JP5742075B2 - Gas decomposition element, power generator - Google Patents

Description

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

  For example, ammonia is an indispensable compound for agriculture and industry, but is harmful to humans. Therefore, 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 a hypobromite solution or sulfuric acid. (Patent Document 1). In addition, a method of separating ammonia in the air and burning it with a catalyst in the same process as the above method (Patent Document 2) and a method of decomposing ammonia-containing wastewater into nitrogen and water using a catalyst have been proposed (patent) Reference 3). Further, 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 gases are 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 gas at low running cost without input of energy, chemicals, etc., a waste gas treatment method in a semiconductor manufacturing apparatus that decomposes ammonia with a phosphoric acid fuel cell has also been proposed (Patent Literature). 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, which increases the running cost.

  In addition, the apparatus becomes large and 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 device can be downsized. There was a problem that it 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.
On the other hand, 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.

  In order to improve the decomposition of the gas flowing in the cylindrical MEA, it is necessary to heat the gas to a high temperature. However, the more compact the cylindrical MEA, the more difficult the gas can be heated. was there.

  In addition, in the conventional cylindrical MEA, the connection member was connected to both ends, and the gas was configured to flow in the axial direction of the cylindrical MEA. However, since the entire cylindrical MEA is at a high temperature, there is a problem that the sealing performance between the both end portions of the cylindrical MEA and the connecting member is likely to deteriorate, and the connection reliability is low.

  Therefore, the present invention makes it possible to obtain a large processing capacity while suppressing running costs by utilizing an electrochemical reaction using a solid electrolyte, and to further improve the decomposition efficiency of the gas flowing in the cylindrical MEA. It is an object of the present invention to provide a gas decomposition element that can be produced and a power generation device including the gas decomposition element.

The gas decomposing element of the present invention that solves the above problems includes a cylindrical solid electrolyte layer, a first electrode layer laminated on the inner periphery of the solid electrolyte layer, and a laminate on the outer periphery of the solid electrolyte layer. A cylindrical MEA having a second electrode layer formed; and a first gas flow path for flowing a first gas to be decomposed inside the cylindrical MEA, and the cylindrical MEA. A gas decomposing element comprising a second gas flow path for flowing a second gas to the outside;
An alumina cylinder carrying Ni-YSZ on its surface as a gas decomposition promoting means for promoting decomposition by contacting the first gas flowing in the first gas flow path provided inside the cylindrical MEA , The first feature is that the gas is arranged in parallel with the flow of the first gas .
Here, MEA is an abbreviation of Membrane Electrode Assembly and can be translated as a membrane / electrode assembly, but MEA is also a technical term well known to those skilled in the art, and is used as it is.

According to the first feature of the present invention, the first gas to be decomposed is led to the first gas flow path of the gas decomposition element, where it is heated and heated for decomposition. The first gas flowing through the first gas flow path comes into contact with the gas decomposition promoting means arranged in the first gas flow path, so that more opportunities for decomposition are obtained and the decomposition efficiency is improved. As a result, even if the temperature of the first gas flowing through the first gas flow path is not raised to a sufficient reaction temperature due to the compactness of the apparatus or the like, the lack of temperature can be compensated by improving the decomposition efficiency. it can. Therefore, it is possible to compensate for the shortage of the heating temperature caused by increasing the gas supply amount of the first gas and the degradation of the decomposition efficiency, thereby ensuring efficient decomposition.
Therefore, according to the gas decomposition element according to the first feature of the present invention, the decomposition efficiency of the first gas subjected to decomposition can be improved. In addition, the processing capacity can be increased by increasing the flow rate of the first gas. In addition, the gas decomposition element can be made more compact in its length.

Since or gas decomposition accelerating means is alumina tube, the first gas can be contacted with a Naru sufficient contact area in the cylindrical inner and outer surfaces of the porous alumina tube in the first gas flow path. Thereby, the heat which an alumina cylinder has can be given to 1st gas, and the temperature rise of 1st gas can be aimed at.
Since the gas decomposition promoting means has a cylindrical shape and is arranged in parallel with the first gas flow in the first gas flow path, the pressure loss with respect to the first gas flow can be reduced.
Since Ni—YSZ can move electrons and oxygen ions, it can react in cooperation with the first electrode layer of the MEA. Moreover, since YSZ inhibits the aggregation of Ni, the life of the catalyst can be extended.

The gas decomposition element of 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 first electrode layer formed on the outer periphery of the solid electrolyte layer. A cylindrical MEA having two electrode layers, a first gas flow path for flowing a first gas used for decomposition inside the cylindrical MEA, and a second outside the cylindrical MEA. A gas decomposing element comprising a second gas flow path for flowing the gas,
Gas decomposition promoting means for promoting decomposition by contacting the flowing first gas is disposed in a first gas flow path provided inside the cylindrical MEA, and one end of the cylindrical MEA is connected to the first gas flow path. A sealing portion for sealing is provided, and a cylindrical flow path is formed between the inner end surface of the cylindrical MEA by being inserted into the inner space of the cylindrical MEA from the other end side of the cylindrical MEA. A first 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 cylinder The first gas flow path is configured so as to flow in a direction opposite to the flow in the induction pipe, and Ni as a gas decomposition promoting means is formed in the inner space of the gas induction pipe. -Multiple alumina cylinders carrying YSZ, dense That are arranged on state is set to the second feature.
According to the second aspect of the present invention, the first gas to be decomposed is led to the first gas flow path of the gas decomposition element, where it is heated and heated for decomposition. The first gas flowing through the first gas flow path comes into contact with the gas decomposition promoting means arranged in the first gas flow path, so that more opportunities for decomposition are obtained and the decomposition efficiency is improved. As a result, even if the temperature of the first gas flowing through the first gas flow path is not raised to a sufficient reaction temperature due to the compactness of the apparatus or the like, the lack of temperature can be compensated by improving the decomposition efficiency. it can. Therefore, it is possible to compensate for the shortage of the heating temperature caused by increasing the gas supply amount of the first gas and the degradation of the decomposition efficiency, thereby ensuring efficient decomposition.
Therefore, according to the gas decomposition element according to the second feature of the present invention, it is possible to improve the decomposition efficiency of the first gas subjected to decomposition. In addition, the processing capacity can be increased by increasing the flow rate of the first gas. In addition, the gas decomposition element can be made more compact in its length.

