JP5297251B2 - Hydrogen supply method and hydrogen supply apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen supply apparatus efficiently supplying hydrogen to other apparatus even at a low temperature of &le;200&deg;C. <P>SOLUTION: The hydrogen supply apparatus 1 produces hydrogen and a dehydrogenated body of a hydrogen storage body, by carrying out dehydrogenation-reaction by bringing the hydrogen storage body chemically storing hydrogen into contact with a catalyst, and supplies produced hydrogen to other apparatus; and is provided with: an evaporation part 11 for evaporating the hydrogen storage body; a catalyst part 13 having catalysts different in the adsorption power to hydrogen, adsorption power to the dehydrogenated body and the adsorption power to the hydrogen storage body unreacted in the dehydrogenation reaction, while producing hydrogen and the dehydrogenated body by supplying the hydrogen storage body storing hydrogen evaporated in the evaporation part 11 and dehydrogenating the hydrogen storage body; and a supply part 12 provided between the evaporation part 11 and the catalyst part 13 and for supplying the hydrogen storage body evaporated in the evaporation part 11 with a time interval necessary for removing at least dehydrogenated body from the catalyst part 13, wherein the catalyst part 13 is heated to &le;200&deg;C. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  In the present invention, a hydrogen storage body capable of storing hydrogen chemically is brought into contact with a catalyst to cause a dehydrogenation reaction to generate hydrogen and a dehydrogenated body of the hydrogen storage body, and the generated hydrogen is transferred to another apparatus. The present invention relates to a hydrogen supply method and a hydrogen supply apparatus.

As global warming due to carbon dioxide and the like becomes serious, hydrogen is attracting attention as an energy source for the next generation instead of fossil fuels.
For example, a fuel cell power generation system that generates power using hydrogen, a hydrogen supply fuel cell cogeneration system that promotes energy saving that effectively uses energy to reduce CO ₂ emissions, a hydrogen supply device, and a micro turbine Development of a combined generator and a generator combining a hydrogen supply device and a micro engine is also underway (hereinafter collectively referred to as a “hydrogen-based power generation system”). Development of hydrogen fuel engines that use hydrogen directly as a fuel is also in progress.

  The hydrogen-based power generation system is rapidly developing as a power source for automobiles, household power generation facilities, vending machines, portable devices, etc. Among them, the fuel cell power generation system is used when hydrogen and oxygen react to become water. Since electricity can be generated and hot water and air conditioning can be performed using the heat energy generated at the same time, it is suitable for a home-use distributed power source.

Here, since hydrogen-based power generation systems and hydrogen fuel engines use hydrogen as a fuel, a hydrogen transportation, storage, and supply system is a major issue.
In other words, hydrogen is a gas at room temperature, so it is not only difficult to store and transport compared to liquids and solids, but hydrogen is a flammable substance, and if it is mixed with air at a predetermined mixing ratio, there is a risk of explosion. is there.

Techniques for solving such problems are described in Patent Documents 1 to 3 and Non-Patent Document 1.
Among these, Patent Documents 1 and 2 and Non-Patent Document 1 describe techniques related to so-called organic hydride systems using hydrocarbons such as cyclohexane and decalin.
This organic hydride system will be described by taking an example using cyclohexane. Cyclohexane and benzene are cyclic hydrocarbons having the same carbon number, whereas cyclohexane is a saturated hydrocarbon having no double bond, whereas benzene Is an unsaturated hydrocarbon having a portion where carbons are bonded by a double bond. In other words, benzene is obtained by the dehydrogenation reaction of cyclohexane, and cyclohexane is obtained by the hydrogenation reaction of benzene. Therefore, such an organic hydride system uses the dehydrogenation reaction and hydrogenation reaction of these hydrocarbons to generate hydrogen. It can be supplied and stored.
In Patent Documents 1 and 2, in order to generate hydrogen from hydrocarbons such as cyclohexane and decalin, liquid hydrocarbons are directly sprayed on a high-temperature catalyst in the reactor to perform a dehydrogenation reaction. And separation of hydrogen using a hydrogen separation membrane.

  According to these organic hydride systems, safety, storage capacity, and cost reduction are excellent, and since these hydrocarbons are liquid at room temperature, it is possible to implement a hydrogen storage and supply method with excellent transportability. it can.

  Further, Patent Document 3 discloses that while hydrogen is dehydrogenated in a flow reaction system equipped with a dehydrogenation catalyst and a hydrogen separation membrane, the produced hydrogen is continuously permeated and separated by the hydrogen separation membrane. A method for producing hydrogen is described, wherein a hydrogen storage alloy stores at least a part of the generated hydrogen flow so that the pressure on the hydrogen permeation side of the hydrogen separation membrane is lower than the pressure on the non-permeation side. In the organic hydride system, hydrogen separation, reaction temperature reduction, and hydrogen recovery rate are improved.

JP 2002-274801 A JP 2002-184436 A JP 2005-281103 A

Nobuko Kariya, Atsushi Fukuoka and Masaru Ichikawa, “Efficient evolution of hydrogen from liquid cycloalkanes over Pt-containing catalysts supported on active carbons under“ wet-dry multiphase conditions ””, Applied Catalysis A: General, Volume 233, Issues 1-2, 10 July 2002, p.91-102.

  However, Patent Documents 1 and 2 and Non-Patent Document 1 have many problems in practical use. For example, in order to put to practical use a hydrogen supply apparatus utilizing a dehydrogenation reaction represented by the reaction between cyclohexane and benzene, it is necessary to further lower the reaction temperature at the catalyst.

  In Patent Documents 1 to 3 and Non-Patent Document 1, the reaction temperature is lowered by reducing the hydrogen partial pressure in the reaction system by using a hydrogen separation membrane. In the configuration described in Document 1, even if the dehydrogenation reaction can be performed at a high conversion rate up to about 250 ° C., the durability of the hydrogen separation membrane is drastically reduced if the temperature is lower than this. There is a problem in practicality.

  The present invention has been made to solve the above problems, and an object of the present invention is to provide a hydrogen supply method and a hydrogen supply apparatus that can efficiently supply hydrogen to other apparatuses even at a low temperature of 200 ° C. or lower. .

In the hydrogen supply method according to the present invention, a hydrogen storage body capable of chemically storing hydrogen is brought into contact with a catalyst to cause a dehydrogenation reaction, thereby generating hydrogen and a dehydrogenation body of the hydrogen storage body. A hydrogen supply method for supplying hydrogen to another apparatus, wherein the hydrogen storage body is vaporized, and the vaporized hydrogen storage body is heated to 200 ° C. or less at a time interval at which the dehydrogenation body is removed from the catalyst. The hydrogen and the dehydrogenated product produced in the dehydrogenation reaction while the hydrogen and the dehydrogenated product are produced by bringing the dehydrogenated product into contact with the produced catalyst. The unreacted hydrogen storage body is sent out of the system at different timings due to the action of the catalyst , and the catalyst has an adsorption power with the hydrogen, an adsorption power with the dehydrogenated substance, and the Prolapse The strength of the attractive force between the hydrogen storage material that did not react under the reaction is characterized by satisfying the relationship of the hydrogen <the dehydrogenation body <the hydrogen reservoir.

