JP2006176815A - Hydrogen pump and method for operating it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen pump which provides adequate permeability to gases of hydrides such as water vapor generated at an anode, provides the adequate permeability to gases of hydrogen and an hydrogen isotope generated at a cathode, and thus can increase the amount of the generated gases of hydrogen and the hydrogen isotope, and to provide a method for operating it. <P>SOLUTION: The hydrogen pump 10 comprises: an electrolyte substrate 14 formed of a proton-conducting ceramic; the anode 15 and the cathode 16 formed on both sides of the electrolyte substrate 14; and an anode chamber 12 arranged in an anode 15 side and a cathode chamber 13 arranged in a cathode 16 side. The operation method comprises: storing objective gases such as hydrogen and water vapor in the anode chamber 12; and applying direct voltage between the anode 15 and the cathode 16 while heating the gases to form hydrogen gas and the like in the cathode chamber 13. A porous platinum paste electrode is used for the anode 15 and a platinum-plated electrode of permeating the gases of hydrogen and the hydrogen isotope is used for the cathode 16. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrogen pump that is used, for example, as a tritium monitor for detecting a tritium concentration in a target gas containing tritium, or to recover tritium and hydrogen, and an operation method thereof.

Tritium (tritium, T, ³ H), a fuel for fusion reactors, is a radioactive hydrogen isotope and must be used in a controlled environment. At present, the liquid scintillation method is mainly used for measuring the concentration of tritium, but the measurement is batch processing, and workability and real-time performance are not good. Therefore, a hydrogen pump that has platinum electrodes on both sides of proton conductive ceramics and generates hydrogen has been proposed (see, for example, Non-Patent Document 1).

That is, the proton conductive ceramic is formed in a covered cylinder shape with CaZr _0.9 In _0.1 O ₃ -α, and the anode and cathode electrodes obtained by the electroless plating method of platinum are provided on the inner and outer peripheral surfaces thereof. Yes. Then, water vapor is supplied to the inside of the proton conductive ceramics, and a direct current voltage of 2 V is applied between the anode electrode and the cathode electrode at 800 ° C. to electrolyze the water vapor. As a result, the platinum-plated electrode has a current value increased from 32 mA to 112 mA and a hydrogen production rate increased to 0.25 ml / min compared to the conventional platinum paste electrode.
Journal of NUCLEAR SCIENCE and TECHNOLOGY, Vol.41, No.1, p.95-97 (January 2004)

  However, in the prior art described in Non-Patent Document 1 described above, the platinum electrode by the electroless plating method used as the anode electrode and the cathode electrode has good hydrogen permeability, but it is about hydrogen compounds such as water vapor. The permeability was not sufficient and the permeation rate was low. Therefore, generation and permeation of hydrogen ions by electrolysis of water vapor are not sufficiently performed at the anode electrode, and hydrogen ions that permeate the proton conductive ceramics are reduced, resulting in generation of hydrogen gas and the like generated from the cathode electrode. Less. Although the reason is not clear, it is considered that the pore diameter and porosity of the anode electrode and the cathode electrode have the most influence. Accordingly, there is a problem that the amount of hydrogen and hydrogen isotope gas produced by the hydrogen pump is not sufficient.

  The present invention has been made paying attention to such problems existing in the prior art. The purpose is to have good hydrogen compound gas permeability at the anode electrode and good hydrogen and hydrogen isotope gas permeability at the cathode electrode, increasing the amount of hydrogen and hydrogen isotope gas produced. It is an object of the present invention to provide a hydrogen pump and a method of operating the same.

  In order to achieve the above object, the hydrogen pump according to the first aspect of the present invention includes an anode electrode and a cathode electrode on both surfaces of an electrolyte substrate formed of proton conductive ceramics, and an anode chamber on the anode electrode side. A cathode chamber is provided on the cathode electrode side, a target gas containing hydrogen and hydrogen isotopes is accommodated in the anode chamber, and a DC voltage is applied between the electrodes to remove hydrogen and hydrogen isotopes in the target gas. In the hydrogen pump that decomposes the gas containing on the anode electrode, the generated hydrogen and hydrogen isotope ions pass through the electrolyte substrate, generates hydrogen and hydrogen isotope gas on the cathode electrode, and accommodates in the cathode chamber, A metal or metal oxide electrode having hydrogen gas permeability is used for the anode electrode, and hydrogen and hydrogen isotopes are used for the cathode electrode. And it is characterized in that using an electrode with a metal or metal oxide having a gas permeability.

