JP2017178683A - Hydrogen supply device and hydrogen supply method - Google Patents

Abstract

A hydrogen supply apparatus and a hydrogen supply method for continuously supplying hydrogen generated from formic acid as a hydrogen storage material while suppressing a significant temperature rise. SOLUTION: Formic acid is supplied, hydrogen is generated by a formic acid decomposition reaction using a catalyst, and hydrogen is supplied to the outside. The hydrogen-containing gas containing the hydrogen and the catalyst-containing liquid containing the catalyst in the hydrogen generating means that has been connected to at least two of the heating means and the hydrogen generating means and that has finished supplying hydrogen, A hydrogen supply apparatus and a hydrogen supply method, comprising: a transfer pipe configured to bring the hydrogen-containing gas into contact with the catalyst-containing liquid from a completed hydrogen generation means to a hydrogen generation means other than the hydrogen generation means. [Selection figure] None

Description

  The present invention relates to a hydrogen supply apparatus and a hydrogen supply method.

  In recent years, taking into account the deterioration of the global environment due to global warming, the response to the global environment has been studied in various fields. For example, in the energy field, hydrogen gas is used as a fuel in mobile devices such as automobiles or power supply facilities, or as a negative electrode active material for fuel cells, instead of fossil fuels such as oil and coal that have been used as main energy. The technology used is advancing. Hydrogen can be said to be clean energy in that the only substance discharged when burned or reacted is water.

Since hydrogen is a highly reactive gas, in order to stably supply a large amount as main energy, establishment of a technology that enables safe and stable transportation and storage is required.
For example, a technique for hydrogenating carbon dioxide and transporting or storing it as formic acid or methanol has been proposed. Formic acid has been attracting attention as a material for storing hydrogen because it is obtained by hydrogenation reaction of carbon dioxide and easily generates hydrogen by dehydrogenation reaction of formic acid after hydrogenation.

  As an example of a technique for generating hydrogen using formic acid, it is disclosed that a specific metal complex is used as a catalyst in the dehydrogenation reaction of formic acid and a salt of formic acid (see, for example, Patent Document 1). Furthermore, a technique for continuously separating and producing high-pressure hydrogen exceeding 120 MPa from formic acid using an iridium metal complex as a catalyst has been proposed (for example, see Non-Patent Documents 1 and 2).

International Publication No. 2015/053317

ChemCatChem, Masayuki Iguchi, Yuichiro Himeda, Yuichi Manaka, Koichi Matsuoka, December 10, 2015 “Simple Continuous High-Pressure Hydrogen Production and Separation System from Formic Acid under Mild Temperatures” `` Development of a high-pressure hydrogen continuous supply method that does not use a compressor '', National Institute of Advanced Industrial Science and Technology, http://www.aist.go.jp/aist_j/press_release/pr2015/pr20151211/pr20151211.html

  However, the techniques described in Patent Document 1 and Non-Patent Documents 1 and 2 described above are expected as a technique for generating high-pressure hydrogen. However, continuous hydrogen is generated by continuously operating even after high-pressure hydrogen is generated. There are challenges in generating In other words, the concentration of formic acid in the reaction vessel decreases with hydrogen generation, so it is necessary to add consumed formic acid to continue the production of hydrogen. In the method of generating hydrogen by batch processing, it is difficult to add formic acid into a system filled with high-pressure hydrogen. In addition, it is possible to generate hydrogen continuously by using a plurality of reaction tanks, but every time the generation of high-pressure hydrogen is completed, if the components in the reaction tank are discharged and replaced, Not only is the hydrogen remaining in the tank discarded wastefully, but the reaction catalyst cannot be used repeatedly.

  In addition, in order to effectively use the generated hydrogen in the reaction tank, when transferring from the reaction tank used for hydrogen generation to another reaction tank or storage tank, the destination of the transfer is caused by the Joule-Thompson effect that hydrogen has as an inherent property. There may be a significant exotherm in the bath (for example, a temperature rise reaching 200 ° C.). Excessive heat generation is considered to impair safety when considered from the viewpoint of the durability of the container.