Further , the gas to be decomposed is caused to flow in the gas induction pipe toward one end side where the sealing portion is provided, and is reversely flowed in the vicinity of the sealing portion. A cylindrical flow path formed between the cylindrical MEA and the inner peripheral surface is allowed to flow in the opposite direction to the flow in the gas induction pipe.
Therefore, the first gas can flow a distance twice as long as the cylinder length of the cylindrical MEA. For this reason, after it is heated enough in the induction pipe to raise the temperature, it can act on the 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.
In addition, since the gas decomposition promoting means, such as Ni-YSZ, is disposed in the inner space of the inserted gas guide pipe, the decomposition efficiency of the first gas can be further enhanced in synergy. .

The Ni-YSZ is preferably carried on the inner and outer surfaces of the gas induction pipe. Thereby, the movement of electrons and oxygen ions with the first electrode layer of the MEA can be ensured, and the decomposition efficiency of the first gas can be further improved.

In addition, according to the second feature, the part where the first gas enters and exits the cylindrical MEA can be provided concentrated on one end of the cylindrical MEA. For this reason, the reliability of the seal | sticker between the said cylindrical MEA and gas piping can be improved.
The gas inlet / outlet in the cylindrical MEA can be configured with a piping member having a double structure so that the first gas before decomposition and the first gas after decomposition do not mix.

The structure which seals the one end part of the said cylindrical MEA is not specifically limited. For example, as in the invention described in the seventh feature described later, one end of the cylindrical MEA can be sealed with a bottom formed by extending the solid electrolyte layer integrally. Since the bottom is integrally formed with the cylindrical MEA, there is no risk of gas leaking, and one end of the cylindrical MEA can be reliably sealed.
Moreover, like the invention described in the eighth feature described later, one end portion of the cylindrical MEA can be sealed by fitting a sealing member to the end portion of the cylindrical MEA. By adopting this configuration, the present invention can be applied to a conventional cylindrical MEA having both ends opened.

In addition, by arranging the alumina cylinder carrying Ni-YSZ in a dense state in the inner space of the gas induction pipe, a sufficient contact area between the first gas and the alumina cylinder carrying Ni-YSZ is secured, and the gas Decomposition efficiency can be maximized. Of course, the dense state can suppress the free movement of the alumina cylinder and ensure the stability of the position. Further, the pressure loss can be made smaller than other structures having the same surface area.

The gas decomposition device of the present invention, in addition to the second characteristics, the into the above gas guiding pipe, which are constitute positioning portions for determining the position of the alumina tube carrying the Ni-YSZ This is the third feature.
According to the third feature, in addition to the operation and effect of the second feature, when a plurality of alumina cylinders are inserted and fixed in the gas guide pipe, the positioning portion configured in the gas guide pipe is used. Thus, the alumina cylinder can be positioned at a predetermined position. Therefore, the alumina cylinder can be easily, easily and reliably inserted, arranged and fixed.
The fixing can be performed by bonding and fixing with a ceramic adhesive or Ni paste.

Further, in the gas decomposition element of the present invention, in addition to the second or third feature, the gas induction pipe is formed of a conductive material, and is electrically connected to the first electrode layer. The fourth feature is that the current collector of the first electrode layer is configured .

According to the fourth feature, in addition to the operation and effect of the second or third feature, the gas induction pipe is used as a current collector for the first electrode layer, thereby improving the gas decomposition efficiency. In addition, the space in the cylindrical MEA can be effectively utilized.
In addition, although the material which comprises a gas induction pipe is not specifically limited, It is necessary to form with the material which corrosion etc. do not produce with the gas to decompose | disassemble. For example, it can be formed using an alloy containing iron, chromium, niobium, molybdenum and the like based on Ni such as stainless steel, copper, nickel, inconel and inconel.

The method for connecting the first electrode layer and the gas induction pipe is not particularly limited. For example, a porous metal body 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 gas induction pipe are connected. It can be made conductive. Also, by providing the porous metal body, the gas induction pipe can be held in the cylindrical MEA, and the inner peripheral surface of the first electrode layer and the outer peripheral surface of the gas induction pipe A cylindrical channel between them can be secured.

