WO2021192136A1

WO2021192136A1 - Hydrogen generation system and hydrogen generation method

Info

Publication number: WO2021192136A1
Application number: PCT/JP2020/013589
Authority: WO
Inventors: 石川　敬郎
Original assignee: 株式会社日立製作所
Priority date: 2020-03-26
Filing date: 2020-03-26
Publication date: 2021-09-30
Also published as: JPWO2021192136A1

Abstract

The purpose of the present disclosure is to provide a hydrogen generation system or a hydrogen generation method in which a dehydrogenation reaction can be carried out at a low temperature. The present embodiment is a hydrogen generation system for generating hydrogen by subjecting a hydrogen storage material to a dehydrogenation reaction using a catalyst, the hydrogen generation system being characterized by comprising: a feeding unit for feeding the hydrogen storage material intermittently; a vaporization unit for vaporizing the hydrogen storage material fed by the feeding unit; a dehydrogenation reaction unit for bringing the hydrogen storage material from the vaporization unit into contact with a catalyst and performing a dehydrogenation reaction to convert the hydrogen storage material into hydrogen and a dehydrogenated product; a sucking unit for reducing the pressure of the atmosphere in the dehydrogenation reaction unit by sucking; and a gas-liquid separation unit for separating a mixture containing a hydrogen gas and the dehydrogenated product which have been sucked by the sucking unit into a gas mainly containing hydrogen and a liquid mainly containing the dehydrogenated product.

Description

Hydrogen generation system and hydrogen generation method

This embodiment relates to a hydrogen generation system that produces hydrogen from a hydrogen reservoir. The present embodiment also relates to a hydrogen generation method for producing hydrogen from a hydrogen reservoir.

Amid global warming caused by carbon dioxide, hydrogen is attracting attention as an energy source that will carry the next generation in place of fossil fuels. As a means for producing hydrogen, a system or method for extracting hydrogen by a dehydrogenation reaction from a hydrogen storage such as organic hydride as a hydrogen storage has been proposed.

For example, in Patent Document 1, hydrogen and a dehydrogenated product of the hydrogen reservoir are produced by contacting a hydrogen reservoir capable of chemically storing hydrogen with a catalyst to cause a dehydrogenation reaction, and the produced hydrogen is used. A method of supplying hydrogen to another apparatus, in which the hydrogen reservoir is vaporized, and the vaporized hydrogen reservoir is heated to 200 ° C. or lower at least at intervals at which the dehydrogenated substance is removed from the catalyst. The hydrogen and the dehydrogenate are generated by contacting with the catalyst to carry out the dehydrogenation reaction, and the generated hydrogen and the generated dehydrogenate are unreacted in the dehydrogenation reaction. Disclosed is a hydrogen supply method characterized in that the hydrogen storage body and the hydrogen storage body, which have been used above, are sent out of the system at different timings by the action of the catalyst. Patent Document 1 aims to efficiently carry out a dehydrogenation reaction even at a low temperature.

Japanese Unexamined Patent Publication No. 2010-235359

As in Patent Document 1, the realization of a dehydrogenation reaction at a low temperature is desirable from the viewpoint of energy efficiency and energy saving. For example, by realizing the dehydrogenation reaction at a low temperature, the catalyst can be heated to a temperature sufficient for the reaction even if factory waste heat, hot water waste heat, solar heat, etc., which are relatively low temperatures, are used. Therefore, the development of a new hydrogen generation system capable of performing a dehydrogenation reaction at a low temperature is required.

Therefore, an object of the present disclosure is to provide a hydrogen generation system or a hydrogen generation method capable of carrying out a dehydrogenation reaction at a low temperature.

This embodiment can be expressed as follows, for example.

A hydrogen generation system that produces hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
A supply unit that intermittently supplies hydrogen storage and
A vaporizer that vaporizes the hydrogen reservoir supplied from the supply unit,
A dehydrogenation reaction section that brings the hydrogen reservoir from the vaporization section into contact with a catalyst to perform a dehydrogenation reaction and converts it into hydrogen and a dehydrogenated product.
A suction part that decompresses the atmosphere inside the dehydrogenation reaction part by suction,
A gas-liquid separator that separates a mixture containing hydrogen gas and dehydrogenated material sucked by the suction unit into a gas that mainly contains hydrogen and a liquid that mainly contains dehydrogenated material.
A hydrogen generation system characterized by being equipped with.

A method of producing hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
The process of supplying hydrogen storage and
The process of vaporizing the supplied hydrogen reservoir and
A step of bringing a vaporized hydrogen reservoir into contact with a catalyst to carry out a dehydrogenation reaction to convert hydrogen into a dehydrogenated product, which is a step of carrying out the dehydrogenation reaction under reduced pressure by suction.
A step of separating the suctioned mixture containing hydrogen and dehydrogenated product into a gas containing mainly hydrogen and a liquid containing mainly dehydrogenated product.
A method characterized by including.

According to the present disclosure, it is possible to provide a hydrogen generation system or a hydrogen generation method capable of carrying out a dehydrogenation reaction at a low temperature.

It is a block diagram for demonstrating the configuration example of the hydrogen supply system which concerns on this embodiment. It is a schematic diagram for demonstrating the structural example of the dehydrogenation reaction part in the hydrogen supply system which concerns on this embodiment. It is a schematic diagram explaining the structural example of the gas-liquid separation part in the hydrogen supply system which concerns on this embodiment. It is a block diagram for demonstrating the configuration example of the hydrogen supply system which concerns on this embodiment. It is a block diagram which shows the structural example of the power generation system which combined the hydrogen supply system and the polymer electrolyte fuel cell which concerns on this Embodiment. It is a block diagram which shows the structural example of the engine system which combined the hydrogen supply system and the engine which concerns on this embodiment. It is a block diagram which shows the structural example of the hydrogen storage system which combined the hydrogen supply system and the compressor which concerns on this embodiment. It is a block diagram which shows the composition example of the hydrogen community using the hydrogen supply system which concerns on this embodiment.

Hereinafter, this embodiment will be described with reference to the drawings. The following description and drawings are examples for explaining the present embodiment, and are appropriately omitted and simplified for clarification of the description. This embodiment can also be implemented in various other forms. Unless otherwise specified, each component may be singular or plural.

When there are a plurality of components having the same or similar functions, they are basically given the same reference numerals, but even if the functions are the same, the means for realizing the functions may be different.

Further, in the following description, a process of executing a program may be described, but the program is executed by a processor (for example, a CPU) which is a central processing unit, so that a predetermined process can be appropriately performed. Since it is performed while using a storage resource (for example, memory) and / or an interface device (for example, a communication port), the main body of processing is a processor, but a program that facilitates understanding of the invention may be explained as a subject.

The program may be installed from the program source on a device such as a calculator. The program source may be, for example, a program distribution server or a computer-readable storage medium. When the program source is a program distribution server, the program distribution server includes a processor and a storage resource for storing the program to be distributed, and the processor of the program distribution server may distribute the program to be distributed to other computers. Further, in the following description, two or more programs may be realized as one program, or one program may be realized as two or more programs.

