JP5787269B2 - Gas decomposition element, power generation device and gas decomposition method - Google Patents

Description

  The present invention relates to a gas decomposition element, a power generation device, and a gas decomposition method. Specifically, the present invention relates to a gas decomposition element capable of efficiently decomposing a predetermined gas, a power generation device including the gas decomposition element, and a gas decomposition method.

  For example, ammonia is an indispensable compound for agriculture and industry, but is harmful to humans, so various methods for decomposing ammonia in water and air are known. In order to decompose and remove ammonia from water containing a high concentration of ammonia, a method has been proposed in which ammonia water is sprayed and contacted with an air stream to separate ammonia in the air and contacted with hypobromous acid solution or sulfuric acid. (Patent Document 1). In addition, a method of separating ammonia in the air by the same process as the above method and burning it with a catalyst (Patent Document 2) and a method of decomposing ammonia-containing wastewater into nitrogen and water using a catalyst have been proposed. (Patent Document 3). Furthermore, the waste gas of the semiconductor manufacturing apparatus often contains ammonia, hydrogen, etc., and in order to completely remove the odor of ammonia, it is necessary to remove it to the ppm order. For this purpose, many methods have been used in which harmful gas is absorbed in water containing chemicals through a scrubber when the waste gas of the semiconductor device is released. On the other hand, in order to decompose harmful gases at a low running cost without input of energy, chemicals, etc., a waste gas treatment method in a semiconductor manufacturing apparatus or the like that decomposes ammonia with a phosphoric acid fuel cell has been proposed (patent) Reference 4).

JP-A-7-31966 Japanese Patent Laid-Open No. 7-116650 Japanese Patent Laid-Open No. 11-347535 JP 2003-45472 A Japanese Patent No. 3238086

  A method using a chemical such as a neutralizing agent as described in Patent Document 1, a method of burning as described in Patent Document 2, and a thermal decomposition using a catalyst as described in Patent Document 3 Ammonia can be decomposed by a reaction method. However, these methods require chemicals and external energy (fuel), and further require periodic replacement of the catalyst, resulting in increased running costs.

  In addition, since the apparatus becomes large, it is difficult to secure a space when it is additionally provided in existing facilities. In addition, for the device that uses phosphoric acid fuel cells to remove ammonia in the exhaust gas from the production of compound semiconductors, the electrolyte is liquid, so the partition between the air side and the ammonia side cannot be made compact, and the size of the device is reduced. There was a problem that was difficult.

  In order to solve the above problem, as described in Patent Document 5, a cylindrical solid electrolyte layer, and a first electrode layer and a second electrode layer formed so as to sandwich the solid electrolyte layer from inside and outside A cylindrical MEA (Membrane Electrode Assembly) configured with the above can be employed. A gas containing a gas to be decomposed is caused to flow in the axial direction in the inner space of the cylindrical MEA.

  In order to decompose the gas, it is preferable that the temperature of the gas containing the gas is increased as much as possible to act on the first electrode layer (fuel electrode) of the cylindrical MEA. For this reason, the heater which heats the whole said cylindrical MEA is provided. Further, in order to decompose a large amount of gas, it is necessary to increase the flow rate of the gas flowing in the cylindrical MEA. However, when the gas flow rate is increased, a gas that is not sufficiently heated is caused to act on the cylindrical MEA, resulting in a problem that the gas decomposition efficiency is lowered.

  Moreover, in the conventional cylindrical MEA, the connection member was connected to both ends, and the gas was configured to flow in one direction in the internal space of the cylindrical MEA. However, as described above, since the entire tubular MEA is maintained at a high temperature, the sealing performance between the both ends of the tubular MEA and the connecting member is likely to be deteriorated, and the connection reliability is low. It was.

  In the present invention, by utilizing an electrochemical reaction using a solid electrolyte, it is possible to obtain a large processing capacity while suppressing running cost, and to increase the temperature of the gas flowing in the cylindrical MEA to further increase the decomposition efficiency. It is an object of the present invention to provide a gas decomposition element that can be used.

The present invention relates to a cylindrical solid electrolyte layer, a first electrode layer laminated on the inner periphery of the solid electrolyte layer, and a second electrode layer laminated on the outer periphery of the solid electrolyte layer, A gas decomposing element comprising a cylindrical MEA (Membrane Electrode Assembly) having a sealing portion formed by sealing one end of the cylindrical MEA, and the other end of the cylindrical MEA A gas guide pipe that is inserted into the inner space of the cylindrical MEA from the side of the tube and forms a cylindrical flow path between the inner periphery of the cylindrical MEA, and the inside of the gas guide pipe is sealed The gas flowing toward the section is caused to flow reversely by flowing out of the gas induction pipe in the vicinity of the sealing section, and the cylindrical flow path is caused to flow in a direction opposite to the flow in the gas induction pipe. While the first electrode To be configured to decompose by the action, in the gas induction pipe, Rutotomoni provided heating acceleration means for promoting heat transfer by increasing the contact area between the flowing gas, among the first electrode layer A conductive metal mesh sheet is disposed on the peripheral surface, and an end portion of the metal mesh sheet is connected to the gas induction pipe in the vicinity of the sealing portion, whereby the first electrode layer, the gas induction pipe, Is made conductive .

  In the gas decomposition element according to the present invention, the gas to be decomposed is reciprocated in the axial direction in the cylindrical MEA.

  By employ | adopting the said structure, the said gas can be made to flow the distance twice as long as the cylinder length of cylindrical MEA. For this reason, after raising the temperature of gas in the said gas induction pipe, it can be made to act on the said cylindrical MEA. Therefore, it is possible to increase the gas decomposition efficiency, and it is possible to increase the gas throughput by increasing the gas flow rate.

  Further, in the present invention, in order to increase the heating efficiency of the gas in the gas induction pipe, a heating promoting means is provided in the gas induction pipe to increase the contact area with the flowing gas and promote heat conduction. Yes.

The configuration of the heating promoting means is not particularly limited as long as it increases the contact area with the flowing gas. For example , the heating accelerating means can be configured by providing irregularities on the inner surface of the gas induction pipe.

  The means for forming the irregularities is not particularly limited. The unevenness is preferably configured so as not to increase the flow resistance of the gas. The irregularities can be provided by processing the gas induction pipe itself, or can be configured by adding another member.

