JP2021187698A - Hydrogen system and hydrogen system operation method - Google Patents

Abstract

To provide a hydrogen system capable of suppressing deterioration of a reforming catalyst of a hydrogen generator more than before.SOLUTION: A hydrogen system comprises: a hydrogen generator which generates a hydrogen-containing gas by a reforming reaction by using a raw material; a compressor which applies a voltage between an anode and a cathode to move and compress hydrogen in the hydrogen-containing gas supplied to the anode to the cathode through an electrolyte membrane; a first flow path which supplies a cathode-off gas discharged from the cathode of the compressor to the hydrogen generator; a first on-off valve provided in the first flow path; and a controller which opens the first on-off valve when the hydrogen system is stopped.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to hydrogen systems and methods of operating hydrogen systems.

In recent years, hydrogen has been attracting attention as a clean alternative energy source to replace fossil fuels due to environmental problems such as global warming and energy problems such as depletion of petroleum resources. Even if hydrogen burns, it basically produces only water, carbon dioxide that causes global warming is not emitted, and nitrogen oxides are hardly emitted, so it is expected as a clean energy. Further, as a device that uses hydrogen as a fuel with high efficiency, for example, there is a fuel cell, which is being developed and popularized for a power source for automobiles and a private power generation for home use.

In the coming hydrogen society, in addition to producing hydrogen, there is a need for technological development that can store hydrogen at high density and transport or utilize it in a small capacity and at low cost. In particular, in order to promote the spread of fuel cells, which are distributed energy sources, it is necessary to develop a hydrogen supply infrastructure. Therefore, in order to stably supply hydrogen, high-purity hydrogen is produced, refined, and stored at high density. Various studies are being conducted.

For example, Patent Document 1 describes a hydrogen purification boosting system in which an electrolyte membrane is provided between an anode and a cathode, and hydrogen is purified and boosted by applying a voltage between the anode and the cathode. The laminated structure of the anode, the electrolyte membrane and the cathode is called a membrane-electrode assembly (MEA). Further, Patent Document 1 discloses that when the hydrogen purification pressurization system is stopped, the gas remaining in the system is purged with nitrogen. At this time, the hydrogen supplied to the anode may contain impurities. For example, hydrogen may be a reformed gas obtained by reforming the city gas with a reformer.

Here, for example, the hydrogen gas used in a fuel cell vehicle is generally filled in a hydrogen tank in the vehicle at a high pressure of several tens of MPa. At this time, the international standard (ISO14687-2) stipulates that the hydrogen gas for filling the hydrogen tank of the fuel cell vehicle has a hydrogen purity of 99.97% or more, and the upper limit of each impurity. Is stipulated.

Japanese Patent No. 6299027

It is an object of the present disclosure to provide, as an example, a hydrogen system and a method for operating a hydrogen system, which can suppress deterioration of a reforming catalyst of a hydrogen generator more than before.

The hydrogen system of one aspect of the present disclosure is a hydrogen generator that generates a hydrogen-containing gas by a reforming reaction using a raw material, and hydrogen supplied to the anode by applying a voltage between the anode and the cathode. A compressor that moves hydrogen in the contained gas to the cathode via an electrolyte membrane and compresses the hydrogen, a first flow path that supplies the cathode off gas discharged from the cathode of the compressor to the hydrogen generator, and the first flow path. A first on-off valve provided in one flow path and a controller for opening the first on-off valve when stopped are provided.

One aspect of the present disclosure is a method of operating a hydrogen system, in which a hydrogen generator is used to generate a hydrogen-containing gas generated by a reforming reaction using a raw material, and a voltage is applied between the anode and cathode of the compressor. Then, the step of moving the hydrogen in the hydrogen-containing gas supplied to the anode to the cathode via the electrolyte membrane and compressing it, and the cathode off gas discharged from the cathode of the compressor at the time of stopping are the hydrogen generator. With a step to supply to.

The hydrogen system of one aspect of the present disclosure and the method of operating the hydrogen system have an effect that deterioration of the reforming catalyst of the hydrogen generator can be suppressed more than before.

FIG. 1 is a diagram showing an example of the hydrogen system of the first embodiment. FIG. 1A is a diagram showing an example of a hydrogen system according to an embodiment of the first embodiment. FIG. 1B is a diagram showing an example of a hydrogen system according to an embodiment of the first embodiment. FIG. 2 is a diagram showing an example of the hydrogen system of the second embodiment. FIG. 3 is a diagram showing an example of the hydrogen system of the third embodiment. FIG. 4 is a diagram showing an example of the hydrogen system of the fourth embodiment. FIG. 5 is a diagram showing an example of the hydrogen system of the fifth embodiment. FIG. 6 is a diagram showing an example of the hydrogen system of the sixth embodiment. FIG. 7 is a diagram showing an example of the hydrogen system of the seventh embodiment. FIG. 8 is a diagram showing an example of the hydrogen system of the eighth embodiment. FIG. 9 is a diagram showing an example of the hydrogen system of the ninth embodiment. FIG. 10 is a diagram showing an example of the hydrogen system of the tenth embodiment. FIG. 11 is a diagram showing an example of the hydrogen system of the eleventh embodiment. FIG. 12 is a diagram showing an example of the hydrogen system of the twelfth embodiment. FIG. 13 is a diagram showing an example of the hydrogen system of the thirteenth embodiment. FIG. 14 is a diagram showing an example of the hydrogen system of the 14th embodiment. FIG. 15 is a diagram showing an example of the hydrogen system of the fifteenth embodiment. FIG. 16 is a diagram showing an example of the hydrogen system of the 17th embodiment. FIG. 17 is a diagram showing an example of the hydrogen system of the 18th embodiment. FIG. 18 is a diagram showing an example of the hydrogen system of the 19th embodiment.

In Patent Document 1, the reforming catalyst of the reformer 2a may deteriorate when stopped. Specifically, when the hydrogen purification boosting system is in operation, for example, a steam reforming reaction, an autothermal reaction, or the like is performed in the reformer 2a, and when the reformer 2a is stopped, steam in the reformer 2a is present. There is. Therefore, if the temperature drops while the steam remains as it is in the reformer 2a, the steam may condense. Here, in general, the reforming catalyst has a property of being deteriorated by water wetting, so that when the reforming catalyst gets wet with the above-mentioned condensed water, the reforming catalyst deteriorates.

Therefore, as a result of diligent studies in view of such a situation, the present disclosers have improved the hydrogen generator by purging the inside of the hydrogen generator with a low-humidity cathode-off gas before the reforming catalyst gets wet with condensed water. We have found that the deterioration of the quality catalyst can be suppressed, and have conceived the following aspect of the present disclosure.

That is, the hydrogen system of the first aspect of the present disclosure is a hydrogen generator that generates a hydrogen-containing gas by a reforming reaction using a raw material, and hydrogen supplied to the anode by applying a voltage between the anode and the cathode. A compressor that moves hydrogen in the contained gas to the cathode via an electrolyte membrane and compresses it, a first flow path that supplies the cathode off gas discharged from the cathode of the compressor to the hydrogen generator, and a first flow. It includes a first on-off valve provided on the road and a controller that opens the first on-off valve when stopped.

According to such a configuration, the hydrogen system of the first aspect of the present disclosure can suppress deterioration of the reforming catalyst of the hydrogen generator more than before.

Specifically, in the hydrogen system of this embodiment, the high humidity hydrogen-containing gas existing in the hydrogen generator is supplied from the cathode of the compressor by opening the first on-off valve when the system is stopped. Can be replaced with a cathode off gas. That is, since the high-humidity hydrogen-containing gas is pushed out of the hydrogen generator by the low-humidity cathode-off gas, the gas existing in the hydrogen generator is replaced with the latter cathode-off gas from the former hydrogen-containing gas. As a result, in the hydrogen system of this embodiment, even if the temperature of the hydrogen generator is lowered, the condensation of water vapor is less likely to occur in the hydrogen generator. Then, the reforming catalyst of the hydrogen generator can reduce the possibility of deterioration due to water wetting.

The hydrogen system of the second aspect of the present disclosure includes a second flow path for supplying a reactant for a reforming reaction to a hydrogen generator in the hydrogen system of the first aspect, and the first flow path is a second flow. You may join the road. Further, in the hydrogen system of the third aspect of the present disclosure, the reaction product may be a raw material in the hydrogen system of the second aspect.

According to the above configuration, the hydrogen system of this embodiment can consolidate the points for introducing the reactant and the cathode off gas in the hydrogen generator.

The hydrogen system of the fourth aspect of the present disclosure is provided upstream of the compressor in any one of the first to third aspects of the hydrogen system, and a voltage is applied between the anode and the cathode by a voltage applyer. A hydrogen purifier may be provided in which hydrogen in the hydrogen-containing gas supplied from the hydrogen generator to the anode is moved to the cathode via the electrolyte membrane to generate a purified hydrogen-containing gas.

_{According to such a configuration, the hydrogen system of this embodiment can appropriately remove impurities (for example, CO 2} , steam, nitrogen, etc.) in the hydrogen-containing gas generated by the hydrogen generator using a hydrogen purifier. can.

Here, it is possible to remove the above-mentioned impurities in the hydrogen-containing gas also in the compressor, but the reason for providing the hydrogen purifier in the front stage of the compressor as in the hydrogen system of this embodiment is as follows. ..

In the compressor, the ability of the electrolyte membrane to remove impurities in the hydrogen-containing gas is generally improved as the thickness of the electrolyte membrane is thicker. Therefore, in order to purify the hydrogen present at the cathode of the compressor, either increase the thickness of the electrolyte film of the compressor or increase the purity of the hydrogen-containing gas supplied to the anode of the compressor. It needs to be configured.

However, considering the case where hydrogen is compressed to a high pressure (for example, about several tens of MPa) at the cathode of the compressor, the former configuration means an increase in power consumption required for the hydrogen compression operation of the compressor.

Therefore, in the hydrogen system of this embodiment, the purity of the hydrogen-containing gas supplied to the anode of the compressor is increased by using a hydrogen purifier, so that the thickness of the electrolyte film of the compressor is not increased. The hydrogen present in the cathode has been purified. As a result, the hydrogen system of this embodiment can reduce the power consumption required for the hydrogen compression operation of the compressor as compared with the case where the hydrogen purifier is not provided in front of the compressor.

The hydrogen purifier can also compress hydrogen to a predetermined pressure at the cathode of the hydrogen purifier by applying a voltage between the cathode and the anode, but by setting such a predetermined pressure appropriately, it is possible. (For example, about several hundred KPa), it is possible to appropriately suppress the power consumption in the hydrogen purifier.

In the hydrogen system of the fifth aspect of the present disclosure, in the hydrogen system of the fourth aspect, the controller may apply the above voltage by a voltage applyer when the first on-off valve is open.

According to such a configuration, in the hydrogen system of this embodiment, when the first on-off valve is opened and a voltage is applied between the cathode and the anode of the hydrogen purifier, the hydrogen system is inside the hydrogen purifier as well as inside the hydrogen purifier. High-humidity hydrogen-containing gas present in the flow path between the hydrogen generator and the hydrogen purifier and in the flow path between the hydrogen purifier and the compressor is supplied from the cathode of the compressor with low humidity. Can be replaced with a cathode off gas. As a result, it is possible to suppress the flow path blockage (flooding) due to condensed water in the flow path between the hydrogen purifier, the hydrogen generator and the hydrogen purifier, and the flow path between the hydrogen purifier and the compressor. can.

The hydrogen system of the sixth aspect of the present disclosure is the third flow path through which the hydrogen-containing gas supplied from the hydrogen purifier to the anode of the compressor flows in the hydrogen system of the fourth or fifth aspect, and the cathode of the compressor. A fourth flow path for supplying the cathode off gas discharged from the third flow path and a second on-off valve provided in the fourth flow path are provided, and the controller has a first on-off valve and a second on-off valve when stopped. The on-off valve may be opened.

According to this configuration, the hydrogen system of this embodiment exists in the third flow path between the hydrogen purifier and the compressor by opening the first on-off valve and the second on-off valve when stopped. The high humidity hydrogen-containing gas can be replaced with a low humidity cathode off gas supplied from the cathode of the compressor. That is, the hydrogen system of this embodiment can suppress flooding in the third flow path between the hydrogen purifier and the compressor while improving the power consumption efficiency of the voltage adapter.

The hydrogen system of the seventh aspect of the present disclosure may include a fifth flow path in the hydrogen system of the fifth or sixth aspect, which supplies the anode off gas discharged from the anode of the compressor to the anode of the hydrogen purifier. good.

In the hydrogen purifier, the higher the purity of the hydrogen-containing gas at the anode of the hydrogen purifier, the higher the purity of the hydrogen-containing gas purified at the cathode of the hydrogen purifier. The higher the purity of the hydrogen-containing gas purified at the cathode of the hydrogen purifier, the more advantageous it is in purifying the hydrogen compressed by the compressor.

Therefore, the hydrogen system of this embodiment uses the fifth flow path to recirculate the high-purity anode off gas discharged from the anode of the compressor to the anode of the hydrogen purifier to generate hydrogen at the anode of the hydrogen purifier. The purity of the contained gas can be increased. As a result, in the hydrogen system of this embodiment, for example, when hydrogen compressed by the cathode of the compressor is supplied to the hydrogen reservoir, the hydrogen purity of the hydrogen reservoir can be easily controlled so as to satisfy the above-mentioned international standard.

The hydrogen system of the eighth aspect of the present disclosure is a combustor that supplies heat for a reforming reaction to a hydrogen generator and an anode of a hydrogen purifier in any one of the hydrogen systems of the fourth to seventh aspects. A sixth flow path for supplying the anode off gas discharged from the combustor may be provided.

According to such a configuration, the hydrogen system of this embodiment can supply the anode off gas discharged from the anode of the hydrogen purifier to the combustor which supplies heat for the reforming reaction to the hydrogen generator.