The gas decomposition element of 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 first electrode layer formed on the outer periphery of the solid electrolyte layer. A cylindrical MEA having two electrode layers, a first gas flow path for flowing a first gas used for decomposition inside the cylindrical MEA, and a second outside the cylindrical MEA. A gas decomposing element comprising a second gas flow path for flowing the gas,
Gas decomposition promoting means for promoting decomposition by contacting the flowing first gas is disposed in a first gas flow path provided inside the cylindrical MEA, and one end of the cylindrical MEA is connected to the first gas flow path. A sealing portion for sealing is provided, and a cylindrical flow path is formed between the inner end surface of the cylindrical MEA by being inserted into the inner space of the cylindrical MEA from the other end side of the cylindrical MEA. A first 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 cylinder The first gas flow path is configured to flow in a direction opposite to the flow in the induction pipe, and the gas decomposition is promoted in the inner space of at least a part of the gas induction pipe. Means for disposing the first electrode layer A conductive metal mesh sheet is disposed on the inner peripheral surface, and the metal mesh sheet is connected to the gas induction pipe to thereby establish electrical connection between the first electrode layer and the gas induction pipe. 5 features.
According to the fifth aspect of the present invention, the first gas to be decomposed is led to the first gas flow path of the gas decomposition element, where it is heated and heated for decomposition. The first gas flowing through the first gas flow path comes into contact with the gas decomposition promoting means arranged in the first gas flow path, so that more opportunities for decomposition are obtained and the decomposition efficiency is improved. As a result, even if the temperature of the first gas flowing through the first gas flow path is not raised to a sufficient reaction temperature due to the compactness of the apparatus or the like, the lack of temperature can be compensated by improving the decomposition efficiency. it can. Therefore, it is possible to compensate for the shortage of the heating temperature caused by increasing the gas supply amount of the first gas and the degradation of the decomposition efficiency, thereby ensuring efficient decomposition.
Therefore, according to the gas decomposition element according to the fifth feature of the present invention, the decomposition efficiency of the first gas subjected to decomposition can be improved. In addition, the processing capacity can be increased by increasing the flow rate of the first gas. In addition, the gas decomposition element can be made more compact in its length.
Further, the gas to be decomposed is caused to flow in the gas induction pipe toward one end side where the sealing portion is provided, and is reversely flowed in the vicinity of the sealing portion. A cylindrical flow path formed between the cylindrical MEA and the inner peripheral surface is allowed to flow in the opposite direction to the flow in the gas induction pipe.
Therefore, the first gas can flow a distance twice as long as the cylinder length of the cylindrical MEA. For this reason, after it is heated enough in the induction pipe to raise the temperature, it can act on the 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.

In addition, since Ni-YSZ or the like, which is the gas decomposition promoting means, is disposed in the inner space of at least a part of the inserted gas induction pipe, the decomposition efficiency of the first gas is further increased in synergy. Can be increased.
The Ni-YSZ is preferably carried on the inner and outer surfaces of the gas induction pipe. Thereby, the movement of electrons and oxygen ions with the first electrode layer of the MEA can be ensured, and the decomposition efficiency of the first gas can be further improved.
In addition, according to the fifth feature, the portion where the first gas enters and exits the cylindrical MEA can be provided concentrated on one end of the cylindrical MEA. For this reason, the reliability of the seal | sticker between the said cylindrical MEA and gas piping can be improved.
The gas inlet / outlet in the cylindrical MEA can be configured with a piping member having a double structure so that the first gas before decomposition and the first gas after decomposition do not mix.
The structure which seals the one end part of the said cylindrical MEA is not specifically limited. For example, as in the invention described in the seventh feature described later, one end of the cylindrical MEA can be sealed with a bottom formed by extending the solid electrolyte layer integrally. Since the bottom is integrally formed with the cylindrical MEA, there is no risk of gas leaking, and one end of the cylindrical MEA can be reliably sealed.
Moreover, like the invention described in the eighth feature described later, one end portion of the cylindrical MEA can be sealed by fitting a sealing member to the end portion of the cylindrical MEA. By adopting this configuration, the present invention can be applied to a conventional cylindrical MEA having both ends opened.

In addition , a conductive mesh sheet is disposed on the inner peripheral surface of the first electrode layer, and the metal mesh sheet is connected to the gas induction pipe, whereby the first electrode layer, the gas induction pipe, Can be conducted.
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, by directly connecting the metal mesh sheet to the gas induction pipe, the contact resistance with the current collector can be reduced. For example, one metal mesh sheet can be disposed so as to be in contact with the entire inner peripheral surface of the first electrode layer.
Further, by adopting the above configuration, it is possible to increase the area of the current collector by using the gas induction pipe, and the gas decomposition efficiency can be further increased.

Further the multi porosifying metal body, is inserted between the inner and the gas conducting pipe of the metal mesh sheet, with the configuration to back up the metal mesh sheet from the inside, the first electrode layer and the current The contact resistance between the electric body 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. Further, a metal mesh sheet having a silver plating layer or the like formed on the surface layer can also 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.

In addition to any one of the first to fifth features, the gas decomposition element of the present invention has a sixth feature that a porous conductive layer is provided on the surface of the first electrode layer.
According to the sixth feature, in addition to the function and effect of any one of the first to fifth features, the conductive layer is formed on the surface of the first electrode layer, whereby the first electrode Conductivity between the layer and the mesh sheet can be ensured throughout. Further, since the conductive layer is porous, it does not hinder gas contact with each 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, the contact pressure between the surface of the first electrode layer and the metal mesh sheet may be different, or a part of the contact pressure may rise from the surface of the first electrode layer. By providing a porous conductive layer on the surface of the first electrode layer, such a situation can be prevented.

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. In addition, the electrical resistance between the first electrode layer and the metal mesh sheet 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. Further, the entire surface of the metal mesh sheet can be brought into uniform contact 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 ensured. It becomes possible to do. 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. Moreover, 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 treatment 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. In addition, it is stable and hardly oxidizes.

Further, in addition to any one of the second to sixth features, the gas decomposition element of the present invention has one end of the cylindrical MEA sealed with a bottom formed by extending the solid electrolyte layer integrally. The seventh feature is that it is stopped.
According to the seventh feature, in addition to the function and effect of any one of the second to sixth features, the solid electrolyte layer is formed in a cylindrical shape with a bottom so that one end is The sealed cylindrical MEA can be configured very simply. Therefore, the gas flow path in the gas decomposition element can be easily reversed.