The hydrogen generation system according to this embodiment is
A hydrogen generation system that produces hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
A supply unit that intermittently supplies hydrogen storage and
A vaporizer that vaporizes the hydrogen reservoir supplied from the supply unit,
A dehydrogenation reaction section that brings the hydrogen reservoir from the vaporization section into contact with a catalyst to perform a dehydrogenation reaction and converts it into hydrogen and a dehydrogenated product.
A suction part that decompresses the atmosphere inside the dehydrogenation reaction part by suction,
A gas-liquid separator that separates a mixture containing hydrogen gas and dehydrogenated material sucked by the suction unit into a gas that mainly contains hydrogen and a liquid that mainly contains dehydrogenated material.
It is characterized by having.

The hydrogen generation method according to this embodiment is
A method of producing hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
The process of supplying hydrogen storage and
The process of vaporizing the supplied hydrogen reservoir and
A step of bringing a vaporized hydrogen reservoir into contact with a catalyst to carry out a dehydrogenation reaction to convert hydrogen into a dehydrogenated product, which is a step of carrying out the dehydrogenation reaction under reduced pressure by suction.
A step of separating the suctioned mixture containing hydrogen and dehydrogenated product into a gas containing mainly hydrogen and a liquid containing mainly dehydrogenated product.
It is characterized by including.

According to this embodiment, it is possible to provide a hydrogen generation system or a hydrogen generation method capable of carrying out a dehydrogenation reaction at a low temperature.

In the present embodiment, after the hydrogen reservoir supplied from the supply section is vaporized in the vaporization section, the vaporized hydrogen reservoir is dehydrogenated in the dehydrogenation reaction section to generate hydrogen. Further, in the present embodiment, the dehydrogenation reaction of the vaporized hydrogen reservoir is carried out under reduced pressure by suction. In the dehydrogenation reaction of hydrogen in a hydrogen reservoir to hydrogen and a dehydrogenated product, multiple moles of hydrogen molecules are generated from one mol of hydrogen reservoir, and since the reaction is an equilibrium reaction, dehydration is performed by lowering the pressure. The elementary reaction can proceed. As a result, the dehydrogenation reaction can proceed at a temperature lower than the high temperature (for example, 350 to 400 ° C.) conventionally required for the dehydrogenation reaction (for example, 200 ° C. or lower). By suction for depressurization, the mixture containing the produced hydrogen and dehydrogenated product is also discharged from the dehydrogenation reaction section and sent to the next step. The mixture discharged from the dehydrogenation reaction section is separated into a gas and a liquid at the gas-liquid separation section.

The hydrogen generation system according to this embodiment will be described below. The hydrogen generation system according to the present embodiment is a system that realizes the hydrogen generation method according to the present embodiment. The hydrogen generation method according to the present embodiment can be clarified by the description of the hydrogen generation system.

As shown in FIG. 1, the hydrogen generation system 1 according to the present embodiment includes a supply unit 11, a vaporization unit 12, a dehydrogenation reaction unit 13, a suction unit 14, and a gas-liquid separation unit 15. The supply unit 11 intermittently supplies the raw material containing the hydrogen storage to the vaporization unit 12. In FIG. 1, reference numeral 20 indicates a supply control unit. The vaporization unit 12 vaporizes a raw material containing a hydrogen storage body such as an organic hydride supplied from the supply unit 11. One batch (one supply amount) of the hydrogen reservoir from the vaporization unit 12 comes into contact with the catalyst at the dehydrogenation reaction unit 13 and is dehydrogenated. During this dehydrogenation reaction, the atmosphere of the dehydrogenation reaction unit 13 is depressurized by suction by the suction unit 14. The pressure of the dehydrogenation reaction unit 13 is reduced to, for example, 30 kPa or less. By carrying out the dehydrogenation reaction under reduced pressure, the reaction equilibrium can be greatly tilted toward the dehydrogenation side, and the dehydrogenation reaction can proceed. As a result, the dehydrogenation reaction can be carried out at a low temperature. Along with the suction by the suction unit 14, a mixture mainly containing hydrogen gas and a dehydrogenated product is discharged from the dehydrogenation reaction unit 13. The gas-liquid separation unit 15 performs a gas-liquid separation treatment on the mixture discharged from the dehydrogenation reaction unit 13 to separate the mixture into a gas mainly containing hydrogen and a liquid mainly containing a dehydrogenated product.

(Hydrogen reservoir)
A hydrogen storage body is a material capable of storing hydrogen and producing hydrogen by a dehydrogenation reaction. Examples of the hydrogen storage include organic hydride (for example, chain saturated hydrocarbon, cyclic saturated hydrocarbon, heterocyclic saturated hydrocarbon), ammonia, hydrazine, sodium borate, or a mixture thereof. Ammonia, hydrazine and sodium borate can also use their respective aqueous solutions as hydrogen stores. The aqueous solution may optionally contain hydrogen peroxide.

The hydrogen storage is preferably in a liquid state at normal temperature and pressure, and has a boiling point of 250 ° C. or lower (preferably 200 ° C. or lower) at normal temperature and pressure.

Organic hydride is a hydride of an organic compound having an unsaturated bond. The organic hydride can be converted into a dehydrogenation reaction product containing hydrogen and a dehydrogenated product (organic compound having an unsaturated bond) using a dehydrogenation catalyst. As a typical example of organic hydride, for example, methylcyclohexane (hereinafter, also referred to as MCH) is known. The organic compound having an unsaturated bond is an organic compound having one or more double bonds or triple bonds in the molecule. The double bond includes a carbon-carbon double bond (C = C), a carbon-nitrogen double bond (C = N), a carbon-oxygen double bond (C = O), or a nitrogen-oxygen double bond ( N = O) is illustrated. Examples of the triple bond include a carbon-carbon triple bond and a carbon-nitrogen triple bond. The organic compound having an unsaturated bond is preferably a liquid organic compound under normal temperature and pressure from the viewpoint of storability and transportability.

Examples of the organic hydride include chain saturated hydrocarbons, cyclic saturated hydrocarbons, and heterocyclic saturated hydrocarbons. As the organic hydride, one type may be used alone, or two or more types may be used in combination. Chain saturated hydrocarbons include, for example, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, structural isomers thereof, or substitutions thereof. Cyclic saturated hydrocarbons include, for example, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, or alkyl substituents thereof. Examples of the alkyl substituent of the cyclic saturated hydrocarbon include methylcyclohexane. Further, as the cyclic saturated hydrocarbon, a plurality of single bonds thereof can also be used. Examples of such a compound include biphenyl. Examples of heterocyclic saturated hydrocarbons include decalin, tetralin, and alkyl substituents thereof. Examples of the alkyl substituent of the heterocyclic saturated hydrocarbon include methyldecalin. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The hydrogen storage may contain additives, if necessary. Examples of the additive include a stabilizer.

(Supply section)
The supply unit 11 intermittently supplies the hydrogen storage body to the vaporization unit 12. The supply unit 11 intermittently supplies the hydrogen storage as a raw material to the vaporization unit 12 for each batch of a predetermined amount. Preferably, the supply unit 11 intermittently uses the dehydrogenated product of the previously supplied hydrogen storage unit (the hydrogen storage unit introduced as the previous batch) at intervals of time when the dehydrogenated product is discharged from the dehydrogenation reaction unit 13. It is supplied to the dehydrogenation reaction unit 13.