The hydrogen system of the ninth aspect of the present disclosure is the combustor that supplies heat for the reforming reaction to the hydrogen generator and the anode discharged from the anode of the compressor in the hydrogen system of the fifth or sixth aspect. A seventh flow path for supplying off-gas to the combustor may be provided.

According to such a configuration, the hydrogen system of this embodiment can supply the anode off gas discharged from the anode of the compressor to the combustor which supplies heat for the reforming reaction to the hydrogen generator.

The hydrogen system of the tenth aspect of the present disclosure comprises an air supply device for supplying combustion air to the combustor in the hydrogen system of the eighth aspect or the ninth aspect, and the controller operates the air supply device when stopped. Then, the anode off gas supplied to the combustor may be diluted and exhausted.

According to such a configuration, the hydrogen system of this embodiment mixes the anode off gas and an appropriate amount of air in the combustor to appropriately dilute the combustible component of the anode off gas, and then exhausts the anode off gas from the combustor to the outside. be able to. As a result, the hydrogen system of this embodiment can appropriately suppress the excessive temperature rise of the hydrogen generator as compared with the case where the anode off gas is combusted and exhausted in the combustor when the system is stopped.

The hydrogen system of the eleventh aspect of the present disclosure includes an eighth flow path through which the cathode off gas discharged from the cathode of the compressor flows in any one of the hydrogen systems of the first aspect to the tenth aspect, and is the first flow path. Branches from the 8th flow path, and flows in the 8th flow path downstream from the branching point of the 1st flow path in the direction opposite to the direction of the flow of the cathode off gas discharged from the cathode of the compressor. A first check valve for prevention may be provided.

According to such a configuration, in the hydrogen system of this embodiment, by providing the first check valve in the eighth flow path, even if the first on-off valve is opened at the time of stopping, the amount of hydrogen passing through the first flow path is an appropriate amount. Can be limited to.

For example, when high-pressure hydrogen generated at the cathode of a compressor is supplied to a hydrogen reservoir through an eighth flow path, the first on-off valve is opened unless the first check valve is provided in the eighth flow path. At that time, hydrogen in the hydrogen reservoir may move through the eighth flow path and the first flow path in this order, but the hydrogen system of this embodiment has the first reverse to the eighth flow path. By providing a check valve, such a possibility can be reduced. As a result, the decrease in efficiency of the hydrogen compression operation of the compressor is suppressed.

Here, it is possible to limit the movement of hydrogen in the hydrogen reservoir to the first flow path by closing an appropriate on-off valve provided in the eighth flow path. However, if a malfunction occurs in this on-off valve, it becomes difficult to limit the movement of hydrogen to the first flow path.

On the other hand, in the hydrogen system of this embodiment, the above-mentioned inconvenience can be alleviated by using the first check valve having a simple structure.

The hydrogen system of the twelfth aspect of the present disclosure is a reactant supplied from the reactant source to the second flow path upstream of the point where the first flow path merges in the hydrogen system of the second aspect or the third aspect. A second check valve may be provided to prevent the flow in the direction opposite to the direction of the flow.

According to this configuration, the hydrogen system of this embodiment is provided with a second check valve in the second flow path, so that when the first on-off valve is opened at the time of stopping, the hydrogen system is supplied from the cathode of the compressor to the hydrogen generator. It is possible to prevent the high-pressure cathode off gas from flowing into the low-pressure reaction product supply system. As a result, the hydrogen system of this embodiment can reduce damage to low-pressure equipment and the like provided in the reactant supply system, as compared with the case where the second check valve is not provided in the second flow path.

Here, by closing an appropriate on-off valve provided in the second flow path, it is possible to suppress the inflow of the high-pressure cathode off gas into the reaction product supply system of the low-pressure specification. However, if a malfunction occurs in this on-off valve, it becomes difficult to suppress the inflow of such cathode off gas.

On the other hand, in the hydrogen system of this embodiment, the above-mentioned inconvenience can be alleviated by using the second check valve having a simple structure.

The hydrogen system of the thirteenth aspect of the present disclosure includes a ninth flow path through which a hydrogen-containing gas supplied from a hydrogen generator to a hydrogen purifier flows in the hydrogen system of the seventh aspect, and the fifth flow path is a ninth flow path. A third flow path that is merging with the flow path and prevents the flow of hydrogen-containing gas discharged from the hydrogen generator in the direction opposite to the direction of the flow in the ninth flow path upstream from the point where the fifth flow path joins. A check valve may be provided.

According to this configuration, the hydrogen system of this embodiment uses the fifth flow path to return the high-purity anode off gas discharged from the anode of the compressor to the anode of the hydrogen purifier in the ninth flow path. By providing the third check valve, it is possible to suppress the backflow of the anode off-gas to the hydrogen generator. As a result, for example, if a low-temperature anode off-gas flows into the hydrogen generator during the hydrogen generation operation of the hydrogen generator, the temperature of the high-temperature hydrogen generator drops, but the hydrogen system of this embodiment has the above configuration. Therefore, such inconvenience can be alleviated.

The hydrogen system of the 14th aspect of the present disclosure includes a third flow path through which hydrogen-containing gas supplied from the hydrogen purifier to the anode of the compressor flows in the hydrogen system of the fourth aspect, and hydrogen is provided in the third flow path. A fourth check valve may be provided to prevent the flow of the hydrogen-containing gas discharged from the purifier in the direction opposite to the direction of the flow.

According to this configuration, the hydrogen system of this embodiment is provided with the fourth check valve in the third flow path, so that even if the electrolyte membrane of the compressor is damaged, the high pressure existing at the cathode of the compressor is high. Since hydrogen can be prevented from flowing back to the hydrogen purifier through the third flow path, the hydrogen purifier is less likely to fail.

The hydrogen system of the fifteenth aspect of the present disclosure is the fifth reverse flow of the hydrogen system of the seventh aspect to prevent the flow of the anode off gas discharged from the anode of the compressor in the fifth flow path in the direction opposite to the direction of the flow. A stop valve may be provided.

According to this configuration, the hydrogen system of this embodiment is provided with a fifth check valve in the fifth flow path, so that when a low-purity hydrogen-containing gas is supplied from the hydrogen generator to the hydrogen purifier, the purity is low. Hydrogen-containing gas is suppressed from flowing into the anode of the compressor.

The hydrogen system of the 16th aspect of the present disclosure includes a pressure reducing valve for reducing the pressure of the cathode off gas discharged from the cathode of the compressor in the first flow path in any one of the hydrogen systems of the 1st to 15th aspects. You may.

According to such a configuration, the hydrogen system of this embodiment can reduce the pressure of the cathode off gas supplied to the hydrogen generator through the first flow path by the pressure reducing valve even if the first on-off valve is opened at the time of stopping. can. This makes it possible to reduce the possibility of damage to the members used in the hydrogen generator.

The hydrogen system of the 17th aspect of the present disclosure is the hydrogen system of the 16th aspect, in which the direction of the flow of the hydrogen-containing gas discharged from the cathode of the compressor is opposite to that in the first flow path downstream of the pressure reducing valve. A sixth check valve may be provided to prevent flow.

According to this configuration, in the hydrogen system of this embodiment, by providing the sixth check valve in the first flow path, when the reactant is supplied from the reactant source to the hydrogen generator, the reactant is sent to the first flow. It is suppressed from flowing into the road.

The hydrogen system of the 18th aspect of the present disclosure may be provided with a first flow rate regulator for adjusting the flow rate of the cathode off gas in the first flow path downstream of the pressure reducing valve in the hydrogen system of the 16th or 17th aspect. ..

According to such a configuration, in the hydrogen system of this embodiment, even if the first on-off valve is opened at the time of stop, the flow rate of the cathode off gas flowing through the first flow path can be limited to a desired flow rate by the first flow rate controller. .. Then, in the hydrogen system of this embodiment, by reducing the flow rate of the cathode off gas, the cathode off gas can be stably supplied from the cathode to the hydrogen generator through the first flow path. Further, in the hydrogen system of this embodiment, by reducing the flow rate of the cathode off gas, the time for the low humidity cathode off gas to pass through the hydrogen generator can be lengthened. This makes it more difficult for the reforming catalyst of the hydrogen generator to get wet.

The hydrogen system of the 19th aspect of the present disclosure is the hydrogen system of the 6th aspect, in which the controller first opens and closes between the start of activation and the start of supply of the cathode off gas of the compressor to the hydrogen reservoir. The valve may be closed and the second on-off valve may be opened.

In Patent Document 1, when the hydrogen purification boosting system is started, the cathode off gas containing impurities is supplied to the hydrogen reservoir, so that the hydrogen purity in the hydrogen reservoir may not satisfy the above international standard.

Specifically, a solid polymer membrane is generally used for the electrolyte membrane, and the solid polymer membrane is not a perfect dense membrane. Therefore, if the composition of the gas (for example, the gas concentration of the impurity component) existing in each of the anode and the cathode arranged across the electrolyte membrane is different, the chemical potential difference due to the concentration of the gas is used as a driving force. The impurities and hydrogen cross-diffuse (cross-leak) through the electrolyte membrane, and finally the composition of the gas at the anode and the cathode becomes the same. The rate of gas that cross-leaks through the electrolyte membrane depends on the material and film thickness of the electrolyte membrane.

In addition, the hydrogen purification boosting system applies a voltage between the anode and the cathode by the reaction of the anode and the cathode below, electrochemically selectively moves hydrogen from the anode side to the cathode side, and seals the cathode side. As a result, hydrogen purification and pressurization can be performed.

Anode: H ₂ (low pressure) → 2H ⁺ + 2e ^{−
_{Cathode: 2H + + 2e - → H}} 2 ( high pressure)
During the hydrogen compression operation of the hydrogen purification booster system, as described above, the amount of hydrogen that is electrochemically selectively transferred from the anode to the cathode is transferred from the cathode to the cathode by the cross leak and from the anode to the cathode. Since it is sufficiently large compared to the amount of impurities to be added, the hydrogen in the cathode gas is maintained at high purity even if the hydrogen-containing gas in the anode contains impurities. On the other hand, when the hydrogen compression operation of the hydrogen purification booster system is stopped, hydrogen does not move electrochemically from the anode to the cathode. Therefore, if the hydrogen-containing gas in the anode contains impurities, a cross leak occurs. As a result, the influence of the transfer of impurities from the anode to the cathode or the transfer of hydrogen from the cathode to the anode becomes large, and the purity of hydrogen in the cathode gas decreases. In this case, if the cathode off gas is supplied to the hydrogen reservoir as it is when the hydrogen purification boosting system is started, the purity of hydrogen in the hydrogen reservoir may decrease.

Further, if the gas pressure in the cathode becomes lower than the outside air pressure while the hydrogen compression operation of the hydrogen purification boosting system is stopped, impurities may be mixed in the cathode from the outside. In this case as well, if the cathode off gas is supplied to the hydrogen reservoir as it is when the hydrogen purification boosting system is started, the purity of hydrogen in the hydrogen reservoir may decrease.

Therefore, as a result of diligent studies in view of such a situation, the present disclosers consider the cathode off gas containing impurities to be a hydrogen reservoir between the start of activation and the start of supply of the cathode off gas to the hydrogen reservoir. We have found that the above problems can be alleviated by exhausting air to different supply destinations, and have arrived at the 19th aspect of the present disclosure.

According to such a configuration, the hydrogen system of this embodiment can improve the purity of hydrogen in the hydrogen reservoir as compared with the conventional case.

Specifically, for example, when the hydrogen compression operation of the hydrogen system is stopped, hydrogen does not move electrochemically from the anode to the cathode, so that the difference in chemical potential due to the gas concentration of impurities present in each of the anode and the cathode. The effect of the impurity cross leak becomes large. In this case, if the cathode off gas is supplied to the hydrogen reservoir as it is when starting the hydrogen system, the purity of hydrogen in the hydrogen reservoir may decrease.

Further, for example, if the gas pressure in the cathode becomes lower than the outside air pressure while the hydrogen compression operation of the hydrogen system is stopped, impurities may be mixed in the cathode from the outside. In this case as well, if the cathode off gas is supplied to the hydrogen reservoir as it is when starting the hydrogen system, the purity of hydrogen in the hydrogen reservoir may decrease.

However, in the hydrogen system of this embodiment, the cathode off gas containing impurities is exhausted to the anode of the compressor by opening the second on-off valve between the start of activation and the start of supply of the cathode off gas to the hydrogen reservoir. can do. Thereby, the hydrogen system of this embodiment can purify the cathode off gas (hydrogen) supplied from the compressor to the hydrogen reservoir.

Further, in the hydrogen system of this embodiment, the high humidity hydrogen-containing gas existing in the anode of the compressor is supplied from the cathode of the compressor by opening the second on-off valve during the above period. It can be replaced with a cathode off gas. As a result, in the hydrogen system of this embodiment, flooding of the anode gas flow path of the compressor is less likely to occur, so that the efficiency of the hydrogen compression operation can be appropriately maintained after the second on-off valve is opened.

In the hydrogen system of the sixth aspect, the hydrogen system of the twentieth aspect of the present disclosure includes a pressure reducing valve in the first flow path for reducing the pressure of the cathode off gas discharged from the cathode of the compressor, and the fourth flow path is reduced in pressure. It may branch to the downstream of the valve after being shared with the first flow path.

According to such a configuration, in the hydrogen system of this embodiment, even if the second on-off valve is opened at the time of stop, the pressure of the cathode off gas supplied to the anode of the compressor through the fourth flow path by the pressure reducing valve is reduced. Can be done. This makes it possible to reduce the possibility of damage to the member used for the anode of the compressor.

Further, in the hydrogen system of this embodiment, the fourth flow path is shared with the first flow path to the downstream of the pressure reducing valve, so that it is not necessary to provide a pressure reducing valve in each of the first flow path and the fourth flow path. Therefore, in the hydrogen system of this embodiment, the manufacturing cost can be reduced as compared with the case where the pressure reducing valves are provided in each of the first flow path and the fourth flow path.