Further, in addition to any one of the second to sixth features, the gas decomposition element of the present invention has one end of the cylindrical MEA sealed by fitting a sealing member to the end of the cylindrical MEA. The eighth feature is that it is stopped.
According to the eighth feature, in addition to the operation and effect of any one of the second to sixth features, a separate sealing member is fitted to seal one end of the cylindrical MEA. Thus, the solid electrolyte layer of the cylindrical MEA can be used as it is, and the manufacturing of the cylindrical MEA is easy.

Further, in the gas decomposition element of the present invention, in addition to any one of the first to eighth features, the first electrode layer and / or the second electrode layer is mainly composed of nickel (Ni). The ninth feature is that it is a fired body containing a chain of metal particles and an ionic conductive ceramic.
Here, the metal particle chain refers to a bead-like elongated metal body formed by continuous metal particles.
The metal particle chain is preferably Ni, Fe-containing Ni, or Ni, Fe-containing Ni containing a trace 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 (it may be 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, for example, a proton is generated in the first electrode layer (anode), and the second electrode layer ( The cation is moved to the cathode), and the above-described acceleration effect by the charge can be obtained in the same manner.
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 the gas molecules in the gas led to () 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. Similarly to (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, as in the case of being included in the second electrode layer (cathode), the electrochemical reaction involving charge transfer in the second electrode layer (cathode) can be accelerated as a whole. 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 increasing the temperature, not only the ion transfer rate but also a chemical reaction involving 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 gas decomposition element of the present invention has a tenth feature that, in addition to any one of the first to ninth features, the solid electrolyte layer has oxygen ion conductivity or proton conductivity.
According to the tenth feature, in addition to the function and effect of any one of the first to ninth features, when an oxygen ion conductive solid electrolyte layer is used, for example, the second electrode layer (cathode) ) Reacts electrons with oxygen molecules to generate oxygen ions, which can move the solid electrolyte layer to cause a predetermined electrochemical reaction in the first 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 (BaZrO3) is known as a proton conductive solid electrolyte layer. When a proton conductive solid electrolyte layer is used, for example, ammonia is decomposed in the first electrode layer (anode) to generate protons, nitrogen molecules and electrons, and the protons are passed through the solid electrolyte layer to form the second electrode layer. It moves to (cathode) and reacts with oxygen in the second electrode layer (cathode) to produce water (H 2 O). Since protons are small compared to oxygen ions, the moving speed in the solid electrolyte layer is large, so that a practical decomposition level 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.

Moreover, in addition to any one of the first to tenth features, the power generation device of the present invention further includes a heater for heating the entire device, and the gas decomposition element. An eleventh feature is that a preheating pipe for preliminarily heating the first gas guided to the flow path is provided.

According to the eleventh feature, in addition to the operation and effect of any one of the first to tenth features, the first gas used for decomposition is the first gas flow path of the gas decomposition element. Is led to a preheating pipe, and is preheated by a heater there. Then, since the first gas that has been preheated is guided to the first gas flow path, the heating to the predetermined temperature in the first gas flow path is performed efficiently and promptly.
Therefore, the decomposition efficiency of the first gas can be improved. In addition, the processing capacity can be increased by increasing the flow rate of the first gas. In addition, the gas decomposition element can be made more compact in its length.

A twelfth feature of the power generator of the present invention is that it includes the gas decomposition element according to any one of the first to eleventh features.
According to the power generation device of the twelfth feature, it is possible to obtain a power generation using gas decomposition that exhibits the function and effect of the gas decomposition element according to any one of the first to eleventh features, that is, a fuel cell. it can.

  By the way, the gas to be decomposed is not particularly limited. For example, any one of the gas decomposition elements described above is used, a gas containing ammonia is used as the first gas supplied to the first electrode layer, and oxygen molecules are used as the second gas supplied to the second electrode layer. A gas containing can be employed. 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 in the first electrode layer are catalyzed by the metal particle chain. By reacting under the action and the accelerating action by ions, electrons generated as a result of the reaction can be moved quickly.

  The gas decomposing element and the power generation device according to the present invention are intended to decompose and detoxify harmful gases contained in exhaust gas etc., and also to the fields of fuel cells using fuel gas and unique electrochemical reaction devices using gas decomposition Thus, it is possible to contribute to obtaining downsizing, high efficiency, low running cost and the like of the apparatus.

  A gas decomposing element having a low running cost and high gas decomposing efficiency, and a power generation apparatus including the gas decomposing element can be provided.

It is a longitudinal cross-sectional view which shows the front end side (sealing side) of the gas decomposition element which concerns on the 1st Embodiment of this invention. It is a cross-sectional block diagram which follows the II 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 block diagram by the side of the 1st gas entrance / exit of the gas decomposition element shown in FIG. It is a longitudinal cross-section block diagram which shows the modification of the front end side (sealing side) of the gas decomposition element which concerns on the 1st Embodiment of this invention. FIG. 2 shows a gas decomposition element according to a second embodiment of the present invention, and FIG. 2 is a cross-sectional configuration diagram of a single gas decomposition element, whereas a cross section of a gas decomposition element as a plurality of gas decomposition element groups A block diagram is shown. It is a section lineblock diagram explaining the concrete arrangement of the gas decomposition promotion means used for the gas decomposition element concerning the 1st and 2nd embodiment of the present 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 a first embodiment of the present invention. 2 is a cross-sectional view taken along the line II in FIG. In the present embodiment, a gas decomposition element in the case where the first gas used for decomposition is an ammonia-containing 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.
In the present embodiment, as described above, the ammonia-containing gas flows as the first gas inside the cylindrical MEA 7 (1, 2, 5). In addition, air that is an oxygen-containing gas flows as the second gas outside the cylindrical MEA 7 (1, 2, 5). The flow path inside the cylindrical MEA 7 (1, 2, 5) through which the first gas flows is defined as a first gas flow path. The flow path outside the cylindrical MEA 7 (1, 2, 5) through which the second gas flows is defined as a second gas flow path.
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 7 (1, 2, 5) 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 7 (1, 2, 5) is sealed and the above-described Ni such as stainless steel, copper, nickel, Inconel, etc. is used as a base from the other end. A gas induction pipe 11k made of an alloy containing iron, chromium, niobium, molybdenum or the like, that is, a material having heat resistance to 600 to 1000 ° C. and ammonia gas corrosion resistance is inserted. The one end portion is provided with a sealing portion 44 by extending the solid electrolyte layer 1 and the inner electrode layer 2 of the cylindrical MEA 7 (1, 2, 5) and providing a bottom portion.