  For example, a small unevenness can be provided in the gas induction pipe by sand blasting, etching, or the like to provide a heating promoting means. Moreover, a heating promotion means can be comprised by providing the fin and groove | channel which extend in the axial direction of the said gas induction pipe. By providing fins and grooves in the axial direction, it is possible to provide a heating promoting means while preventing an increase in gas flow resistance.

Further, the heating acceleration means, in the gas induction pipe can be configured by filling a porous body having gas permeability and thermal conductivity. For example, the gas guide pipe can be filled with a porous metal body having air permeability.

  As the porous metal body, one having high thermal conductivity and high porosity is adopted. For example, as a porous metal body, in order to reduce pressure loss of gas such as ammonia gas, it is preferable to use a metal plating body capable of increasing the porosity, for example, Celmet (registered trademark: Sumitomo Electric Industries, Ltd.).

  By providing the heating promoting means, it is possible to sufficiently raise the temperature of the gas before the gas is allowed to act on the cylindrical MEA. For this reason, it becomes possible to decompose | disassemble a part of gas by temperature within the said gas induction pipe. As a result, the gas decomposition efficiency can be greatly increased.

  Moreover, in this invention, the part where the said gas comes in and out of cylindrical MEA can be concentrated and provided in the one side edge part of cylindrical MEA. For this reason, the reliability of the seal structure between the cylindrical MEA and the connection pipe or the like can be enhanced.

  The structure which seals the one end part of the said cylindrical MEA is not specifically limited. For example, one end of the cylindrical MEA can be sealed with a bottom formed by integrally extending the solid electrolyte layer. Since the bottom part is integrally formed with the cylindrical MEA in the molding and sintering steps, there is no risk of gas leakage, and one end of the cylindrical MEA can be reliably sealed.

  Further, one end of the cylindrical MEA can be sealed by fitting a sealing member to the end of the cylindrical MEA. By adopting this configuration, the present invention can be applied to a conventional cylindrical MEA having both ends opened.

  The gas inlet / outlet in the cylindrical MEA can be configured with a piping member having a double structure so that the gas before decomposition and the gas after decomposition do not mix. For example, a pipe joint that has heat resistance and allows gas to enter and exit can be provided at the opening end of the cylindrical MEA. The pipe joint may include a gas introduction portion that communicates with the gas induction pipe, and may include an annular exhaust space that surrounds the outer periphery of the gas induction pipe and includes a gas discharge portion on a side portion. By employ | adopting the said pipe joint, while introducing the gas containing the gas decomposed | disassembled from the one side of the said cylindrical MEA, the gas containing the decomposed gas can be discharged | emitted.

In the present invention, the gas induction pipe can be used as a current collector for the first electrode layer. That is , the gas induction pipe can be formed from a conductive material, and can be electrically connected to the first electrode layer to constitute a current collector of the first electrode layer.

  By using the gas induction pipe as a current collector for the first electrode layer, not only the gas decomposition efficiency can be increased, but also the space in the cylindrical MEA can be effectively utilized.

  Although the material which comprises the said gas induction pipe is not specifically limited, It is necessary to form with the material which corrosion etc. do not produce by the gas to decompose | disassemble. For example, it can be formed using a nickel alloy such as stainless steel, copper, nickel, Inconel (registered trademark of Special Metal Co.).

  The method for electrically connecting the first electrode layer and the gas induction pipe is not particularly limited. For example, a porous metal body having conductivity is inserted into a cylindrical flow path formed between the inner peripheral surface of the cylindrical MEA and the outer peripheral surface of the gas induction pipe, and the first electrode layer and the above The gas induction pipe can be conducted. Further, by providing the porous metal body, it is possible to secure a cylindrical flow path between the inner peripheral surface of the first electrode layer and the outer peripheral surface of the gas induction pipe, and the gas induction pipe. Can be positioned and held in the cylindrical MEA.

  Furthermore, in order to increase the current collection efficiency, it is desirable to set the electrical resistance between the first electrode layer and the gas induction pipe as low as possible. For this reason, it is desired to increase the contact area and the contact pressure between the porous metal body, the first electrode layer, and the gas induction pipe.

In the present invention, in order to set a low electrical resistance between the first electrode layer and the gas induction pipe, the inner peripheral surface of the first electrode layer, with disposing the conductive metal mesh sheet By connecting the metal mesh sheet to the gas induction pipe, the first electrode layer and the gas induction pipe are electrically connected .

  By holding the metal mesh sheet in contact with the first electrode layer, the resistance between the electrode layer and the metal mesh sheet can be reduced. Further, the contact resistance between the current collectors can be further reduced by directly connecting the metal mesh sheet to the gas induction pipe. For example, a configuration in which one metal mesh sheet is disposed so as to be in contact with the entire inner peripheral surface of the first electrode layer, and an end portion of the metal mesh sheet is wound around the outer peripheral surface of the gas induction pipe. Can be adopted.

  In addition, by adopting the above configuration, it is possible to increase the area of the current collector by using the gas induction pipe, and it is possible to further improve the gas decomposition efficiency.

  Further, by inserting the metal porous body between the inside of the metal mesh sheet and the gas induction pipe, and backing up the metal mesh sheet from the inside, the first electrode layer and the current collector The contact resistance between them can be reduced. In addition, this configuration forms two conductive paths: (1) Ni mesh sheet / porous metal body / gas induction pipe, and (2) Ni mesh sheet / gas induction pipe. As a result, the contact resistance of the anode current collector can be further reduced, and an increase in pressure loss can be prevented.

  The form of the metal mesh sheet is not particularly limited. For example, the metal mesh sheet can be formed in a cylindrical shape and disposed so as to cover the entire surface of the first electrode layer.

  The appearance configuration of the metal mesh sheet is not particularly limited. For example, a woven fabric, a non-woven fabric, a punched sheet, or the like can be used. In order to ensure flexibility, pore diameter uniformity, etc., it is preferable to employ a woven fabric.

  The metal material constituting the metal mesh sheet is not particularly limited. For example, it is preferable to employ a metal mesh sheet formed of a material such as Ni, Ni—Fe, Ni—Co, Ni—Cr, or Ni—W. Also, a metal mesh sheet having a silver plating layer or the like formed on the surface layer can be employed. When a catalytic reaction is expected, it is preferable to employ a metal mesh sheet formed from a material such as Ni-W.