The hydrogen system of the 21st aspect of the present disclosure may be provided with a second flow rate regulator in the 4th flow path after branching from the 1st flow path in the hydrogen system of the 20th aspect.

According to such a configuration, in the hydrogen system of this embodiment, even if the second on-off valve is opened at the time of stop, the flow rate of the cathode off gas flowing through the fourth flow path can be limited to a desired flow rate by the second flow rate controller. .. Then, in the hydrogen system of this embodiment, by reducing the flow rate of the cathode off gas, the cathode off gas can be stably supplied from the cathode of the compressor to the anode through the fourth flow path. Further, in the hydrogen system of this embodiment, by reducing the flow rate of the cathode off gas, the time for the low humidity cathode off gas to pass through the anode of the compressor can be lengthened. As a result, flooding of the anode gas flow path of the compressor is less likely to occur.

The hydrogen system of the 22nd aspect of the present disclosure is provided in the 5th flow path and the 5th flow path of supplying the anode off gas discharged from the anode of the compressor to the anode of the hydrogen purifier in the hydrogen system of the 9th aspect. The third on-off valve provided and the fourth on-off valve provided in the seventh flow path are provided, and the controller opens the third on-off valve and closes and stops the fourth on-off valve during operation. Occasionally, the third on-off valve may be closed and the fourth on-off valve may be opened.

As described above, in the hydrogen purifier, the higher the purity of the hydrogen-containing gas at the anode of the hydrogen purifier, the higher the purity of the hydrogen-containing gas purified at the cathode of the hydrogen purifier.

Therefore, in the hydrogen system of this embodiment, the purity of the hydrogen system discharged from the anode of the compressor by using the fifth flow path by opening the third on-off valve and closing the fourth on-off valve during operation is achieved. High anode off gas can be refluxed to the anode of the hydrogen purifier. Thereby, the hydrogen system of this embodiment can increase the purity of the hydrogen-containing gas at the cathode of the hydrogen purifier. As a result, in the hydrogen system of this embodiment, for example, when hydrogen compressed by the cathode of the compressor is supplied to the hydrogen reservoir, the hydrogen purity of the hydrogen reservoir can be easily controlled so as to satisfy the above-mentioned international standard.

On the other hand, in the hydrogen system of this embodiment, the third on-off valve is closed and the fourth on-off valve is opened when the system is stopped, so that the anode off gas discharged from the anode of the compressor is discharged by using the seventh flow path. It can be supplied to the combustor.

The method of operating the hydrogen system according to the 23rd aspect of the present disclosure is a step of generating a hydrogen-containing gas generated by a reforming reaction using a raw material in a hydrogen generator, and applying a voltage between the anode and the cathode of the compressor. As a result, the hydrogen in the hydrogen-containing gas supplied to the anode is moved to the cathode via the electrolyte membrane and compressed, and the cathode off gas discharged from the cathode of the compressor at the time of stop is transferred to the hydrogen generator. It comprises a step of supplying.

Based on the above, the method of operating the hydrogen system of this embodiment can suppress deterioration of the reforming catalyst of the hydrogen generator more than before. The details of the action and effect can be easily understood by taking into consideration the action and effect of the hydrogen system of the first aspect, and thus the description thereof will be omitted.

The method of operating the hydrogen system according to the 24th aspect of the present disclosure is the method of operating the hydrogen system according to the 23rd aspect, in which the cathode off gas discharged from the cathode of the compressor is supplied with a reactant for a reforming reaction when stopped. It may be supplied to the hydrogen generator through the flow path. Further, in the method of operating the hydrogen system according to the 25th aspect of the present disclosure, the reactant may be a raw material in the method of operating the hydrogen system according to the 24th aspect.

The effects of the hydrogen system operating methods of these embodiments are the same as those of the hydrogen systems of the second and third aspects, and thus the description thereof will be omitted.

The method of operating the hydrogen system according to the 26th aspect of the present disclosure is the method of operating the hydrogen system according to any one of the 23rd to 25th aspects, between the anode and the cathode of the hydrogen purifier provided upstream of the compressor. By applying a voltage to the hydrogen generator, hydrogen in the hydrogen-containing gas supplied from the hydrogen generator to the anode is moved to the cathode through the electrolyte membrane to generate a purified hydrogen-containing gas. , The cathode off gas discharged from the cathode of the compressor may be supplied to the anode of the hydrogen purifier via the hydrogen generator.

Based on the above, the method of operating the hydrogen system of this embodiment is to supply the cathode off gas discharged from the cathode of the compressor to the anode of the hydrogen purifier via the hydrogen generator when the hydrogen system is stopped. In addition to the above, the high-humidity hydrogen-containing gas existing in the flow path between the hydrogen generator and the hydrogen purifier can be replaced with the low-humidity cathode off gas supplied from the cathode of the compressor. This makes it possible to suppress flooding in the hydrogen generator and the flow path between the hydrogen generator and the hydrogen purifier. The action and effect of the method of operating the hydrogen system of the present embodiment is the same as that of the hydrogen system of the fourth aspect, except for the above-mentioned action and effect.

The method of operating the hydrogen system according to the 27th aspect of the present disclosure is the method of operating the hydrogen system according to the 26th aspect, from the cathode of the compressor by applying a voltage between the anode and the cathode of the hydrogen purifier when stopped. The discharged cathode off gas may be supplied to the anode of the compressor via a hydrogen generator and a hydrogen purifier.

Since the action and effect of the operation method of the hydrogen system of the present embodiment is the same as the action and effect of the hydrogen system of the fifth aspect, the description thereof will be omitted.

The method of operating the hydrogen system of the 28th aspect of the present disclosure is the method of operating the hydrogen system of the 26th aspect or the 27th aspect, in which the cathode off gas discharged from the cathode of the compressor at the time of stop is hydrogen-purified with a hydrogen generator. It may be supplied to the anode of the compressor without going through the device.

Since the action and effect of the operation method of the hydrogen system of the present embodiment is the same as the action and effect of the hydrogen system of the sixth aspect, the description thereof will be omitted.

The method of operating the hydrogen system according to the 29th aspect of the present disclosure is the method of operating the hydrogen system according to the 27th or 28th aspect, in which the anode off gas discharged from the anode of the compressor is supplied to the anode of the hydrogen purifier when stopped. May be provided with steps to do.

Since the action and effect of the operation method of the hydrogen system of this embodiment is the same as the action and effect of the hydrogen system of the seventh aspect, the description thereof will be omitted.

The method for operating the hydrogen system according to the thirtieth aspect of the present disclosure is the method for operating the hydrogen system according to any one of the 26th to the 29th aspects, in which hydrogen is generated from the anode off gas discharged from the anode of the hydrogen purifier when stopped. It may be provided with a step of supplying to the combustor of the combustor and a step of diluting and exhausting the anode off gas supplied to the combustor by supplying combustion air to the combustor.

Since the action and effect of the method of operating the hydrogen system of this embodiment is the same as that of the hydrogen system of the tenth aspect, the description thereof will be omitted.

In the method of operating the hydrogen system according to the 31st aspect of the present disclosure, in the method of operating the hydrogen system according to any one of the 26th to the 29th aspects, the anode off gas discharged from the anode of the compressor at the time of shutdown is used as a hydrogen generator. A step of supplying combustion air to the combustor and a step of diluting and exhausting the anode off gas supplied to the combustor by supplying combustion air to the combustor may be provided.

Since the action and effect of the method of operating the hydrogen system of this embodiment is the same as that of the hydrogen system of the tenth aspect, the description thereof will be omitted.

Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. In addition, all of the embodiments described below show an example of each of the above-mentioned embodiments. Therefore, the shapes, materials, components, the arrangement positions of the components, the connection form, and the like shown below are merely examples, and do not limit each of the above embodiments unless stated in the claims. .. Further, among the following components, the components not described in the independent claims indicating the top-level concept of each of the above embodiments will be described as arbitrary components. Further, in the drawings, those having the same reference numerals may omit the description. The drawings schematically show each component for the sake of easy understanding, and may not be an accurate display of the shape, dimensional ratio, and the like.

(First Embodiment)
In the following embodiments of the present disclosure, the configuration and operation of an electrochemical hydrogen pump, which is an example of a compression device, will be described.

[Device configuration]
FIG. 1 is a diagram showing an example of the hydrogen system of the first embodiment.

In the example shown in FIG. 1, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a first flow path 11, a first on-off valve 21, and a controller 50.

The cell (MEA) of the electrochemical hydrogen pump 100 includes an electrolyte membrane 30A, an anode AN1, and a cathode CA1. The electrochemical hydrogen pump 100 may include a stack in which a plurality of such cells are stacked. Here, the electrochemical hydrogen pump 100 transfers hydrogen in the hydrogen-containing gas supplied to the anode AN1 to the cathode CA1 via the electrolyte membrane 30A by applying a voltage between the anode AN1 and the cathode CA1. And it is a device that compresses.

Here, in the hydrogen system 200 of the present embodiment, the hydrogen-containing gas (reformed gas) generated by the hydrogen generator 110 can be used as the hydrogen-containing gas.

The details of the stack and the details of the voltage applyer for applying the above voltage will be described later.

The anode AN1 is provided on one main surface of the electrolyte membrane 30A. The anode AN1 is an electrode including an anode catalyst layer and an anode gas diffusion layer. The cathode CA1 is provided on the other main surface of the electrolyte membrane 30A. The cathode CA1 is an electrode including a cathode catalyst layer and a cathode gas diffusion layer. As a result, the electrolyte membrane 30A is sandwiched between the anode AN1 and the cathode CA1 so as to be in contact with each of the anode catalyst layer and the cathode catalyst layer.

The electrolyte membrane 30A may have any structure as long as it has proton conductivity. For example, examples of the electrolyte membrane 30A include a fluorine-based polymer electrolyte membrane, a hydrocarbon-based electrolyte membrane, and the like. Specifically, as the electrolyte membrane 30A, for example, Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Corporation) and the like can be used, but the present invention is not limited thereto.

The anode catalyst layer is provided on one main surface of the electrolyte membrane 30A. The anode catalyst layer contains, but is not limited to, carbon capable of supporting the catalyst metal (eg, platinum) in a dispersed state.

The cathode catalyst layer is provided on the other main surface of the electrolyte membrane 30A. The cathode catalyst layer contains, but is not limited to, carbon capable of supporting the catalyst metal (eg, platinum) in a dispersed state.

As for the cathode catalyst layer and the anode catalyst layer, various methods can be mentioned as a method for preparing the catalyst, but the method is not particularly limited. For example, examples of the carbon-based powder include powders such as graphite, carbon black, and conductive activated carbon. The method of supporting platinum or other catalytic metal on the carbon carrier is not particularly limited. For example, a method such as powder mixing or liquid phase mixing may be used. Examples of the latter liquid phase mixing include a method in which a carrier such as carbon is dispersed in a colloidal liquid as a catalyst component and adsorbed. The supported state of the catalyst metal such as platinum on the carbon carrier is not particularly limited. For example, the catalyst metal may be atomized and supported on a carrier with high dispersion.

The cathode gas diffusion layer is provided on the cathode catalyst layer. The cathode gas diffusion layer is made of a porous material and has conductivity and gas diffusivity. It is desirable that the cathode gas diffusion layer has elasticity so as to appropriately follow the displacement and deformation of the constituent members generated by the differential pressure between the cathode CA1 and the anode AN1 during the operation of the electrochemical hydrogen pump 100. As the base material of the cathode gas diffusion layer, for example, a carbon fiber sintered body or the like can be used, but the substrate is not limited thereto.

The anode gas diffusion layer is provided on the anode catalyst layer. The anode gas diffusion layer is made of a porous material and has conductivity and gas diffusivity. It is desirable that the anode gas diffusion layer has a rigidity sufficient to withstand the pressing of the electrolyte membrane 30A due to the above differential pressure during the operation of the electrochemical hydrogen pump 100. As the base material of the anode gas diffusion layer, for example, a carbon particle sintered body, a titanium particle sintered body coated with a noble metal such as platinum, or the like can be used, but the substrate is not limited thereto.

Here, although not shown in FIG. 1, members and equipment necessary for the hydrogen compression operation of the electrochemical hydrogen pump 100 are appropriately provided.

For example, each of the pair of separators may sandwich each of the anode AN1 and the cathode CA1 from the outside. In this case, the separator in contact with the anode AN1 is a conductive plate-shaped member for supplying the hydrogen-containing gas to the anode AN1. This plate-shaped member includes a serpentine-shaped gas flow path through which a hydrogen-containing gas supplied to the anode AN1 flows. The separator in contact with the cathode CA1 is a conductive plate-shaped member for deriving hydrogen from the cathode CA1. This plate-shaped member includes a gas flow path through which hydrogen derived from the cathode CA1 flows.

Further, in the electrochemical hydrogen pump 100, sealing materials such as gaskets are usually provided from both sides of the cell so that high-pressure hydrogen does not leak to the outside, and are assembled in advance by being integrated with the cell of the electrochemical hydrogen pump 100. Then, on the outside of this cell, the above-mentioned separator for mechanically fixing the cell and electrically connecting the adjacent cells to each other in series is arranged.

Cells and separators are alternately stacked, about 10 to 200 cells are laminated, the laminated body (stack) is sandwiched between end plates via a current collector plate and an insulating plate, and both end plates are tightened with a fastening rod. Is a general laminated structure. In this case, in order to supply an appropriate amount of hydrogen-containing gas to each gas flow path of the separator, a groove-shaped branch path is branched from an appropriate pipeline in each of the separators, and the downstream ends thereof are the separator. It is necessary to configure it so as to be connected to each gas flow path of. Such a pipeline is called a manifold, and the manifold is composed of, for example, a series of through holes provided at appropriate positions of the members constituting the stack.