The supply unit 11 is, for example, a pressure applicator (for example, a booster pump) that applies pressure to the vaporized hydrogen storage body in order to supply the hydrogen storage body to the vaporization unit 12, and a control valve that adjusts the flow rate of the hydrogen storage body. And can also include a supply control unit 20 (FIG. 1) that controls a pressure feeder and a control valve to adjust the time interval and amount of supply of the hydrogen reservoir. The supply unit 11 is provided with a pressure applicator such as a booster pump and a control valve to apply an appropriate pressure to the hydrogen reservoir and supply the appropriate amount to the vaporization unit 12 and the dehydrogenation reaction unit 13. can. For example, when the supply control unit 20 transmits a signal to open the control valve for a predetermined time, the control valve is opened for a predetermined time, and the pressure-applied hydrogen reservoir is vaporized. It can be supplied to 12 and the dehydrogenation reaction unit 13. Examples of the booster pump include, but are not limited to, a plunger type or a piston type. Examples of the control valve include, but are not limited to, commonly used valves such as an air valve or a solenoid valve, an injection valve, and the like. Examples of the supply method include a method in which pressure is applied by a pump to intermittently inject a raw material (for example, a liquid raw material) with an on-off valve, an injector, or the like. The jetted liquid is vaporized by the vaporizer.

The supply control unit 20 is a CPU capable of executing a program capable of controlling the pressure applyer and the control valve. The program can be stored in, for example, a ROM or a RAM. Control methods for operating the pressure applyer at an appropriate timing include, for example, (1) control based on the supply time and supply suspension interval specified by the temperature and pressure conditions in the operating environment of the pressure applyer, (2). ) Control by a predetermined time interval, (3) Feedback control by signals detected by various sensors, and the like can be mentioned. These methods may be used alone or in combination. The control of (1) above is realized by, for example, having a temperature sensor for detecting the temperature in the operating environment of the pressure applicator and a pressure sensor for detecting the pressure, and executing a program based on the detected temperature and pressure. can. The control of (2) above can be realized by grasping the temperature and pressure of the dehydrogenation reaction unit 13 and the performance of the catalyst in advance and executing the program at a specified time. The control of (3) above detects a pressure sensor that detects the pressure of the dehydrogenation reaction unit 13, a temperature sensor that detects the temperature, a flow sensor that detects the flow rate of the vaporized hydrogen reservoir, or a concentration of generated hydrogen. It can be realized by providing a hydrogen sensor or a combination thereof, calculating the reaction conversion rate from the information obtained from these sensors, and controlling so as to minimize the fluctuation of the reaction conversion rate.

(Vaporization department)
The vaporization unit 12 is provided between the supply unit 11 and the dehydrogenation reaction unit 13, and includes a vaporizer that vaporizes the hydrogen storage. Examples of the vaporizer include a carburetor or a spray gun. Further, as the vaporizer, for example, one having a heat exchange type flow path structure capable of utilizing the residual heat of an electric heater or another reactor can be mentioned. Further, from the viewpoint of vaporization, it is preferable that the vaporized portion is depressurized.

(Dehydrogenation reaction part)
The dehydrogenation reaction unit 13 converts the hydrogen reservoir from the vaporization unit 12 into hydrogen and a dehydrogenated product by a dehydrogenation reaction.

FIG. 2 shows a configuration example of the dehydrogenation reaction unit 13. The dehydrogenation reaction unit 13 shown in FIG. 2 includes a catalyst unit 31, a distribution unit 34, an aggregation unit 37, and a heat medium flow unit 40.

The catalyst unit 31 includes a dehydrogenation catalyst 32, and the catalyst 32 is arranged inside, for example, a reaction tube constituting the outer periphery of the catalyst unit 31. The catalyst unit 31 is configured such that the hydrogen storage and their reactants flow from the upstream (distribution unit 34) to the downstream (aggregation unit 37). In FIG. 2, the catalyst unit 31 is configured to include a plurality of reaction tubes arranged in parallel, but the present embodiment is not limited to such a configuration. The shape of the reaction tube shown in FIG. 2 is cylindrical, but is not limited to this shape, and may be, for example, a double tubular shape, a box shape, or a honeycomb shape.

The dehydrogenation catalyst 32 has a function of converting a hydrogen reservoir such as an organic hydride into hydrogen and a dehydrogenated product by a dehydrogenation reaction. In FIG. 2, the dehydrogenation catalyst is arranged inside each reaction tube.

The distribution unit 34 is located upstream of each reaction tube and has a function of distributing the hydrogen storage body supplied from the vaporization unit 12 through the supply port 36 to each reaction tube.

The aggregation unit 37 is located downstream of each reaction tube and has a function of aggregating dehydrogenation reactants (gas mainly containing hydrogen and dehydrogenated products) coming out of each reaction tube. A discharge port 38 is arranged downstream of the aggregation part 37, and a suction part 14 is arranged downstream of the discharge port 38.

The heat medium flow unit 40 is configured so that the heat medium flows around each reaction tube, and has a function of heating each reaction tube. The heating of the catalyst unit 31 can be controlled based on a control signal from the control unit (not shown). In this embodiment, since the dehydrogenation reaction can be carried out at a low temperature, the temperature of the heat medium can also be lowered. The heat medium may be a gas or a liquid. In this embodiment, a configuration in which a reaction tube in which a catalyst is arranged is heated using a heat medium is illustrated, but the present embodiment is not limited to this configuration. For example, in one embodiment, the reaction tube in which the catalyst is arranged may be directly heated by using an electric heater, a heater that burns flammable fuel, or the like. Further, for heating the dehydrogenation reaction unit 13, the heat of a cooling medium that cools a power generation device that converts heat energy into electricity or a heat engine that converts heat energy into mechanical energy may be used. Examples of the power generation device that converts thermal energy into electricity include a generator and a nuclear reactor. Further, as a heat engine that converts thermal energy into mechanical energy, for example, an engine can be mentioned. When such a device (heating device) that generates heat is used in combination with the hydrogen generation system 1 of the present embodiment, the dehydrogenation reaction unit 13 is heated by a cooling medium for cooling these heat generating devices. May be good. Examples of such a cooling medium include cooling water for cooling the engine, exhaust gas discharged from the engine, secondary cooling water for a nuclear reactor, and the like.

The heat medium flow unit 40 is located so as to surround the reaction tube in which the dehydrogenation catalyst is arranged, and communicates with the inflow port 44 and the discharge port 46 for the heat medium. The inflow port 44 is for allowing the supplied heat medium to flow into the heat medium flow section 40, and is located near the downstream end of the catalyst section 31. The discharge port 46 is for discharging the heat medium from the heat medium flow unit 40, and is located near the upstream end of the catalyst unit 31. By configuring the hydrogen storage body to flow and the heat medium to flow in opposite directions in this way, the temperature on the downstream side is relatively higher than that on the upstream side of the catalyst unit 31. Therefore, it is suitable for increasing the conversion rate of the hydrogen storage.