Furthermore , it is preferable to provide a porous conductive layer on the surface of the first electrode layer. It may be difficult to bring the metal mesh sheet into uniform contact with the entire inner peripheral surface of the first electrode layer. That is, it is conceivable that the contact pressure between the surface of the first electrode layer and the metal mesh sheet is different, or a part of the contact pressure rises from the surface of the first electrode layer.

  By forming the conductive layer on the surface of the first electrode layer, conductivity between the first electrode layer and the metal mesh sheet can be ensured in the entire region. Further, since the conductive layer is porous, it does not hinder gas contact with the first electrode layer.

  As the porous conductive layer, a porous conductive paste coating layer can be provided. By providing a porous conductive paste coating layer on the inner peripheral surface of the first electrode layer, the first electrode layer and the metal mesh sheet are reliably connected via the conductive paste coating layer. The electrical resistance between the first electrode layer and the gas guiding path is also reduced.

  That is, by providing the conductive paste coating layer, a part of the surface of the metal mesh sheet is embedded in the conductive paste coating layer, and the gap between the metal mesh sheet and the first electrode layer is ensured. Can be conducted. For this reason, the contact resistance between these can be reduced significantly. In addition, the entire surface of the metal mesh sheet can be uniformly contacted with the first electrode layer. For this reason, the electrical resistance between the first electrode layer and the metal mesh sheet does not partially increase. Further, by applying the conductive paste coating layer to the entire surface of the first electrode layer, even when the metal mesh sheet is separated from the conductive paste coating layer, current collection on the surface of the first electrode layer is performed. It can be secured. For this reason, even if a part of the metal mesh sheet is separated from the conductive paste coating layer by the action of temperature or the like, the current collection effect is not lowered. In addition, since the conductive paste coating layer is porous, it does not prevent the gas from coming into contact with the first electrode layer. Therefore, it is possible to generate an electrochemical reaction uniformly in the entire region of the first electrode layer to greatly improve the efficiency of the gas decomposition reaction, and to increase the gas decomposition processing capacity.

  The porous conductive paste coating layer can be formed from a paste containing various conductive particles. For example, the porous conductive paste coating layer can be formed from a paste containing silver particles. Silver particles have high conductivity, and can reduce the electrical resistance of the first electrode layer as a current collector, thereby improving the gas decomposition treatment capacity. Also, it is stable and hardly oxidizes.

The materials constituting the first electrode layer and the second electrode layer are not particularly limited. For example , the first electrode layer and / or the second electrode layer can be a fired body including a metal particle chain mainly composed of nickel (Ni) and an ion conductive ceramic. The metal particle chain refers to a bead-like elongated metal body formed by a series of metal particles. Ni, Fe-containing Ni, or Ni, Fe-containing Ni may be a metal containing a small amount of Ti. When the surface of Ni or the like is oxidized, the surface of the metal particle chain is oxidized, and the contents (portion inside the surface layer) are not oxidized and retain the conductivity of the metal.

For this reason, for example, when the ion moving in the solid electrolyte layer is an anion (in some cases, it is a cation), the following effects are produced.
(A1) When the metal particle chain is contained in the first electrode layer (anode), in the first electrode layer (anode), the anion moving from the solid electrolyte layer and the first electrode layer ( The chemical reaction with the gas molecules in the gas led from the outside of the anode) to the first electrode layer (anode) is promoted by the oxidized layer of the metal particle chain (catalysis), and an anion is added. The chemical reaction in the first electrode layer (anode) is promoted (acceleration effect by electric charge). And as a result of the chemical reaction, the conductivity of the generated electrons can be ensured by the metal portion of the metal particle chain. As a result, the electrochemical reaction involving charge transfer in the first electrode layer (anode) can be accelerated as a whole. When the metal particle chain is contained in the first electrode layer (anode), a cation such as a proton is generated in the first electrode layer (anode), and the second electrode layer (cathode) is generated in the solid electrolyte layer. The cation can be moved to the surface, and the above-mentioned promoting action by the charge can be obtained similarly.
However, the oxide layer of the metal particle chain is surely formed by a firing treatment before use, but the oxide layer is often lost due to a reduction reaction during use. Even if the oxide layer disappears, the above-described catalytic action may or may not be reduced. In particular, Ni containing Fe or Ti has high catalytic action even without an oxide layer.
(A2) When the metal particle chain is contained in the second electrode layer (cathode), in the second electrode layer (cathode), the second electrode layer (cathode) from the outside of the second electrode layer (cathode). The chemical reaction of gas molecules in the gas led to gas) is promoted by the oxidation layer of the metal particle chain (catalysis), and the conductivity of the electrons from the external circuit is improved and the electrons are allowed to participate. The chemical reaction at the second electrode layer (cathode) is promoted (acceleration effect by electric charge). Then, anions can be efficiently generated from the molecules and delivered to the solid electrolyte layer. As in (A1), in the case of (A2), the electrochemical reaction between the cation that has moved through the solid electrolyte layer, the electrons that have flowed through the external circuit, and the second gas can be promoted. For this reason, the electrochemical reaction accompanied by transfer of electric charge in the second electrode layer (cathode) can be accelerated as a whole, as in the case of being included in the first electrode layer (anode). In which case the metal particle chain is included in the second electrode layer (cathode) depends on the gas to be decomposed.
(A3) When the metal particle chain is contained in the first electrode layer (anode) and the second electrode layer (cathode), the effects (A1) and (A2) can be obtained.

  In many cases, the electrochemical reaction is limited by the moving speed or moving time of the solid electrolyte layer of ions. In order to increase the moving speed of ions, the gas decomposition element is usually provided with a heating device such as a heater, and is usually set at a high temperature, for example, 600 ° C to 1000 ° C. By raising the temperature, not only the ion transfer speed but also a chemical reaction accompanied by charge transfer in the electrode layer is promoted.