  The gas induction pipe 11k is inserted from the other end portion side of the cylindrical MEA 7 (1, 2, 5) toward the sealing portion 44 side which is the one end portion. A cylindrical flow path 43 is set between the inner peripheral surface of the electrode layer 2 and the outer peripheral surface of the gas induction pipe 11k. 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 peripheral surface.

In the gas decomposition element 10 according to the present embodiment, the first gas is caused to flow toward the sealing portion 44 in the internal space 42 of the gas guiding pipe 11k, and the gas guiding pipe is disposed in the vicinity of the sealing portion 44. The first gas is allowed to flow out from the inside of 11k and reversed, and the first gas is caused to flow in the direction opposite to the flow in the internal space 42 through the cylindrical flow path 43.
The internal space 42 and the cylindrical flow path 43 constitute the first gas flow path.

  By adopting the above-described configuration, the gas can be used as the first gas flow path in the space inside the cylindrical MEA 7 at a distance approximately twice the cylinder length of the cylindrical MEA 7. For this reason, it is heated in the gas induction pipe 11k and acts on the cylindrical MEA 7 in a state where the temperature is raised. Therefore, the decomposition efficiency of the first gas can be increased, and the gas flow rate can be increased to increase the gas throughput.

In the embodiment of the present invention, the gas decomposition promoting means 71 is disposed in the first gas flow path configured inside the cylindrical MEA 7. The gas decomposition promoting means 71 is a means for promoting the decomposition of the first gas by coming into contact with the first gas flowing through the first gas flow path.
As the gas decomposition promoting means 71, specifically, an alumina cylinder carrying Ni-YSZ on its surface is used.
Further, the gas decomposition promoting means 71 made of an alumina cylinder carrying Ni-YSZ on its surface has an inner space of at least a part of the gas induction pipe 11k in the first gas flow path, that is, the inner space 42. Arranged in at least one part. Ni-YSZ is a cermet that is a mixture of nickel and yttria stabilized zirconia.
Further, the gas decomposition promoting means 71 is arranged so as to be parallel to the flow of the first gas.
By configuring the gas decomposition promoting means 7 with an alumina cylinder, the first gas can be brought into contact with the porous inner surface of the alumina cylinder with a sufficient contact area in the first gas flow path. Thereby, the heat which an alumina cylinder has can be given to 1st gas, and the temperature rise of 1st gas can be aimed at. Further, since the gas decomposition promoting means 71 has a cylindrical shape and is arranged in parallel with the flow of the first gas in the first gas flow path (internal space 42), the pressure loss with respect to the flow of the first gas is reduced. Can be small.
Moreover, since YSZ inhibits the aggregation of Ni, the life of the catalyst can be extended.

The Ni—YSZ is preferably supported on the inner surface and the outer surface of the alumina cylinder in order to increase the contact area with the first gas. Ni-YSZ is preferably carried on the inner surface and the outer surface of the gas induction pipe 11k.
The Ni—YSZ support need not necessarily be an alumina cylinder. It is possible to use one having a fin having a large surface area other than a cylindrical shape.
The alumina cylinder is excellent in heat resistance, corrosion resistance and porosity, and is good for supporting Ni-YSZ, but other metal and ceramic cylinders having excellent heat resistance and corrosion resistance are also possible.
The Ni-YSZ is a metal material (Ni, Fe, etc.) or a composite material (NiFe, NiCu, NiCr, etc.) and a heat-resistant and corrosion-resistant material (YSZ, alumina, silica, etc.) that assists the decomposition of ammonia and can move electrons. Etc.) can be used. Moreover, you may add noble metals, such as Pt and Ru, alkalis, alkaline earths, and rare earth metals, such as K, Li, Na, and Ca.

Referring to FIG. 7, when an alumina cylinder (gas decomposition promoting means 71) carrying Ni-YSZ on its surface is arranged in the inner space of the gas induction pipe 11k, a plurality of alumina cylinders which are the gas decomposition promoting means 71 are arranged. Is preferably densely arranged in the inner space of the gas induction pipe 11k. By arranging the alumina cylinders densely, a sufficient contact area with the first gas can be secured, and the gas decomposition efficiency can be maximized. Of course, the dense state can suppress the free movement of the alumina cylinder and ensure the stability of the position.
When an alumina cylinder carrying Ni-YSZ as the gas decomposition promoting means 71 is disposed in the interior of the gas induction pipe 11k, the positioning part 11k1 can be configured in advance in the gas induction pipe 11k. . The positioning portion 11k1 can be configured, for example, by narrowing the inner diameter of the gas guide pipe 11k so as to be an inwardly protruding line.
By providing the positioning portion 11k1, it is possible to easily, simply and reliably insert, arrange, and fix the alumina cylinder as the gas decomposition promoting means 71 at a predetermined position. Fixing can be performed by bonding and fixing with a ceramic adhesive or Ni paste.