Further, the hydrogen supply device according to the present invention generates a dehydrogenated product of hydrogen and a hydrogen storage unit by bringing a hydrogen storage unit capable of chemically storing hydrogen into contact with a catalyst to cause a dehydrogenation reaction, A hydrogen supply device that supplies the generated hydrogen to another device, wherein a vaporization unit that vaporizes the hydrogen storage body, and the hydrogen storage body vaporized by the vaporization unit are supplied to perform the dehydrogenation reaction. While producing the hydrogen and the dehydrogenated body, a catalyst having different adsorption power with the hydrogen, adsorption power with the dehydrogenated body, and different adsorption power with the hydrogen storage body that has not been reacted in the dehydrogenation reaction. The hydrogen storage body, which is provided between the catalyst section and the vaporization section and the catalyst section, and is vaporized in the vaporization section is supplied to the catalyst section at a time interval at which the dehydrogenated body is removed from the catalyst section. A supply section For example, the catalyst portion is heated at 200 ° C. or less, sending the strength of the suction force, satisfy the relationship of the hydrogen <the dehydrogenation body <the H2 storage, out of the system at different times by the action of the catalyst It is characterized by letting .

A hydrogen supply method and a hydrogen supply apparatus according to the present invention include a hydrogen storage body by vaporizing the hydrogen storage body with a vaporizer and then supplying the vaporized hydrogen storage body to the catalyst section at a specific time interval by the supply section. Can be dehydrogenated to produce hydrogen. The catalyst used in the present invention is different in adsorption power with hydrogen, adsorption power with dehydrogenated substance, and adsorption power with hydrogen storage body, so these are sent out of the system at different timings by contacting with the catalyst. Can be made. In addition, such a catalyst can quickly remove hydrogen and dehydrogenated substance from a reaction system containing hydrogen, dehydrogenated substance, and hydrogen storage element. Therefore, dehydrogenation reaction is performed by shifting the chemical equilibrium state in the catalyst. Can be promoted. As a result, even at a low temperature of 200 ° C. or lower, hydrogen can be efficiently generated and supplied to other devices.
Therefore, according to the hydrogen supply method and the hydrogen supply apparatus according to the present invention, not only is it easy to store and transport hydrogen, but also at a temperature exceeding 200 ° C. to supply hydrogen to automobiles and distributed power sources. Hydrogen can be supplied using an existing gasoline infrastructure or the like without providing a heat source for heating.

It is a block diagram which shows the basic structural example of the hydrogen supply apparatus which concerns on this invention. (A)-(d) is explanatory drawing explaining the mode of the dehydrogenation reaction in a catalyst. It is a block diagram which shows the other structural example of the hydrogen supply apparatus which concerns on this invention. It is a block diagram which shows the other structural example of the hydrogen supply apparatus which concerns on this invention. It is the block diagram which showed the structural example of the electric power generation system which combined the hydrogen supply apparatus and solid polymer fuel cell which concern on this invention. It is the block diagram which showed the structural example of the engine system which combined the hydrogen supply apparatus and engine which concern on this invention. It is the block diagram which showed the structural example of the hydrogen storage system which combined the hydrogen supply apparatus and compressor which concern on this invention. It is the block diagram which showed the structural example of the hydrogen community using the hydrogen supply apparatus which concerns on this invention. (A) is a graph showing hydrogen generation temperature [° C.] and reaction conversion rate [%] in Examples and Conventional Examples, and (b) is a toluene mixing rate [%] and reaction conversion rate in methylcyclohexane. It is a graph which showed [%].

Below, the form for implementing the hydrogen supply method and hydrogen supply apparatus which concern on this invention is demonstrated.
In the hydrogen supply method according to the present invention, a hydrogen storage body capable of chemically storing hydrogen is brought into contact with a catalyst to cause a dehydrogenation reaction, thereby generating hydrogen and a dehydrogenation body of the hydrogen storage body. A method of supplying hydrogen to another apparatus, wherein the hydrogen storage body is vaporized, and the vaporized hydrogen storage body is heated to 200 ° C. or less with a time interval at which at least the dehydrogenation body of the hydrogen storage body is removed from the catalyst. While generating hydrogen and a dehydrogenated product by bringing the catalyst into contact with a catalyst to perform a dehydrogenation reaction, produced hydrogen, the produced dehydrogenated product, and a hydrogen storage body that has not been reacted in the dehydrogenated reaction, They are sent out of the system at different timings depending on the action of the catalyst.
By performing such treatment, hydrogen can be efficiently generated from the hydrogen storage body even at a temperature of 200 ° C. or lower, and the generated hydrogen can be supplied to other devices.

  An apparatus that embodies this hydrogen supply method is a hydrogen supply apparatus described below. Since the details of the hydrogen supply method can be clarified by describing the details of the hydrogen supply apparatus, the hydrogen supply apparatus will be described below.

As shown in FIG. 1, the hydrogen supply device 1 according to the present invention mainly includes a vaporization unit 11, a catalyst unit 13, and a supply unit 12.
Here, the hydrogen storage body maintains a liquid state at room temperature, and has a boiling point of room temperature to 200 ° C. or less, preferably room temperature to 150 ° C. or less, and can generate hydrogen in the molecular structure by a dehydrogenation reaction. A chain saturated hydrocarbon, a cyclic saturated hydrocarbon, a heterocyclic saturated hydrocarbon, an aqueous ammonia solution, an aqueous hydrazine solution, sodium borate, or a mixture of ammonia or an aqueous hydrazine solution and hydrogen peroxide can be used.

  As the chain saturated hydrocarbon, for example, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, structural isomers thereof, and substituted products thereof can be used.

  As the cyclic saturated hydrocarbon, for example, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and alkyl-substituted products thereof can be used. Examples of the alkyl substituent of the cyclic saturated hydrocarbon include methylcyclohexane. Further, as the cyclic saturated hydrocarbon, those obtained by single bonding a plurality of them can be used. Examples of such a compound include biphenyl.

  As the heterocyclic saturated hydrocarbon, for example, decalin, tetralin, and alkyl-substituted products thereof can be used. Examples of the alkyl-substituted product of the heterocyclic saturated hydrocarbon include methyl decalin.

  In addition, as long as the hydrogen storage body can isolate | separate hydrogen, the dehydrogenation body of a hydrogen storage body, and an unreacted hydrogen storage body in the catalyst part 13 mentioned later, it is selected from any one of the above-mentioned compounds. Only seeds can be used, or two or more kinds can be mixed and used. Furthermore, as long as there is no hindrance to the dehydrogenation reaction in the catalyst part 13, other compounds, for example, additives such as hydrocarbons having no cyclohexane ring and stabilizers may be included.

The vaporization unit 11 is a device that vaporizes the hydrogen storage body, and preferably a device that obtains the vapor of the hydrogen storage body.
As such a vaporization part 11, a carburetor, a spray gun, etc. are mentioned, for example. In addition, for example, a heat exchange type flow path using the residual heat of an electric heater or a reactor is filled with a filler such as granular or honeycomb, a fine flow path is formed, or a heat exchange fin It can comprise by providing.

The catalyst unit 13 is supplied with the hydrogen storage body vaporized in the vaporization unit 11 and performs a dehydrogenation reaction to generate hydrogen and a dehydrogenated product, while adsorbing with hydrogen, adsorbing power with the dehydrogenated product, and The catalyst has a different adsorption force from the hydrogen storage body that has not been reacted in the dehydrogenation reaction. Therefore, hydrogen, a dehydrogenated body, and a hydrogen storage body can be obtained at different timings by the catalyst.
The strength of the adsorption force is preferably hydrogen <dehydrogenated material <unreacted hydrogen storage material. If a catalyst having such an adsorption power is used, it is possible to obtain hydrogen, a dehydrogenated body, and a hydrogen storage body at different timings.