In the present embodiment, after the hydrogen storage is supplied to the dehydrogenation reaction unit 13, the dehydrogenation reaction unit 13 is depressurized by the suction unit 14. The dehydrogenation reaction is carried out under the reduced pressure. As described above, since the dehydrogenation reaction is an equilibrium reaction, the dehydrogenation reaction can proceed by lowering the pressure. As a result, the dehydrogenation reaction can be carried out at a temperature lower than the high temperature (for example, 350 to 400 ° C.) conventionally required for the dehydrogenation reaction. The temperature of the dehydrogenation reaction is, for example, 200 ° C. or lower, preferably 180 ° C. or lower or 150 ° C. or lower. The pressure in the dehydrogenation reaction unit 13 is, for example, 30 kPa or less. Further, the vaporization unit 12 may be depressurized together with the dehydrogenation reaction unit 13. By reducing the pressure in the vaporization section 12, the vaporization of the hydrogen reservoir is promoted.

Specifically, in the embodiment shown in FIG. 2, after the hydrogen storage body is supplied from the vaporization unit 12 to the distribution unit 34, dehydrogenation including the catalyst unit is performed by the suction unit 14 arranged downstream of the discharge port 38. The atmosphere of the reaction section 13 is sucked and the pressure is reduced. At this time, it is preferable that the control valve of the supply unit 11 is sucked in a closed state. By suction by the suction unit 14, the pressure inside the dehydrogenation reaction unit 13 decreases, and the dehydrogenation reaction is promoted. At this time, the pressure inside the vaporization unit 12 may also decrease. The reactants (hydrogen and dehydrogenated material) generated by the dehydrogenation reaction are discharged from the dehydrogenation reaction unit 13 by suction by the suction unit 14 and sent downstream. Further, the hydrogen storage as an unreacted product may also be mixed with the reaction product and discharged from the dehydrogenation reaction unit 13.

The catalyst is not particularly limited, and includes, for example, a catalyst metal and a carrier that supports the catalyst metal. The catalyst metal is not particularly limited, and examples thereof include Ni, Pd, Pt, Rh, Ir, Re, Ru, Mo, W, V, Os, Cr, Co, Fe, and alloys thereof. .. As the catalyst metal, one type may be used alone, or two or more types may be used in combination. The carrier is not particularly limited, and examples thereof include activated carbon, carbon nanotubes, silica, alumina, alumina silicate, porous polyimide, zinc oxide, zirconium oxide, diatomaceous earth, niobium oxide, vanadium oxide, or a mixture thereof. Be done. As the carrier, one type may be used alone, or two or more types may be used in combination. Specifically, examples of the catalyst include those in which a catalyst metal such as platinum, ruthenium, palladium, rhodium, tin, rhenium or germanium is supported on a porous carrier such as alumina.

The dehydrogenation catalyst usually has different adsorption powers for hydrogen storage, dehydrogenated products and hydrogen, and has the weakest adsorption power for hydrogen. The hydrogen reservoir introduced into the dehydrogenation reaction unit 13 is converted into hydrogen and a dehydrogenated product by the dehydrogenation reaction, but the adsorption power of the dehydrogenation catalyst for hydrogen is larger than the adsorption power of the dehydrogenation catalyst for the dehydrogenated product. Since it is weak, the generated hydrogen is preferentially released from the catalyst and discharged from the dehydrogenation reaction unit 13.

In the present embodiment, it is preferable that the adsorption force of the catalyst for hydrogen, hydrogen reservoir or dehydrogenate has a relationship of adsorption force for hydrogen <adsorption force for hydrogen reservoir <adsorption force for dehydrogenate. By using a catalyst having such an adsorptive power, the displacement between hydrogen and dehydrogenation in the catalyst section can be increased, and the hydrogenation reaction between hydrogen and dehydrogenation (opposite to the dehydrogenation reaction). Directional reaction) can be reduced.

The difference in the adsorptive power of the catalyst to hydrogen, hydrogen reservoir or dehydrogenated product is mainly caused by the adsorptive power and polarity of the carrier used for the catalyst. However, since hydrogen is not usually adsorbed on the carrier, when selecting the carrier, attention should be paid to the difference in the adsorptive power to the dehydrogenated product and the hydrogen reservoir. Since the adsorption power may differ depending on the hydrogen storage body used, it is desirable to conduct an experiment in advance and select a carrier suitable for the hydrogen storage body to be used.

Examples of the carrier having a relationship of adsorption power for hydrogen <adsorption power for hydrogen storage <adsorption power for dehydrogenated product include silica when an organic hydride such as methylcyclohexane is used as the hydrogen storage. Silica has a lower adsorption power for hydrogen storage than for dehydrogenated products, and by using a carrier containing silica, the displacement between hydrogen and dehydrogenated products in the catalyst section can be increased, and hydrogen can be increased. The hydrogenation reaction between dehydrogenation and dehydrogenation (reaction in the opposite direction to the dehydrogenation reaction) can be reduced. Specifically, for example, when methylcyclohexane is used as the hydrogen storage, the positions of hydrogen and toluene as a dehydrogenated product in the catalyst portion can be shifted, and the rebonding of hydrogen to toluene can be reduced. Can be done.

As a configuration of the dehydrogenation reaction unit 13, for example, as shown in FIG. 2, a type in which a catalyst is filled and fixed inside a tube-shaped container or a box-shaped container can be mentioned. In the case of such a form, the form of the catalyst can be a porous body, a honeycomb body or a particle body. When the catalyst is formed as a porous body or a honeycomb body, it can be formed by supporting a catalyst metal in the pores of alumina, zeolite, porous polyimide or the like. Further, as the configuration of the dehydrogenation reaction unit 13, for example, a type in which the catalyst is fixed to the inner surface of the thin tube or the inner surface of the housing can be mentioned. In the case of such a form, the catalyst can be provided so as to cover the inner surface of the thin tube or the inner surface of the housing. Further, as the configuration of the dehydrogenation reaction unit 13, for example, a type in which a flow path or unevenness for allowing the hydrogen storage to flow is provided on the surface of the flat plate and the catalyst is fixed on the flow path or unevenness can be mentioned. Such flow paths and recesses can be formed by using, for example, machining such as cutting or pressing the surface of a flat plate, or techniques such as etching, plating process, nanoprinting, vapor deposition, and sputtering. In the case of such a form, the catalyst can be provided so as to cover the surface of the flat plate provided with the flow path and the unevenness.

The catalyst containing the catalyst metal and the carrier can be formed by, for example, the following method. When the dehydrogenation reaction unit 13 is of a type in which a catalyst is filled and fixed, the catalyst metal can be supported on a carrier and fixed. For example, using a catalyst metal and a carrier, a catalyst can be obtained by a coprecipitation method or a thermal decomposition method by a conventional method. Further, in the case where the dehydrogenation reaction unit 13 is of a type in which a catalyst is provided so as to cover the surface of a flat plate provided with a flow path or unevenness, a carrier layer is formed by a sol-gel method or a CVD method, and a catalyst is formed on this carrier layer. By supporting the metal, the catalyst can be formed as a catalyst layer. When the dehydrogenation reaction unit 13 is of a type in which the catalyst is fixed to the inner surface of the thin tube or the housing, an oxide-based carrier layer is directly formed on the inner surface of the thin tube by anodizing the inner surface of the thin tube. Then, the catalyst can be formed as a catalyst layer by supporting the catalyst metal on the carrier layer.

The dehydrogenation reaction unit 13 is preferably of a type in which the catalyst is fixed in a robust housing in order to prevent the catalyst from being destroyed by an external stimulus. Examples of the material of such a housing include metal, ceramics, glass and plastic.