  When the ions moving through the solid electrolyte layer are anions, they are generated and supplied by a chemical reaction at the second electrode layer (cathode) as described above. Molecules in the fluid and electrons introduced in the second electrode layer (cathode) react to generate anions. The generated anion moves in the solid electrolyte layer to the first electrode layer (anode). The electrons participating in the reaction at the second electrode layer (cathode) include an external circuit (capacitor, power source, and power consuming device) that connects the first electrode layer (anode) and the second electrode layer (cathode). ) Comes in. When the ions moving through the solid electrolyte layer are cations, they are generated by an electrochemical reaction in the first electrode layer (anode) and move through the solid electrolyte layer to the second electrode layer (cathode). Electrons are generated at the first electrode layer (anode), flow through an external circuit to the second electrode layer (cathode), and participate in the electrochemical reaction at the second electrode layer (cathode). The electrochemical reaction may be a power generation reaction as a fuel cell, or may be an electrolysis reaction.

The solid body electrolyte layer can have a structure having oxygen ion conductivity or proton conductivity. In the case of using an oxygen ion conductive solid electrolyte, for example, the second electrode layer (cathode) reacts electrons and oxygen molecules to generate oxygen ions, which are moved in the solid electrolyte layer to form the first electrolyte layer. A predetermined electrochemical reaction can be caused in the electrode layer (anode). In this case, since the moving speed of oxygen ions in the solid electrolyte layer is not large compared to protons, the temperature is sufficiently increased and / or the thickness of the solid electrolyte layer is sufficiently thin to obtain a practical level of decomposition capacity. Such measures are necessary.

On the other hand, barium zirconate (BaZrO ₃ ) is known as a proton conductive solid electrolyte. When a proton conductive solid electrolyte is used, for example, ammonia is decomposed at the first electrode layer (anode) to generate protons, nitrogen molecules and electrons, and this proton is passed through the solid electrolyte layer to the second electrode layer. It moves to (cathode) and reacts with oxygen in the second electrode layer (cathode ) to generate water (H ₂ O) . Since protons are small compared to oxygen ions, the moving speed in the solid electrolyte layer is high, and a practical decomposition capacity can be obtained by lowering the heating temperature.

  For example, when ammonia decomposition is performed using a cylindrical MEA, the oxygen ion conductive solid electrolyte layer is a reaction that generates water in the first electrode layer (anode) of the cylindrical MEA. Water forms water droplets near the outlet where the temperature is low, causing pressure loss. In contrast, when a proton conductive solid electrolyte layer is used, protons, oxygen molecules, and electrons are generated at the second electrode layer (cathode) (outside). Since the outside is almost open, even if it adheres as water droplets, pressure loss is unlikely to occur.

The decomposition target gas as fuel, it is also possible to configure the fuel cell by a gas decomposition device.

The gas decomposition method according to the present invention includes a cylindrical solid electrolyte layer, a first electrode layer formed on the inner periphery of the solid electrolyte layer, and a second electrode formed on the outer periphery of the solid electrolyte layer. A cylindrical MEA (Membrane Electrode Assembly) having an electrode layer and sealed at one end, and inserted into the internal space of the cylindrical MEA from the other end of the cylindrical MEA, in the vicinity of the sealed portion A gas decomposition method performed by a gas decomposition element including a gas induction pipe that guides gas to the inner peripheral surface of the cylindrical MEA and that forms a cylindrical flow path between the gas ME pipe and the gas induction pipe. A heating step for increasing the temperature of the gas flowing in the gas induction pipe by the heating promotion means provided, and for allowing the gas to flow out of the gas induction pipe in the vicinity of the sealing portion. The gas flows in the opposite direction to the flow in the gas induction pipe in the cylindrical flow path formed between the inner peripheral surface of the cylindrical MEA and the gas induction pipe. A decomposition step of causing the first electrode layer to decompose and disposing the metal mesh sheet on the inner peripheral surface of the first electrode layer, and the end portion of the metal mesh sheet being By connecting to the gas induction pipe in the vicinity of the sealing portion, the first electrode layer and the gas induction pipe are connected.

  The gas to be decomposed is not particularly limited. For example, any of the gas decomposition elements described above can be provided, and a gas containing ammonia can be introduced into the first electrode layer, and a gas containing oxygen molecules can be introduced into the second electrode layer. As a result, oxygen ions generated in the second electrode layer (cathode) are moved to the first electrode layer (anode), and ammonia and oxygen ions are converted into a catalyst by a metal particle chain in the first electrode layer. By reacting under the action and the accelerating action by ions, electrons generated as a result of the reaction can be rapidly moved. Further, the gas decomposition element according to the present invention is used not only for gas detoxification but also as a base of the apparatus in the field of a fuel cell and an original electrochemical reaction apparatus utilizing gas decomposition, and the efficiency of the electrochemical reaction It can contribute to improvement, downsizing of the apparatus, and low running cost.

  A gas decomposition apparatus with high gas decomposition efficiency, low running cost, and high gas decomposition efficiency can be provided.

It is a longitudinal cross-sectional view which shows the front end side (sealing side) of the gas decomposition element in Embodiment 1 of this invention. It is sectional drawing which follows the IB-IB line | wire in FIG. It is a figure which shows the electrical wiring system | strain of the gas decomposition element of FIG. It is a longitudinal cross-sectional view by the side of the gas inlet / outlet side of the gas decomposition element shown in FIG. It is a principal part enlarged view of FIG. It is a longitudinal cross-sectional view which shows the 2nd Embodiment of this invention.

Hereinafter, embodiments of the present invention will be specifically described with reference to the drawings.
FIG. 1 is a longitudinal sectional view of a gas decomposition element 10 according to Embodiment 1 of the present invention. 2 is a cross-sectional view taken along line IB-IB in FIG. In the present embodiment, the case where the present invention is applied to a gas decomposition element that decomposes ammonia gas will be described.

  The gas decomposition element 10 is provided with a first electrode layer (anode) 2 so as to cover the inner surface of the cylindrical solid electrolyte layer 1 and a second electrode layer (cathode) 5 so as to cover the outer surface. The cylindrical MEA 7 (1, 2, 5) is provided. The first electrode layer (anode) 2 may be called a fuel electrode, and the second electrode layer (cathode) 5 may be called an air electrode. The cylindrical MEA 7 (1, 2, 5) according to the present embodiment is formed in a right cylindrical shape as shown in FIG. The inner diameter of the cylindrical MEA is, for example, about 20 mm, but the dimensions and the like can be set according to the device to be applied.