  A hydrogen pump according to a second aspect of the present invention is the hydrogen pump according to the first aspect, wherein the anode electrode is an electrode made of a porous metal or metal oxide, and the cathode electrode is a polycrystalline metal or metal oxide. It is characterized by using an electrode made of material.

  A hydrogen pump according to a third aspect of the present invention is the hydrogen pump according to the first or second aspect, wherein the anode electrode is formed by a paste baking method, and the cathode electrode is formed by an electroless plating method. Is.

  According to a fourth aspect of the present invention, there is provided a method for operating the hydrogen pump, wherein the hydrogen pump according to any one of the first to third aspects is used, a DC voltage is applied between the anode electrode and the cathode electrode, The gas containing hydrogen and hydrogen isotopes in the target gas in the anode chamber is decomposed on the anode electrode, the generated hydrogen and hydrogen isotope ions pass through the electrolyte substrate, and the hydrogen and hydrogen isotope gas are formed on the cathode electrode. And is operated so as to be housed in the cathode chamber.

  According to a fifth aspect of the present invention, there is provided a method of operating a hydrogen pump according to the fourth aspect of the present invention, wherein oxygen or a mixed gas containing oxygen is vented to the cathode electrode during the operation to oxidize the proton conductive ceramic. It is characterized by performing.

  A method for operating a hydrogen pump according to a sixth aspect of the invention is characterized in that, in the invention according to the fifth aspect, the oxidation treatment is performed in a state where a DC voltage is applied between an anode electrode and a cathode electrode. To do.

  According to a seventh aspect of the present invention, there is provided a method for operating a hydrogen pump according to the fifth or sixth aspect, wherein the target gas to be processed in the anode chamber is used as the mixed gas containing oxygen. Is.

According to the present invention, the following effects can be exhibited.
In the hydrogen pump according to the first aspect of the present invention, a metal or metal oxide electrode having permeability of a hydrogen compound gas such as water vapor is used for the anode electrode, and hydrogen and hydrogen isotope gas are used for the cathode electrode. An electrode made of a metal or metal oxide having a transparent property is used. The permeability of the gas containing hydrogen and hydrogen isotopes as well as hydrogen compounds such as water vapor is improved at the anode electrode, and the permeability of hydrogen and hydrogen isotopes is improved at the cathode electrode. Therefore, the amount of hydrogen and hydrogen isotope gas produced at the cathode electrode can be increased.

  In the hydrogen pump according to the second aspect of the invention, a porous metal or metal oxide electrode is used for the anode electrode, and a polycrystalline metal or metal oxide electrode is used for the cathode electrode. For this reason, the anode electrode is porous and has a large pore size, so that the permeability of hydrogen compound gas such as water vapor is further improved, and the cathode and the gas of hydrogen and hydrogen isotopes are permeated by the polycrystalline material. The property is further improved. Therefore, the effect of the invention according to claim 1 can be improved.

  In the hydrogen pump according to the third aspect of the present invention, the anode electrode is formed by a paste baking method, and the cathode electrode is formed by an electroless plating method. For this reason, it is possible to easily form a porous anode electrode and a cathode electrode having good permeability of hydrogen and hydrogen isotope gas.

  In the operation method of the hydrogen pump according to the fourth aspect of the present invention, a DC voltage is applied between the anode electrode and the cathode electrode, and the gas containing the hydrogen compound in the target gas in the anode chamber is decomposed on the anode electrode. The generated hydrogen and hydrogen isotope ions permeate the electrolyte substrate, generate hydrogen and hydrogen isotope gas on the cathode electrode, and operate so as to be accommodated in the cathode chamber. Therefore, the operation of the hydrogen pump is easy, and the effects of the invention according to any one of claims 1 to 3 can be exhibited.