Further, the electrochemical hydrogen pump 100 includes a voltage applyer that applies a voltage between the anode AN1 and the cathode CA1. The voltage applyer may have any configuration as long as a voltage can be applied between the anode AN1 and the cathode CA1. Specifically, the high potential side terminal of the voltage applyer is connected to the anode AN1, and the low potential side terminal of the voltage applyer is connected to the cathode CA1. Examples of the voltage applyer include a DC / DC converter and an AC / DC converter. The DC / DC converter is used when the voltage applyer is connected to a DC power source such as a solar cell, a fuel cell, or a battery. The AC / DC converter is used when the voltage applyer is connected to an AC power supply such as a commercial power supply. Further, the voltage applyer flows between the anode AN1 and the cathode CA1 and the voltage applied between the anode AN1 and the cathode CA1 so that the electric power supplied to the cell of the electrochemical hydrogen pump 100 becomes a predetermined set value, for example. It may be a power supply whose current is adjusted.

Further, in the electrochemical hydrogen pump 100, the electrolyte membrane 30A generally exhibits the desired proton conductivity in a wet state. Therefore, in order to maintain the desired value of the operating efficiency of the electrochemical hydrogen pump 100, it is necessary to keep the electrolyte membrane 30A in a wet state. Therefore, conventionally, a high humidity hydrogen-containing gas is often supplied to the anode AN1 of the electrochemical hydrogen pump 100. Therefore, the hydrogen system 200 includes a temperature detector that detects the temperature of the cell of the electrochemical hydrogen pump 100, a temperature regulator that adjusts the temperature of the cell, and a hydrogen-containing gas supplied to the anode AN1 of the electrochemical hydrogen pump 100. A dew point adjuster for adjusting the dew point, a heater for heating a flow path through which a high-humidity hydrogen-containing gas flows, and the like may be provided.

The members and devices (not shown above) are examples and are not limited to this example.

The hydrogen generator 110 is a device that generates a hydrogen-containing gas by a reforming reaction using a raw material. The hydrogen generator 110 may have any configuration as long as it can generate a hydrogen-containing gas by a reforming reaction using a raw material. The hydrogen generator 110 includes, for example, a reformer. That is, in the reforming catalyst of the reformer, hydrogen-containing gas (reforming gas) is generated by the reforming reaction of the raw material. The raw material may be a hydrocarbon gas containing an organic compound composed of at least carbon and hydrogen such as city gas containing methane as a main component or natural gas, or may be a liquid. Examples of the liquid include alcohols such as methanol. Further, the hydrogen generator 110 may be provided with a CO reducer for reducing carbon monoxide (CO) in the reformed gas.

When the reforming reaction is performed in the hydrogen generator 110, in addition to the reformer, for example, a combustor, a raw material supply device, a water supply device, and various detectors (for example, a temperature detector and a flow meter). Various devices and devices such as) are required, but all of them are known. The details of the combustor will be described in the fifth embodiment. Illustrations and detailed explanations of devices and devices other than combustors will be omitted.

Next, the flow path configuration of the hydrogen system 200 of the present embodiment will be described.

The first flow path 11 is a flow path for supplying the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 to the hydrogen generator 110.

The upstream end of the first flow path 11 may be connected to any location as long as it communicates with the cathode CA1 of the electrochemical hydrogen pump 100. When the electrochemical hydrogen pump 100 includes the above stack, the upstream end of the first flow path 11 may communicate with, for example, a cathode off gas lead-out manifold. The downstream end of the first flow path 11 may be connected to any location as long as it communicates with the hydrogen generator 110. Specific examples of such connection points will be described in Examples.

The first on-off valve 21 is a valve provided in the first flow path 11. The first on-off valve 21 may have any configuration as long as it can open and close the first flow path 11. As the first on-off valve 21, for example, a drive valve or a solenoid valve driven by nitrogen gas or the like can be used, but the first on-off valve 21 is not limited thereto.

The controller 50 opens the first on-off valve 21 when stopped. Further, the controller 50 may control the entire operation of the hydrogen system 200. Here, "when stopped" means when the hydrogen generation operation of the hydrogen generator 110 is stopped, for example, the supply of the reactant used for the reforming reaction in the reforming catalyst of the hydrogen generator 110 is stopped. It is possible to exemplify when there is. Examples of the reaction product include raw materials, water, and air. For example, when the reforming reaction is a steam reforming reaction or an autothermal reaction, examples of the above-mentioned reactants include raw materials and steam, or raw materials, steam and oxygen.

The controller 50 includes, for example, an arithmetic circuit (not shown) and a storage circuit (not shown) for storing a control program. Examples of the arithmetic circuit include an MPU, a CPU, and the like. Examples of the storage circuit include a memory and the like. The controller 50 may be composed of a single controller that performs centralized control, or may be composed of a plurality of controllers that perform distributed control in cooperation with each other.

[motion]
Hereinafter, an example of the operation of the hydrogen system 200 will be described with reference to the drawings. The following operation may be performed, for example, by the arithmetic circuit of the controller 50 reading a control program from the storage circuit of the controller 50. However, it is not always essential to perform the following operations on the controller 50. The operator may perform some of the operations. In the following example, the case where the operation is controlled by the controller 50 will be described.

First, the hydrogen generator 110 performs a hydrogen generation operation to generate a hydrogen-containing gas generated by a reforming reaction using a raw material. For example, in the reforming catalyst of the hydrogen generator 110, a steam reforming reaction or an autothermal reaction of the raw material is performed. Since the hydrogen generation operation by such a steam reforming reaction or an autothermal reaction is known, detailed description thereof will be omitted.

Next, a low-pressure and high-humidity hydrogen-containing gas is supplied to the anode AN1 of the electrochemical hydrogen pump 100, and a voltage between the anode AN1 and the cathode CA1 is applied. The voltage of the voltage applyer (not shown) is supplied to the electrochemical hydrogen pump 100. At this time, the first on-off valve 21 is closed. As the hydrogen-containing gas supplied to the anode AN1 of the electrochemical hydrogen pump 100, the hydrogen-containing gas (reformed gas) generated by the hydrogen generator 110 can be used.

Then, in the anode catalyst layer of the anode AN1, hydrogen molecules are separated into protons and electrons (formula (1)). Protons conduct in the electrolyte membrane 30A and move to the cathode catalyst layer. Electrons move to the cathode catalyst layer through a voltage applyer (not shown). Then, hydrogen molecules are generated again in the cathode catalyst layer (Equation (2)). It is known that when protons conduct through the electrolyte membrane 30A, a predetermined amount of water moves from the anode AN1 to the cathode CA1 as electroosmotic water along with the protons.

At this time, for example, when the cathode off gas containing hydrogen generated by the cathode CA1 of the electrochemical hydrogen pump 100 is supplied to the hydrogen reservoir through the cathode off gas flow path, an on-off valve provided in the cathode off gas supply flow path or the like. By increasing the pressure loss of the cathode off gas supply flow path, hydrogen can be compressed by the cathode CA1. Here, increasing the pressure loss of the cathode off gas flow path corresponds to reducing the opening degree of the on-off valve. As the hydrogen reservoir, for example, a hydrogen tank can be mentioned. The hydrogen storage device may be in the form of directly filling and storing hydrogen in a container without using a hydrogen storage material such as a hydrogen storage alloy, or hydrogen is stored in a container for storing a hydrogen storage material such as a hydrogen storage alloy. It may be in the form of storage.

Anode: _{H 2} (low ^{pressure) → 2H + + 2e - ···} (1)
_{^{Cathode: 2H + + 2e - → H}} 2 ( high pressure) (2)
In this way, in the hydrogen system 200, by applying a voltage between the anode AN1 and the cathode CA1 of the electrochemical hydrogen pump 100, hydrogen in the hydrogen-containing gas supplied to the anode AN1 is transferred through the electrolyte membrane 30A. A hydrogen compression operation is performed in which the cathode CA1 is moved and compressed. The high-pressure hydrogen generated by the cathode CA1 is temporarily stored in a hydrogen reservoir such as a dispenser or a hydrogen tank installed in a hydrogen station, for example. Further, the hydrogen stored in the hydrogen reservoir is supplied to the hydrogen demander in a timely manner. Examples of hydrogen demanders include fuel cells that generate electricity using hydrogen.

Next, the operation of the hydrogen generator 110 is stopped. For example, in this operation stop, the supply of the reactant used for the reforming reaction in the reforming catalyst of the hydrogen generator 110 is stopped. As a result, the operation of generating the hydrogen-containing gas (hydrogen generation operation) in the hydrogen generator 110 is stopped.

Here, when the electrochemical hydrogen pump 100 is, for example, a compressor for a fuel cell forklift, when the hydrogen generation operation is stopped, the cathode CA1 side has a high pressure of about 40 MPa and a low humidity (for example, about about 40 MPa). Hydrogen has a relative humidity of about 300 ppm at about 50 ° C.). Further, on the anode AN1 side, there is a hydrogen-containing gas having a low pressure of about 0.1 MPa and a high humidity (for example, about 50 ° C. and a relative humidity of about 12%).

Therefore, when the hydrogen generation operation is stopped, the first on-off valve 21 is opened. Then, the operation of supplying the high-pressure hydrogen compressed by the cathode CA1 to the hydrogen generator 110 as the cathode off gas is performed.

As described above, the method of operating the hydrogen system 200 and the hydrogen system 200 of the present embodiment can suppress deterioration of the reforming catalyst of the hydrogen generator 110 more than before.

Specifically, in the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment, when the hydrogen generation operation of the hydrogen generator 110 is stopped, the first on-off valve 21 is opened to enter the hydrogen generator 110. The existing high humidity hydrogen-containing gas can be replaced with a low humidity cathode off gas supplied from the cathode CA1 of the electrochemical hydrogen pump 100. That is, since the high-humidity hydrogen-containing gas is pushed out of the hydrogen generator 110 by the low-humidity cathode-off gas, the gas existing in the hydrogen generator 110 is replaced with the latter cathode-off gas from the former hydrogen-containing gas. To. As a result, in the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment, even if the temperature of the hydrogen generator 110 is lowered, the condensation of water vapor in the hydrogen generator 110 is less likely to occur. Then, the reforming catalyst of the hydrogen generator 110 can reduce the possibility of deterioration due to water wetting.

(Example)
1A and 1B are diagrams showing an example of a hydrogen system according to an embodiment of the first embodiment.

In the example shown in FIG. 1A, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11A, a second flow path 12A, and a first on-off valve 21. And a controller 50.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted.

The second flow path 12A is a flow path for supplying the reactant for the reforming reaction to the hydrogen generator 110. That is, the downstream end of the second flow path 12A is connected to the hydrogen generator 110. Further, the first flow path 11A merges with the second flow path 12A. That is, the first flow path 11A extends to the point C1 where the first flow path 11A joins the second flow path 12A.

As a result, when the first on-off valve 21 is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped, the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 is used as a reactant for the reforming reaction. The operation of supplying the hydrogen generator 110 to the hydrogen generator 110 is performed via the second flow path 12A.

As the reactant, raw materials, water, air and the like can be exemplified as described above. For example, as shown in FIG. 1B, when the reactant is a raw material, the second flow path 12B is a flow path for supplying the raw material for the reforming reaction to the hydrogen generator 110. The first flow path 11B merges with the second flow path 12B. In this case, the upstream end of the second flow path 12B is connected to an appropriate raw material source. For example, when city gas is used as a raw material, the upstream end of the second flow path 12B is connected to the city gas main plug as the raw material source.

As described above, in the operation method of the hydrogen system 200 and the hydrogen system 200 of this embodiment, the points for introducing the reactant and the cathode off gas can be integrated in the hydrogen generator 110.

The operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment may be the same as that of the first embodiment except for the above-mentioned features.

(Second Embodiment)
[Device configuration]
FIG. 2 is a diagram showing an example of the hydrogen system of the second embodiment.

In the example shown in FIG. 2, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a first on-off valve 21, a controller 50, and the like. To prepare for.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted.

The hydrogen purifier 120 is provided upstream of the electrochemical hydrogen pump 100, and contains hydrogen supplied from the hydrogen generator 110 to the anode AN2 by applying a voltage between the anode AN2 and the cathode CA2 by the voltage applicator 10. This is a device that transfers hydrogen in the gas to the cathode CA2 via the electrolyte membrane 30B to generate a purified hydrogen-containing gas.

In the example shown in FIG. 2, the low-purity hydrogen-containing gas (reformed gas) generated by the hydrogen generator 110 is supplied to the anode AN2 of the hydrogen purifier 120 and is purified by the hydrogen purifier 120. A pure hydrogen-containing gas is supplied to the anode AN1 of the electrochemical hydrogen pump 100.

In the hydrogen system 200 of the present embodiment, the hydrogen purifier 120 may be composed of an electrochemical hydrogen pump having a low pressure specification. Then, by applying a voltage between the cathode CA2 of the hydrogen purifier 120 and the anode AN2, hydrogen can be compressed to about several hundred KPa by the cathode CA2 of the hydrogen purifier 120. In this case, the stack of the hydrogen purifier 120 may be configured in the same manner as the stack of the electrochemical hydrogen pump 100, except that the laminated member is made of a material and a form having a low pressure specification. Further, the voltage applicator 10 of the hydrogen purifier 120 may be configured in the same manner as the voltage applicator of the electrochemical hydrogen pump 100.

[motion]
Hereinafter, an example of the operation of the hydrogen system 200 will be described with reference to the drawings. The following operation may be performed, for example, by the arithmetic circuit of the controller 50 reading a control program from the storage circuit of the controller 50. However, it is not always essential to perform the following operations on the controller 50. The operator may perform some of the operations. In the following example, the case where the operation is controlled by the controller 50 will be described.

Here, since the hydrogen generation operation of the hydrogen generator 110 and the hydrogen compression operation of the electrochemical hydrogen pump 100 are the same as those of the first embodiment, the description thereof will be omitted.