  In the gas decomposing element 10 of the present embodiment, one end of the cylindrical MEA is sealed, and a stainless steel gas induction pipe 11k is inserted from the other end. The one end portion is provided with a sealing portion 44 by extending the solid electrolyte layer 1 and the inner first electrode layer 2 of the cylindrical MEA 7 and providing a bottom portion.

  The gas induction pipe 11k is inserted from the other end side of the cylindrical MEA toward the one end side, and the inner peripheral surface of the first electrode layer 2 of the cylindrical MEA and the gas induction pipe 11k. The cylindrical flow path 43 is set so as to be formed between the outer peripheral surface and the outer peripheral surface. A porous metal body 11s is inserted into the cylindrical flow path 43, and the gas guide pipe 11k is held at the center while the outer peripheral surface of the gas guide pipe 11k and the first electrode layer 2 are in contact with each other. A cylindrical flow path 43 is formed between the inner surface and the inner surface.

  A heater 41 is provided around the gas decomposition element 10 having the above-described configuration, and is configured to heat the entire gas decomposition element to about 800 ° C. to decompose the gas flowing in the cylindrical MEA. ing.

  In the gas decomposition element 10 according to the present invention, the gas flowing in the gas induction pipe 11k toward the sealing portion 44 is caused to flow out of the gas induction pipe 11k in the vicinity of the sealing portion 44. The cylindrical flow path 43 is configured to flow in the direction opposite to the flow in the guide pipe 11k.

  By adopting the above configuration, the gas is allowed to flow in the inside of the cylindrical MEA 7 for a distance of about twice the cylinder length of the cylindrical MEA. For this reason, after it is heated enough in the gas induction pipe 11k and the temperature is raised, it can act on the cylindrical MEA 7. Therefore, it is possible to increase the gas decomposition efficiency, and it is possible to increase the gas throughput by increasing the gas flow rate.

  Further, in order to further increase the temperature of the gas in the gas induction pipe 11k, the gas induction pipe 11k is provided with heating promotion means 50 that increases the contact area with the flowing gas and promotes heat conduction. Yes.

  In the present embodiment, as shown in FIG. 5, the heating promoting means 50 is configured by providing irregularities 50a on the inner peripheral portion of the gas induction pipe 11k. The method of providing the unevenness 50a is not particularly limited. Moreover, if the area of the internal peripheral surface of the said gas induction pipe 11k can be increased, the form dimension of the said unevenness | corrugation 50a will not be limited, either. For example, the unevenness 50a can be formed on the surface of the gas induction pipe by a sandblast method or the like. The unevenness 50a can also be formed by etching the inner surface of the gas induction pipe.

  By providing the unevenness 50a as the heating promoting means 50, the contact area between the inner peripheral portion of the gas induction pipe 11k and the gas can be increased. For this reason, the temperature of the gas flowing in the gas induction pipe 11k can be increased efficiently. As a result, in the process of flowing through the gas induction pipe 11k, it is possible to cause the gas to act on the first electrode layer 2 after sufficiently increasing the temperature of the gas, thereby improving the gas decomposition efficiency. It is possible to increase the decomposition throughput by increasing the gas flow rate.

  In the present embodiment, the gas induction pipe 11k is made of a conductive metal such as stainless steel, and is configured to function as a component of the anode-side current collector 11. On the other hand, the cathode current collector 12 is arranged so as to wrap around the outer surface of the second electrode layer (cathode) 5.

  The anode side current collector 11 includes a silver paste coating layer 11g, a Ni mesh sheet 11a, a porous metal body 11s, and the gas induction pipe 11k. The Ni mesh sheet 11a is in contact with the first electrode layer 2 (anode) on the inner surface side of the cylindrical MEA 7 through the silver paste coating layer 11g, and conducts from the porous metal body 11s to the gas induction pipe 11k. Is configured to do. The Ni mesh sheet 11a tip W1 is conductively connected in the vicinity of the sealing portion 44 so as to be wound around the outer periphery of the gas guiding pipe 11k via a band-shaped joining member W2. Therefore, the Ni mesh sheet 11a includes, in parallel, a conductive path of (1) Ni mesh sheet 11a / porous metal body 11s / gas induction pipe 11k, and (2) Ni mesh sheet 11a / gas induction pipe 11k, The conductive path is formed. As a result, it is possible to configure the anode-side current collector 11 that is located on the inner surface of the cylindrical MEA 7 and can prevent an increase in pressure loss while maintaining a low electrical resistance.

  As the porous metal body 11s, in order to reduce the pressure loss of gas such as ammonia gas, it is preferable to use a metal plated body capable of increasing the porosity, for example, Celmet (registered trademark: Sumitomo Electric Industries, Ltd.). In order to reduce the electrical resistance between the first electrode layer (anode) 2 and the anode-side current collector 11, the silver paste coating layer 11g and the Ni mesh sheet 11a are disposed.

  The cathode current collector 12 includes a silver paste coated wiring 12g and a Ni mesh sheet 12a. In the present embodiment, the Ni mesh sheet 12a is in contact with the outer surface of the cylindrical MEA 7 and is conducted to the external wiring. The silver paste coated wiring 12g contains silver which acts as a catalyst for promoting the decomposition of oxygen gas in the second electrode layer (cathode) 5 into oxygen ions, and lowers the electrical resistance of the cathode-side current collector 12. It contributes to that. The silver paste coated wiring 12g having a predetermined property is equivalent to the silver particles contained in the second electrode layer (cathode) 5 because the silver particles contact the second electrode layer (cathode) 5 while passing oxygen molecules. The catalytic action is expressed. Moreover, it is less expensive than the inclusion in the second electrode layer (cathode).

FIG. 3 is a diagram showing an electrical wiring system of the gas decomposition element 10 of FIG. 1 when the solid electrolyte layer 1 is oxygen ion conductive. The gas containing ammonia is guided through the gas guide pipe 11k to the innermost part of the inner cylinder of the cylindrical MEA 7 with strict airtightness, that is, near the sealing part 44. The entire cylindrical MEA 7 is heated to about 800 ° C. by the heater 41, and the temperature of the gas is raised while flowing in the gas induction pipe 11k. During this time, a part of the ammonia gas is decomposed as 2NH ₃ → N 2 + 3H ₂ by heating in the gas induction pipe 11k.