The catalyst is formed including a metal catalyst and a carrier supporting the metal catalyst, and preferably includes a holding body for holding the carrier.
The metal catalyst is formed of, for example, one or more transition metals selected from Ni, Pd, Pt, Rh, Ir, Re, Ru, Mo, W, V, Os, Cr, Co, and Fe or alloys thereof. It is preferable to use particles. The size of the metal catalyst particles may be, for example, those having a particle size distribution of about 2 nm in diameter. However, the present invention is not limited to this, and any method can be used as long as the dehydrogenation reaction of the hydrogen storage body can be performed. Any size is acceptable.

Examples of the carrier that can be used include activated carbon, carbon nanotubes, alumina silicates such as silica, alumina, and zeolite, porous polyimide, zinc oxide, zirconium oxide, diatomaceous earth, niobium oxide, and vanadium oxide. Such a carrier can be in any form according to the fixing mode of the catalyst.
For example, when the catalyst part 13 is of a type in which the catalyst is filled and fixed, such as a straight tube type, a box type, or a microreactor type, the form of the carrier is a porous body, a honeycomb body, or It can be a particulate body.
When the catalyst unit 13 is of a type that fixes the catalyst to the inner surface of the thin tube body or the inner surface of the microreactor type housing, a carrier is provided so as to cover the inner surface of the thin tube body or the inner surface of the housing. be able to.
Further, the catalyst part 13 is formed by machining the flat plate surface using mechanical processing such as cutting and pressing, etching, plating process, soft lithography technology such as nanoprinting, and dry process technology such as vapor deposition and sputtering. In the case of a type in which the flow path part and the uneven part for allowing the hydrogen storage body to flow through are provided and the catalyst is fixed thereon, the surface of the flat plate provided with the flow path part and the uneven part should be covered. A carrier can be provided on the substrate.
In addition, it is needless to say that the above-described flat plate can be provided with a supply port for supplying the vaporized hydrogen storage body and a discharge port for discharging reaction products in an arbitrary number of places. Absent.

The catalyst using the metal catalyst and the carrier described above can be formed as follows.
When the catalyst unit 13 is of a type in which the catalyst is filled and fixed, it is preferable that the metal catalyst is supported on the carrier and fixed. For example, it can be obtained by a coprecipitation method or a thermal decomposition method by a conventional method using a metal catalyst and a carrier.
When the catalyst part 13 is provided with a catalyst so as to cover the surface of the flat plate provided with the flow path part and the uneven part, a carrier layer is formed by a sol-gel method or a CVD method, and a metal catalyst is supported on the carrier layer. Thus, the catalyst can be formed as a catalyst layer.
Further, the catalyst portion 13 is a flat tube or a microreactor-type casing made of a metal such as aluminum, zirconium, niobium, vanadium or an alloy mainly composed of these, or a flat plate provided with a flow path portion or an uneven portion. In the case of a type in which the catalyst is fixed to the surface, an oxide-based carrier layer is directly formed on the inner surface or the surface of the flat plate by anodizing the inner surface of the thin tube or the surface of the flat plate. The catalyst can be formed as a catalyst layer by supporting the metal catalyst on the carrier layer.
And when forming as a catalyst of a porous body or a honeycomb body, it can form by making a metal catalyst carry | support in the void | hole which an alumina, a zeolite, a porous polyimide, etc. have.

  The catalyst unit 13 preferably fixes the catalyst in a robust housing in order to prevent destruction of the catalyst due to external stimulation. In the present invention, since the dehydrogenation reaction of the hydrogen storage body is performed at 200 ° C. or lower, such a housing can be formed using various metals, ceramics, glass, plastics, and the like. Of course, it is preferable to form it so that no leakage of hydrogen gas occurs.

  The catalyst unit 13 includes the carrier formed of the above-described material and the catalyst, so that the hydrogen storage body can be dehydrogenated to generate hydrogen and a dehydrogenated body of the hydrogen storage body. It is possible to differentiate the adsorption power with the generated hydrogen, the adsorption power with the dehydrogenated body, and the adsorption power with the hydrogen storage body that has not been reacted in the dehydrogenation reaction. It can be sent out. Therefore, it is possible to individually collect and use the generated hydrogen and the like.

The supply unit 12 is provided between the vaporization unit 11 and the catalyst unit 13, and supplies the hydrogen storage body vaporized by the vaporization unit 11 to the catalyst unit 13 at a time interval at which at least the dehydrogenated body is removed from the catalyst unit 13. It is.
The supply unit 12 operates the pressure applying device 121 that applies pressure to the hydrogen storage body and the pressure applying device 121 at an appropriate timing in order to supply the vaporized hydrogen storage body to the catalyst unit 13. A supply timing control device 123 that controls to supply the vaporized hydrogen storage body to the catalyst unit 13 may be included.

The pressure applying device 121 includes a booster pump for boosting the vaporized hydrogen storage body, and a control valve 122 for controlling a time interval and a flow rate for supplying the vaporized hydrogen storage body, thereby vaporizing the hydrogen storage. Appropriate pressure can be applied to the body and supplied to the catalyst unit 13.
As the booster pump, for example, a plunger type, a piston type, or the like can be used, but the present invention is not limited to this, and any pump that can pressurize the hydrogen storage body can be used. .
The control valve 122 for controlling the time interval and the flow rate for supplying the vaporized hydrogen storage body can be performed by, for example, a commonly used one such as an air valve or a solenoid valve, an automobile injection valve, or the like. it can.

The supply timing control device 123 is a CPU capable of executing a program that can operate the pressure applying device 121 at an appropriate timing. Such a program can be stored in, for example, a ROM or a RAM.
As a control method for operating at an appropriate timing, for example, (1) control based on the supply time and supply stop interval defined by the temperature and pressure conditions in the operating environment of the pressure applying device 121, (2) pre-designated It is possible to perform control based on the time interval, or (3) feedback control based on signals detected by various sensors, alone or in combination.

  The control (1) can be implemented by including a temperature sensor that detects the temperature in the operating environment of the pressure applying device 121 and a pressure sensor that detects the pressure, and executing a program based on the detected temperature and pressure. The control of (2) can be realized by grasping the temperature and pressure of the catalyst unit 13 and the performance of the catalyst in advance and executing the program at a specified time. The control of (3) It is equipped with a pressure sensor that detects pressure, a temperature sensor that detects temperature, a flow sensor that detects the flow rate of the vaporized hydrogen storage body, a hydrogen sensor that detects the concentration of generated hydrogen, etc. This can be realized by calculating the reaction conversion rate and controlling it so as to minimize the fluctuation of the reaction conversion rate.

  The recovery unit 14 that recovers the generated hydrogen gas-liquid separates and recovers the hydrogen gas with high purity. For gas-liquid separation, a cooler, a separation membrane, a combination thereof, or the like can be used. Further, since the discharge timing of the reactants is different, the valves can be switched during each discharge time and collected in separate containers. Further, the collection unit 14 can be provided with a suction system to suck out the reactant. It is effective to use an exhaust pump for the suction system, and any exhaust pump that can reduce the pressure of the hydrogen storage body in the pressure applying device 121 may be used. Pistons, turbines, commercially available air pumps, vacuum pumps, micro turbines, automobile over-intake turbines, and the like can be used. In the case of an engine, the power of the engine may be directly used as the power of the pump, and when applied to an automobile, the power of the axle of the automobile can be used as pump power. Furthermore, when hydrogen is used as a high-pressure gas, it can be carried out by direct suction using a compressor.