  In the operation method of the hydrogen pump of the invention described in claim 5, during the operation, for example, oxygen or a mixed gas containing oxygen is intermittently ventilated to the cathode electrode, and the proton conductive ceramic is oxidized. By this oxidation treatment, the proton conductive ceramic is gradually reduced by hydrogen or the like generated from the cathode electrode, and the reduction in permeation performance can be recovered by oxidation. Therefore, in addition to the effect of the invention according to claim 4, it is possible to suppress the performance of the proton conductive ceramic from being deteriorated.

  In the operation method of the hydrogen pump according to the sixth aspect of the invention, the oxidation treatment is performed in a state where a DC voltage is applied between the anode electrode and the cathode electrode. For this reason, in addition to the effect of the invention according to claim 5, the penetration of oxygen ions into the proton conductive ceramics can be promoted, the oxidation treatment can be performed quickly, and the characteristics of the hydrogen pump are changed. The hydrogen pump can be operated in a stable state.

  In the operation method of the hydrogen pump according to the seventh aspect of the present invention, the target gas accommodated in the anode chamber is used as the mixed gas containing oxygen. In this case, the mixed gas containing oxygen can also be used as the target gas supplied to the anode chamber, and in addition to the effect of the invention according to claim 5 or 6, the operation of the hydrogen pump can be performed efficiently. .

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic explanatory view showing a hydrogen pump 10 in the present embodiment. As shown in this figure, an electrolyte substrate 14 made of proton conductive ceramics is fixed at a central position in the hydrogen pump main body 11 so as to be divided into two substantially equally divided into an anode chamber 12 and a cathode chamber 13. . As the proton conductive ceramic constituting the electrolyte substrate 14, a CaZrO-based oxide (for example, CaZr _0.9 In _0.1 O ₃ ) or the like is used.

  An anode electrode 15 is provided on one surface (surface on the anode chamber 12 side) of the electrolyte substrate 14, and a cathode electrode 16 is provided on the other surface (surface on the cathode chamber 13 side). The anode electrode 15 is composed of an electrode made of a metal or metal oxide having permeability of a hydrogen compound gas such as water vapor, and is preferably composed of an electrode made of a porous metal or metal oxide. On the other hand, the cathode electrode 16 is made of an electrode made of a metal or metal oxide that transmits hydrogen and a hydrogen isotope gas, and preferably made of an electrode made of polycrystalline metal or metal oxide. Here, the term “polycrystalline” refers to a solid in which minute crystal grains having different sizes and orientations are fixed and assembled. Platinum, gold, silver or the like is used as a metal constituting the anode electrode 15 and the cathode electrode 16. Further, platinum oxide, gold oxide, silver oxide or the like is used as the metal oxide constituting the anode electrode 15 and the cathode electrode 16. The anode electrode 15 is preferably formed by a paste baking method, and the cathode electrode 16 is preferably formed by an electroless plating method. The paste baking method is performed by applying a metal or metal oxide paste on the electrolyte substrate 14 to a predetermined thickness and then baking it. The pore diameter of the anode electrode 15 formed by the paste baking method is 1 to 10 μm, and the pore diameter of the cathode electrode 16 formed by the electroless plating method is 100 nm or more and less than 1 μm.

A target gas introduction pipe 17 is connected to the anode chamber 12, and the target gas is supplied to the anode chamber 12 by an introduction pump 18 provided in the target gas introduction pipe 17. The target gas is a gas containing a hydrogen isotope composed of hydrogen (H) and deuterium (deuterium, D, ² H) or tritium (tritium, T, ³ H). The target gas includes water vapor (light water, water vapor composed of ¹ H and ¹⁶ O), as well as heavy water, tritium water, and mixtures thereof. Here, the hydrogen compound is light water, heavy water, tritium water or the like. In this specification, hydrogen and a hydrogen isotope gas mean a gas such as H ₂ , D ₂ , HD, and HT, and a gas containing hydrogen and a hydrogen isotope means a hydrogen compound such as water vapor or methane gas. Means gas.

  A lead-out pipe 19 is further connected to the anode chamber 12 so as to discharge nitrogen gas, oxygen gas and the like in the anode chamber 12. In the middle of the target gas introduction pipe 17, one end of a first connection pipe 20 for supplying the target gas to the cathode chamber 13 is connected, and the other end is connected to the cathode chamber 13. A first opening / closing valve 20 a is provided on one end side of the first connection pipe 20. One end of the second connection pipe 21 for introducing the target gas in the anode chamber 12 into the cathode chamber 13 is connected to the middle of the outlet pipe 19, and the other end is connected to the cathode chamber 13. A second opening / closing valve 21 a is provided on one end side of the second connection pipe 21. In addition, it is enough if either the 1st connection piping 20 or the 2nd connection piping 21 is installed.