The cylinder diameter, length, and several of the Ni-YSZ-supported alumina cylinder (gas decomposition promoting means 71) disposed in the internal space 42 that is the inner space of the gas induction pipe 11k are not particularly limited. However, for example, when the diameter of the gas induction pipe 11k is 8 to 10 mm, the diameter of the alumina cylinder can be 2 to 3 mm.
The diameter, length, number, etc. of the cylinders are determined in consideration of the diameter, length, etc. of the gas induction pipe 11k, and from the viewpoint of increasing the reaction area by increasing the contact area with the first gas. The relationship with the increase in pressure loss will be optimal.

  The gas induction pipe 11k is made of a conductive metal such as SUS, and is configured to function as a component of the anode 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 distal portion W ₁ of the Ni mesh sheet 11a is in the vicinity of the sealing portion 44 is conductively connected to wind through the bonding member W ₂ of the band-on the outer periphery of the gas guiding pipe 11k. 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 prevent an increase in pressure loss while being located on the inner surface of the cylindrical MEA 7 and maintaining a low electrical resistance.

  As the porous metal body 11s, in order to reduce the pressure loss of the first gas, it is preferable to use a metal plated body that can increase the porosity, such as 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 contacts the outer surface of the cylindrical MEA 7 and conducts to the external wiring 12e.
The silver paste coated wiring 12g contains silver that acts as a catalyst for promoting the decomposition of oxygen in the oxygen-containing gas (air), which is the second gas, into oxygen ions in the second electrode layer (cathode) 5. In addition, this contributes to lowering the electrical resistance of the cathode current collector 12.
The silver paste coated wiring 12g has a catalytic action equivalent to that of the silver particles contained in the second electrode layer (cathode) 5 by contacting the silver particles with the second electrode layer (cathode) 5 while passing oxygen molecules. To express. Moreover, it is less expensive than the inclusion in the second electrode layer (cathode) 5.

A space S for flowing the second gas is provided outside the cylindrical MEA 7 (1, 2, 5). The outside of the space S is covered with the entire outer body 51 with the cylindrical MEA 7. A heater 52 is disposed outside the exterior body 51.
In the space S, a preheating pipe 53 is disposed so as to penetrate the exterior body 51.

The heater 52 is for heating the entire element. The heater 52 heats the entire gas decomposition element 10 to a temperature suitable for the decomposition of the first gas.
The preheating pipe 53 is a pipe for preheating the first gas. By passing the first gas through the preheating pipe 53 before being introduced into the cylindrical MEA 7, the first gas is preheated, and the first gas having a low temperature is suddenly introduced into the cylindrical MEA 7. To eliminate the lack of reaction. As a result, it is possible to improve the decomposition performance and make the gas decomposition element 10 compact.
The preheating pipe 53 includes a connection end 53a connected to the pipe from the first gas source, and the downstream side is connected to the gas introduction pipe 45.
As the preheating pipe 53, a heat-resistant pipe such as a Ni pipe, an Inconel pipe, or other metal or ceramic heat-resistant or corrosion-resistant pipe can be used.
Although only one preheating pipe 53 is shown in FIG. 1, a plurality of preheating pipes 53 may be provided.
The exterior body 51 is made of a heat-resistant material, but may be made of a refractory material to be thick and have a heater 52 embedded therein. Moreover, it can also be set as the structure which embed | buried and penetrated the preheating piping 53 in the thickness of the exterior body 51 which consists of a thick refractory material.
Originally, the heater 52 for heating the cylindrical MEA 7 is also used, and the preheating pipe 53 is heated by the heater 52, so that the first gas used for decomposition is preheated well. .

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 first gas containing ammonia passes through the preheating pipe 53, and then passes through the gas induction pipe 11k to the innermost part of the inner cylinder of the cylindrical MEA 7 with strict airtightness, that is, the sealing part. It is guided to the vicinity of 44. The entire cylindrical MEA 7 is heated to about 800 ° C. by the heater 52, and the temperature of the first gas is raised while flowing in the gas induction pipe 11k. During this time, ammonia in the first gas is decomposed as 2NH ₃ → N ₂ + 3H ₂ by heating in the gas induction pipe 11k.

  When the cylindrical MEA 7 is used, the porous metal body 11s is used to pass the first gas containing the decomposition gas on the inner surface side and hold the gas induction pipe 11k. From the viewpoint of reducing the pressure loss, 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-described Celmet can be used. The first gas containing ammonia flows through the first gas flow path from the internal space 42 into the cylindrical flow path 43, and the porous metal body 11s, the Ni mesh sheet 11a, and the porous silver paste coating layer The following ammonia decomposition reaction is performed in contact with the first electrode layer (anode) 2 while passing through the 11 g gap.

Oxygen ions O ²⁻ are generated by an oxygen gas decomposition reaction at 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) 2, 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 second electrode layer (cathode), 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 52 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 52 may be partial. In many cases, the supply amount of private power generation is less than half of the electric power required for the entire heater 52.

  In the gas decomposition element 10, in the first electrode layer (anode) 2 on the inner surface side of the cylindrical MEA 7, the pressure loss of the first gas passing through the anode-side current collector 11 is lowered while the electrical resistance of the anode-side current collector 11 is lowered. Is important. Further, on the second electrode layer (cathode) 5 side, the contact portion between the second gas, air, and the second electrode layer (cathode) 5 is densified to reduce the resistance of the cathode-side current collector 12. It is important to do.

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 proton conductive solid electrolyte layer 1 is used, for example, when ammonia in the first gas is decomposed, ammonia is decomposed at first electrode layer (anode) 2 to generate protons, nitrogen molecules, and electrons. Then, protons move to the second electrode layer (cathode) 5 through the solid electrolyte layer 1 and react with oxygen in the second electrode layer (cathode) 5 to generate water (H ₂ O). Since protons are smaller than oxygen ions, the moving speed in the solid electrolyte layer 1 is large. Therefore, a practical decomposition capacity can be obtained while lowering the heating temperature. The thickness of the solid electrolyte layer 1 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 and the gas introduction pipe 45 and the exhaust pipe 65. These connections are made through a pipe joint 30 made of fluororesin.