In a conventional hydrogen supply apparatus, a hydrogen separation membrane is used to generate hydrogen from a hydrogen storage body, hydrogen is preferentially removed from the reaction system, and the dehydrogenation reaction is promoted by shifting the equilibrium. However, even in this case, 220 to 400 ° C. is necessary (see Patent Documents 1 to 3 and Non-Patent Document 1).
Therefore, when hydrogen is generated from the hydrogen storage body at a low temperature of 200 ° C. or less, which is more difficult to promote the dehydrogenation than this, hydrogen is further preferentially and forcibly removed by the hydrogen separation membrane, and the equilibrium is further shifted. Therefore, it is necessary to promote the dehydrogenation reaction, which is very difficult because the hydrogen separation membrane may deteriorate as described above.

In the hydrogen supply apparatus 1 according to the present invention, as already described in detail, the hydrogen produced by dehydrogenating the hydrogen storage body with the catalyst in the catalyst section 13, the dehydrogenation body of the hydrogen storage body, and the dehydrogenation reaction And an unreacted hydrogen storage body can be obtained. And as already stated, these are sent from the catalyst unit 13 at different timings depending on the difference in the adsorption power with the hydrogen, the adsorption power with the dehydrogenated substance, and the strength of the adsorption power with the hydrogen storage body. It is possible to make it.
The difference in the strength of the adsorption force is given mainly by the adsorption force and polarity of the carrier used for the catalyst. In the present invention, it is desirable to preferentially remove hydrogen produced by the dehydrogenation reaction and the dehydrogenated substance from the reaction system among the hydrogen, dehydrogenated substance, and hydrogen storage element. It is preferable that generally satisfy the relationship of hydrogen <dehydrogenated body <hydrogen storage body. All of the above-mentioned carrier materials satisfy this relationship. However, since hydrogen does not adsorb on the above-described carrier, the carrier may be selected by paying attention to the strength of the adsorptive power of the dehydrogenated body and the hydrogen storage body. In addition, since a suitable support | carrier may differ with the hydrogen storage body to be used, it is good to select the support | carrier suitable for the hydrogen storage body to be used by performing an experiment etc. previously.

  As an example of selection of a hydrogen storage body and a catalyst, it can mention using methylcyclohexane as a hydrogen storage body, using activated carbon as a support | carrier of a catalyst, and using Pt as a metal catalyst of a catalyst. In this case, hydrogen and toluene, which is a dehydrogenated product, can be generated by dehydrogenating methylcyclohexane with a catalyst.

Here, the operation of the hydrogen supply apparatus 1 will be described with reference to FIG.
As shown in FIG. 1, when the hydrogen storage body is supplied to the vaporization unit 11 of the hydrogen supply device 1, the hydrogen storage body is heated and vaporized by the vaporization unit 11. Next, the vaporized hydrogen storage body is sent to the supply unit 12, and pressure is applied by the pressure applying device 121 of the supply unit 12. Since the control valve 122 is closed during normal times, the supply of the hydrogen storage body that has been vaporized and pressured is restricted to the catalyst unit 13 by the control valve 122. However, when the supply timing control device 123 sends a signal indicating that the control valve 122 is opened for a predetermined time at an appropriate time interval, the control valve 122 is opened for a predetermined time and is vaporized. The hydrogen storage body to which pressure is applied is supplied to the catalyst unit 13. The catalyst unit 13 dehydrogenates the supplied hydrogen storage body to generate hydrogen and a dehydrogenated body, and sequentially discharges these to the outside of the hydrogen supply apparatus 1. Further, after discharging the hydrogen and the dehydrogenated body, the hydrogen storage body that has not been reacted in the dehydrogenation reaction described above is discharged out of the hydrogen supply apparatus 1.

  The state of the dehydrogenation reaction in the catalyst part 13 at this time will be described with reference to FIG. As shown in FIG. 2A, when the methylcyclohexane vaporized from the upstream side to which the supply unit 12 is connected is supplied to the catalyst in the catalyst unit 13, the methylcyclohexane and the catalyst come into contact with each other. Thereby, methylcyclohexane is dehydrogenated to generate hydrogen and toluene. Next, as shown in FIG. 5B, the generated hydrogen is not adsorbed on the catalyst, and therefore is removed from the reaction system at an early stage and sent out from the catalyst unit 13. As a result, the equilibrium is shifted, so that the dehydrogenation reaction can be promoted. Next, as shown in FIG. 3C, the generated toluene has a lower adsorption power to the catalyst than unreacted methylcyclohexane, so that it moves to the downstream side of the catalyst portion 13 earlier than methylcyclohexane. As a result, the equilibrium can be further shifted, so that the dehydrogenation reaction can be further promoted. Therefore, the dehydrogenation reaction of unreacted methylcyclohexane is promoted by the catalyst, and hydrogen and toluene can be newly generated. The generated hydrogen is removed from the reaction system at an early stage and sent out from the catalyst unit 13 as described above. Next, as shown in FIG. 4D, the product hydrogen and toluene are removed from the reaction system at an early stage and the equilibrium is lost. Therefore, the dehydrogenation reaction of the remaining methylcyclohexane is promoted, and hydrogen and toluene can be newly generated.

As described above, the hydrogen supply device 1 of the present invention can remove the product hydrogen and toluene from the spot at an early stage when the dehydrogenation reaction of methylcyclohexane is performed, thereby realizing an extreme equilibrium shift. It is possible to strongly promote the dehydrogenation reaction. Therefore, the hydrogen storage body can be converted into the dehydrogenated body at a high reaction conversion rate even at a low temperature of 200 ° C. or lower, and hydrogen can be generated. This point will be described later.
Further, the hydrogen supply apparatus 1 of the present invention is a fuel in which a hydrogen storage body and a dehydrogenation body are mixed, and the purity of the hydrogen storage body is low and a large amount of dehydrogenation body is contained. It is possible to generate hydrogen by converting a hydrogen storage body to a dehydrogenation body at a high reaction conversion rate. This point will also be described later.
Therefore, according to the hydrogen supply apparatus 1 according to the present invention, it is possible to recover the unreacted hydrogen storage body and reuse it as a fuel. Even in such a case, the hydrogen generation efficiency is kept high. It is possible.

The operating temperature of PEFC (solid polymer fuel cell) and DMFC (direct methanol fuel cell) using hydrogen as a fuel is about 70 to 100 ° C., and the operating temperature of PAFC (phosphoric acid fuel cell) is about Since the temperature is about 200 ° C., when the hydrogen supply device of the present invention and these fuel cells are used in combination, they can be used as a heat source by providing them adjacent to or in close proximity to these fuel cells. Moreover, also when using combining the hydrogen supply apparatus 1 and a hydrogen fuel engine etc., the heat | fever of the waste gas discharged | emitted from the said hydrogen fuel engine can be utilized as a heat source.
However, if these are the only heat sources, the hydrogen storage device may not be smoothly dehydrogenated because the temperature of the catalyst unit 13 is low when the operation of the hydrogen supply device 1 is started or when the temperature is low.

Therefore, the hydrogen supply apparatus 1 according to the present invention preferably further includes a heating unit 14 that heats at least one of the vaporization unit 11 and the catalyst unit 13 at a temperature of 200 ° C. or lower, as shown in FIG. It is more preferable to include a heating unit 14 that heats all of the vaporization unit 11, the supply unit 12, and the catalyst unit 13 at a temperature of 200 ° C. or less.
For example, even when the temperature of the catalyst unit 13 is low and the dehydrogenation reaction of the hydrogen storage body may not be performed smoothly, the heating unit 14 heats the catalyst unit 13 to dehydrogenate the hydrogen storage body. Can be performed smoothly.
As the heating unit 14, an electric heater controlled so as to be able to heat them to 200 ° C. or less, a heater that burns and burns combustible fuel, and the like can be used.

