition immersed in the electrolytic bath,
The opening is provided in the liquid partition;
The electrolyzer according to any one of claims 5 to 7, wherein the liquid partition is made of a perfluoro resin.
The electrolyzer according to any one of claims 5 to 8, wherein a conductive diamond coating is applied to a surface of the anode.