  A positive side of the DC power source 22 is connected to the anode electrode 15, and a negative side of the DC power source 22 is connected to the cathode electrode 16. A DC voltage of preferably 0.1 to 5 V is preferably applied between the anode electrode 15 and the cathode electrode 16. It is designed to be applied. Further, the inside of the hydrogen pump body 11 is configured to be heated to a high temperature of preferably 200 to 1500 ° C., more preferably 300 to 1000 ° C., by a heating device (not shown). Then, by applying a DC voltage between the anode electrode 15 and the cathode electrode 16 in a heated state, electrolysis of water vapor or the like is performed on the anode electrode 15 to generate hydrogen ions or the like, and hydrogen ions are generated on the cathode electrode 16. Hydrogen gas or the like is generated from ions or the like.

One end and the other end of the circulation pipe 23 are connected to the cathode chamber 13, and a tritium monitor 24 is connected to an intermediate portion of the circulation pipe 23 to measure the tritium concentration in the gas flowing through the circulation pipe 23 with a radiation monitor. It is like that. A first adjustment valve 23a and a second adjustment valve 23b are connected to one end and the other end of the circulation pipe 23, and a circulation pump 25 is provided on one end side. In addition, one end of the cathode chamber 13 is connected to a carrier gas cylinder 26 and the other end of a carrier gas supply pipe 28 provided with a valve 27 in the middle is connected. A carrier gas such as argon (Ar) or nitrogen (N ₂ ) is supplied from the carrier gas cylinder 26 to the cathode chamber 13 from the carrier gas supply pipe 28. Further, one end of a first exhaust pipe 29 is connected to the cathode chamber 13, and the other end is opened to the outside through a first exhaust valve 30 and an exhaust pump 31. A second exhaust pipe 33 including a second exhaust valve 32 is connected between one end of the first exhaust pipe 29 and the first exhaust valve 30.

  Then, the target gas containing hydrogen and a hydrogen isotope contained in the anode chamber 12 is ionized on the anode electrode 15 by a DC voltage in a heated state, and the ions pass through the electrolyte substrate 14 made of proton conductive ceramics. Then, hydrogen and hydrogen isotope gas are generated on the cathode electrode 16 and accommodated in the cathode chamber 13.

Next, an operation method of the hydrogen pump 10 configured as described above will be described.
First, the introduction pump 18 is operated to introduce the target gas into the anode chamber 12 from the target gas introduction pipe 17. In this state, a voltage of 2 V, for example, is applied between the anode electrode 15 and the cathode electrode 16 by the DC power source 22 and heated to 650 ° C., for example. As a result, water vapor, hydrogen, hydrogen isotope, and other gases contained in the target gas in the anode chamber 12 are decomposed on the anode electrode 15 and ionized into hydrogen and hydrogen isotope ions, such as hydrogen ions and tritium ions. Is done. For example, on the anode electrode 15, water vapor is decomposed into hydrogen ions and oxygen gas based on the following reaction formula (1).

2H ₂ O → 4H ⁺ + 4e ⁻ + O ₂ (1)
Hydrogen and hydrogen isotope ions such as generated hydrogen ions and tritium ions permeate through proton conductive ceramics constituting the electrolyte substrate 14. Hydrogen ions, tritium ions, and the like that have permeated through the proton conductive ceramics are generated as hydrogen and hydrogen isotope gases such as hydrogen gas and tritium gas on the cathode electrode 16 and are stored in the cathode chamber 13. For example, hydrogen ions are generated on the cathode electrode 16 as hydrogen based on the following reaction formula (2).

2H ⁺ + 2e ⁻ → H ₂ (2)
At this time, the carrier gas is supplied and filled in the cathode chamber 13 from the carrier gas supply pipe 28 in advance. Then, the first adjustment valve 23 a and the second adjustment valve 23 b of the circulation pipe 23 are opened and the circulation pump 25 is operated, so that gas such as hydrogen gas and tritium gas in the cathode chamber 13 is supplied to the tritium monitor 24. The flow is detected there.