Further, the heating unit 14 heats the catalyst unit 13 using heat of a cooling medium of 200 ° C. or less that cools a power generation device that converts thermal energy into electricity or a heat engine that converts thermal energy into mechanical energy. It may be the one.
Examples of the power generation device that converts thermal energy into electricity include a generator and a nuclear reactor. An example of a heat engine that converts thermal energy into mechanical energy is an engine. When the device (heat generating device) that generates such heat and the hydrogen supply device 1 of the present invention are used in combination, the catalyst unit 13 is heated at 200 ° C. or less by a cooling medium for cooling these heat generating devices. May be. Examples of the cooling medium include cooling water for cooling the engine, exhaust gas discharged from the engine, and secondary cooling water for the reactor.

In addition, as shown in FIG. 4, the hydrogen supply device 1 according to the present invention further includes a recovery unit 15 that individually recovers at least hydrogen among the hydrogen, the dehydrogenated body, and the hydrogen storage body sent from the catalyst unit 13. Is preferred. In this way, it is possible to obtain at least hydrogen with high purity and store it. In addition, it is preferable that the dehydrogenated body and the hydrogen storage body can be recovered separately.
The hydrogen supply apparatus 1 of the present invention supplies the hydrogen storage body vaporized in the vaporization unit 11 to the catalyst unit 13 at least at a time interval at which the dehydrogenation agent is removed from the catalyst unit 13 by the supply unit 12 to perform the dehydrogenation reaction. In order to carry out, the produced | generated hydrogen, a dehydrogenation body, and a hydrogen storage body are sent from the catalyst part 13 at a respectively different timing. Therefore, it is preferable to provide an operation valve that operates in accordance with each delivery timing so that it can be individually collected.

  Further, an exhaust pump may be connected to the hydrogen supply device, and hydrogen may be sucked by this exhaust pump. The hydrogen recovered from the hydrogen supply device can be stored, for example, at several to several tens of atmospheres in the reserve tank. By providing a spare tank storing hydrogen, the next start-up of the fuel cell or the like can be performed immediately. Further, by storing hydrogen in the reserve tank, hydrogen can be stably supplied to the fuel cell or the like.

  Further, dehydrogenated bodies and hydrogen storage bodies that have not been reacted in the dehydrogenation reaction can be recovered individually or simultaneously. The recovered dehydrogenation body or hydrogen storage body can be stored in a recovery unit (not shown in FIG. 4) such as a waste liquid tank or returned to the fuel tank as appropriate.

As described above, according to the hydrogen supply device of the present invention, it is possible to efficiently generate hydrogen and supply it to other devices even at a low temperature of 200 ° C. or lower. Further, it is possible to supply hydrogen using an existing gasoline infrastructure or the like without providing a heat source for heating at a temperature exceeding 200 ° C. in order to supply hydrogen to an automobile or a distributed power source.
Therefore, the hydrogen supply apparatus according to the present invention can be used as follows. Below, the example using the hydrogen supply apparatus which concerns on this invention is demonstrated.

First, a power generation system 100 in which the hydrogen supply device 1 of the present invention and the polymer electrolyte fuel cell 101 are combined and integrated will be described with reference to FIG.
As shown in FIG. 5, the power generation system 100 includes a vaporization unit 11, a supply unit 12, and a catalyst unit 13 on the polymer electrolyte fuel cell 101 so as to contact the polymer electrolyte fuel cell 101. A hydrogen supply device 1 is attached. In this way, since the operation temperature of the polymer electrolyte fuel cell 101 is 80 to 100 ° C., the operation temperature is used as it is, and the entire hydrogen supply device 1 is extended, and the vaporization unit 11 and the catalyst unit 13 are extended. At least one, preferably both, can be heated. Therefore, it is possible to suitably perform the dehydrogenation reaction of the hydrogen storage body in the catalyst unit 13.

  The power generation system 100 includes a storage tank 102 for storing the hydrogen storage body, a liquid supply line 104 for supplying the hydrogen storage body stored in the storage tank 102 to the hydrogen supply device 1, A liquid feed pump 105 that is provided on the liquid feed line 104 and generates a pressure for feeding the hydrogen storage body from the storage tank 102 to the hydrogen supply apparatus 1; and the hydrogen produced by the hydrogen supply apparatus 1 is converted into a solid polymer form. Hydrogen supply line 108 for supplying to the fuel cell 101, dehydrogenated hydrogen storage body generated and discharged by the hydrogen supply device 1, and hydrogen storage that has not been reacted in the dehydrogenation reaction of the hydrogen supply device 1 The body is cooled and condensed, and the hydrogen storage body is returned from the vaporized state to the liquefied state and recovered as waste liquid, and the dehydration sent through the waste liquid recovery line 106 The body and the hydrogen reservoir and a waste tank 103 for keeping collected as waste. A hydrogen supply pump 107 is provided on the hydrogen supply line 108 for sucking the hydrogen generated in the hydrogen supply device 1 and supplying it to the polymer electrolyte fuel cell 101. The generated hydrogen can be forcibly supplied to the polymer electrolyte fuel cell 101. As this hydrogen supply pump 107, for example, a turbine-type exhaust pump can be used.

  Moreover, when the temperature of the vaporization part 11 of the hydrogen supply apparatus 1 and the catalyst part 13 is low, it is difficult for the dehydrogenation reaction of a hydrogen storage body to advance, and there exists a possibility that hydrogen cannot be produced | generated suitably. Therefore, as shown in FIG. 5, for example, the vaporization unit 11 and the catalyst unit 13 are close to the vaporization unit 11 and the catalyst unit 13 so that the dehydrogenation reaction of a suitable hydrogen storage body can be performed at an early stage by heating. The heating unit 14 (not shown in FIG. 5, see FIG. 3) is supplied with fuel such as city gas, kerosene, heavy oil, or dehydrogenated product after reaction from a tank (not shown) or the like. The gas may be supplied by a pump and a heating fuel line (not shown), and the vaporization unit 11 and the catalyst unit 13, preferably the entire hydrogen supply device 1, may be heated at 200 ° C. or lower.

  The polymer electrolyte fuel cell 101 includes a cell stack (not shown) configured by stacking a plurality of unit cells S formed of an electrolyte membrane E, an anode A and a cathode C sandwiching the electrolyte membrane E. Then, hydrogen generated by the hydrogen supply device 1 is supplied to the anode A through the hydrogen supply line 108. On the other hand, air (oxygen) fed from the air pump 109 and processed by a humidifier (not shown) or the like as needed is supplied to the cathode C. Then, the hydrogen of the anode A and the oxygen of the cathode C react with each other through the above-described electrolyte membrane E, thereby generating electrons (electricity) and water. The generated water is discharged outside the power generation system 100, and electricity is supplied to an electric system including a motor and 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.

  In such a power generation system 100, as a result of using the hydrogen storage body, when there is no hydrogen storage body in the storage tank 102 and the dehydrogenation body is filled in the waste liquid tank 103, for example, the hydrogen storage body supply port of the tank truck and storage Hydrogen can be supplied by connecting the tank 102 by piping to supply the hydrogen storage body, and connecting the waste liquid circulation port of the tank truck and the waste liquid tank 103 by piping to collect the waste liquid. .