(Suction part)
As described above, the suction unit 14 decompresses the dehydrogenation reaction unit 13 by suction. As described above, by carrying out the dehydrogenation reaction under reduced pressure, the dehydrogenation reaction can be promoted, and as a result, the temperature required for the dehydrogenation reaction can be lowered. Along with the suction by the suction unit 14, a mixture mainly containing hydrogen gas and a dehydrogenated product is discharged from the dehydrogenation reaction unit 13 and sent to the gas-liquid separation unit 15.

As the suction unit 14, for example, a suction pump can be used. Suction pumps include, for example, pistons, turbines, air pumps, vacuum pumps, microturbines, or combinations thereof. Further, a turbine for over-intake of an automobile may be used. Further, the power of the engine may be used as the power source of the pump. When applied to an automobile, the power of the axle of the automobile can be used as the power of the pump.

(Gas-liquid separation part)
The gas-liquid separation unit 15 performs a gas-liquid separation treatment on the mixture discharged from the dehydrogenation reaction unit 13 to separate the mixture into a gas mainly containing hydrogen and a liquid mainly containing a dehydrogenated product. The configuration of the gas-liquid separation unit 15 is not limited, and can be appropriately configured by using, for example, a cooler, a separation membrane, a pressure regulating valve, or a combination thereof.

It is preferable that the gas-liquid separation unit 15 has at least a container to which the mixture discharged by suction from the dehydrogenation reaction unit 13 is sent and a pressure adjusting valve for adjusting the pressure in the container. By adopting such a configuration, the suction force of the suction unit 14 is used to improve the pressure of the mixture in the gas-liquid separation unit 15, and the mixture mainly contains a gas containing mainly hydrogen and a dehydrogenated product. It can be easily separated from the liquid. For example, as in the gas-liquid separation unit 15 shown in FIG. 3, the suction unit 14 is operated with the pressure adjusting valve 52 closed to increase the pressure in the container 51. The pressure in the container 51 is controlled within a range in which the mixture can be separated into a gas mainly containing hydrogen and a liquid mainly containing dehydrogenated products. For example, when methylcyclohexane (MCH) is used as the hydrogen storage, the pressure inside the container is preferably adjusted to about 1.2 atm. The pressure in the container 51 can be adjusted by appropriately controlling the pressure adjusting valve 52. In FIG. 3, it is possible to recover the gas from the pressure regulating valve 52, and a liquid feeding port for recovering the liquid may be separately provided. With such a configuration, the configuration of the gas-liquid separation unit 15 can be simplified, and the gas-liquid separation process can be performed by utilizing the suction force of the suction unit 14, so that the gas-liquid separation process can be performed from the viewpoint of energy. Is also advantageous.

The hydrogen generation system according to this embodiment may include a plurality of gas-liquid separation units. Since the discharge timing of hydrogen as a reactant, dehydrogenated product, and hydrogen storage as an unreacted product may differ depending on the adsorption power of the catalyst, the valve is switched according to each discharge time and sent to separate gas-liquid separators. Thereby, each component can be recovered more effectively. For example, as shown in FIG. 4, two gas-liquid separation units (first gas-liquid separation unit 151 and second gas-liquid separation unit 152) are provided and discharged from the dehydrogenation reaction unit 13 in an early time zone. A gas containing a relatively large amount of hydrogen can be sent to the first gas-liquid separation unit 151, and subsequent gases can be sent to the second gas-liquid separation unit 152. As a result, hydrogen gas having a higher purity can be easily obtained in the first gas-liquid separation unit 151. In addition, three gas-liquid separation units (first gas-liquid separation unit, second gas-liquid separation unit, and third gas-liquid separation unit) are provided, and hydrogen discharged from the dehydrogenation reaction unit 13 in an early time zone. The gas containing a large amount of gas is sent to the first gas-liquid separation unit, the gas containing a large amount of the next discharged substance (for example, a hydrogen reservoir) is sent to the second gas-liquid separation unit, and the last discharged substance (for example) is sent. A gas containing a large amount of dehydrogenate) can also be sent to the third gas-liquid separation section. The gas can be delivered to each gas-liquid separation unit by operating a valve (actuating valve) according to the timing.

The hydrogen generation system according to the present embodiment may further include a hydrogen purification unit. The hydrogen purification unit has a function of purifying hydrogen from the hydrogen-containing gas obtained in the gas-liquid separation unit 15. The hydrogen purification unit can have a function of increasing hydrogen purity by further removing dehydrogenated substances, unreacted hydrogen reservoirs, and the like from the hydrogen-containing gas supplied from the gas-liquid separation unit 15. As the hydrogen purification unit, for example, a membrane separator containing a hydrogen separation membrane, an adsorption remover using a PSA (Pressure swing attachment) method or a TSA (Temperature swing advertisement) method can be used.

The hydrogen generation system according to the present embodiment may further include a compression unit. The compression unit has a function of increasing the pressure (for example, 20 MPa to 90 MPa) of the high-purity hydrogen gas obtained in the hydrogen purification unit. The high-purity hydrogen (purified gas) obtained by the hydrogen purification unit is directly or indirectly supplied to the compression unit. Here, indirect means, for example, temporarily storing high-purity hydrogen in a tank or the like.

The hydrogen generation system according to the present embodiment may further include a pressure accumulator. The pressure accumulator has a function of storing high-purity hydrogen while maintaining it in a high-pressure state. The high-purity hydrogen stored in the pressure accumulator in a high-pressure state can be supplied to the FCV or the like by a dispenser. Further, in the present embodiment, for example, high-purity hydrogen in a high-pressure state may be directly supplied to the dispenser without going through the accumulator.

The hydrogen generation system according to the present embodiment may further include a recovery unit. The recovery unit has a function of storing the dehydrogenated product (for example, toluene) and the hydrogen storage body (for example, MCH) separated by the gas-liquid separation unit 15. The dehydrogenated product recovered in the recovery unit is transported to a refinery or the like by a tank truck, for example, and is rehydrogenated to be converted into a hydrogen storage body.

The operating temperature of PEFCs (solid polymer fuel cells) and DMFCs (direct methanol fuel cells) that use hydrogen as fuel is about 70 to 100 ° C. The operating temperature of the PAFC (phosphoric acid fuel cell) is about 200 ° C. Therefore, when the hydrogen generation system according to the present embodiment is used in combination with these fuel cells, they can be used as a heat source by providing them adjacent to or close to these fuel cells. Further, when the hydrogen generation system according to the present embodiment and the hydrogen fuel engine are used in combination, the heat of the exhaust gas discharged from the hydrogen fuel engine can be used as a heat source.

An example using the hydrogen generation system according to the present embodiment will be described below.

First, with reference to FIG. 5, a power generation system 100 in which the hydrogen generation system 1 of the present embodiment and the polymer electrolyte fuel cell 101 are combined and integrated will be described.

As shown in FIG. 5, the power generation system 100 includes the hydrogen generation system 1 of the present embodiment. Further, in the power generation system 100, at least one of the supply unit 11, the vaporization unit 12, and the dehydrogenation reaction unit 13 is arranged so as to be in contact with or close to the polymer electrolyte fuel cell 101. In this way, at least one of the supply unit 11, the vaporization unit 12, and the dehydrogenation reaction unit 13 can be heated by utilizing the operating temperature (for example, 80 to 100 ° C.) of the polymer electrolyte fuel cell 101. ..