  The porous metal body 11s is used to position and hold the gas guide pipe 11k inside the cylindrical MEA 7 to secure the cylindrical flow path 43 and to flow a gas containing decomposition gas. From the viewpoint of reducing the pressure loss of the cylindrical flow path, as described above, as the porous metal body 11s disposed in the cylindrical flow path 43, a porous metal plated body, for example, the above-mentioned Celmet is used. Can do. The gas containing ammonia passes through the voids of the porous metal body 11s, the Ni mesh sheet 11a, and the porous silver paste coating layer 11g through the cylindrical channel 43, and the first electrode layer (anode) 2 The following ammonia decomposition reaction is carried out in contact with.

Oxygen ions O ²⁻ are generated by an oxygen gas decomposition reaction in the second electrode layer (cathode) 5 and reach the first electrode layer (anode) 2 through the solid electrolyte layer 1. That is, it is an electrochemical reaction when oxygen ions, which are anions, move through the solid electrolyte layer 1.

In the first electrode layer (anode), the following reaction occurs.
(Anode reaction): 2NH ₃ + 3O ²⁻ → N ₂ + 3H ₂ O + 6e ⁻
More specifically, a part of ammonia causes a reaction of 2NH ₃ → N ₂ + 3H ₂ , and this 3H ₂ reacts with oxygen ions 3O ²⁻ to generate 3H ₂ O. Air, particularly oxygen gas, is introduced into the second electrode layer (cathode) 5 so as to pass through the space S, and oxygen ions decomposed from oxygen molecules in the second electrode layer (cathode) 5 are converted into the first electrode layer. (Anode) 2 is sent to the solid electrolyte layer 1.

In the first electrode layer (cathode) 5, the following reaction occurs.
(Cathode reaction): O ₂ + 4e ⁻ → 2O ²⁻
As a result of the above electrochemical reaction, electric power is generated, and a potential difference is generated between the first electrode layer (anode) 2 and the second electrode layer (cathode) 5, and the anode side current collector 12 performs the anode side current collection. A current I flows to the electric body 11. If a load, for example, a heater 41 for heating the gas decomposition element 10 is connected between the cathode-side current collector 12 and the anode-side current collector 11, electric power for that purpose can be supplied. The supply of the power to the heater 41 may be partial. In many cases, the supply amount of private power generation is often less than half of the power required for the entire heater.

In the gas decomposition element 10, in the first electrode layer (anode) 2 on the inner surface side of the cylindrical MEA 7, the electric resistance of the anode current collector 11 is reduced, and the pressure loss of the gas passing therethrough is reduced. It is important to. Further, on the second electrode layer (cathode) 5 side, air does not pass through the cylinder, but the contact portion between the air and the second electrode layer (cathode) 5 is densified, and the cathode-side current collector 12. It is important to reduce the resistance.

The above is an electrochemical reaction in which oxygen ions, which are anions, move through the solid electrolyte layer 1. For example, barium zirconate (BaZrO ₃ ) is used for the solid electrolyte layer 1 to transfer protons to the first electrode layer (anode The reaction that is generated in step 2 and moves in the solid electrolyte layer 1 to the second electrode layer (cathode) 5 is also a desirable embodiment of the present invention.

When the proton conductive solid electrolyte layer is used, for example, when ammonia is decomposed, the first electrode layer (anode) 2 decomposes ammonia to generate protons, nitrogen molecules and electrons, and the protons are converted into solid electrolyte layers. Then, it moves to the second electrode layer (cathode) 5 and reacts with oxygen in the second electrode layer (cathode) to generate water (H ₂ O). Since protons are smaller than oxygen ions, the moving speed in the solid electrolyte layer is large. Therefore, a practical decomposition capacity can be obtained while lowering the heating temperature. The thickness of the solid electrolyte layer can also be set to a thickness that can ensure strength.

  FIG. 4 is a diagram showing a connection form between the gas induction pipe 11k and the external wiring 11e and a connection form between the cylindrical MEA 7, the gas transport path 45, and the gas exhaust path 55. A pipe joint 30 made of fluororesin is fitted into the opening end of the cylindrical MEA 7.

  In the pipe joint 30, the O-ring 33 housed on the inner surface side of the fastening portion 31 b extending from the main body portion 31 to the solid electrolyte layer 1 is in contact with the outer surface of the ceramic solid electrolyte layer 1 that is a fired body. Connected with. The fastening portion 31b of the pipe joint 30 has an outer diameter tapered, and a screw is cut there, and an annular screw 32 is screwed into the screw. By fastening the annular screw in the direction in which the outer diameter increases, the fastening portion 31b is tightened from the outer surface, and the airtightness by the O-ring 33 can be adjusted.

  On the side opposite to the fastening portion 31b of the pipe joint 30, a gas introduction portion 31a for introducing a gas containing the gas into the gas induction pipe 11k, and a gas discharge portion for discharging the gas decomposed by the cylindrical MEA 7 31c.

  Inside the pipe joint 30, a gas introduction path 45e having a fitting portion 45d capable of fitting the base end portion 11d of the gas guiding pipe 11k with airtightness is formed. The gas containing the cracked gas is caused to flow to the vicinity of the sealing portion 44 of the cylindrical MEA 7 through the gas introduction path 45e and the gas induction pipe 11k.

  As the gas conveyance path 45, it is preferable to use a pipe line made of elastically deformable resin or the like. By fitting the end portion of the pipe line to the outer periphery of the introduction portion 31a and fastening with the fastener 47, an airtight connection can be obtained. Further, the gas exhaust path 55 is also formed by a pipe line similar to the gas transport path 45, fitted to the outer periphery of the gas exhaust part 31 c and connected by a fastener 57.

  An annular exhaust space 46 that communicates with the internal space of the cylindrical MEA 7 and surrounds the gas guiding pipe 11k is formed on the inner side in the axial direction of the fitting portion 45d. The gas discharge part 31 c is provided on the side of the exhaust space 46, and the gas exhaust decomposed in the cylindrical MEA 7 is discharged through the gas discharge part 31 c and the gas exhaust path 55. By adopting the pipe joint, it is possible to allow gas to enter and exit from one side of the cylindrical MEA 7 without mixing the gas before decomposition and the gas after decomposition.