In addition, the power generation system 100 is provided with a heat exchanger (not shown) between the storage tank 102 and the vaporization unit 11, and the high-temperature dehydrogenated body recovered from the hydrogen supply device 1 is supplied to the heat exchanger and then disposed in the waste liquid tank. 103, the hydrogen storage body fed from the storage tank 102 can be preheated using the heat of the dehydrogenated body recovered by the heat exchanger, and the hydrogen storage body can be more efficiently It becomes possible to vaporize.
Further, the exhaust gas discharged from the polymer electrolyte fuel cell 101 can be reused as power for the hydrogen supply pump 107 attached to the power generation system 100 by using the exhaust pressure. Thus, by providing a device that uses the waste heat of the dehydrogenated body or the exhaust gas of the polymer electrolyte fuel cell 101 as an energy source, the energy efficiency of the power generation system 100 can be improved. With such a power generation system 100, since the hydrogen supply device 1 and the polymer electrolyte fuel cell 101 are combined in contact with each other, it can be made compact and highly efficient. It is suitable as a generator.

Next, an engine system 200 in which the hydrogen supply device 1 according to the present invention and the engine 201 are combined will be described with reference to FIG.
As shown in FIG. 6, the engine system 200 includes a storage tank 202, a waste liquid tank 203, a liquid feed line 204, a liquid feed pump 205, a waste liquid recovery, which have the same functions and configurations as the power generation system 100 described above. A line 206 and a hydrogen supply pump 207 are provided. Since these have already been described in detail, the description thereof is omitted here.
The engine system 200 includes a hydrogen supply device 1, an engine 201 such as a hydrogen fuel engine capable of burning using hydrogen as fuel, and a hydrogen supply for supplying the engine 201 with hydrogen generated by the hydrogen supply device 1. A line 208 and an exhaust gas line 210 for exhausting the exhaust gas from the engine 201 are provided, and the hydrogen supply device 1 is brought into contact with the exhaust gas line 210 at a subsequent stage. This is because the engine 201 has a higher operating temperature and higher exhaust gas temperature than the polymer electrolyte fuel cell 101, and therefore the hydrogen supply device is brought into contact with the hydrogen supply device 1 at the rear stage of the exhaust gas line 210. 1 as a whole, and thus, at least one of the vaporization part 11 and the catalyst part 13, preferably both, can be heated to 200 ° C. or less. Note that the hydrogen supply device 1 may be heated using the waste water of cooling water or oil of the engine 201. The hydrogen supply pump 207 in the engine system 200 corresponds to the hydrogen supply system in the claims, and the engine 201 corresponds to another device in the claims.

  Further, the purity of the hydrogen gas supplied from the hydrogen supply device 1 is greatly different between the engine 201 and the polymer electrolyte fuel cell 101. When sucking from the hydrogen supply device 1 with the hydrogen supply pump 207, there is a possibility that the dehydrogenated material corresponding to the vapor pressure is sucked together with hydrogen. Can be burned. Since the engine 201 used in the engine system 200 is a hydrogen fuel engine, even if some hydrocarbons, that is, dehydrogenated bodies or hydrogen storage bodies are mixed as impurities, they can be burned. In some cases, when some hydrocarbon is mixed in the hydrogen gas, the control may be relatively easy. Therefore, when the hydrogen produced by the hydrogen supply device 1 and the dehydrogenated substance are separated, some dehydrogenated substance or hydrogen storage element may be mixed in the hydrogen. As described above, since hydrogen may be gradually separated, the configuration can be simplified as compared with the power generation system 100.

  As shown in FIG. 6, the engine system 200 is configured such that the vaporizer 11 converts the hydrogen storage body that has been pressurized from the storage tank 202 via the liquid supply line 204 by the liquid supply pump 205 and sent to the hydrogen supply device 1. Vaporized and supplied to the catalyst unit 13 by the supply unit 12 at the appropriate time interval described above to perform a dehydrogenation reaction to generate hydrogen and a dehydrogenated product. The hydrogen storage body that has not been reacted in the dehydrogenation reaction with the dehydrogenation body is recovered in the waste liquid tank 203 by the waste liquid recovery line 206. Then, the hydrogen generated in the catalyst 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 driving force. Exhaust gas generated by combustion in the engine 201 is supplied to the heating unit 14 provided in contact with the hydrogen supply device 1 by the exhaust gas line 210, heated at 200 ° C. or less, and then discharged from the exhaust port of the exhaust gas line 210. Discharged.

Next, a hydrogen storage system 300 that combines the hydrogen supply device 1 and the compressor 301 according to the present invention will be described with reference to FIG.
As shown in FIG. 7, the hydrogen storage system 300 includes a storage tank 302 having a function and configuration similar to those of the power generation system 100, a waste liquid tank 303, a liquid supply line 304, a liquid supply pump 305, hydrogen A supply line 308 and a waste liquid recovery line 306 are provided. Since these have already been described in detail, the description thereof is omitted here.
And this hydrogen storage system 300 compressed the hydrogen supply apparatus 1, the hydrogen supply line 308 which supplies the hydrogen produced | generated with the hydrogen supply apparatus 1 to the compressor 301, the compressor 301 which compresses the supplied hydrogen, and compressed And a hydrogen tank 307 for storing hydrogen. The hydrogen tank 307 may store hydrogen in a gas or liquid state under high pressure conditions, and may be AB ₂ type, AB ₅ type, iron-titanium type, magnesium type, vanadium type, palladium type, It may have a built-in calcium-based hydrogen storage alloy. The compressor 301 in the hydrogen storage system 300 corresponds to the hydrogen supply system in the claims, and the hydrogen tank 307 corresponds to another device in the claims.

  As shown in FIG. 7, the hydrogen storage system 300 is configured to vaporize the hydrogen storage body that has been pressurized from the storage tank 302 via the liquid supply line 304 by the liquid supply pump 305 and supplied to the hydrogen supply device 1. And is supplied to the catalyst unit 13 by the supply unit 12 at an appropriate time interval as described above to perform a dehydrogenation reaction to generate hydrogen and a dehydrogenated product. The hydrogen storage body that has not been reacted in the dehydrogenation reaction with the dehydrogenation body is recovered in the waste liquid tank 303 by the waste liquid recovery line 306. Then, the hydrogen generated in the catalyst unit 13 is sent to the compressor 301 through the hydrogen supply line 308 and compressed, and stored in the hydrogen tank 307.

Next, a hydrogen community 400 using the hydrogen supply apparatus 1 according to the present invention will be described with reference to FIG.
FIG. 8 schematically shows a community in which a distributed power source and a hydrogen vehicle that use renewable energy such as grid power, wind power, or sunlight are taken as an example.

As shown in FIG. 8, the hydrogen community 400 includes wind power generation 411, solar cells 412, system power 413, an inverter 414 connected thereto, and an electric device 416 that consumes electricity. In addition, the hydrogen community 400 includes a water electrolysis device 420 that electrolyzes water to generate hydrogen, and hydrogen that is generated by the water electrolysis device 420 to add hydrogen to the dehydrogenator of the hydrogen storage body to generate hydrogen again. A hydrogen storage body manufacturing apparatus 421 for manufacturing a storage body and a hydrogen storage body tank 422 for storing the hydrogen storage body manufactured by the hydrogen storage body manufacturing apparatus 421, and a hydrogen storage station 423 using an existing gasoline infrastructure, include.
The hydrogen community 400 includes a power generation system 100 to which a hydrogen storage body supplied from the hydrogen storage station 423 is supplied, an engine system 200, and a hydrogen storage system 300. The hydrogen supply device 1 of the present invention includes: Used as part of this hydrogen community 400.