The power generation system 100 includes a storage tank 102 for storing the hydrogen storage body, a liquid feeding line 104 for sending the hydrogen storage body stored in the storage tank 102 to the hydrogen generation system 1, and a liquid feeding line. A liquid feed pump 105, which is provided on the 104 and generates a pressure to send a hydrogen storage body from the storage tank 102 to the hydrogen generation system 1, and hydrogen generated by the hydrogen generation system 1 to the solid polymer fuel cell 101. The hydrogen supply line 108 for supply, the waste liquid recovery line 106 for liquefying and recovering the dehydrogenated product and the hydrogen storage as an unreacted product produced in the hydrogen generation system 1, and the waste liquid recovery line 106 are used for feeding. It is provided with a effluent tank 103 for recovering the liquefied dehydrogenated product and the hydrogen storage as waste liquor. A hydrogen supply pump 107 for sucking the hydrogen generated by the hydrogen generation system 1 and supplying it to the polymer electrolyte fuel cell 101 is provided on the hydrogen supply line 108. The hydrogen supply pump 107 can forcibly supply the hydrogen generated by the hydrogen generation system 1 to the polymer electrolyte fuel cell 101. As the hydrogen supply pump 107, for example, a turbine type exhaust pump can be used.

If the temperatures of the vaporization unit 12 and the dehydrogenation reaction unit 13 of the hydrogen generation system 1 are low, the dehydrogenation reaction of the hydrogen reservoir is difficult to proceed, and hydrogen may not be produced suitably. Therefore, as shown in FIG. 5, for example, a heating unit (not shown) for heating the vaporization unit 12 and the dehydrogenation reaction unit 13 may be provided. The heating unit can quickly heat the vaporization unit 12 and / or the dehydrogenation reaction unit 13 to a temperature at which the dehydrogenation reaction can be suitably performed. The fuel in the heating section can be stored in, for example, a tank (not shown). Examples of the fuel for the heating unit include city gas, kerosene, heavy oil, and the like.

The polymer electrolyte fuel cell 101 includes a cell stack (not shown) composed of a plurality of single cells S formed by an electrolyte membrane E and an anode A and a cathode C sandwiching the electrolyte membrane E. The hydrogen generated by the hydrogen generation system 1 is supplied to the anode A via the hydrogen supply line 108. Air is supplied from the air pump 109 to the cathode C. The air may be treated with a humidifier (not shown) if necessary. Electrons (electricity) and water are generated by the reaction between hydrogen at the anode A and oxygen at the cathode C via the electrolyte membrane E. The generated water is discharged to the outside of the power generation system 100, and electricity is supplied to an electric system such as a motor or a secondary battery. The exhaust gas discharged from the polymer electrolyte fuel cell 101 is sucked by the hydrogen supply pump 107 and discharged from the exhaust gas line 110.

The power generation system 100 may include a heat exchanger (not shown) between the storage tank 102 and the vaporization unit 12. By subjecting the high-temperature dehydrogenated product recovered from the hydrogen generation system 1 to this heat exchanger before collecting it in the waste liquid tank 103, the hydrogen storage body can be heated by utilizing the heat of the dehydrogenated product.

The exhaust gas discharged from the polymer electrolyte fuel cell 101 can be reused as power for the hydrogen supply pump 107 mounted on the power generation system 100 by utilizing the exhaust pressure. By providing such a device, it is possible to improve the energy efficiency of the power generation system 100.

Next, with reference to FIG. 6, the engine system 200 in which the hydrogen generation system 1 and the engine 201 according to the present embodiment are combined will be described.

As shown in FIG. 6, the engine system 200 has a storage tank 202, a waste liquid tank 203, a liquid feed line 204, a liquid feed pump 205, and a waste liquid recovery line 206 having the same functions as the power generation system 100 described above. And a hydrogen supply pump 207.

The engine system 200 exhausts the hydrogen generation system 1, the engine 201 such as a hydrogen fuel engine, the hydrogen supply line 208 for supplying the hydrogen generated by the hydrogen generation system 1 to the engine 201, and the exhaust gas from the engine 201. It has an exhaust gas line 210 for the purpose, and is configured to come into contact with the hydrogen generation system 1 at the subsequent stage of the exhaust gas line 210. The operating temperature of the engine 201 is higher than that of the polymer electrolyte fuel cell 101, and the exhaust gas temperature is also higher. Therefore, in the engine system 200, the vaporization section 12 and / or the dehydrogenation reaction section of the hydrogen generation system 1 is heated by contacting the hydrogen generation system 1 at the subsequent stage of the exhaust gas line 210. The hydrogen generation system 1 may be designed to be heated by utilizing the waste heat of the cooling water or oil of the engine 201.

The major difference between the engine 201 and the polymer electrolyte fuel cell 101 is the purity of the hydrogen gas supplied from the hydrogen generation system 1. When sucking from the hydrogen generation system 1 with the hydrogen supply pump 207, the vapor pressure dehydrogenated product may be sucked together with hydrogen. However, even in such a case, it can be burned without any particular problem for the following reasons. Since the engine 201 used in the engine system 200 is a hydrogen fuel engine, even if some hydrocarbons, that is, dehydrogenates and hydrogen reservoirs are mixed as impurities, they can be burned. Further, in some cases, if a small amount of hydrocarbon is mixed in the hydrogen gas, control may be facilitated. Therefore, when separating the hydrogen produced by the hydrogen generation system 1 from the dehydrogenated product, some dehydrogenated product or hydrogen reservoir may be mixed in the hydrogen. As described above, since high purity of hydrogen gas is not required, the structure of the engine system 200 can be simplified as compared with that of the power generation system 100.

As shown in FIG. 6, in the engine system 200, the dehydrogenated product and the unreacted hydrogen reservoir are collected in the waste liquid tank 203 by the waste liquid recovery line 206. Then, the hydrogen generated in the dehydrogenation reaction unit 13 is sent to the engine 201 by the hydrogen supply pump 207 via the hydrogen supply line 208, and is burned together with the air taken in by the engine 201 to generate a driving force. The exhaust gas generated by combustion in the engine 201 is supplied by the exhaust gas line 210 to the heating unit 14 provided in contact with the hydrogen generation system 1, and then discharged from the exhaust port of the exhaust gas line 210.

Next, with reference to FIG. 7, a hydrogen storage system 300 that combines the hydrogen generation system 1 and the compressor 301 according to the present embodiment will be described.

As shown in FIG. 7, the hydrogen storage system 300 includes a storage tank 302, a waste liquid tank 303, a liquid feed line 304, a liquid feed pump 305, and a hydrogen supply line 308 having the same functions as the power generation system 100 described above. And a waste liquid recovery line 306.

The hydrogen storage system 300 stores the hydrogen generation system 1, the hydrogen supply line 308 that supplies the hydrogen generated by the hydrogen generation system 1 to the compressor 301, the compressor 301 that compresses the supplied hydrogen, and the compressed hydrogen. It has a hydrogen tank 307 and a hydrogen tank 307. The hydrogen tank 307 may store hydrogen in a gas or liquid state under high pressure conditions. Further, the hydrogen tank 307 may contain a hydrogen storage alloy such as AB2 type, AB5 type, iron-titanium type, magnesium type, vanadium type, palladium type, calcium type and the like.