  The main body portion 31 of the pipe joint 30 is provided with a conductive through portion 37c that penetrates the main body portion 31 while maintaining airtightness, and is coated with a sealing resin 38 or the like to maintain airtightness. The conductive penetrating portion 37c is a cylindrical rod, and a screw for screwing the nut 39 is preferably cut in order to make a reliable conductive connection with the external wiring 11e. A conductive wire 37b is joined to the distal end of the conductive through portion 37c in the tube, and the other end 37a of the conductive wire 37b is joined to the outer peripheral portion of the gas induction pipe 11k via an annular fastening tool 34. .

  By adopting the above configuration, the connection resistance between the gas induction pipe 11k and the external wiring 11e can be reduced.

  On the other hand, external wiring 12e can be circulated around the outer periphery of the end portion of the Ni mesh sheet 12a of the cathode-side current collector 12, thereby leading to the outside. Since the second electrode layer (cathode) 5 is located on the outer surface side of the cylindrical MEA 7, it is not as difficult as withdrawing from the anode current collector 11 to the outside.

  As shown in FIG. 4, the connection between the anode-side current collector 11 and the external wiring 11 e and the connection between the pipe joint 30, the gas transport path 45, and the gas exhaust path 55 can be performed in a small space. In addition, the above two types of connections are made at positions away from the main flow portion of the heat flow from the heater. For this reason, long-term repeated durability can be ensured by a heat-resistant resin such as a fluororesin or a corrosion-resistant resin.

  In the present embodiment, a silver paste coating layer 11g is provided as a porous conductive layer on the inner periphery of the first electrode layer (anode) 2, and the Ni mesh sheet 11a is interposed via the silver paste coating layer 11g. And connected to the first electrode layer (anode) 2.

Silver paste that becomes porous after being applied and dried (fired) is commercially available, and for example, DD-1240 manufactured by Kyoto Elex Co., Ltd. can be used. By making the silver paste coating layer 11g porous, many ammonia molecules (NH ₃ ) enter the porous pores and come into contact with the catalyst in the first electrode layer (anode) 2 to undergo an anodic reaction. Is likely to occur.

  In order to increase the efficiency of the gas decomposition reaction, the porosity of the silver paste coating layer 11g is preferably set to 20 to 80%. When the porosity is less than 20%, it becomes difficult to guide the gas into the conductive paste coating layer, and the efficiency cannot be increased. On the other hand, if the porosity exceeds 80%, it is difficult to ensure sufficient conductivity and the strength of the coating layer cannot be ensured. Furthermore, it is more preferable to set the porosity to 40 to 60%.

  The thickness of the silver paste coating layer 11g can be set to 5 to 300 μm. If it is less than 5 μm, the entire area of the Ni mesh sheet 11a cannot be uniformly contacted with the silver paste coating layer 11g, and it is difficult to ensure sufficient conductivity. On the other hand, if it exceeds 300 μm, it becomes difficult to form a paste coating layer having a sufficient porosity. In order to ensure conductivity and porosity, it is more preferable to provide a silver paste coating layer 11g having a thickness of 5 to 100 μm.

  The method for forming the silver paste coating layer 11g is not particularly limited. The silver paste coating layer 11g can be formed by a dipping method in which the cylindrical MEA 7 is immersed in an immersion layer filled with a silver paste, a technique of inserting a coating nozzle for spraying the silver paste on the inner surface of the cylindrical MEA 7, or the like. .

  Further, the method for forming the silver paste coating layer 11g to be porous is not particularly limited. In order to ensure the required porosity described above, a silver paste containing a predetermined amount of a binder that disappears at a predetermined temperature can be employed. In order to prevent shrinkage of the conductive paste coating layer when the binder disappears, it is preferable to add a sublimation binder. For example, it is preferable to employ a silver paste containing a naphthalene binder.

  The range in which the silver paste coating layer 11g is provided is not particularly limited, but the silver paste coating layer 11g is preferably provided on the entire surface of the first electrode layer (anode) 2. By forming the silver paste coating layer 11g on the entire surface of the first electrode layer (anode) 2, even when a part of the Ni mesh sheet is separated from the silver paste coating layer, the first electrode layer (anode) The current collection performance in 2 is not reduced.

  As the powder material constituting the solid electrolyte layer 1, a solid oxide, molten carbonate, phosphoric acid, solid polymer, or the like can be used. Solid oxides are preferred because they can be miniaturized and are easy to handle. Examples of the solid oxide include oxygen ion conductive SSZ (scandium stabilized zirconia), YSZ (yttrium stabilized zirconia), SDC (samarium stabilized ceria), LSGM (lanthanum gallate), GDC (gadria stabilized ceria), and the like. Should be used. Proton conductive barium zirconate can also be used. Each said powder material can be baked by hold | maintaining at 1000 degreeC-1600 degreeC for about 30 minutes-180 minutes by air | atmosphere atmosphere.

  The first electrode layer (anode) 2 can be formed as a fired body mainly composed of a metal particle chain body that is oxidized on the surface and has an oxide layer, and an oxygen ion conductive ceramic. As oxygen ion conductive ceramics, SSZ (scandium stabilized zirconia), YSZ (yttrium stabilized zirconia), SDC (samarium stabilized ceria), LSGM (lanthanum gallate), GDC (gadria stabilized ceria), etc. should be used. Can do.

  When adopting the above SSZ, it is preferable to use one having an average diameter of about 0.5 μm to 50 μm. The firing step can be performed by holding at 1000 ° C. to 1600 ° C. for about 30 minutes to 180 minutes in an air atmosphere. The average diameter of the raw material powder of SSZ is preferably about 0.5 μm to 50 μm. The compounding ratio between the surface-oxidized metal particle chain and SSZ is in the range of 0.1 to 10 in terms of mol ratio.

  The metal of the metal particle chain is preferably nickel (Ni) or Ni containing iron (Fe). More preferably, it contains a very small amount of titanium (Ti) of about 2 to 10000 ppm.

  The metal particle chain is preferably produced by a reduction precipitation method. The reduction precipitation method of the metal particle chain is described in detail in JP-A No. 2004-332047. The average diameter D of the metal particle chain contained in the first electrode layer (anode) 2 is preferably in the range of 5 nm to 500 nm. The average length L is preferably in the range of 0.5 μm or more and 1000 μm or less. The ratio of the average length L to the average diameter D is preferably 3 or more. However, it may have dimensions outside these ranges.