Specifically, the hydrogen supply device 1 of the present invention is provided and used in the power generation system 100, the engine system 200, and the hydrogen storage system 300.
For example, the hydrogen supply device 1 included in the power generation system 100 generates hydrogen using the hydrogen storage body supplied from the hydrogen storage station 423 and uses the generated hydrogen to generate electricity by the polymer electrolyte fuel cell 101. Generate electricity.
Further, for example, the hydrogen supply device 1 included in the engine system 200 of the hydrogen automobile 417 generates hydrogen using the hydrogen storage body supplied from the hydrogen storage station 423, and directly burns the generated hydrogen in the engine 201. Driving power is obtained and the hydrogen automobile 417 is caused to travel.
Further, for example, the hydrogen supply device 1 included in the hydrogen storage system 300 generates hydrogen using the hydrogen storage body supplied from the hydrogen storage station 423, and the generated hydrogen is high-pressure in the hydrogen tank 307 by the compressor 301. Stored in.

  In such a hydrogen community 400, for example, direct current electricity generated by renewable energy such as wind power generation 411 and solar cells 412 can be converted into alternating current electricity by the inverter 414. The electricity converted into alternating current is usually used for household electrical equipment 416. The electricity converted into alternating current is supplied to the water electrolysis apparatus 420 to electrolyze water, thereby generating hydrogen and oxygen. Then, the hydrogen generated in the water electrolysis apparatus 420 is supplied to the hydrogen storage body manufacturing apparatus 421, and hydrogen is added to the dehydrogenated body of the hydrogen storage body to make it a hydrogen storage body again.

Here, electricity (electric power) is divided into peak power corresponding to daytime load fluctuations and base power for supplying constant basic power day and night. Therefore, it is preferable that the power generation system 100 shown in FIG. 5 supplies peak power corresponding to daytime load fluctuations to the home distributed power supply 418 and the electric equipment 416. The power generation system 100 can use the system power 413 of an electric power company or the like as the base power, but the system power 413 also preferably uses the above-described renewable energy in order to reduce CO ₂ .
In addition, it is preferable to operate the water electrolysis apparatus 420 with surplus power from the viewpoint of the efficiency of the hydrogen community 400 and the reduction of CO ₂ .

  As the renewable energy, in addition to the wind power generation 411 and the solar cell 412, geothermal, ocean temperature difference, tidal power, biomass, and the like can be used. Since these renewable energies can generate electricity at night and generate surplus power, they are suitable for producing a hydrogen storage body by operating the water electrolysis apparatus 420 described above and storing it in a large amount in the hydrogen storage tank 422. is there. Of course, it is preferable that the power generation by renewable energy during the day is positively supplied as the peak power of the system power 413.

  The hydrogen automobile 417 may be provided with a water electrolysis device (not shown) similar to the water electrolysis device 420. In this way, it becomes possible to use the hydrogen storage body during the daytime, and the dehydrogenated body recovered as waste liquid can be made into a hydrogen storage body using surplus power at night, which improves convenience. To do.

Next, examples in which the effects of the present invention have been confirmed will be described.
The catalyst used for dehydrogenating the hydrogen storage body at a low temperature of 200 ° C. or lower to produce hydrogen can be produced with a metal catalyst and a support. This example shows the results of studies on the carrier material.

(Carrier)
Activated carbon, Al ₂ O ₃ , ZrO ₂ , Nb ₂ O ₅ , V ₂ O ₅ , and SnO ₂ were used as the support material.
Of these, ZrO ₂ , Nb ₂ O ₅ , V ₂ O ₅ , and SnO ₂ were those manufactured by Kojun Kagaku. The activated carbon used was a Cabot Vulcan. For Al ₂ O ₃ , 20 g of aluminum isopropoxide manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 80 g of hot water at 80 ° C., 5 mL of nitric acid was added dropwise to gelate, dried at 120 ° C. for 5 hours, and then 450 ° C. And treated for 2 hours was used as a carrier.

Also, an Al ₂ O ₃ composite carrier and an Nb ₂ O ₅ composite carrier were prepared as composite carriers.
The Al ₂ O ₃ composite carrier was added with a predetermined amount of an aqueous solution of zirconyl nitrate and an alcohol solution of niobium ethoxide, dried at 120 ° C. for 5 hours, and then treated at 450 ° C. for 2 hours to obtain 2% by mass Nb ₂ O _5. a -Al ₂ O _3, to prepare a ZrO ₂ -Al ₂ O ₃ of 2 wt%.
The Nb ₂ O ₅ composite carrier is impregnated with a predetermined amount of an aqueous solution of zirconyl nitrate and an aqueous solution of ammonium tungstate, dried at 120 ° C. for 5 hours, and then treated at 450 ° C. for 2 hours to give 2% by mass of ZrO ₂ —V _2. and O _5, to prepare a 2 wt% WO ₃ -V ₂ O _5.

(Supporting metal catalyst)
As the metal catalyst, Pt colloid manufactured by Tanaka Kikinzoku Co., Ltd. (particle diameter: 2 nm, concentration: 4% by mass) was used.
The operation of supporting the metal catalyst on the support was performed as follows. A predetermined amount of Pt colloid and the carrier prepared above, that is, activated carbon, Al ₂ O ₃ subjected to the predetermined treatment, and 2% by mass Nb ₂ so that the supported amount of the metal catalyst is 5% by mass with respect to the catalyst. Weighing 2 g each for a total of 6 types of O ₅ -Al ₂ O ₃ , 2% by weight ZrO ₂ -Al ₂ O ₃ , 2% by weight ZrO ₂ -V ₂ O ₅ , 2% by weight WO ₃ -V ₂ O ₅ did. The Pt colloid was then diluted with water and impregnated into each carrier material. Next, after drying at 80 ° C. for 20 minutes, the metal catalyst was supported on the support by treatment in a He stream at 400 ° C. for 2 hours.

(Catalyst performance evaluation test)
The performance evaluation test of the catalyst was performed by using methylcyclohexane as the hydrogen storage body and measuring the reaction conversion rate (%) of the hydrogen storage body to toluene, which is a dehydrogenation body.
A hydrogen supply device 1 shown in FIG. 1 was used as a device for performing a catalyst performance evaluation test. A microreactor heat exchanger having a fine flow path was used as the vaporization unit 11, and the pressure applying device 121 of the supply unit 12 was maintained at 3 atm using a pressure regulating valve. Although not shown in the figure, a 1/8 inch SUS reaction tube is used as the catalyst unit 13, and 0.3 g of a carrier carrying the metal catalyst is filled in the reaction tube to perform dehydrogenation of methylcyclohexane. I decided to make it. In this test, in order to heat the catalyst to 150 ° C., a heater was attached to the catalyst portion 13 to heat it.

The reaction conversion rate from methylcyclohexane to toluene was measured as follows.
As described above, although not shown under the condition of 150 ° C., a carrier gas line was provided between the catalyst unit 13 and the control valve 122, and He was separately supplied to the catalyst unit 13 at a flow rate of 10 mL / min.
On the other hand, a control valve 122 composed of an injector for gasoline is provided between the vaporization section 11 and the reaction tube corresponding to the catalyst section 13, and methylcyclohexane is injected at the above flow rate for a few seconds with a 20 second interval. Cyclohexane was supplied at 10 μL / min (in pulses).

As for the reaction conversion rate, the toluene conversion rate of methylcyclohexane was examined from the peak area ratio of 98 (methylcyclohexane) and 92 (toluene) using GC-mass (GC6500 manufactured by SHIMAZU). As a result, activated carbon supporting 5% by mass of Pt colloid as a metal catalyst, Al ₂ O ₃ subjected to the predetermined treatment, 2% by mass Nb ₂ O ₅ -Al ₂ O ₃ , 2% by mass of ZrO ₂ — A reaction conversion rate of 60 to 90% at 150 ° C. could be obtained in any of Al ₂ O ₃ , 2% by mass ZrO ₂ —V ₂ O ₅ , and 2% by mass WO ₃ —V ₂ O ₅ .