  If the operation of the hydrogen pump 10 is continued in this manner, the proton conductive ceramics forming the electrolyte substrate 14 are reduced by the reducing gas such as hydrogen generated in the cathode chamber 13, and the performance is degraded. In order to suppress this, oxygen or a mixed gas containing oxygen is passed through the cathode electrode 16 to perform an oxidation treatment operation of the proton conductive ceramic. This oxidation treatment operation is preferably performed in a state where a DC voltage is applied between the anode electrode 15 and the cathode electrode 16 in order to promote the penetration of oxygen ions into the proton conductive ceramic. Moreover, it is preferable that the target gas introduced into the anode chamber 12 is also used as the mixed gas containing oxygen. After the oxidation treatment operation, gas such as oxygen gas in the cathode chamber 13 is exhausted from the first exhaust pipe 29 or the second exhaust pipe 33, that is, an oxygen replacement operation is performed.

A typical operation method of the hydrogen pump 10 is shown in FIG. That is, during a steady operation, an oxidation treatment operation is performed for a short time every fixed operation time, and then an oxygen replacement operation is performed. Then, return to steady operation. This is repeated and the operation of the hydrogen pump 10 is continued. As shown in FIG. 3, in the steady operation, the hydrogen ion permeation rate permeating through the proton conductive ceramics constituting the electrolyte substrate 14 gradually decreases, and when the oxidation treatment operation is performed, the hydrogen ion permeation rate shows a recovery. Is repeated. As shown in FIG. 4, regarding the relationship between the oxidation treatment time and the oxidation treatment effect, CaZr _0.9 In _0.1 O ₃ was used as proton conductive ceramics, and a direct current of 2 V was applied between the anode electrode 15 and the cathode electrode 16 at 650 ° C. It can be seen that when a voltage is applied, the oxidation treatment effect reaches a substantially sufficient level in 1 to 5 minutes.

  When the hydrogen pump 10 is operated, the target gas such as water vapor, hydrogen gas, or tritium gas is heated while being introduced into the anode chamber 12 from the target gas introduction pipe 17, and the anode electrode 15 and the cathode A constant DC voltage is applied between the electrode 16 and a DC power source. Water vapor is decomposed on the anode electrode 15 to generate hydrogen ions, and tritium is ionized to generate tritium ions. At this time, since the anode electrode 15 is a porous material formed by a paste baking method and has a large pore diameter, it has good permeability not only for hydrogen gas and hydrogen isotope gas but also for hydrogen compound gas such as water vapor. Accordingly, hydrogen ions, tritium ions and the like can be sufficiently generated on the anode electrode 15. The generated hydrogen ions, tritium ions, and the like can permeate the proton conductive ceramics of the electrolyte substrate 14.

  Hydrogen ions, tritium ions, and the like that have passed through the proton conductive ceramics are converted to hydrogen and hydrogen isotope gases such as hydrogen gas and tritium gas on the cathode electrode 16. At this time, since the cathode electrode 16 is formed by an electroless plating method and has good permeability to hydrogen and hydrogen isotopes, hydrogen gas, tritium gas, and the like can be sufficiently generated on the cathode electrode 16. The generated hydrogen gas, tritium gas and the like are accommodated in the cathode chamber 13. The cathode electrode 16 is excellent in hydrogen and hydrogen isotope gas permeability because hydrogen ions are combined with electrons and converted into hydrogen atoms, and the micropores present in the polycrystal are hydrogen and It is presumed that the hydrogen isotope is suitable for gas permeation. The generated tritium gas or the like in the cathode chamber 13 is circulated through the circulation pipe 23 and detected by the tritium monitor 24.

  Incidentally, as shown in FIG. 5, when the platinum paste electrode is used as the anode electrode 15 and the platinum plating electrode is used as the cathode electrode 16 as in the hydrogen pump 10 of the present embodiment, the conventional electrode is transmitted through the cathode electrode 16. The hydrogen permeation rate was measured. As a conventional electrode, an electrode using a platinum paste electrode as an anode electrode and a cathode electrode, and an electrode using a platinum plating electrode as an anode electrode and a cathode electrode were used. As a result, in the case of the electrode of this embodiment, the hydrogen permeation rate was 3.2 times that of the conventional electrode.