When the hydrogen generation operation of the hydrogen generator 110 starts, hydrogen in the hydrogen-containing gas supplied from the hydrogen generator 110 to the anode AN2 is applied by applying a voltage between the anode AN2 and the cathode CA2 of the hydrogen purifier 120. , It is moved to the cathode CA2 via the electrolyte membrane 30B, and an operation of producing a purified hydrogen-containing gas is performed. The high-purity hydrogen-containing gas purified by the hydrogen purifier 120 is supplied to the anode AN1 of the electrochemical hydrogen pump 100. As a result, in the electrochemical hydrogen pump 100, a hydrogen-containing gas having a predetermined hydrogen purity or higher can be stably and continuously obtained except for the water content. The predetermined hydrogen purity satisfies the value specified in the above international standard (ISO14687-2).

As an example, the hydrogen purity of the hydrogen-containing gas supplied from the hydrogen generator 110 may be about 75%. Further, the hydrogen purity of the hydrogen-containing gas purified by the hydrogen purifier 120 may be 99.97% or more. The purity of hydrogen produced by the cathode CA1 of the electrochemical hydrogen pump 100 may be set to 99.99%. However, the above hydrogen purity values are examples and are not limited to this example.

Next, when the hydrogen generation operation of the hydrogen generator 110 is stopped, the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 is supplied to the anode AN2 of the hydrogen purifier 120 via the hydrogen generator 110. Is done.

As described above, in the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment, impurities (for example, CO ₂ , steam, etc.) in the hydrogen-containing gas generated by the hydrogen generator 110 using the hydrogen purifier 120 are used. Nitrogen etc.) can be removed appropriately.

Here, the electrochemical hydrogen pump 100 can also remove the above-mentioned impurities in the hydrogen-containing gas, but as in the hydrogen system 200 of the present embodiment, the hydrogen purifier 120 is placed in front of the electrochemical hydrogen pump 100. The reason for providing is as follows.

In the electrochemical hydrogen pump 100, the ability of the electrolyte membrane 30A to remove impurities in the hydrogen-containing gas is generally improved as the thickness of the electrolyte membrane 30A is thicker. Therefore, in order to purify the hydrogen existing in the cathode CA1 of the electrochemical hydrogen pump 100, the thickness of the electrolyte membrane 30A of the electrochemical hydrogen pump 100 may be increased, or the electrolytic hydrogen pump 100 may be used. It is necessary to increase the purity of the hydrogen-containing gas supplied to the anode AN1.

However, considering the case where hydrogen is compressed to a high pressure (for example, about several tens of MPa) by the cathode CA1 of the electrochemical hydrogen pump 100, the former configuration is the power consumption required for the hydrogen compression operation of the electrochemical hydrogen pump 100. Means an increase in.

Therefore, in the hydrogen system 200 of the present embodiment, the hydrogen purifier 120 is used to increase the purity of the hydrogen-containing gas supplied to the anode AN1 of the electrochemical hydrogen pump 100, whereby the electrolyte membrane of the electrochemical hydrogen pump 100 is increased. The hydrogen present in the cathode CA1 of the electrochemical hydrogen pump 100 is purified without increasing the thickness of 30A. As a result, the hydrogen system 200 of the present embodiment reduces the power consumption required for the hydrogen compression operation of the electrochemical hydrogen pump 100 as compared with the case where the hydrogen purifier 120 is not provided in front of the electrochemical hydrogen pump 100. be able to.

The hydrogen purifier 120 can compress hydrogen to a predetermined pressure at the cathode CA2 of the hydrogen purifier 120 by applying a voltage between the cathode CA2 and the anode AN2, but such a predetermined pressure is appropriate. By setting to (for example, about several hundred KPa), it is possible to appropriately suppress the power consumption in the hydrogen purifier 120.

Further, in the operation method of the hydrogen system 200 of the present embodiment, when the hydrogen generation operation of the hydrogen generator 110 is stopped, the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 is passed through the hydrogen generator 110. By supplying to the anode AN2 of the hydrogen purifier 120, the high-humidity hydrogen-containing gas existing in the flow path between the hydrogen generator 110 and the hydrogen purifier 120 as well as in the hydrogen generator 110 is electrochemically expressed. It can be replaced with a low humidity cathode off gas supplied from the cathode CA1 of the hydrogen pump 100. This makes it possible to suppress flooding in the flow path between the hydrogen generator 110 and the hydrogen generator 110 and the hydrogen purifier 120.

The operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment may be the same as that of the first embodiment or the first embodiment except for the above-mentioned features.

(Example)
The operation method of the hydrogen system 200 and the hydrogen system 200 of this embodiment is the same as that of the second embodiment except for the control contents of the controller 50 described below.

When the first on-off valve 21 is open, the controller 50 applies a voltage by the voltage applyr 10. Then, when the hydrogen generation operation of the hydrogen generator 110 is stopped, a voltage is applied between the anode AN2 and the cathode CA2 of the hydrogen purifier 120 to dissipate the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100. The operation of supplying to the anode AN1 of the electrochemical hydrogen pump 100 is performed via the hydrogen generator 110 and the hydrogen purifier 120.

As described above, in the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment, when the hydrogen generation operation of the hydrogen generator 110 is stopped, the first on-off valve 21 is opened and the cathode CA2 and the anode of the hydrogen purifier 120 are used. By applying a voltage between AN2, in addition to the inside of the hydrogen generator 110, in the hydrogen purifier 120, in the flow path between the hydrogen generator 110 and the hydrogen purifier 120, and in the hydrogen purifier 120 and the electrochemical hydrogen pump. The high humidity hydrogen-containing gas existing in the flow path between the 100 and the 100 can be replaced with the low humidity cathode off gas supplied from the cathode CA1 of the electrochemical hydrogen pump 100. This makes it possible to suppress flooding in the hydrogen purifier 120, the flow path between the hydrogen generator 110 and the hydrogen purifier 120, and the flow path between the hydrogen purifier 120 and the electrochemical hydrogen pump 100. ..

The operation method of the hydrogen system 200 and the hydrogen system 200 of this embodiment may be the same as any of the first embodiment, the first embodiment, and the second embodiment except for the above-mentioned features.

(Third Embodiment)
[Device configuration]
FIG. 3 is a diagram showing an example of the hydrogen system of the third embodiment.

In the example shown in FIG. 3, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a third flow path 13, and a fourth flow path 14. A first on-off valve 21, a second on-off valve 22, and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted.

The third flow path 13 is a flow path through which the hydrogen-containing gas supplied from the hydrogen purifier 120 to the anode AN1 of the electrochemical hydrogen pump 100 flows. The upstream end of the third flow path 13 may be connected to any location as long as it communicates with the cathode CA2 of the hydrogen purifier 120. When the hydrogen purifier 120 includes the above stack, the upstream end of the third flow path 13 may communicate with, for example, a manifold for deriving a hydrogen-containing gas, but the present invention is not limited to this. The downstream end of the third flow path 13 may be connected to any location as long as it communicates with the anode AN1 of the electrochemical hydrogen pump 100. When the electrochemical hydrogen pump 100 includes the above stack, the downstream end of the third flow path 13 may communicate with, for example, a manifold for introducing a hydrogen-containing gas, but the present invention is not limited to this.

The fourth flow path 14 is a flow path for supplying the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 to the third flow path 13. The upstream end of the fourth flow path 14 may be connected to any location as long as it communicates with the cathode CA1 of the electrochemical hydrogen pump 100. The downstream end of the fourth flow path 14 may be connected to any point as long as it communicates with the third flow path 13. In the example shown in FIG. 3, the fourth flow path 14 branches from the portion B1 of the first flow path 11 upstream of the first on-off valve 21, and the fourth flow path 14 merges with the third flow path 13. It extends to location C2. As a result, the hydrogen system 200 of the present embodiment can consolidate the locations for discharging the cathode off gas from the cathode CA1 and the locations for introducing the hydrogen-containing gas into the anode AN1 in the electrochemical hydrogen pump 100. can.

The second on-off valve 22 is a valve provided in the fourth flow path 14. The second on-off valve 22 may have any configuration as long as it can open and close the fourth flow path 14. As the second on-off valve 22, for example, a drive valve or a solenoid valve driven by nitrogen gas or the like can be used, but the second on-off valve 22 is not limited thereto.

The controller 50 opens the first on-off valve 21 and the second on-off valve 22 when the hydrogen generation operation of the hydrogen generator 110 is stopped.

[motion]
Hereinafter, an example of the operation of the hydrogen system 200 will be described with reference to the drawings. The following operation may be performed, for example, by the arithmetic circuit of the controller 50 reading a control program from the storage circuit of the controller 50. However, it is not always essential to perform the following operations on the controller 50. The operator may perform some of the operations. In the following example, the case where the operation is controlled by the controller 50 will be described.

Here, since the hydrogen generation operation of the hydrogen generator 110 and the hydrogen compression operation of the electrochemical hydrogen pump 100 are the same as those of the first embodiment, the description thereof will be omitted. Further, since the operation of producing the purified hydrogen-containing gas in the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted.

When the hydrogen generation operation of the hydrogen generator 110 is stopped, the first on-off valve 21 and the second on-off valve 22 are opened. Then, the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 can be supplied to the anode AN1 of the electrochemical hydrogen pump 100 without passing through the hydrogen generator 110 and the hydrogen purifier 120. ..

As described above, the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment is to open the first on-off valve 21 and the second on-off valve 22 when the hydrogen generation operation of the hydrogen generator 110 is stopped. , High-humidity hydrogen-containing gas existing in the third flow path 13 between the hydrogen purifier 120 and the electrochemical hydrogen pump 100 is used as a low-humidity cathode off gas supplied from the cathode CA1 of the electrochemical hydrogen pump 100. Can be replaced. That is, in the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment, the third flow path 13 between the hydrogen purifier 120 and the electrochemical hydrogen pump 100 is improved while improving the power consumption efficiency of the voltage adapter 10. Flooding can be suppressed.

The operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment is the same as any one of the first embodiment, the first embodiment, the second embodiment, and the second embodiment except for the above-mentioned features. May be.

(Fourth Embodiment)
[Device configuration]
FIG. 4 is a diagram showing an example of the hydrogen system of the fourth embodiment.

In the example shown in FIG. 4, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a fifth flow path 15, and a first on-off valve 21. And a controller 50.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted.

The fifth flow path 15 is a flow path for supplying the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the anode AN2 of the hydrogen purifier 120.

The upstream end of the fifth flow path 15 may be connected to any location as long as it communicates with the anode AN1 of the electrochemical hydrogen pump 100. When the electrochemical hydrogen pump 100 includes the above stack, the upstream end of the fifth flow path 15 may communicate with, for example, a manifold for deriving a hydrogen-containing gas, but the present invention is not limited to this. The downstream end of the fifth flow path 15 may be connected to any location as long as it communicates with the anode AN2 of the hydrogen purifier 120. In the example shown in FIG. 4, the fifth flow path 15 extends to a point C3 where the fifth flow path 15 joins the flow path between the hydrogen generator 110 and the hydrogen purifier 120. As a result, the hydrogen system 200 of the present embodiment can consolidate the locations for introducing the hydrogen-containing gas into the anode AN2 in the hydrogen purifier 120.

[motion]
Hereinafter, an example of the operation of the hydrogen system 200 will be described with reference to the drawings. The following operation may be performed, for example, by the arithmetic circuit of the controller 50 reading a control program from the storage circuit of the controller 50. However, it is not always essential to perform the following operations on the controller 50. The operator may perform some of the operations. In the following example, the case where the operation is controlled by the controller 50 will be described.

Here, since the hydrogen generation operation of the hydrogen generator 110 and the hydrogen compression operation of the electrochemical hydrogen pump 100 are the same as those of the first embodiment, the description thereof will be omitted. Further, since the operation of producing the purified hydrogen-containing gas in the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted.

When the hydrogen generation operation of the hydrogen generator 110 is stopped, the operation of supplying the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the anode AN2 of the hydrogen purifier 120 is performed.

In the hydrogen purifier 120, the higher the purity of the hydrogen-containing gas at the anode AN2 of the hydrogen purifier 120, the higher the purity of the hydrogen-containing gas purified by the cathode CA2 of the hydrogen purifier 120. The higher the purity of the hydrogen-containing gas purified by the cathode CA2 of the hydrogen purifier 120, the more advantageous it is in purifying the hydrogen compressed by the electrochemical hydrogen pump 100.

Therefore, in the method of operating the hydrogen system 200 and the hydrogen system 200 of the present embodiment, the hydrogen purifier 120 uses the fifth flow path 15 to remove the high-purity anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100. By refluxing to the anode AN2 of the hydrogen purifier 120, the purity of the hydrogen-containing gas in the anode AN2 of the hydrogen purifier 120 can be increased. As a result, in the hydrogen system 200 of the present embodiment, for example, when hydrogen compressed by the cathode CA1 of the electrochemical hydrogen pump 100 is supplied to the hydrogen reservoir, the hydrogen purity of the hydrogen reservoir satisfies the above international standard. It becomes easier to control.

Except for the above features, the hydrogen system 200 and the operation method of the hydrogen system 200 of the present embodiment include the first embodiment, the first embodiment, the second embodiment, the second embodiment, and the third embodiment. It may be similar to any of the forms.

(Fifth Embodiment)
FIG. 5 is a diagram showing an example of the hydrogen system of the fifth embodiment.

In the example shown in FIG. 5, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a combustor 130, a first flow path 11, and a sixth flow path 16. A first on-off valve 21 and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted.

The combustor 130 is a device that supplies heat for the reforming reaction to the hydrogen generator 110. That is, the combustion heat of the combustor 130 heats the reforming catalyst of the hydrogen generator 110 to a temperature suitable for the reforming reaction (for example, about 600 ° C.).

The sixth flow path 16 is a flow path for supplying the anode off gas discharged from the anode AN2 of the hydrogen purifier 120 to the combustor 130. That is, in this case, the anode off gas discharged from the anode AN2 of the hydrogen purifier 120 is used as the fuel for the combustor 130.

