JP2004256326A - Hydrogen production and storage apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen production and storage apparatus which employs the dehydrogenation reaction of an organic hydride or the hydrogenation of an aromatic compound, has simple structure of a reaction vessel yet has high efficiency by supplying the heat of reaction using no electric heater. <P>SOLUTION: In the hydrogen production and storage apparatus, the heat is supplied by combusting a part of one of hydrogen, the organic hydride, the aromatic compound and the mixture. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an apparatus for generating and storing hydrogen by a dehydrogenation reaction of an organic hydride or a hydrogenation reaction of an aromatic compound.
[0002]
[Prior art]
Using a catalyst to dehydrogenate organic hydrides such as cyclohexane and decalin and a hydrogenation reaction of aromatic compounds such as benzene and naphthalene to create a hydrogen supply and storage device for fuel cell systems JP-A-2001-110439, JP-A-2001-198469, JP-A-2002-134141, JP-A-2002-184436, JP-A-2002-187702, JP-A-2002-274801, It is known from Japanese Unexamined Patent Application Publication No. 2002-274802, Japanese Patent Application Laid-Open No. 2002-274803, and Japanese Patent Application Laid-Open No. 2002-274804.
[0003]
The hydrogen generation / storage device using organic hydride described above, when generating hydrogen, brings the organic hydride into contact with a catalyst supplied with a constant reaction temperature in a reaction vessel to reform it into hydrogen and gaseous aromatic compounds. Then, hydrogen is selectively separated and used by an aromatic compound separation by a cooler or a hydrogen separation membrane.
In addition, during hydrogen storage, in a hydrogen storage device utilizing a hydrogenation reaction of an aromatic compound, a liquid aromatic compound is brought into contact with a catalyst in a hydrogen atmosphere in a reaction vessel maintained at a constant reaction temperature. It promotes the hydrogenation reaction and stores hydrogen as an organic hydride.
[0004]
Research on hydrogen storage and supply equipment for fuel cell systems using organic hydrides is being actively pursued by researchers in Japan and overseas, including catalyst systems that provide reformed products at high conversion and high selectivity. There has been progress in the technology of reaction systems. In particular, the research by the present inventors and other researchers in order to supply a necessary amount of hydrogen to a fuel cell system corresponding to an automobile or home use is expected to improve the reaction efficiency of the apparatus. Studies are being conducted on a practical implementation method.
[0005]
In each of the above prior arts, hydrogen is generated or hydrogen is stored by controlling the catalyst at a reaction temperature of about 50 to 350 ° C. In the prior art, a heating method using an electric heater is used because of the easiness of temperature control. However, according to recent studies by the present inventors, hydrogen required for operating a 1 kW polymer electrolyte fuel cell is required. In order to generate the amount (18 l / min), 3.6 kW of electric power for the electric heater was consumed, and it was found that a large practical problem was assumed.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to supply reaction heat without using an electric heater while having a simple apparatus configuration in view of the problem of the method for supplying reaction heat of the organic hydride or aromatic compound hydrogen generation / storage apparatus. It is an object of the present invention to provide a hydrogen generation / storage device capable of performing the method.
[0007]
[Means for Solving the Problems]
The inventors of the present application have conducted intensive studies to achieve the above object, and as a result, a configuration in which hydrogen or organic hydride or an aromatic compound or a mixture thereof which is retained or generated by the device is burned to supply heat of reaction, It has been found that the reaction heat for hydrogen supply or hydrogen storage can be supplied without using hydrogen, and the inventors have invented a hydrogen generation / storage device corresponding to the above problem.
[0008]
That is, the invention of claim 1 utilizes an organic hydride that becomes an aromatic compound by dehydrogenation and an aromatic compound that becomes an organic hydride by hydrogenation, and is used in a reaction vessel 20 having a reaction catalyst 10. A hydrogen generation / storage device for generating or storing hydrogen by supplying reaction heat to generate a dehydrogenation reaction or a hydrogenation reaction, wherein the reaction heat is hydrogen or organic hydride or aroma that is held or generated by the device. Provided is a hydrogen generation / storage device characterized in that any one of the group III compounds or a mixture thereof is burned by a heating device 30 and supplied.