  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 of the pipe joint 30 to the solid electrolyte layer 1 contacts the outer surface of the ceramic solid electrolyte layer 1 that is a fired body. Connected in contact. 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 screwing in the direction in which the outer diameter of the annular screw 32 is increased, the fastening portion 31b is fastened from the outer surface, and the airtightness by the O-ring 33 can be adjusted.

  On the inner side of the pipe joint 30, there is provided a fitting portion 36 that can be fitted to the proximal end portion 11d of the gas guiding pipe 11k with airtightness. Thereby, the gas induction pipe 11k and the pipe joint 30 are connected, and the first gas passage is formed.

  The pipe joint 30 is provided with a gas introduction part 31 a for connecting to the gas introduction pipe 45 for the first gas. By fitting the end of the gas introduction pipe 45 to the outer periphery of the gas introduction part 31 a of the pipe joint 30 and fastening with the fastener 47, an airtight connection can be obtained. The first gas flows from the gas introduction pipe 45 through the gas introduction part 31a into the gas induction pipe 11k. The first gas that has flowed into the gas induction pipe 11k flows through the internal space 42 to the vicinity of the sealing portion 44 of the cylindrical MEA 7.

  Further, the pipe joint 30 is provided with a gas discharge part 31 c for connecting to the exhaust pipe 65. By fitting the end of the exhaust pipe 65 to the outer periphery of the gas discharge part 31 c of the pipe joint 30 and fastening it with the fastener 67, a highly airtight connection can be obtained. The first gas that has passed through the cylindrical MEA 7 is discharged to the exhaust pipe 65 through the exhaust space 35 in the pipe joint 30 and the gas discharge portion 31c.

  By adopting the pipe joint 30 as described above, the first gas before decomposition and the first gas after decomposition do not mix, and the first position from the same side of the cylindrical MEA 7 is the first. It is possible to enter and exit the gas.

  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 11e and the connection between the pipe joint 30, the gas introduction pipe 45 and the exhaust pipe 65 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 52. For this reason, it becomes possible to ensure long-term repeated durability with 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 a silver paste coating in which the Ni mesh sheet 11a is the porous conductive layer is provided. It is connected to the first electrode layer 2 through the layer 11g.

A 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 cause an anodic reaction. It becomes easy.

  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 20% or less, it becomes difficult to guide the gas into the conductive paste coating layer, and the efficiency cannot be increased. On the other hand, when the porosity is 80% or more, 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 5 μm or less, the entire area of the Ni mesh sheet 11a cannot be uniformly brought into contact with the silver paste coating layer 11g, and it is difficult to ensure sufficient conductivity. On the other hand, when the thickness is 300 μm or more, it is 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 type 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 12a is separated from the silver paste coating layer 11g, the first electrode layer ( The current collecting performance in the anode 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 to 1000 μm. The ratio between the average length L and 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. 5 shows a modification of the distal end side (sealing side) of the gas decomposition element according to the first embodiment of the present invention. In this modification, the sealing member 44 is used to seal one end of the cylindrical MEA 7 to form the sealing portion 44. Since the configuration other than the sealing portion 44 is the same as that of the first embodiment, the description thereof is omitted.

  The sealing member 60 is formed of a heat-resistant resin such as Teflon (registered trademark) resin, and a side wall 60a that can be fitted to the outer periphery of the solid electrolyte layer 1 and one side of the side wall 60a. And a bottom portion 60b to be sealed.

  The O-ring 63 housed on the inner surface side of the side wall portion 60a is connected so as to maintain a state in which the O-ring 63 is in contact with the outer surface of the ceramic solid electrolyte layer 1 as a fired body. The outer side of the side wall 60a has a tapered outer diameter, and a screw is cut there, and an annular screw 62 is screwed into the screw. By screwing the annular screw 62 in the direction in which the outer diameter increases, the side wall portion 60c is tightened from the outer surface, and the airtightness by the O-ring 63 can be adjusted.

  By employ | adopting the said structure, the gas decomposition element 10 which concerns on this invention can be easily comprised using the cylindrical MEA7 by which both ends were opened.

  In the embodiment described above, 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 gas abatement and a tubular 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.

FIG. 6 shows a gas decomposition element according to the second embodiment of the present invention. In FIG. 6, the gas decomposition element as a plurality of gas decomposition element groups is shown by the cross-sectional block diagram.
In the gas decomposition element 100 according to the second embodiment, an exterior body 101, a heater 102, and a preheating pipe 103 are provided in common with respect to an arrangement in which a plurality of gas decomposition elements 10 are arranged in parallel as a group. Thus, one gas decomposition element 100 is obtained. Therefore, the gas decomposition element 100 does not include the heater 102 and the preheating pipe 103 for each gas decomposition element 10. This is different from the gas decomposing element 10 of the first embodiment in which the heater 52 and the preheating pipe 53 are individually provided.
In the present embodiment, the exterior body 101 is made of a refractory material, and the heater 102 and the preheating pipe 103 are embedded therein.
The preheating pipe 103 may be provided so as to penetrate the space S inside the exterior body 101. Further, a plurality of preheating pipes 103 may be provided corresponding to the number of arrangements of the individual gas decomposition elements 10. Since the supply amount of the first gas increases as the number of gas decomposition elements 10 increases, it is preferable to increase the number of corresponding preheating pipes 103. Alternatively, the preheating pipe 103 with a larger diameter may be used.
As the heater 102, the outer package 101 itself can be used as a heater.