The upstream end of the sixth flow path 16 may be connected to any location as long as it communicates with the anode AN2 of the hydrogen purifier 120. When the electrochemical hydrogen pump 100 includes the above stack, the upstream end of the sixth flow path 16 may communicate with, for example, a manifold for deriving a hydrogen-containing gas, but the present invention is not limited to this.

As described above, the hydrogen system 200 of the present embodiment supplies the anode off gas discharged from the anode AN2 of the hydrogen purifier 120 to the combustor 130 that supplies heat for the reforming reaction to the hydrogen generator 110. Can be done. Thereby, for example, during the operation of the hydrogen generator 110, the reforming catalyst of the hydrogen generator 110 can be heated to a temperature suitable for the reforming reaction by the combustion heat generated in the combustor 130.

Further, in the hydrogen system 200 of the present embodiment, for example, when the first on-off valve 21 is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped, the anode off gas discharged from the anode AN2 of the hydrogen purifier 120 is used. After being supplied to the combustor 130 through the sixth flow path 16, the combustor 130 appropriately exhausts the hydrogen.

Except for the above features, the hydrogen system 200 and the operation method of the hydrogen system 200 of the present embodiment are the first embodiment, the first embodiment, the second embodiment, the second embodiment, and the third embodiment. It may be similar to any of the embodiments and the fourth embodiment.

(Sixth Embodiment)
FIG. 6 is a diagram showing an example of the hydrogen system of the sixth embodiment.

In the example shown in FIG. 6, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a combustor 130, a first flow path 11, and a seventh flow path 17. A first on-off valve 21 and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted. Further, since the combustor 130 is the same as that of the fifth embodiment, the description thereof will be omitted.

The seventh flow path 17 is a flow path for supplying the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the combustor 130. That is, in this case, the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 is used as the fuel for the combustor 130.

The upstream end of the seventh flow path 17 may be connected to any location as long as it communicates with the anode AN1 of the electrochemical hydrogen pump 100. When the electrochemical hydrogen pump 100 includes the above stack, the upstream end of the seventh flow path 17 may communicate with, for example, a manifold for deriving a hydrogen-containing gas, but the present invention is not limited to this.

As described above, the hydrogen system 200 of the present embodiment supplies the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the combustor 130 that supplies heat for the reforming reaction to the hydrogen generator 110. be able to. Thereby, for example, during the operation of the hydrogen generator 110, the reforming catalyst of the hydrogen generator 110 can be heated to a temperature suitable for the reforming reaction by the combustion heat generated in the combustor 130.

Further, in the hydrogen system 200 of the present embodiment, for example, when the first on-off valve 21 is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped, the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 Is supplied to the combustor 130 through the seventh flow path 17, and then appropriately exhausted by the combustor 130.

Except for the above features, the hydrogen system 200 and the operation method of the hydrogen system 200 of the present embodiment are the first embodiment, the first embodiment, the second embodiment, the second embodiment, and the third embodiment. It may be the same as any one of the embodiment, the fourth embodiment and the fifth embodiment. For example, in the hydrogen system 200 of FIG. 6, the fourth flow path 14 and the second on-off valve 22 (see FIG. 3) described in the third embodiment may be provided. Then, in the hydrogen system 200 of the present embodiment, the second on-off valve 22 may be opened when the hydrogen generation operation of the hydrogen generator 110 is stopped.

(7th Embodiment)
[Device configuration]
FIG. 7 is a diagram showing an example of the hydrogen system of the seventh embodiment.

In the example shown in FIG. 7, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a combustor 130, an air supply device 140, a first flow path 11, and a first channel. It includes 6 flow paths 16, a first on-off valve 21, and a controller 50.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted. Further, since the combustor 130 and the sixth flow path 16 are the same as those in the fifth embodiment, the description thereof will be omitted.

The air supply device 140 is a device that supplies combustion air to the combustor 130. The air supply device 140 may have any configuration as long as such combustion air can be supplied to the combustor 130. As the air supply device 140, for example, a fan or the like can be mentioned.

When the hydrogen generation operation of the hydrogen generator 110 is stopped, the controller 50 operates the air supply device 140 to dilute and exhaust the anode off gas supplied to the combustor 130.

[motion]
Hereinafter, an example of the operation of the hydrogen system 200 will be described with reference to the drawings. The following operation may be performed, for example, by the arithmetic circuit of the controller 50 reading a control program from the storage circuit of the controller 50. However, it is not always essential to perform the following operations on the controller 50. The operator may perform some of the operations. In the following example, the case where the operation is controlled by the controller 50 will be described.

Here, since the hydrogen generation operation of the hydrogen generator 110 and the hydrogen compression operation of the electrochemical hydrogen pump 100 are the same as those of the first embodiment, the description thereof will be omitted. Further, since the operation of producing the purified hydrogen-containing gas in the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted.

When the hydrogen generation operation of the hydrogen generator 110 is stopped, the first on-off valve 21 is opened and the air supply device 140 is operated. Then, the anode off gas discharged from the anode AN2 of the hydrogen purifier 120 was supplied to the combustor 130 by the operation of supplying the combustor 130 of the hydrogen generator 110 and the combustion air to the combustor 130. The operation of diluting and exhausting the anode off-gas can be performed.

As described above, in the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment, the combustible component of the anode off gas is appropriately diluted by mixing the anode off gas and an appropriate amount of air in the combustor 130, and then the combustion is performed. The anode off gas can be exhausted to the outside from the vessel 130. As a result, in the operation method of the hydrogen system 200 and the hydrogen system 200 of the present embodiment, the hydrogen generator 110 is compared with the case where the anode off gas is burned and exhausted in the combustor 130 when the hydrogen generation operation of the hydrogen generator 110 is stopped. The excessive temperature rise can be appropriately suppressed.

Except for the above features, the hydrogen system 200 and the operation method of the hydrogen system 200 of the present embodiment are the first embodiment, the first embodiment, the second embodiment, the second embodiment, and the third embodiment. It may be the same as any one of the embodiment, the fourth embodiment, the fifth embodiment and the sixth embodiment. For example, in the hydrogen system 200 of FIG. 7, the seventh flow path 17 (see FIG. 6) described in the sixth embodiment may be provided together with the sixth flow path 16. As a result, when the hydrogen generation operation of the hydrogen generator 110 is stopped, the operation of supplying the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the combustor 130 of the hydrogen generator 110 and the operation of supplying the combustor 130 for combustion. By supplying air, the operation of diluting and exhausting the anode off gas supplied to the combustor 130 can be performed.

(8th Embodiment)
FIG. 8 is a diagram showing an example of the hydrogen system of the eighth embodiment.

In the example shown in FIG. 8, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a first flow path 11C, an eighth flow path 18, a first on-off valve 21, and a first check valve. A valve 31 and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted.

The eighth flow path 18 is a flow path through which the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 flows.

The upstream end of the eighth flow path 18 may be connected to any location as long as it communicates with the cathode CA1 of the electrochemical hydrogen pump 100. When the electrochemical hydrogen pump 100 includes the above stack, the upstream end of the eighth flow path 18 may communicate with, for example, a cathode off gas lead-out manifold. The eighth flow path 18 is extended so as to supply the cathode off gas (hydrogen) discharged from the cathode CA1 of the electrochemical hydrogen pump 100 to the hydrogen reservoir.

In the example shown in FIG. 8, the first flow path 11C is branched from the eighth flow path 18. That is, the first flow path 11C extends from the portion B2 where the first flow path 11C branches to the hydrogen generator 110. As a result, the hydrogen system 200 of the present embodiment can consolidate the locations for discharging the cathode off gas from the cathode CA1 in the electrochemical hydrogen pump 100.

The first check valve 31 is provided in the eighth flow path 18 downstream of the branch point B2 where the first flow path 11C branches, and the direction of the flow of the cathode off gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100. A valve that prevents reverse flow.

As described above, in the hydrogen system 200 of the present embodiment, by providing the first check valve 31 in the eighth flow path 18, the first on-off valve 21 is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped. Also, the amount of hydrogen passing through the first flow path 11 can be limited to an appropriate amount.

For example, when high-pressure hydrogen generated by the cathode CA1 of the electrochemical hydrogen pump 100 is supplied to the hydrogen reservoir through the eighth flow path 18, the first check valve 31 must be provided in the eighth flow path 18. When the first on-off valve 21 is opened, hydrogen in the hydrogen reservoir may move through the eighth flow path 18 and the first flow path 11C in this order. The system 200 can reduce such a possibility by providing the first check valve 31 in the eighth flow path 18. As a result, the decrease in efficiency of the hydrogen compression operation of the electrochemical hydrogen pump 100 is suppressed.

Here, by closing an appropriate on-off valve (not shown) provided in the eighth flow path 18, it is possible to limit the movement of hydrogen in the hydrogen reservoir to the first flow path 11C. However, if a malfunction occurs in this on-off valve, it becomes difficult to limit the movement of hydrogen to the first flow path 11C.

On the other hand, in the hydrogen system 200 of the present embodiment, the above-mentioned inconvenience can be alleviated by using the first check valve 31 having a simple structure.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. It may be the same as any one of the 5th embodiment, the 6th embodiment and the 7th embodiment.

(9th Embodiment)
FIG. 9 is a diagram showing an example of the hydrogen system of the ninth embodiment.

In the example shown in FIG. 9, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a first flow path 11B, a second flow path 12B, a first on-off valve 21, and a second check valve. A valve 32 and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the first flow path 11B and the second flow path 12B are the same as those in the first embodiment, the description thereof will be omitted.

The second check valve 32 is provided in the second flow path 12B upstream of the point C1 where the first flow path 11B joins, and allows the flow in the direction opposite to the direction of the flow of the reactant supplied from the reaction source. It is a valve to prevent.

As described above, in the hydrogen system 200 of the present embodiment, by providing the second check valve 32 in the second flow path 12B, when the first on-off valve 21 is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped. In addition, it is possible to prevent the high-pressure cathode off gas supplied from the cathode CA1 of the electrochemical hydrogen pump 100 to the hydrogen generator 110 from flowing into the reactant supply system of the low-pressure specification. As a result, the hydrogen system 200 of the present embodiment reduces damage to low-pressure equipment and the like provided in the reactant supply system as compared with the case where the second check valve 32 is not provided in the second flow path 12B. be able to.

Here, by closing an appropriate on-off valve (not shown) provided in the second flow path 12B, it is possible to suppress the inflow of high-pressure cathode off gas into the low-pressure reaction product supply system. However, if a malfunction occurs in this on-off valve, it becomes difficult to suppress the inflow of such cathode off gas.

On the other hand, in the hydrogen system 200 of the present embodiment, the above-mentioned inconvenience can be alleviated by using the second check valve 32 having a simple structure.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. It may be the same as any one of the 5th embodiment, the 6th embodiment, the 7th embodiment and the 8th embodiment.

(10th Embodiment)
FIG. 10 is a diagram showing an example of the hydrogen system of the tenth embodiment.

In the example shown in FIG. 10, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a fifth flow path 15, and a ninth flow path 19. A first on-off valve 21, a third check valve 33, and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted.

The ninth flow path 19 is a flow path through which the hydrogen-containing gas supplied from the hydrogen generator 110 to the hydrogen purifier 120 flows. The downstream end of the ninth flow path 19 may be connected to any location as long as it communicates with the anode AN2 of the hydrogen purifier 120. When the hydrogen purifier 120 includes the above stack, the downstream end of the ninth flow path 19 may communicate with, for example, a manifold for introducing a hydrogen-containing gas, but is not limited thereto.

In the example shown in FIG. 10, the fifth flow path 15 merges with the ninth flow path 19. Since the fifth flow path 15 is the same as the fifth flow path 15 described in the fourth embodiment, detailed description thereof will be omitted.

The third check valve 33 is provided in the ninth flow path 19 upstream of the point C3 where the fifth flow path 15 joins, and is in the direction opposite to the direction of the flow of the hydrogen-containing gas discharged from the hydrogen generator 110. It is a valve that prevents flow.

As described above, in the hydrogen system 200 of the present embodiment, the high-purity anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 is returned to the anode AN2 of the hydrogen purifier 120 by using the fifth flow path 15. By providing the third check valve 33 in the ninth flow path 19, it is possible to suppress the backflow of the anode off gas to the hydrogen generator 110. As a result, for example, when the anode off gas at a low temperature (for example, about 50 ° C. to 60 ° C.) flows into the hydrogen generator 110 during the hydrogen generation operation of the hydrogen generator 110, it is in a high temperature state (for example, about 600 ° C.). Although the temperature of the hydrogen generator 110 of the above is lowered, the hydrogen system 200 of the present embodiment can alleviate such inconvenience by the above configuration.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. It may be the same as any one of the 5th embodiment, the 6th embodiment, the 7th embodiment, the 8th embodiment and the 9th embodiment.

(11th Embodiment)
FIG. 11 is a diagram showing an example of the hydrogen system of the eleventh embodiment.

In the example shown in FIG. 11, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a third flow path 13, and a first on-off valve 21. A fourth check valve 34 and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted. Further, since the third flow path 13 is the same as that of the third embodiment, the description thereof will be omitted.

The fourth check valve 34 is a valve provided in the third flow path 13 to prevent the flow of the hydrogen-containing gas discharged from the hydrogen purifier 120 in the direction opposite to the flow direction.

As described above, in the hydrogen system 200 of the present embodiment, by providing the fourth check valve 34 in the third flow path 13, even if the electrolyte membrane 30A of the electrochemical hydrogen pump 100 is damaged, the electrochemical formula is used. Since high-pressure hydrogen existing in the cathode CA1 of the hydrogen pump 100 can be prevented from flowing back to the hydrogen purifier 120 through the third flow path 13, the hydrogen purifier 120 is less likely to fail.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. It may be the same as any one of the 5th embodiment, the 6th embodiment, the 7th embodiment, the 8th embodiment, the 9th embodiment and the 10th embodiment.

(12th Embodiment)
FIG. 12 is a diagram showing an example of the hydrogen system of the twelfth embodiment.