[0009]
The invention according to claim 2 provides the hydrogen generation / storage device according to claim 1, wherein the heat generating device 30 for supplying the reaction heat is a combustion burner 40.
[0010]
The invention according to claim 3 provides the hydrogen generation / storage device according to claim 1, wherein the heat generating device 30 for supplying the reaction heat is based on an oxidation reaction by the combustion catalyst 50.
[0011]
The invention according to claim 4 is characterized in that the supply of the reaction heat is performed by directly heating the reaction catalyst 10 by the heat generating device 30. Provide equipment.
[0012]
The invention according to claim 5 is characterized in that the supply of the reaction heat is carried out by heating the reaction catalyst 10 by feeding the combustion exhaust gas from the heating device 30 through a pipe 60. A hydrogen generation / storage device according to any one of the above.
[0013]
The invention according to claim 6 is characterized in that the reaction heat is supplied by heating or reacting the reaction catalyst 10 by feeding or circulating a heat medium heated by the heat generating device 30 through a pipe 60. And a hydrogen generation / storage device according to any one of claims 3 to 3.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
FIG. 1 is a diagram schematically showing an embodiment of the present invention. In the present embodiment, the heating device 30 is heated using air as a heat medium by using a burner that uses organic hydride as a fuel, and the hot air is fed into the reaction vessel 20 through a pipe 60 to cause the reaction catalyst 10 to be heated. It has a configuration for heating. In this embodiment, not only the method of heating and feeding air as a heat medium but also the reaction heat can be supplied by directly feeding the combustion exhaust gas through the pipe 60.
[0015]
The organic hydride supplied to the heat generating device 30 may be any of decalin, cyclohexane, methylcyclohexane and the like, and may be a mixed solution of dehydrogenated naphthalene, benzene, toluene and the like. Further, the dehydrogenated hydrogen may be used in a fuel cell and mixed with an off-gas containing unreacted hydrogen. In the case where the amount of heat remaining in the hot air discharged through the reactor is supplied to the organic hydride tank, the heat may be used as residual heat of the organic hydride.
[0016]
FIG. 2 is a diagram schematically showing another embodiment of the present invention. In this embodiment, similarly to the embodiment shown in FIG. 1, a heating medium is heated by using a burner using an organic hydride as a heating device 30, and the heating medium is supplied to a reaction vessel 20 through a pipe 60. And the reaction catalyst 10 is heated, circulated, and heated again by the heat generating device.
[0017]
As a heat medium circulated between the reaction catalyst 10 and the heat generating device 30, an organic oil, a molten salt, or the like is used. If the physical properties are not changed even at the high temperature of 350 ° C., any known circulating medium may be used. A heating medium can be used.
[0018]
FIG. 3 is a diagram schematically showing another embodiment of the present invention. In the present embodiment, the heat generating device 30 supplies a mixed gas of an oxidizing agent (such as air) and hydrogen or an organic hydride to the combustion catalyst 50 integrated with the reaction catalyst 10 in the reaction vessel 20 through a pipe 60. The oxidation reaction is performed by the combustion catalyst 50, and the heat generation of the combustion catalyst 50 supplies the reaction heat. As the combustion catalyst 50, a catalyst carrying any catalytic metal such as platinum, palladium, and rhodium which promotes an oxidation reaction is used.
[0019]
FIG. 4 is a diagram schematically showing still another embodiment of the present invention. In the present embodiment, a burner as the heat generating device 30 is installed in the reaction vessel 20 to directly heat the reaction catalyst 10. Of course, in this case, the fuel can utilize organic hydride or hydrogen or aromatic compounds or mixtures thereof.
[0020]
However, when the reaction catalyst 10 is directly heated, a vessel portion for causing a dehydrogenation or hydrogenation reaction in the reaction vessel 20 and a portion for causing a combustion reaction or discharging a combustion exhaust gas are separated from each other, and dehydration is performed. Avoid mixing with hydrogen or the raw materials or products of the hydrogenation reaction.