  The present invention has been made in view of the above, and provides a hydrogen supply apparatus and a hydrogen supply method for continuously supplying high-pressure hydrogen generated from formic acid, which is a hydrogen storage material, while suppressing a significant temperature increase due to the Joule-Thompson effect. The purpose is to provide and to achieve this purpose.

  The present invention is provided with a plurality of hydrogen generating means for generating hydrogen by a decomposition reaction of formic acid, and when supplying hydrogen by operating the plurality of hydrogen generating means in a rotation, for example, formic acid is consumed and hydrogen generation is commensurate with the amount of formic acid. Is completed, from the viewpoint of effective use of the generated hydrogen or continuous use of the catalyst, a hydrogen-containing gas containing hydrogen in the tank after completion of hydrogen supply (hereinafter also simply referred to as hydrogen-containing gas) and a catalyst are included. It is effective to transfer the catalyst-containing liquid (hereinafter also simply referred to as catalyst-containing liquid) to another tank in which hydrogen supply is planned. However, hydrogen has an inherent property different from that of general gas, and has a property of generating significant heat due to the Joule-Thompson effect when attempting to transfer from one tank to another with a differential pressure. Therefore, in the present invention, for example, the transfer of the hydrogen-containing gas to the tank that is scheduled to supply hydrogen instead of the tank that has completed the hydrogen generation corresponding to the amount of formic acid is performed in a state in contact with the catalyst-containing liquid. In the transfer destination tank, the inventors have obtained knowledge that a significant temperature rise caused by the heat generation of hydrogen can be effectively suppressed by heat exchange with the catalyst-containing liquid, and has been achieved based on such knowledge.

In order to achieve the above object, the first invention provides:
<1> Formic acid is supplied, and hydrogen is generated by a decomposition reaction of formic acid using a catalyst and hydrogen is supplied to the outside. The hydrogen generating means is disposed in each of the at least two hydrogen generating means and the hydrogen generating means, and heats the hydrogen generating means. The hydrogen supply is terminated with the hydrogen-containing gas containing the hydrogen and the catalyst-containing liquid containing the catalyst in the hydrogen generating means that has communicated with at least two of the heating means and the hydrogen generating means, and has finished supplying hydrogen. And a transfer pipe for transferring the hydrogen-containing gas in contact with the catalyst-containing liquid from the hydrogen generating means to a hydrogen generating means other than the hydrogen generating means.

  Hydrogen generation refers to generation of hydrogen in the hydrogen generation means by formic acid decomposition reaction, not preparation of reaction, and the decomposition reaction refers to a reaction in which formic acid is actually decomposed to generate hydrogen. Further, the hydrogen supply refers to sending out the hydrogen in the “hydrogen generation” to the outside of the hydrogen generation means.

  “Contacting the hydrogen-containing gas with the catalyst-containing liquid” means, for example, transfer from one of the two hydrogen generating means to the other by the transfer pipe (for example, from the second hydrogen generating means by the first transfer pipe as described later). 1), the hydrogen-containing gas and the catalyst-containing liquid are mixed in the transfer pipe (for example, the first transfer pipe) by transferring the hydrogen-containing gas and the catalyst-containing liquid together. The hydrogen-containing gas may be brought into contact with the catalyst-containing liquid, or the liquid-containing catalyst-containing liquid is previously transferred and stored in the hydrogen generation means (for example, the second hydrogen generation means) as the transfer destination. The hydrogen-containing gas may be brought into contact with the catalyst-containing liquid by introducing a hydrogen-containing gas that is a gas phase into the catalyst-containing liquid and causing the liquid to float while bubbling.

  In the first invention, at least two hydrogen generating means are connected by a transfer pipe among a plurality of hydrogen generating means for generating hydrogen by heating formic acid supplied from the outside and causing a decomposition reaction using a catalyst. For example, a hydrogen-containing gas containing generated hydrogen is brought into contact with a catalyst-containing liquid containing a catalyst from a hydrogen generating means that has completed hydrogen generation corresponding to the amount of formic acid to another hydrogen generating means other than the hydrogen generating means. Thus, the temperature rise due to the Joule-Thompson effect in the gas phase containing hydrogen is mitigated by heat exchange with the liquid phase. Thereby, the rapid temperature rise (for example, temperature rise which reaches 200 degreeC) in the hydrogen production | generation means to which hydrogen was transferred can be suppressed effectively.