  Further, with respect to the electrode of this embodiment and the conventional electrode, a gas containing 1.2% by volume of water vapor, 19.5% by volume of oxygen and argon was used as the target gas in the anode chamber 12 at 650 ° C. The relationship between the current value (mA) when a DC voltage of 2 V was applied between the electrode 15 and the cathode electrode 16 and the rate of hydrogen generation from the cathode electrode was measured and is shown in FIG. As a conventional electrode, both an anode electrode and a cathode electrode are platinum paste electrodes. As a result, when the anode electrode 15 and the cathode electrode 16 of the present embodiment are used (marked in the figure), the current value is 110 (mA) at a voltage of 2 V, and the hydrogen generation rate is 0.43 (ml / min). Met. On the other hand, when the conventional anode and cathode electrodes were used (circles in the figure), the voltage was 2 V, the current value was 30 (mA), and the hydrogen production rate was only 0.14 (ml / min). In addition, the dashed-two dotted line in a figure is a theoretical value at the time of using the electrode of this embodiment.

The effects exhibited by the embodiment described in detail above will be collectively described below.
In the hydrogen pump 10 of the present embodiment, a metal or metal oxide electrode having permeability of a hydrogen compound gas such as water vapor is used for the anode electrode 15, and hydrogen and hydrogen isotope gas are used for the cathode electrode 16. An electrode made of a metal or metal oxide having a transparent property is used. For this reason, the permeability of the hydrogen compound gas such as water vapor as well as hydrogen and hydrogen isotopes is improved in the anode electrode 15, and the permeability of the hydrogen and hydrogen isotope gas is improved in the cathode electrode 16. Accordingly, the amount of hydrogen and hydrogen isotope gas produced at the cathode electrode 16 can be increased.

  In addition, an electrode made of a porous metal or metal oxide is used for the anode electrode 15, and an electrode made of polycrystalline metal or metal oxide is used for the cathode electrode 16. Therefore, since the anode electrode 15 is porous and has a large pore diameter, it is possible to further improve the gas permeability of a hydrogen compound such as water vapor, and the cathode electrode 16 is made of hydrogen and hydrogen isotopes with a dense polycrystalline material. Hydrogen and hydrogen isotope gas are efficiently generated from body ions, and the permeability of the generated gas is further improved.

  The anode electrode 15 is formed by a paste baking method, and the cathode electrode 16 is formed by an electroless plating method. For this reason, the porous anode electrode 15 and the cathode electrode 16 with good permeability of hydrogen and hydrogen isotope gas can be easily configured.

  In the operation method of the hydrogen pump 10, hydrogen and hydrogen isotope gas in the target gas in the anode chamber 12 are decomposed on the anode electrode 15 to which a DC voltage is applied, and the generated hydrogen and hydrogen isotope ions Operates so that hydrogen and hydrogen isotope gas are generated on the cathode electrode 16 through the electrolyte substrate 14. Thus, the operation of the hydrogen pump is easy, and the generation amount of hydrogen and hydrogen isotope gas can be increased.

  When operating the hydrogen pump 10, oxygen or a mixed gas containing oxygen is passed through the cathode electrode 16 to oxidize the proton conductive ceramics. By this oxidation treatment, the reduction of the proton conductive ceramics by hydrogen or the like generated from the cathode electrode 16 can be recovered by oxidation. Therefore, it is possible to suppress the performance of the proton conductive ceramics from being deteriorated, the effect of the hydrogen pump 10 can be stably exhibited for a long period of time, and the performance of the proton conductive ceramics from being deteriorated. can do.

  -By performing the above oxidation treatment in a state in which a DC voltage is applied between the anode electrode 15 and the cathode electrode 16, it is possible to promote the penetration of oxygen ions into the proton conductive ceramics. Can be performed promptly. In addition, the hydrogen pump 10 can be operated in a stable state without changing the characteristics of the hydrogen pump 10.

  Furthermore, by using the target gas stored in the anode chamber 12 as the mixed gas containing oxygen, the mixed gas containing oxygen can be used also as the target gas contacting the anode electrode 15. Operation can be performed efficiently.