  The second electrode layer (cathode) 5 is formed from a fired body mainly composed of oxygen ion conductive ceramics. As the oxygen ion conductive ceramic in this case, LSM (lanthanum strontium manganite), LSC (lanthanum strontium cobaltite), SSC (samarium strontium cobaltite), or the like can be used. These powder materials can also be fired under the same conditions as described above.

  FIG. 6 shows a second embodiment of the present invention. In this embodiment, the heating promoting means 60 is configured by filling the gas induction pipe 11k with a porous metal body 60a having high thermal conductivity. In the present embodiment, the porous metal body 60a is arranged at a constant interval in the axial direction of the gas induction pipe 11k. In the present embodiment, similarly to the above-described embodiment, the heating promoting means 50 including the unevenness 50a is also provided on the inner peripheral portion of the gas induction pipe.

  As the porous metal body 60a, the above-mentioned Celmet (registered trademark: Sumitomo Electric Industries, Ltd.) can be used. The porous metal body 60a preferably has a high porosity in order to reduce pressure loss. For example, it is preferable to employ a cermet having a porosity of 90% or more.

  The porous metal body 60a has a high thermal conductivity and a large surface area. For this reason, by providing the heating promoting means 60 configured by filling the porous metal body 60a, heat exchange with the gas flowing in the gas induction pipe 11k is promoted, and the gas is efficiently heated. Can do. Therefore, the temperature of the gas acting on the first electrode layer 2 of the upper cylindrical MEA can be efficiently increased. As a result, the gas decomposition efficiency can be increased and the processing flow rate can be increased.

  The heating promoting means is not limited to the above-described embodiment, and various means that can increase the temperature of the gas flowing in the gas induction pipe can be adopted.

  In the above-described embodiment, the present invention is applied to a gas decomposition element for the purpose of gas abatement. However, the present invention can be applied to a gas decomposition element not intended for a gas abatement and a cylindrical MEA of an electrochemical reaction apparatus. For example, it can also be used for a cylindrical MEA constituting a fuel cell or the like.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated by the description of the scope of claims, and further includes meanings equivalent to the description of the scope of claims and all modifications within the scope.

Running cost is low, a small size, can provide a gas decomposition device at a low cost with a higher performance.

DESCRIPTION OF SYMBOLS 1 Solid electrolyte layer 2 1st electrode layer (anode)
5 Second electrode layer (cathode)
7 Tubular MEA
44 Sealing part 11k Gas induction pipe 43 Cylindrical flow path 50 Heating promotion means

Claims (9)

A cylindrical shape having a cylindrical solid electrolyte layer, a first electrode layer stacked on the inner periphery of the solid electrolyte layer, and a second electrode layer stacked on the outer periphery of the solid electrolyte layer A gas decomposing element comprising a MEA (Membrane Electrode Assembly),
A sealing portion formed by sealing one end of the cylindrical MEA;
A gas induction pipe that is inserted into the inner space of the cylindrical MEA from the other end side of the cylindrical MEA and forms a cylindrical channel with the inner peripheral surface of the cylindrical MEA;
The gas flowing in the gas induction pipe toward the sealing portion is caused to flow reversely by flowing out of the gas induction pipe in the vicinity of the sealing portion, and the cylindrical flow path is formed in the gas induction pipe. It is configured to act on the first electrode layer while flowing in the direction opposite to the flow and decompose .
Above the gas induction pipe, Rutotomoni provided heating acceleration means for promoting heat transfer by increasing the contact area between the fluidizing gas,
By disposing a conductive metal mesh sheet on the inner peripheral surface of the first electrode layer and connecting an end of the metal mesh sheet to the gas induction pipe in the vicinity of the sealing portion, A gas decomposition element in which an electrode layer and the gas induction pipe are electrically connected .   The gas decomposition element according to claim 1, wherein the heating accelerating means is configured by providing irregularities on an inner surface of the gas induction pipe.   The gas decomposition element according to claim 1, wherein the heating promoting means is configured by filling the gas induction pipe with a porous body having air permeability and thermal conductivity. The gas induction pipe is made of a conductive material,
The gas decomposing element according to any one of claims 1 to 3, wherein the gas decomposing element is electrically connected to the first electrode layer to constitute a current collector of the first electrode layer. The gas decomposition element according to any one of claims 1 to 4 , wherein a porous conductive layer is provided on the surface of the first electrode layer. At least one of the first electrode layer and the second electrode layer is a fired body including both a metal particle chain mainly composed of nickel (Ni) and an ion conductive ceramic. The gas decomposition element according to any one of claims 1 to 5 . The gas decomposition element according to any one of claims 1 to 6 , wherein the solid electrolyte layer has oxygen ion conductivity or proton conductivity. A power generator comprising the gas decomposition element according to any one of claims 1 to 7 . It has a cylindrical solid electrolyte layer, a first electrode layer formed on the inner periphery of the solid electrolyte layer, and a second electrode layer formed on the outer periphery of the solid electrolyte layer, and has one end portion Sealed tubular MEA (Membrane Electrode Assembly),
The cylindrical MEA is inserted into the inner space of the cylindrical MEA from the other end side of the cylindrical MEA to guide the gas to the vicinity of the sealing portion, and a cylindrical channel is formed between the cylindrical MEA and the inner peripheral surface thereof. A gas decomposition method performed by a gas decomposition element comprising a gas induction pipe to be formed,
A heating step of increasing the temperature of the gas flowing in the gas induction pipe by means of heating promotion provided in the gas induction pipe;
The gas is made to flow reversely by flowing out of the gas induction pipe in the vicinity of the sealing portion,
The first electrode layer while causing the gas to flow in a direction opposite to the flow in the gas induction pipe in a cylindrical flow path formed between the inner peripheral surface of the cylindrical MEA and the gas induction pipe. look including decomposing decomposition process is allowed to act on,
In the disassembling step, the metal mesh sheet is disposed on the inner peripheral surface of the first electrode layer, and an end portion of the metal mesh sheet is connected to the gas induction pipe in the vicinity of the sealing portion. A gas decomposition method , which is performed by electrically connecting a first electrode layer and the gas induction pipe .

Images