In the example shown in FIG. 12, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a fifth flow path 15, and a first on-off valve 21. , A fifth check valve 35, and a controller 50.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted. Further, since the fifth flow path 15 is the same as that of the fourth embodiment, the description thereof will be omitted.

The fifth check valve 35 is a valve provided in the fifth flow path 15 to prevent the flow of the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 in the direction opposite to the flow direction.

As described above, in the hydrogen system 200 of the present embodiment, by providing the fifth check valve 35 in the fifth flow path 15, low-purity hydrogen-containing gas is supplied from the hydrogen generator 110 to the hydrogen purifier 120. At this time, it is suppressed that the low-purity hydrogen-containing gas flows into the anode AN1 of the electrochemical hydrogen pump 100.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. It may be the same as any one of the 5th embodiment, the 6th embodiment, the 7th embodiment, the 8th embodiment, the 9th embodiment, the 10th embodiment and the 11th embodiment.

(13th Embodiment)
FIG. 13 is a diagram showing an example of the hydrogen system of the thirteenth embodiment.

In the example shown in FIG. 13, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a first flow path 11, a first on-off valve 21, a pressure reducing valve 40, and a controller 50. Be prepared.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted.

The pressure reducing valve 40 is provided in the first flow path 11 and is a valve for reducing the pressure of the cathode off gas discharged from the cathode of the electrochemical hydrogen pump 100.

As described above, in the hydrogen system 200 of the present embodiment, even if the first on-off valve 21 is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped, the hydrogen generator is passed through the first flow path 11 by the pressure reducing valve 40. The pressure of the cathode off gas supplied to 110 can be reduced. This makes it possible to reduce the possibility that the member used for the hydrogen generator 110 will be damaged.

In the example shown in FIG. 13, the pressure reducing valve 40 is provided in the first flow path 11 upstream of the first on-off valve 21. As a result, in the hydrogen system 200 of the present embodiment, when the hydrogen existing in the cathode CA1 of the electrochemical hydrogen pump 100 is high pressure, the arrangement of the first on-off valve 21 and the pressure reducing valve 40 is reversed as compared with the case where the arrangement is reversed. The pressure applied to the first on-off valve 21 can be reduced. Then, in the hydrogen system 200 of the present embodiment, the first on-off valve 21 can be configured by an inexpensive valve having a low pressure specification.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. It may be the same as any one of the fifth embodiment, the sixth embodiment, the seventh embodiment, the eighth embodiment, the ninth embodiment, the tenth embodiment, the eleventh embodiment and the twelfth embodiment.

(14th Embodiment)
FIG. 14 is a diagram showing an example of the hydrogen system of the 14th embodiment.

In the example shown in FIG. 14, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a first flow path 11, a first on-off valve 21, a sixth check valve 36, and a pressure reducing valve 40. And a controller 50.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the pressure reducing valve 40 is the same as that of the thirteenth embodiment, the description thereof will be omitted.

The sixth check valve 36 is provided in the first flow path 11 downstream of the pressure reducing valve 40 to prevent the flow of the hydrogen-containing gas discharged from the cathode CA1 of the electrochemical hydrogen pump 100 in the direction opposite to the flow direction. It is a valve to do. In the example shown in FIG. 14, the sixth check valve 36 is provided in the first flow path 11 downstream of the first on-off valve 21.

As described above, in the hydrogen system 200 of the present embodiment, the reaction product is provided when the reaction product is supplied from the reaction product source to the hydrogen generator 110 by providing the sixth check valve 36 in the first flow path 11. , The flow into the first flow path 11 is suppressed.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. It is the same as any one of the fifth embodiment, the sixth embodiment, the seventh embodiment, the eighth embodiment, the ninth embodiment, the tenth embodiment, the eleventh embodiment, the twelfth embodiment, and the thirteenth embodiment. You may.

(15th Embodiment)
FIG. 15 is a diagram showing an example of the hydrogen system of the fifteenth embodiment.

In the example shown in FIG. 15, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a first flow path 11, a first on-off valve 21, a sixth check valve 36, and a pressure reducing valve 40. A first flow rate controller 41 and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the pressure reducing valve 40 is the same as that of the thirteenth embodiment, the description thereof will be omitted. Further, since the sixth check valve 36 is the same as that of the fourteenth embodiment, the description thereof will be omitted.

The first flow rate regulator 41 is a device provided in the first flow path 11 downstream of the pressure reducing valve 40 and adjusts the flow rate of the cathode off gas. In the example shown in FIG. 15, the first flow rate regulator 41 is provided in the first flow path 11 between the first on-off valve 21 and the sixth check valve 36. The first flow rate controller 41 may have any configuration as long as the flow rate of the cathode off gas flowing through the first flow path 11 can be adjusted. As the first flow rate controller 41, for example, a mass flow controller or the like can be mentioned. In this embodiment, the first on-off valve 21 may not be provided and the first flow rate regulator 41 may also serve as the first on-off valve 21.

As described above, in the hydrogen system 200 of the present embodiment, even if the first on-off valve 21 is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped, the cathode off gas flowing through the first flow path 11 by the first flow rate controller 41. The flow rate of can be limited to the desired flow rate. Then, the hydrogen system 200 of the present embodiment stably supplies the cathode off gas from the cathode CA1 of the electrochemical hydrogen pump 100 to the hydrogen generator 110 through the first flow path 11 by reducing the flow rate of the cathode off gas. be able to. Further, in the hydrogen system 200 of the present embodiment, by reducing the flow rate of the cathode off gas, the time for the low humidity cathode off gas to pass through the hydrogen generator 110 can be lengthened. This makes it more difficult for the reforming catalyst of the hydrogen generator 110 to get wet.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. The fifth embodiment, the sixth embodiment, the seventh embodiment, the eighth embodiment, the ninth embodiment, the tenth embodiment, the eleventh embodiment, the twelfth embodiment, the thirteenth embodiment and the fourteenth embodiment. It may be the same as either.

(16th Embodiment)
The hydrogen system 200 of the present embodiment is the same as the hydrogen system 200 of the third embodiment (see FIG. 3) except for the control contents of the controller 50 described below.

The controller 50 closes the first on-off valve 21 and opens the second on-off valve 22 between the start of activation and the start of supply of the cathode off gas of the electrochemical hydrogen pump 100 to the hydrogen reservoir. At this time, if the gas pressure in the cathode CA1 of the electrochemical hydrogen pump 100 is not sufficient, a voltage may be applied between the anode AN1 and the cathode CA1 of the electrochemical hydrogen pump 100.

Here, "starting up" means that the starting up of the hydrogen system 200 is started, and for example, the starting up of the hydrogen system 200 may be started by the user performing an appropriate starting operation. , The start-up of the hydrogen system 200 may be automatically started at a predetermined start-up time.

As described above, the hydrogen system 200 of the present embodiment can improve the purity of hydrogen in the hydrogen reservoir as compared with the conventional case.

Specifically, for example, when the hydrogen compression operation of the hydrogen system 200 is stopped, hydrogen does not electrochemically move from the anode AN1 to the cathode CA1, so that the gas concentration of impurities present in each of the anode AN1 and the cathode CA1 is adjusted. The effect of the impurity cross leak that causes a small difference in chemical potential becomes large. In this case, if the cathode off gas is supplied to the hydrogen reservoir as it is when the hydrogen system 200 is started, the purity of hydrogen in the hydrogen reservoir may decrease.

Further, for example, if the gas pressure in the cathode CA1 becomes equal to or lower than the outside air pressure while the hydrogen compression operation of the hydrogen system 200 is stopped, impurities may be mixed into the cathode CA1 from the outside. In this case as well, if the cathode off gas is supplied to the hydrogen reservoir as it is when the hydrogen system 200 is started, the purity of hydrogen in the hydrogen reservoir may decrease.

However, in the hydrogen system 200 of the present embodiment, the cathode off gas containing impurities is electrochemically hydrogen by opening the second on-off valve 22 between the start of activation and the start of supply of the cathode off gas to the hydrogen reservoir. It can be exhausted to the anode AN1 of the pump 100. As a result, the hydrogen system 200 of the present embodiment can purify the cathode off gas (hydrogen) supplied from the electrochemical hydrogen pump 100 to the hydrogen reservoir.

Further, in the hydrogen system 200 of the present embodiment, by opening the second on-off valve 22 during the above period, the high-humidity hydrogen-containing gas existing in the anode AN1 of the electrochemical hydrogen pump 100 is electrochemically hydrogen pumped. It can be replaced with a low humidity cathode off gas supplied from 100 cathode CA1. As a result, in the hydrogen system 200 of the present embodiment, flooding of the anode gas flow path of the electrochemical hydrogen pump 100 is less likely to occur. Then, after opening the second on-off valve 22, the efficiency of the hydrogen compression operation can be appropriately maintained.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. 5th Embodiment, 6th Embodiment, 7th Embodiment, 8th Embodiment, 9th Embodiment, 10th Embodiment, 11th Embodiment, 12th Embodiment, 13th Embodiment, 14th Embodiment and It may be the same as any of the fifteenth embodiments.

(17th Embodiment)
FIG. 16 is a diagram showing an example of the hydrogen system of the 17th embodiment.

In the example shown in FIG. 16, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a fourth flow path 14A, and a first on-off valve 21. A second on-off valve 22A, a pressure reducing valve 40, and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted. Further, since the pressure reducing valve 40 is the same as that of the thirteenth embodiment, the description thereof will be omitted.

The fourth flow path 14A is shared with the first flow path 11 to the downstream of the pressure reducing valve 40, and then branches. In the example shown in FIG. 16, the fourth flow path 14A branches from the portion B3 of the first flow path 11 upstream of the first on-off valve 21 and downstream of the pressure reducing valve 40, and the fourth flow path 14A Extends to the point C2 where it joins the third flow path 13. This makes it possible to consolidate the locations for discharging the cathode off gas from the cathode CA1 and the locations for introducing the hydrogen-containing gas into the anode AN1 in the electrochemical hydrogen pump 100.

The second on-off valve 22A is a valve provided in the fourth flow path 14A. The second on-off valve 22A may have any configuration as long as it can open and close the fourth flow path 14A. As the second on-off valve 22A, for example, a drive valve or a solenoid valve driven by nitrogen gas or the like can be used, but the second on-off valve 22A is not limited thereto.

As described above, in the hydrogen system 200 of the present embodiment, even if the second on-off valve 22A is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped, the pressure reducing valve 40 passes through the fourth flow path 14A to provide an electrochemical hydrogen pump. The pressure of the cathode off gas supplied to the anode AN1 of 100 can be reduced. This makes it possible to reduce the possibility of damage to the member used for the anode AN1 of the electrochemical hydrogen pump 100.

Further, in the hydrogen system 200 of the present embodiment, the fourth flow path 14A is shared with the first flow path 11 to the downstream of the pressure reducing valve 40, so that the pressure is reduced in each of the first flow path 11 and the fourth flow path 14A. There is no need to provide a valve 40. Therefore, in the hydrogen system 200 of the present embodiment, the manufacturing cost can be reduced as compared with the case where the pressure reducing valves 40 are provided in each of the first flow path 11 and the fourth flow path 14A.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. A fifth embodiment, a sixth embodiment, a seventh embodiment, an eighth embodiment, a ninth embodiment, a tenth embodiment, an eleventh embodiment, a twelfth embodiment, a thirteenth embodiment, a fourteenth embodiment, It may be the same as any one of the fifteenth embodiment and the sixteenth embodiment.

(18th Embodiment)
FIG. 17 is a diagram showing an example of the hydrogen system of the 18th embodiment.

In the example shown in FIG. 17, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a first flow path 11, a fourth flow path 14A, and a first on-off valve 21. A second on-off valve 22A, a pressure reducing valve 40, a second flow rate regulator 42, and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted. Further, since the pressure reducing valve 40 is the same as that of the thirteenth embodiment, the description thereof will be omitted. Further, since the fourth flow path 14A and the second on-off valve 22A are the same as those in the 17th embodiment, the description thereof will be omitted.

The second flow rate regulator 42 is provided in the fourth flow path 14A after branching from the first flow path 11. In the example shown in FIG. 17, the second flow rate regulator 42 is provided in the fourth flow path 14A between the portion B3 where the fourth flow rate 14A branches and the second on-off valve 22A. The second flow rate regulator 42 may have any configuration as long as the flow rate of the cathode off gas flowing through the fourth flow path 14A can be adjusted. As the second flow rate controller 42, for example, a mass flow controller or the like can be mentioned. In this embodiment, the second on-off valve 22A may not be provided, and the second flow rate regulator 42 may also be used as the second on-off valve 22A.

As described above, in the hydrogen system 200 of the present embodiment, even if the second on-off valve 22A is opened when the hydrogen generation operation of the hydrogen generator 110 is stopped, the cathode off gas flowing through the fourth flow path 14A by the second flow rate controller 42. The flow rate of can be limited to the desired flow rate. Then, the hydrogen system 200 of the present embodiment can stably supply the cathode off gas from the cathode CA1 of the electrochemical hydrogen pump 100 to the anode AN1 through the fourth flow path 14A by reducing the flow rate of the cathode off gas. .. Further, in the hydrogen system 200 of the present embodiment, by reducing the flow rate of the cathode off gas, the time for the low humidity cathode off gas to pass through the anode AN1 of the electrochemical hydrogen pump 100 can be lengthened. As a result, flooding of the anode gas flow path of the electrochemical hydrogen pump 100 is less likely to occur.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. A fifth embodiment, a sixth embodiment, a seventh embodiment, an eighth embodiment, a ninth embodiment, a tenth embodiment, an eleventh embodiment, a twelfth embodiment, a thirteenth embodiment, a fourteenth embodiment, It may be the same as any one of the fifteenth embodiment, the sixteenth embodiment and the seventeenth embodiment.

(19th Embodiment)
FIG. 18 is a diagram showing an example of the hydrogen system of the 19th embodiment.