As shown in FIG. 7, in the hydrogen storage system 300, the dehydrogenated product and the unreacted hydrogen reservoir are collected in the waste liquid tank 303 by the waste liquid recovery line 306. The hydrogen generated in the dehydrogenation reaction unit 13 is sent to the compressor 301 by the hydrogen supply line 308, compressed, and stored in the hydrogen tank 307.

Next, with reference to FIG. 8, the hydrogen community 400 using the hydrogen generation system 1 according to the present embodiment will be described.

FIG. 8 schematically shows a community using a distributed power source that uses renewable energy such as grid power, wind power, or solar power, and a hydrogen vehicle as an example.

As shown in FIG. 8, the hydrogen community 400 includes a wind power generator 411, a solar cell 412, a grid power 413, an inverter 414 connected to these, and an electric device 416 that consumes electricity. Further, the hydrogen community 400 uses the water electrolyzer 420 that electrolyzes water to generate hydrogen and the hydrogen generated by the water electrolyzer 420 to add hydrogen to the dehydrogenated product of the hydrogen storage and store hydrogen again. Includes a hydrogen reservoir production device 421 for manufacturing the body and a hydrogen reservoir station 423 for storing the hydrogen reservoir produced by the hydrogen reservoir production device 421 and utilizing the existing gasoline infrastructure. ing.

The hydrogen community 400 includes a power generation system 100, an engine system 200, and a hydrogen storage system 300 to which a hydrogen storage unit supplied from a hydrogen storage unit station 423 is supplied, and the hydrogen generation system 1 of the present embodiment is the hydrogen. Used as part of Community 400.

Specifically, the hydrogen generation system 1 of the present embodiment is provided and used in the power generation system 100, the engine system 200, and the hydrogen storage system 300.

For example, the hydrogen generation system 1 included in the power generation system 100 generates hydrogen using the hydrogen storage unit supplied from the hydrogen storage unit station 423, and uses the generated hydrogen to generate electricity by the polymer electrolyte fuel cell 101. Generate electricity. Further, for example, the hydrogen generation system 1 included in the engine system 200 of the hydrogen vehicle 417 generates hydrogen using the hydrogen storage body supplied from the hydrogen storage body station 423, and the generated hydrogen is directly burned by the engine 201. The driving force is obtained to drive the hydrogen vehicle 417. Further, for example, the hydrogen generation system 1 included in the hydrogen storage system 300 generates hydrogen using the hydrogen storage body supplied from the hydrogen storage body station 423, and the generated hydrogen is put into the hydrogen tank 307 by the compressor 301. Stored at high pressure.

In the hydrogen community 400, for example, DC electricity generated by renewable energy such as wind power generation 411 and solar cell 412 can be converted into AC electricity by an inverter 414. The electricity converted to alternating current is usually used in household electrical appliances 416. Further, the electricity converted into alternating current is supplied to the water electrolyzer 420 to electrolyze water and generate hydrogen and oxygen. Then, the hydrogen generated by the water electrolyzer 420 is supplied to the hydrogen storage body manufacturing device 421, and hydrogen is added to the dehydrogenated product of the hydrogen storage body to make the hydrogen storage body again.

Electricity (electric power) is divided into peak power corresponding to daytime load fluctuations and base power that supplies constant basic power day and night. The power generation system 100 shown in FIG. 5 preferably supplies peak power corresponding to daytime load fluctuations to the household distributed power source 418 and the electric device 416. The power generation system 100 can use the grid power 413 of an electric power company or the like as the base power, and it is preferable that the grid power 413 also uses the above-mentioned renewable energy for _{CO 2 reduction.} Further, it is preferable to operate the water electrolyzer 420 with surplus electric power from the viewpoint of the efficiency of the hydrogen community 400 and the viewpoint of CO _{2 reduction.}

As renewable energy, in addition to wind power generation 411 and solar cell 412, geothermal energy, ocean thermal energy conversion, tidal power, biomass, etc. can also be used. Since these renewable energies can generate electricity even at night and generate surplus electric power, it is suitable for operating the water electrolyzer 420 to produce a hydrogen reservoir and storing a large amount in the hydrogen reservoir tank 422. .. It is preferable that the power generation by the renewable energy in the daytime is positively supplied as the peak power of the system power 413.

It should be noted that the hydrogen vehicle 417 can be equipped with a water electrolyzer (not shown) similar to the water electrolyzer 420. In this way, it becomes possible to run using the hydrogen storage body in the daytime and use the surplus electric power at night to turn the dehydrogenated product recovered as the waste liquid into a hydrogen storage body, which further improves convenience. do.

The upper limit value and / or the lower limit value of the numerical range described in the present specification can be arbitrarily combined to specify a preferable range. For example, an upper limit value and a lower limit value of the numerical range can be arbitrarily combined to specify a preferable range, an upper limit value of the numerical range can be arbitrarily combined to specify a preferable range, and a lower limit of the numerical range can be specified. A preferable range can be defined by arbitrarily combining the values.

The scope of claims following this stated disclosure is expressly incorporated herein by this stated disclosure, and each claim is independent as a separate embodiment. The present disclosure includes all independent claims replaced by their dependent claims. In addition, additional embodiments derived from the independent claims and subsequent dependent claims are also expressly incorporated herein by this description.

Those skilled in the art can use the above description to make the best use of this disclosure. The claims and embodiments disclosed herein are merely explanatory and exemplary and should be construed as not limiting the scope of the present disclosure in any way. With the help of the present disclosure, changes can be made to the details of the above embodiments without departing from the basic principles of the present disclosure. In other words, the various modifications and improvements of the embodiments specifically disclosed herein are within the scope of this disclosure.