Next, the hydrogen generation temperature [° C.] and the reaction conversion rate [%] in the hydrogen supply apparatus according to the example of the present invention and the hydrogen supply apparatus according to the conventional example were measured.
As a hydrogen supply apparatus according to an example of the present invention, the above-described apparatus was used, and a reaction tube filled with a catalyst in which Pt was supported on ₂ % by mass of Nb ₂ O ₅ —Al ₂ O ₃ was used. In addition, He and methylcyclohexane were supplied continuously in the same manner as described above, and methylcyclohexane was supplied in pulses.
As a hydrogen supply apparatus according to a conventional example, a reaction tube in which a catalyst in which Pt is supported on ₂ % by mass of Nb ₂ O ₅ —Al ₂ O ₃ is filled in a 1/4 inch SUS tube is used, and He is supplied at a flow rate of 10 mL / Min and methylcyclohexane were continuously supplied to the reaction tube by a mass flow controller so as to be 10 μL / min.

The catalyst parts of the hydrogen supply apparatus according to the embodiment of the present invention and the hydrogen supply apparatus according to the conventional example are heated by a heater at 150 ° C., 200 ° C., 250 ° C., and the reaction conversion rate of methylcyclohexane to toluene at that time is described above. Measured in the same manner as above.
The result is shown in FIG. As shown in FIG. 9 (a), the hydrogen supply apparatus according to the example of the present invention had a reaction conversion rate of 90% or higher at any hydrogen generation temperature, whereas the hydrogen supply apparatus according to the conventional example. Was about 80% at 250 ° C, about 60% at 200 ° C, and about 20% at 150 ° C.

Next, the toluene mixing rate [%] and the reaction conversion rate [%] in methylcyclohexane in the hydrogen supply device according to the example of the present invention and the hydrogen supply device according to the conventional example were measured.
Note that both the hydrogen supply apparatus according to the example of the present invention and the hydrogen supply apparatus according to the conventional example were performed using the apparatus and the reaction tube.

A hydrogen supply apparatus according to an embodiment of the present invention in which methylcyclohexane prepared with a mixing ratio of toluene of 0%, 10%, 20%, and 50% was prepared and a catalyst portion was heated at 200 ° C. by a heater and a conventional example Injection into a hydrogen supply device. And the reaction conversion rate to toluene was measured like the above.
The result is shown in FIG. As shown in FIG. 9B, in the hydrogen supply apparatus according to the example of the present invention, the reaction conversion rate of cyclomethylhexane to toluene is 90 even when the mixing ratio of toluene in cyclomethylhexane increases. On the other hand, in the hydrogen supply apparatus according to the conventional example, when the mixing ratio of toluene in cyclomethylhexane exceeded 10%, the reaction conversion ratio to toluene was lowered. The hydrogen supply apparatus according to the conventional example has a reaction conversion rate of about 80% when the mixing ratio of toluene in cyclomethylhexane is 20%, and 65% when the mixing ratio of toluene in cyclomethylhexane is 50%. It became about.

As described above, the hydrogen supply apparatus according to the present invention has a high reaction conversion rate with respect to cyclomethylhexane even at 200 ° C. or less, and the mixing ratio of toluene in cyclomethylhexane increases. However, it was found to have a high reaction conversion.
That is, the hydrogen supply device according to the present invention can stably supply a large amount of hydrogen even at a low temperature of 200 ° C. or lower, and can stably supply a large amount of hydrogen even when the mixing ratio of the hydrogen storage body is low. It was found that it was possible to supply.

DESCRIPTION OF SYMBOLS 1 Hydrogen supply apparatus 11 Vaporization part 12 Supply part 13 Catalyst part 14 Heating part 15 Recovery part 100 Electric power generation system 101 Polymer electrolyte fuel cell 102 Storage tank 103 Waste liquid tank 104 Liquid feed 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 applying device 122 Control valve 123 Supply timing control device 200 Engine system 201 Engine 202 Storage tank 203 Waste liquid tank 204 Liquid feed line 205 Liquid feed 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 battery 413 System power 414 Inverter 416 Electric equipment 417 Hydrogen automobile 418 Home distributed power supply 420 Water electrolysis apparatus 421 Hydrogen storage body production apparatus 422 Hydrogen storage body tank 423 Hydrogen Storage station 0 Carrier A Anode C Cathode E Electrolyte membrane

Claims (8)

A hydrogen storage body capable of chemically storing hydrogen is brought into contact with a catalyst to cause a dehydrogenation reaction to generate hydrogen and a dehydrogenation body of the hydrogen storage body, and the generated hydrogen is supplied to another device. A supply method,
The hydrogen storage body is vaporized, and the dehydrogenation reaction is performed by bringing the vaporized hydrogen storage body into contact with the catalyst heated to 200 ° C. or less at a time interval at which the dehydrogenation body is removed from the catalyst. The generated hydrogen, the generated dehydrogenated product, and the hydrogen storage body that has not been reacted in the dehydrogenation reaction are produced while the hydrogen and the dehydrogenated product are produced. Is sent out of the system at different timings ,
The catalyst has an adsorbing power with the hydrogen, an adsorbing power with the dehydrogenated substance, and an adsorbing power with the hydrogen storage body that has not been reacted in the dehydrogenating reaction. <The hydrogen supply method characterized by satisfy | filling the relationship of the said hydrogen storage body . A hydrogen storage body capable of chemically storing hydrogen is brought into contact with a catalyst to cause a dehydrogenation reaction to generate hydrogen and a dehydrogenation body of the hydrogen storage body, and the generated hydrogen is supplied to another device. A feeding device,
A vaporizing section for vaporizing the hydrogen storage body;
The hydrogen storage body vaporized in the vaporization unit is supplied to perform the dehydrogenation reaction to generate the hydrogen and the dehydrogenated substance, while adsorbing power with the hydrogen, adsorbing power with the dehydrogenated substance, And a catalyst part having a catalyst having a different adsorptive power from the unreacted hydrogen storage body in the dehydrogenation reaction,
A supply unit that is provided between the vaporization unit and the catalyst unit, and supplies the hydrogen storage body vaporized in the vaporization unit to the catalyst unit at a time interval at which the dehydrogenated body is removed from the catalyst unit; With
Heating the catalyst part at 200 ° C. or lower ,
The strength of the adsorption force satisfies the relationship of hydrogen <dehydrogenated body <hydrogen storage body,
A hydrogen supply apparatus, wherein the catalyst is sent out of the system at different timings by the action of the catalyst . The hydrogen supply apparatus according to claim 2 , wherein the catalyst includes a metal catalyst made of one or more transition metals and a carrier that supports the metal catalyst. Hydrogen supply device according to claim 2 or claim 3, wherein, further comprising a heating unit for heating at least one of the 200 ° C. temperature below of the vaporizing portion and the catalyst portion. It said catalyst unit, according to claim 2 or claim characterized in that it is heated by 200 ° C. or less of the cooling medium for cooling the heat engine which converts the mechanical energy of the power generator or thermal energy converting thermal energy into electrical 3. The hydrogen supply device according to 3 . The hydrogen fed from the catalytic section, any of the preceding claims 2, wherein the further comprising a recovery unit for recovering individually at least the hydrogen of the dehydrogenation body and the H2 storage 2. The hydrogen supply apparatus according to item 1. The hydrogen supply device according to claim 6 , further comprising a hydrogen intake system for sucking the hydrogen generated in the catalyst unit and supplying it to the other device in the catalyst unit. The hydrogen supply apparatus according to any one of claims 2 to 7 , wherein a boiling point of the hydrogen storage body is 200 ° C or less.

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