  In the first aspect of the invention, for example, in the hydrogen generation unit scheduled to start the hydrogen supply other than the hydrogen generation unit that has completed the hydrogen supply corresponding to the amount of formic acid, the hydrogen generation unit that has completed the hydrogen supply exists. Gases such as hydrogen and carbon dioxide are not wasted, and hydrogen can be used effectively and the catalyst can be used continuously.

From the above viewpoint, the hydrogen supply device according to the first invention described in <1>
<2> The hydrogen generation unit includes at least a first hydrogen generation unit and a second hydrogen generation unit, and at least one of the transfer pipes has an on-off valve, and the first hydrogen generation unit It is preferable that the means and the second hydrogen generating means are communicated with each other.

Further, in the hydrogen supply device according to the first invention described in <1> or <2>,
<3> The hydrogen generation unit includes at least a first hydrogen generation unit, a second hydrogen generation unit, and a third hydrogen generation unit, and
A first transfer pipe having an on-off valve, communicating between the first hydrogen generation unit and the second hydrogen generation unit, and transferring the hydrogen-containing gas in contact with the catalyst-containing liquid; And a second transfer pipe having an on-off valve and communicating between the second hydrogen generation unit and the third hydrogen generation unit and transferring the hydrogen-containing gas in contact with the catalyst-containing liquid. And a hydrogen generation means (for example, the first hydrogen generation means) different from the third hydrogen generation means and the second hydrogen generation means and the third hydrogen generation means. And a third transfer pipe that transfers the hydrogen-containing gas in contact with the catalyst-containing liquid.

In the case where at least three of the first hydrogen generating means, the second hydrogen generating means, and the third hydrogen generating means are provided as the hydrogen generating means, for example, the third hydrogen generating means generates hydrogen. When hydrogen is supplied, for example, the hydrogen containing gas and the catalyst are contained in the second hydrogen generating means after the hydrogen supply, for example, by the first transfer pipe communicating between the first hydrogen generating means and the second hydrogen generating means. When the liquid is transferred to the first hydrogen generating means by bringing the hydrogen-containing gas into contact with the catalyst-containing liquid, and then hydrogen is supplied, for example, by the first hydrogen generating means, the second hydrogen generating means and the third hydrogen are supplied. For example, the hydrogen-containing gas and the catalyst-containing liquid in the third hydrogen generating means after the hydrogen supply is finished are brought into contact with the catalyst-containing liquid by the second transfer pipe communicating between the generating means and the second hydrogen-containing gas is brought into contact with the catalyst-containing liquid. To hydrogen generation means . Then, for example, when hydrogen is supplied by the second hydrogen generating means, between the third hydrogen generating means and another hydrogen generating means different from the second hydrogen generating means and the third hydrogen generating means. The hydrogen content in other hydrogen generating means (for example, the first hydrogen generating means) different from the second hydrogen generating means and the third hydrogen generating means after the hydrogen supply is completed by the third transfer pipe communicating with The gas and the catalyst-containing liquid are transferred to the third hydrogen generating means by bringing the hydrogen-containing gas into contact with the catalyst-containing liquid.
Thus, hydrogen is generated and supplied by decomposing formic acid at the rotation number in any one of the three or more hydrogen generation means while suppressing a rapid temperature rise, and between the other two hydrogen generation means The hydrogen-containing gas and the catalyst-containing liquid present in one hydrogen generating means can be transferred to the other hydrogen generating means and used effectively.
As the hydrogen generation means, in addition to the first hydrogen generation means, the second hydrogen generation means, and the third hydrogen generation means, one or more hydrogen generation means may be further provided.