(Additional note)
(Appendix 1)
A hydrogen generation system that produces hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
A supply unit that intermittently supplies hydrogen storage and
A vaporizer that vaporizes the hydrogen reservoir supplied from the supply unit,
A dehydrogenation reaction section that brings the hydrogen reservoir from the vaporization section into contact with a catalyst to perform a dehydrogenation reaction and converts it into hydrogen and a dehydrogenated product.
A suction part that decompresses the atmosphere inside the dehydrogenation reaction part by suction,
A gas-liquid separator that separates a mixture containing hydrogen gas and dehydrogenated material sucked by the suction unit into a gas that mainly contains hydrogen and a liquid that mainly contains dehydrogenated material.
A hydrogen generation system characterized by being equipped with.
(Appendix 2)
The hydrogen generation system according to Appendix 1, wherein the gas-liquid separation unit has at least a container to which the sucked mixture is sent and a pressure regulating valve for adjusting the pressure in the container.
(Appendix 3)
The hydrogen generation system according to Appendix 1 or 2, wherein the supply unit intermittently supplies the hydrogen storage unit to the vaporization unit at time intervals in which the dehydrogenated product of the previously supplied hydrogen storage unit is discharged from the dehydrogenation reaction unit. ..
(Appendix 4)
The hydrogen according to any one of Supplementary note 1 to 3, wherein the adsorption force of the catalyst for hydrogen, a hydrogen reservoir or a dehydrogenate has a relationship of an adsorption force for hydrogen <adsorption force for a hydrogen reservoir <adsorption force for a dehydrogenate. Generation system.
(Appendix 5)
The hydrogen generation system according to Appendix 4, wherein the catalyst comprises a catalyst metal and a carrier carrying the catalyst metal, and the carrier comprises silica.
(Appendix 6)
The hydrogen generation system according to any one of Supplementary note 1 to 5, wherein the dehydrogenation reaction unit is heated by a cooling medium that cools a power generation device that converts heat energy into electricity or a heat engine that converts heat energy into mechanical energy. ..
(Appendix 7)
A method of producing hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
The process of supplying hydrogen storage and
The process of vaporizing the supplied hydrogen reservoir and
A step of bringing a vaporized hydrogen reservoir into contact with a catalyst to carry out a dehydrogenation reaction to convert hydrogen into a dehydrogenated product, which is a step of carrying out the dehydrogenation reaction under reduced pressure by suction.
A step of separating the suctioned mixture containing hydrogen and dehydrogenated product into a gas containing mainly hydrogen and a liquid containing mainly dehydrogenated product.
A method characterized by including.
(Appendix 8)
The method according to Appendix 7, wherein the dehydrogenation reaction is carried out under a pressure of 30 kPa or less.
(Appendix 9)
The method according to Appendix 7 or 8, wherein the mixture is separated into a gas and a liquid by putting the mixture into a container by the suction and increasing the pressure.
(Appendix 10)
The method according to any of Supplementary note 7 to 9, wherein the hydrogen reservoir is intermittently used as a catalyst at time intervals during which the dehydrogenated product of the previously supplied hydrogen reservoir is discharged.
(Appendix 11)
The method according to any one of Supplementary note 7 to 10, wherein the adsorption force of the catalyst for hydrogen, a hydrogen reservoir or a dehydrogenate has a relationship of adsorption force for hydrogen <adsorption force for hydrogen reservoir <adsorption force for dehydrogenate. ..
(Appendix 12)
11. The method of Appendix 11, wherein the catalyst comprises a catalyst metal and a carrier carrying the catalyst metal, and the carrier comprises silica.
(Appendix 13)
The method according to any one of Supplementary note 7 to 12, wherein the environment of the dehydrogenation reaction is heated by a cooling medium that cools a power generation device that converts heat energy into electricity or a heat engine that converts heat energy into mechanical energy.

1 Hydrogen generation system 11 Supply part 12 Vaporization part 13 Dehydrogenation reaction part 14 Suction part 15 Gas-liquid separation part 20 Supply control part 31 Catalyst part 32 Dehydrogenation catalyst 34 Distribution part 36 Supply port 37 Consolidation part 38 Discharge port 40 Heat medium flow Part 44 Inflow port 46 Outlet 51 Container 52 Pressure control valve 151 First gas-liquid separation part 152 Second gas-liquid separation part 100 Power generation system 101 Solid polymer fuel cell 102 Storage tank 103 Waste liquid tank 104 Liquid supply line 105 Liquid feed pump 106 Waste liquid recovery line 107 Hydrogen supply pump 108 Hydrogen supply line 109 Air pump 110 Exhaust gas line 121 Pressure applyer 122 Control valve 123 Supply control unit 200 Engine system 201 Engine 202 Storage tank 203 Waste liquid tank 204 Liquid feed line 205 Pump 206 Waste liquid recovery line 207 Hydrogen supply pump 208 Hydrogen supply line 210 Exhaust gas line 300 Hydrogen storage system 301 Compressor 302 Storage tank 303 Waste liquid tank 304 Liquid feed line 305 Liquid feed pump 306 Waste liquid recovery line 307 Hydrogen tank 308 Hydrogen supply line 400 Hydrogen Community 411 Wind power generation 412 Solar cell 413 System power 414 Inverter 416 Electric equipment 417 Hydrogen car 418 Household distributed power supply 420 Water electrolysis device 421 Hydrogen storage storage equipment 422 Hydrogen storage tank 423 Hydrogen storage station A Anode C Cathode E Electrolyte membrane

Claims

A hydrogen generation system that produces hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
A supply unit that intermittently supplies hydrogen storage and
A vaporizer that vaporizes the hydrogen reservoir supplied from the supply unit,
A dehydrogenation reaction section that brings the hydrogen reservoir from the vaporization section into contact with a catalyst to perform a dehydrogenation reaction and converts it into hydrogen and a dehydrogenated product.
A suction part that decompresses the atmosphere inside the dehydrogenation reaction part by suction,
A gas-liquid separator that separates a mixture containing hydrogen gas and dehydrogenated material sucked by the suction unit into a gas that mainly contains hydrogen and a liquid that mainly contains dehydrogenated material.
A hydrogen generation system characterized by being equipped with.
The hydrogen generation system according to claim 1, wherein the gas-liquid separation unit has at least a container to which the sucked mixture is sent and a pressure adjusting valve for adjusting the pressure in the container.
The hydrogen generation system according to claim 1, wherein the supply unit intermittently supplies the hydrogen storage unit to the vaporization unit at time intervals in which the dehydrogenated product of the previously supplied hydrogen storage unit is discharged from the dehydrogenation reaction unit.
The hydrogen generation system according to claim 1, wherein the adsorptive power of the catalyst to hydrogen, a hydrogen reservoir or a dehydrogenated product has a relationship of adsorption power to hydrogen <adsorbent power to hydrogen reservoir <adsorbent power to dehydrogenated product.
The hydrogen generation system according to claim 4, wherein the catalyst contains a catalyst metal and a carrier supporting the catalyst metal, and the carrier contains silica.
The hydrogen generation system according to claim 1, wherein the dehydrogenation reaction unit is heated by a cooling medium that cools a power generation device that converts heat energy into electricity or a heat engine that converts heat energy into mechanical energy.
A method of producing hydrogen by dehydrogenating a hydrogen reservoir with a catalyst.
The process of supplying hydrogen storage and
The process of vaporizing the supplied hydrogen reservoir and
A step of bringing a vaporized hydrogen reservoir into contact with a catalyst to carry out a dehydrogenation reaction to convert hydrogen into a dehydrogenated product, which is a step of carrying out the dehydrogenation reaction under reduced pressure by suction.
A step of separating the suctioned mixture containing hydrogen and dehydrogenated product into a gas containing mainly hydrogen and a liquid containing mainly dehydrogenated product.
A method characterized by including.
The method according to claim 7, wherein the dehydrogenation reaction is carried out under a pressure of 30 kPa or less.
The method according to claim 7, wherein the mixture is put into a container by the suction and the pressure is increased to separate the mixture into a gas and a liquid.
The method according to claim 7, wherein the hydrogen reservoir is intermittently used as a catalyst at time intervals during which the dehydrogenated product of the previously supplied hydrogen reservoir is discharged.
The method according to claim 7, wherein the adsorptive force of the catalyst to hydrogen, a hydrogen reservoir or a dehydrogenated product has a relationship of an adsorbing force to hydrogen <an adsorbing force to a hydrogen reservoir <an adsorbing force to a dehydrogenated product.
The method according to claim 11, wherein the catalyst contains a catalyst metal and a carrier supporting the catalyst metal, and the carrier contains silica.
The method according to claim 7, wherein the environment of the dehydrogenation reaction is heated by a cooling medium that cools a power generation device that converts heat energy into electricity or a heat engine that converts heat energy into mechanical energy.