In the example shown in FIG. 18, the hydrogen system 200 includes an electrochemical hydrogen pump 100, a hydrogen generator 110, a hydrogen purifier 120, a combustor 130, a first flow path 11, and a fifth flow path 15A. A seventh flow path 17A, a first on-off valve 21, a third on-off valve 23, a fourth on-off valve 24, and a controller 50 are provided.

Here, since the electrochemical hydrogen pump 100, the hydrogen generator 110, the first flow path 11 and the first on-off valve 21 are the same as those in the first embodiment, the description thereof will be omitted. Further, since the hydrogen purifier 120 is the same as that of the second embodiment, the description thereof will be omitted. Further, since the combustor 130 is the same as that of the fifth embodiment, the description thereof will be omitted.

The fifth flow path 15A is a flow path for supplying the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the anode AN2 of the hydrogen purifier 120. The seventh flow path 17A is a flow path for supplying the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the combustor 130. In the example shown in FIG. 18, the fifth flow path 15A and the seventh flow path 17A are shared from the anode AN1 of the electrochemical hydrogen pump 100 to the portion B4 where both branches.

The third on-off valve 23 is a valve provided in the fifth flow path 15A. Specifically, the third on-off valve 23 is provided in the fifth flow path 15A downstream of the above-mentioned location B4. The third on-off valve 23 may have any configuration as long as it can open and close the fifth flow path 15A. As the third on-off valve 23, for example, a drive valve or a solenoid valve driven by nitrogen gas or the like can be used, but the third on-off valve 23 is not limited thereto.

The fourth on-off valve 24 is a valve provided in the seventh flow path 17A. Specifically, the fourth on-off valve 24 is provided in the seventh flow path 17A downstream of the above-mentioned location B4. The fourth on-off valve 24 may have any configuration as long as it can open and close the seventh flow path 17A. As the fourth on-off valve 24, for example, a drive valve or a solenoid valve driven by nitrogen gas or the like can be used, but the fourth on-off valve 24 is not limited thereto.

The controller 50 opens the third on-off valve 23 and closes the fourth on-off valve 24 when the hydrogen system 200 is in operation, and closes the third on-off valve 23 when the hydrogen generation operation of the hydrogen generator 110 is stopped. At the same time, the fourth on-off valve 24 is opened.

As described above, in the hydrogen purifier 120, the higher the purity of the hydrogen-containing gas in the anode AN2 of the hydrogen purifier 120, the higher the purity of the hydrogen-containing gas purified by the cathode CA2 of the hydrogen purifier 120.

Therefore, in the hydrogen system 200 of the present embodiment, the third on-off valve 23 is opened and the fourth on-off valve 24 is closed during operation, so that the fifth flow path 15A is used to open the electrochemical hydrogen pump 100. The high-purity anode off-gas discharged from the anode AN1 can be refluxed to the anode AN2 of the hydrogen purifier 120. Thereby, the hydrogen system 200 of the present embodiment can increase the purity of the hydrogen-containing gas in the cathode CA2 of the hydrogen purifier 120. As a result, in the hydrogen system 200 of the present embodiment, for example, when hydrogen compressed by the cathode CA1 of the electrochemical hydrogen pump 100 is supplied to the hydrogen reservoir, the hydrogen purity of the hydrogen reservoir satisfies the above international standard. It becomes easier to control.

On the other hand, in the hydrogen system 200 of the present embodiment, when the hydrogen generation operation of the hydrogen generator 110 is stopped, the third on-off valve 23 is closed and the fourth on-off valve 24 is opened to open the seventh flow path 17A. It can be used to supply the anode off gas discharged from the anode AN1 of the electrochemical hydrogen pump 100 to the combustor 130.

The hydrogen system 200 of the present embodiment has the first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, and the fourth embodiment, except for the above-mentioned features. A fifth embodiment, a sixth embodiment, a seventh embodiment, an eighth embodiment, a ninth embodiment, a tenth embodiment, an eleventh embodiment, a twelfth embodiment, a thirteenth embodiment, a fourteenth embodiment, It may be the same as any one of the 15th embodiment, the 16th embodiment, the 17th embodiment and the 18th embodiment.

The first embodiment, the first embodiment, the second embodiment, the second embodiment, the third embodiment, the fourth embodiment, the fifth embodiment, the sixth embodiment, and the seventh embodiment. Embodiment, 8th embodiment, 9th embodiment, 10th embodiment, 11th embodiment, 12th embodiment, 13th embodiment, 14th embodiment, 15th embodiment, 16th embodiment, 17th embodiment The embodiment, the 18th embodiment and the 19th embodiment may be combined with each other as long as the other party is not excluded from each other.

From the above description, many improvements and other embodiments of the present disclosure will be apparent to those of skill in the art. Accordingly, the above description should be construed as an example only and is provided for the purpose of teaching those skilled in the art the best aspects of carrying out the present disclosure. The details of its structure and / or function may be substantially modified without departing from the spirit of the present disclosure. For example, the present disclosure can also be applied to a hydrogen system including a compressor other than the electrochemical hydrogen pump 100 such as a water electrolyzer.

One aspect of the present disclosure can be used for a hydrogen system and a method for operating a hydrogen system, which can suppress deterioration of a reforming catalyst of a hydrogen generator more than before.

10: Voltage applyer 11: 1st flow path 11A: 1st flow path 11B: 1st flow path 11C: 1st flow path 12: 2nd flow path 12A: 2nd flow path 12B: 2nd flow path 13: 1st 3 flow paths 14: 4th flow path 14A: 4th flow path 15: 5th flow path 15A: 5th flow path 16: 6th flow path 17: 7th flow path 17A: 7th flow path 18: 8th flow path Road 19: 9th flow path 21: 1st on-off valve 22: 2nd on-off valve 22A: 2nd on-off valve 23: 3rd on-off valve 24: 4th on-off valve 30A: Electrolyte membrane 30B: Electrolyte membrane 31: 1st reverse Stop valve 32: 2nd check valve 33: 3rd check valve 34: 4th check valve 35: 5th check valve 36: 6th check valve 40: Pressure reducing valve 41: 1st flow regulator 42: Second flow controller 50: Controller 100: Electrochemical hydrogen pump 110: Hydrogen generator 120: Hydrogen purifier 130: Combustor 140: Air supply device 200: Hydrogen system AN1: Anode AN2: Anode B1: Location B2: Location B3: Location B4: Location C1: Location C2: Location C3: Location CA1: Cathode CA2: Cathode

Claims (31)

A hydrogen generator that generates hydrogen-containing gas by a reforming reaction using raw materials,
A compressor that moves hydrogen in the hydrogen-containing gas supplied to the anode to the cathode via the electrolyte membrane and compresses it by applying a voltage between the anode and the cathode.
A first flow path for supplying the cathode off gas discharged from the cathode of the compressor to the hydrogen generator, and
The first on-off valve provided in the first flow path and
A hydrogen system comprising a controller that opens the first on-off valve when stopped. The hydrogen generator is provided with a second flow path for supplying a reactant for the reforming reaction.
The hydrogen system according to claim 1, wherein the first flow path joins the second flow path. The hydrogen system according to claim 2, wherein the reactant is the raw material. By applying a voltage between the anode and the cathode by a voltage applyer provided upstream of the compressor, hydrogen in the hydrogen-containing gas supplied from the hydrogen generator to the anode is transferred to the cathode via the electrolyte membrane. The hydrogen system according to any one of claims 1-3, comprising a hydrogen purifier that is transferred to and produces a purified hydrogen-containing gas. The hydrogen system according to claim 4, wherein the controller applies a voltage by the voltage applyer when the first on-off valve is open. A third flow path through which hydrogen-containing gas supplied from the hydrogen purifier to the anode of the compressor flows, and
A fourth flow path that supplies the cathode off gas discharged from the cathode of the compressor to the third flow path, and
A second on-off valve provided in the fourth flow path is provided.
The hydrogen system according to claim 4 or 5, wherein the controller opens the first on-off valve and the second on-off valve when stopped. The hydrogen system according to claim 5 or 6, further comprising a fifth flow path for supplying the anode off gas discharged from the anode of the compressor to the anode of the hydrogen purifier. A combustor that supplies heat for the reforming reaction to the hydrogen generator,
The hydrogen system according to any one of claims 4-7, comprising a sixth flow path for supplying the anode off gas discharged from the anode of the hydrogen purifier to the combustor. A combustor that supplies heat for the reforming reaction to the hydrogen generator,
The hydrogen system according to claim 5 or 6, comprising a seventh flow path for supplying the anode off gas discharged from the anode of the compressor to the combustor. The combustor is equipped with an air supply device that supplies combustion air.
The hydrogen system according to claim 8 or 9, wherein the controller operates the air supply device when stopped to dilute and exhaust the anode off gas supplied to the combustor. It is provided with an eighth flow path through which the cathode off gas discharged from the cathode of the compressor flows.
The first flow path is branched from the eighth flow path.
The eighth flow path downstream of the branch of the first flow path is provided with a first check valve for preventing the flow of the cathode off gas discharged from the cathode of the compressor in the direction opposite to the direction of the flow. The hydrogen system according to any one of claims 1-10. A second check valve is provided in the second flow path upstream of the point where the first flow path merges to prevent the flow of the reactants supplied from the reaction source in the direction opposite to the direction of the flow. Item 2. The hydrogen system according to Item 2 or 3. A ninth flow path through which hydrogen-containing gas supplied from the hydrogen generator to the hydrogen purifier flows is provided, and the fifth flow path merges with the ninth flow path.
A third check valve for preventing the flow of hydrogen-containing gas discharged from the hydrogen generator in the direction opposite to the direction of the flow is provided in the ninth flow path upstream of the point where the fifth flow path merges. , The hydrogen system according to claim 7. A third flow path through which hydrogen-containing gas supplied from the hydrogen purifier to the anode of the compressor flows is provided, and the direction of the flow of the hydrogen-containing gas discharged from the hydrogen purifier is reversed in the third flow path. The hydrogen system according to claim 4, further comprising a fourth check valve that prevents directional flow. The hydrogen system according to claim 7, wherein the fifth flow path includes a fifth check valve for preventing a flow of the anode off gas discharged from the anode of the compressor in the direction opposite to the direction of the flow. The hydrogen system according to any one of claims 1-15, wherein the first flow path includes a pressure reducing valve for reducing the pressure of the cathode off gas discharged from the cathode of the compressor. 16. The described hydrogen system. The hydrogen system according to claim 16 or 17, wherein a first flow rate controller for adjusting the flow rate of the cathode off gas is provided in the first flow path downstream of the pressure reducing valve. The controller claims to close the first on-off valve and open the second on-off valve between the start of activation and the start of supply of the cathode off gas of the compressor to the hydrogen reservoir. 6. The hydrogen system according to 6. The first flow path is provided with a pressure reducing valve for reducing the pressure of the cathode off gas discharged from the cathode of the compressor.
The hydrogen system according to claim 6, wherein the fourth flow path is shared with the first flow path to the downstream of the pressure reducing valve and then branched. The hydrogen system according to claim 20, wherein a second flow rate controller is provided in the fourth flow path after branching from the first flow path. A fifth flow path for supplying the anode off gas discharged from the anode of the compressor to the anode of the hydrogen purifier, and
The third on-off valve provided in the fifth flow path and
A fourth on-off valve provided in the seventh flow path is provided.
The controller opens the third on-off valve and closes the fourth on-off valve during operation.
The hydrogen system according to claim 9, wherein the third on-off valve is closed and the fourth on-off valve is opened when the system is stopped. A step to generate a hydrogen-containing gas generated by a reforming reaction using raw materials in a hydrogen generator, and
By applying a voltage between the anode and cathode of the compressor, hydrogen in the hydrogen-containing gas supplied to the anode is moved to the cathode via the electrolyte membrane and compressed.
A method of operating a hydrogen system, comprising a step of supplying a cathode off gas discharged from the cathode of the compressor to the hydrogen generator when the compressor is stopped. 23. The operation of the hydrogen system according to claim 23, wherein when stopped, the cathode off gas discharged from the cathode of the compressor is supplied to the hydrogen generator via a flow path for supplying a reactant for a reforming reaction. Method. The method for operating a hydrogen system according to claim 24, wherein the reactant is the raw material. By applying a voltage between the anode and the cathode of the hydrogen purifier provided upstream of the compressor, hydrogen in the hydrogen-containing gas supplied from the hydrogen generator to the anode is transferred to the cathode via the electrolyte membrane. With steps to generate purified hydrogen-containing gas,
The hydrogen system according to any one of claims 23-25, wherein when stopped, the cathode off gas discharged from the cathode of the compressor is supplied to the anode of the hydrogen purifier via the hydrogen generator. how to drive. By applying a voltage between the anode and the cathode of the hydrogen purifier when stopped, the cathode off gas discharged from the cathode of the compressor is sent to the compressor via the hydrogen generator and the hydrogen purifier. 26. The method of operating a hydrogen system according to claim 26, which is supplied to the anode of the above. The hydrogen system according to claim 26 or 27, wherein when stopped, the cathode off gas discharged from the cathode of the compressor is supplied to the anode of the compressor without passing through the hydrogen generator and the hydrogen purifier. How to drive. 28. The method of operating a hydrogen system according to claim 27 or 28, comprising a step of supplying the anode off gas discharged from the anode of the compressor to the anode of the hydrogen purifier when stopped. The step of supplying the anode off gas discharged from the anode of the hydrogen purifier to the combustor of the hydrogen generator at the time of stopping, and
The method for operating a hydrogen system according to any one of claims 26 to 29, comprising a step of diluting and exhausting the anode off gas supplied to the combustor by supplying combustion air to the combustor. .. A step of supplying the anode off gas discharged from the anode of the compressor to the combustor of the hydrogen generator when the compressor is stopped.
The method for operating a hydrogen system according to any one of claims 26 to 29, comprising a step of diluting and exhausting the anode off gas supplied to the combustor by supplying combustion air to the combustor. ..

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