It should be noted that the embodiments described above can be modified as follows.
As the structure of the hydrogen pump 10, the electrolyte substrate 14 is formed in an inverted U shape, the anode electrode 15 is provided on the inner peripheral surface, the cathode electrode 16 is provided on the outer peripheral surface, and the inner space of the electrolyte substrate 14 is formed in the anode chamber 12. The outer space can be configured as the cathode chamber 13.

  A pipe for ventilating oxygen or a mixed gas containing oxygen may be connected to the cathode chamber 13 so that oxygen or a mixed gas containing oxygen is directly supplied into the cathode chamber 13.

The oxidation treatment in the operation of the hydrogen pump 10 can be performed without applying a DC voltage between the anode electrode 15 and the cathode electrode 16.
The porous anode electrode 15 can be formed by firing a metal or a mixture of a metal oxide and an organic material to make it porous.

Next, the technical idea that can be grasped from the embodiment will be described below.
The operation method of the hydrogen pump according to any one of claims 5 to 7, wherein the operation is performed so that oxygen is exhausted from the cathode chamber after the oxidation treatment. According to this operation method, the production of hydrogen or the like at the cathode electrode can be quickly recovered.

  The method for operating a hydrogen pump according to any one of claims 5 to 7, wherein the oxidation treatment is repeated at regular intervals. According to this operation method, the operation can be continued while maintaining the permeation rate of hydrogen ions that permeate the proton conductive ceramics.

Schematic explanatory drawing which shows the hydrogen pump in embodiment. The graph which shows the operating method of a hydrogen pump. The graph which shows the relationship between the operation time of a hydrogen pump, and the hydrogen ion permeation rate of proton conductive ceramics. The graph which shows the relationship between oxidation treatment time and an oxidation treatment effect. The graph which compares and shows the hydrogen-permeation rate which permeate | transmits a cathode electrode about the electrode of embodiment and the conventional electrode. The graph which shows the relationship between an electric current and a hydrogen production rate.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Hydrogen pump, 12 ... Anode chamber, 13 ... Cathode chamber, 14 ... Electrolyte substrate, 15 ... Anode electrode, 16 ... Cathode electrode.

Claims (7)

An anode electrode and a cathode electrode are formed on both surfaces of an electrolyte substrate made of proton conductive ceramics, an anode chamber is provided on the anode electrode side, a cathode chamber is provided on the cathode electrode side, and hydrogen and hydrogen isotopes are provided in the anode chamber. Gas containing hydrogen and hydrogen isotopes is decomposed on the anode electrode by applying a DC voltage between both electrodes, and the generated hydrogen and hydrogen isotope ions are electrolytes. In a hydrogen pump that passes through the substrate, generates hydrogen and hydrogen isotope gas on the cathode electrode, and accommodates them in the cathode chamber,
A metal or metal oxide electrode having hydrogen gas permeability is used for the anode electrode, and a metal or metal oxide electrode having hydrogen and hydrogen isotope gas permeability is used for the cathode electrode. A hydrogen pump characterized by 2. The hydrogen pump according to claim 1, wherein an electrode made of a porous metal or metal oxide is used for the anode electrode, and an electrode made of a polycrystalline metal or metal oxide is used for the cathode electrode. The hydrogen pump according to claim 1 or 2, wherein the anode electrode is formed by a paste baking method, and the cathode electrode is formed by an electroless plating method. A gas containing hydrogen and hydrogen isotopes in the target gas in the anode chamber by applying a DC voltage between the anode electrode and the cathode electrode using the hydrogen pump according to any one of claims 1 to 3. And the generated hydrogen and hydrogen isotope ions permeate the electrolyte substrate, generate hydrogen and hydrogen isotope gas on the cathode electrode, and operate in a cathode chamber. The operation method of the hydrogen pump characterized. 5. The method of operating a hydrogen pump according to claim 4, wherein during the operation, oxygen or a mixed gas containing oxygen is passed through the cathode electrode to oxidize the proton conductive ceramics. The method for operating a hydrogen pump according to claim 5, wherein the oxidation treatment is performed in a state where a DC voltage is applied between the anode electrode and the cathode electrode. The method for operating a hydrogen pump according to claim 5 or 6, wherein a target gas contained in an anode chamber is used as the mixed gas containing oxygen.

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