  It is possible to provide a gas decomposition element and a power generation device that are low in running cost, small in size, and have higher performance.

DESCRIPTION OF SYMBOLS 1 Solid electrolyte layer 2 1st electrode layer (anode)
5 Second electrode layer (cathode)
7 Tubular MEA
DESCRIPTION OF SYMBOLS 10 Gas decomposition element 11 Anode side collector 11a Ni mesh sheet | seat 11d Base end part 11e External wiring 11g Silver paste application layer 11k Gas induction pipe 11k1 Positioning part 11s Porous metal body 12 Cathode side collector 12a Ni mesh sheet 12g Silver Paste wiring 12e External wiring 30 Pipe joint 31 Main body 31a Gas introduction part 31b Fastening part 31c Gas discharge part 32 Annular screw 33 O-ring 34 Fastening tool 35 Exhaust space 36 Fitting part 37a Other end part 37b Conductive wire 37c Conductive penetration part 38 Sealing resin 39 Nut 42 Internal space 43 Cylindrical flow path 44 Sealing part 45 Gas introduction pipe 46 Exhaust space 47 Fastener 51 Exterior body 52 Heater 53 Preheating pipe 53a Connection end 60 Sealing member 60a Side wall part 60b Bottom part 60c Side wall 62 Ring screw 63 O-ring 65 Exhaust pipe 67 Fastener 71 Gas decomposition accelerating means 100 Gas decomposition element 101 Exterior body 102 Heater 103 Preheating piping S space W ₁ Ni mesh sheet tip W ₂ bonding member

Claims (12)

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 second gas flow including an MEA, a first gas flow path for flowing a first gas used for decomposition inside the cylindrical MEA, and a second gas flowing outside the cylindrical MEA A gas decomposing element with a path,
An alumina cylinder carrying Ni-YSZ on its surface as a gas decomposition promoting means for promoting decomposition by contacting the first gas flowing in the first gas flow path provided inside the cylindrical MEA , A gas decomposition element, wherein the gas decomposition element is arranged in parallel with the flow of the first gas . 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 second gas flow including an MEA, a first gas flow path for flowing a first gas used for decomposition inside the cylindrical MEA, and a second gas flowing outside the cylindrical MEA A gas decomposing element with a path,
Gas decomposition promoting means for promoting decomposition in contact with the flowing first gas is arranged in the first gas flow path provided inside the cylindrical MEA,
While providing a sealing portion for sealing one end of the cylindrical MEA,
A gas induction pipe is provided which is inserted into the inner space of the cylindrical MEA from the other end side of the cylindrical MEA and forms a cylindrical flow path between the inner surface of the cylindrical MEA,
The first gas that flows in the gas induction pipe toward the sealing portion is caused to flow reversely by flowing out from the gas induction pipe in the vicinity of the sealing portion, and the cylindrical flow path is formed in the induction pipe. The first gas flow path is configured to flow in the direction opposite to the flow inside,
And the inner space of the gas guiding pipe, as the gas decomposition accelerator means, features and be Ruga scan separation element that is disposed alumina tube carrying Ni-YSZ plural, dense state. The gas decomposing element according to claim 2 , wherein the gas induction pipe includes a positioning portion for determining an arrangement position of the alumina cylinder carrying the Ni-YSZ . The gas induction pipe is made of a conductive material,
The gas decomposing element according to claim 2 or 3 , wherein the gas decomposing element is electrically connected to the first electrode layer to constitute a current collector of the first electrode layer . 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 second gas flow including an MEA, a first gas flow path for flowing a first gas used for decomposition inside the cylindrical MEA, and a second gas flowing outside the cylindrical MEA A gas decomposing element with a path,
Gas decomposition promoting means for promoting decomposition in contact with the flowing first gas is arranged in the first gas flow path provided inside the cylindrical MEA,
While providing a sealing portion for sealing one end of the cylindrical MEA,
A gas induction pipe is provided which is inserted into the inner space of the cylindrical MEA from the other end side of the cylindrical MEA and forms a cylindrical flow path between the inner surface of the cylindrical MEA,
The first gas that flows in the gas induction pipe toward the sealing portion is caused to flow reversely by flowing out from the gas induction pipe in the vicinity of the sealing portion, and the cylindrical flow path is formed in the induction pipe. The first gas flow path is configured to flow in the direction opposite to the flow inside,
In addition, the gas decomposition promoting means is disposed in the inner space of at least a part of the gas induction pipe,
While disposing a conductive metal mesh sheet on the inner peripheral surface of the first electrode layer,
By connecting the metal mesh sheet to the gas induction pipe, the first electrode layer and the gas conducting pipe and the characterized in that is made conductive to be Ruga scan separation element. The gas decomposing element according to any one of claims 1 to 5 , wherein a porous conductive layer is provided on the surface of the first electrode layer . 7. The gas according to claim 2 , wherein one end of the cylindrical MEA is sealed by a bottom formed by integrally extending the solid electrolyte layer. Decomposition element. 7. The gas according to claim 2 , wherein one end of the cylindrical MEA is sealed by fitting a sealing member to an end of the cylindrical MEA. Decomposition element. The first electrode layer and / or the second electrode layer is a fired body including a chain of metal particles mainly composed of nickel (Ni) and an ion conductive ceramic. The gas decomposition element according to any one of claims 1 to 8 . The gas decomposition element according to any one of claims 1 to 9 , wherein the solid electrolyte layer has oxygen ion conductivity or proton conductivity . In addition, the gas decomposition element includes a heater for heating the entire element, and for preheating for performing preheating by passing the first gas guided to the first gas flow path in advance. gas separation element according to any one of claims 1 to 10, characterized in that it comprises a pipe. A power generator comprising the gas decomposition element according to any one of claims 1 to 11.

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