[0021]
In any of the embodiments, when there is residual heat in the heat medium or the exhaust gas after the heating of the reaction catalyst 10, the reactant in the storage tank such as an organic hydride or an aromatic hydrocarbon is preheated, so that the overall heat utilization is achieved. Efficiency can be improved.
[0022]
It is desirable that the temperature of the reaction catalyst 10 be controlled at approximately 50 to 350 ° C. At the time of hydrogen generation, the higher the temperature, the more the reaction proceeds, and the hydrogenation reaction is exothermic and the conversion decreases when the temperature becomes high. Therefore, in the present invention, the amount of heat generated can be adjusted by controlling the amount of fuel supplied to the heat generating device 30.
[0023]
Regarding the reaction system of dehydration reaction of organic hydride or hydrogenation reaction of aromatic compound, especially the contact system of reaction catalyst and raw material (organic hydride or aromatic hydrocarbon), JP-A-2001-110439 and JP-A-2001-10437 198469, JP-A-2002-134141, JP-A-2002-184436, JP-A-2002-187702, JP-A-2002-274801, JP-A-2002-274802, JP-A-2002-274803 The technology disclosed in Japanese Unexamined Patent Application Publication No. 2002-274804 may be used, or any reaction method that causes a dehydrogenation reaction or a hydrogenation reaction may be used.
[0024]
The present invention is not limited to the above embodiments of the invention, and various modifications can be made within the scope of the invention described in the claims, which are also included in the scope of the invention. Needless to say, it is.
[0025]
【The invention's effect】
According to the hydrogen generation and storage device of the present invention, while having a simple device configuration, efficient hydrogen generation and supply of the reaction heat of the organic hydride or aromatic compound hydrogen generation and storage device without using an electric heater. A storage device can be provided.
[Brief description of the drawings]
FIG. 1 is a diagram schematically showing an embodiment of the present invention in which reaction heat is supplied by hot air from a burner.
FIG. 2 is a diagram schematically showing an embodiment of the present invention in which reaction heat is supplied by a circulating heat medium.
FIG. 3 is a diagram schematically showing an embodiment of the present invention in which reaction heat is supplied by a combustion catalyst.
FIG. 4 is a diagram schematically showing an embodiment of the present invention in which a catalyst is directly heated by a burner in a reaction vessel to supply reaction heat.
[Explanation of symbols]
Reference Signs List 10 reaction catalyst 20 reaction vessel 30 heating device 40 combustion burner 50 combustion catalyst 60 tube

Claims (6)

Reaction heat is supplied in a reaction vessel (20) equipped with a reaction catalyst (10) using an organic hydride that becomes an aromatic compound by dehydrogenation and an aromatic compound that becomes an organic hydride by hydrogenation. A hydrogen generation / storage device that generates or stores hydrogen by causing a dehydrogenation reaction or a hydrogenation reaction,
Hydrogen generation / storage characterized in that the reaction heat is supplied by burning a part of any of hydrogen or organic hydride or aromatic compounds or a mixture thereof, which is retained or generated by the device, in a heating device (30). apparatus. The hydrogen generating and storing device according to claim 1, wherein the heat generating device (30) for supplying the reaction heat is a combustion burner (40). The hydrogen generating / storing device according to claim 1, wherein the heat generating device (30) for supplying the reaction heat is based on an oxidation reaction by a combustion catalyst (50). 4. The hydrogen generation / storage device according to claim 1, wherein the supply of the reaction heat is performed by directly heating the reaction catalyst (10) by a heating device (30). The reaction heat is supplied by heating a reaction catalyst (10) by feeding combustion exhaust gas from a heating device (30) through a pipe (60). A hydrogen generation / storage device as described in the above. 2. The reaction catalyst according to claim 1, wherein the supply of the reaction heat is performed by heating or heating the reaction catalyst by feeding or circulating a heating medium heated by a heating device through a pipe. 4. The hydrogen generation / storage device according to 2 or 3.

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