Therefore, in the hydrogen supply device according to the first invention described in <3>,
<4> When the hydrogen supply is performed by the first hydrogen generation unit, the second hydrogen generation unit is different from the first hydrogen generation unit and the second hydrogen generation unit after the hydrogen supply is completed. The hydrogen-containing gas is brought into contact with the catalyst-containing liquid and transferred to a hydrogen generating means to start a decomposition reaction, and the hydrogen supply is started by the second hydrogen generating means,
When the hydrogen supply is performed by the second hydrogen generation unit, the hydrogen-containing gas is supplied from the first hydrogen generation unit to the third hydrogen generation unit after completion of the hydrogen supply by the first hydrogen generation unit. It is preferable that the decomposition reaction is started by transferring the catalyst containing liquid in contact with the catalyst-containing liquid, and the hydrogen supply is started by the third hydrogen generating means.

For example, when at least three of the first hydrogen generating means, the second hydrogen generating means, and the third hydrogen generating means are provided as the hydrogen generating means, first, for example, the first hydrogen generating means In the case of supplying hydrogen by the decomposition reaction of formic acid, for example, on the condition that a certain time has elapsed since the decrease in the hydrogen generation rate in the first hydrogen generation means or the start of hydrogen generation, A hydrogen-containing gas and a catalyst-containing liquid in a hydrogen generating means (for example, a third hydrogen generating means) different from the first hydrogen generating means and the second hydrogen generating means are brought into contact with the catalyst-containing liquid. The hydrogen generation means is transferred to the second hydrogen generation means to start the decomposition reaction, and the hydrogen supply is started by the decomposition reaction of formic acid by the second hydrogen generation means instead of the first hydrogen generation means. Subsequently, for example, the hydrogen-containing gas and the catalyst-containing liquid in the first hydrogen generating unit are changed to hydrogen under the condition that a certain period of time has elapsed from the decrease in the hydrogen generation rate in the second hydrogen generating unit or the start of hydrogen generation. The contained gas is brought into contact with the catalyst-containing liquid and transferred to the third hydrogen generating means to start the decomposition reaction, and hydrogen is replaced by the formic acid decomposition reaction in the third hydrogen generating means instead of the second hydrogen generating means. The hydrogen-containing gas and the catalyst in the second hydrogen generating means are supplied on the condition that, for example, the hydrogen generation rate in the third hydrogen generating means is reduced or a certain time has elapsed from the start of hydrogen generation. The hydrogen-containing gas is brought into contact with the catalyst-containing liquid, and the second hydrogen generating means and the other hydrogen generating means (for example, the first hydrogen generating means different from the second hydrogen generating means after the hydrogen supply step is completed) Transfer to production means) And the other hydrogen generating means (for example, the first hydrogen generating means) different from the second hydrogen generating means and the third hydrogen generating means instead of the third hydrogen generating means. Hydrogen supply is started by formic acid decomposition reaction.
In this way, by transferring the hydrogen-containing gas and the catalyst-containing liquid while bringing the hydrogen-containing gas into contact with the catalyst-containing liquid, hydrogen is generated by the decomposition reaction of formic acid while suppressing a rapid temperature rise accompanying the transfer of hydrogen. The remaining hydrogen-containing gas and catalyst-containing liquid in the hydrogen generating means can be effectively used in other hydrogen generating means.

In the hydrogen supply device according to the first invention described in any one of <1> to <4>,
<5> It is preferable that one end of the transfer pipe is connected to a bottom portion of a hydrogen generation unit to which the hydrogen-containing gas and the catalyst-containing liquid are transferred.
A transfer pipe for transferring a hydrogen-containing gas and a catalyst-containing liquid (preferably a hydrogen-containing gas containing hydrogen and carbon dioxide and a catalyst-containing liquid containing a catalyst and water) generates hydrogen by which the hydrogen-containing gas and the catalyst-containing liquid are transferred. With the structure connected at the bottom of the means, the hydrogen-containing gas and the catalyst-containing liquid can be transferred to the hydrogen generating means while bubbling the hydrogen-containing gas into the catalyst-containing liquid, and a stirring effect can be provided. . Furthermore, the heat exchange time between the gas phase containing hydrogen which causes heat generation and the liquid phase is secured, which is effective in suppressing a significant temperature rise.

Furthermore, in the hydrogen supply device according to the first invention described in any one of <1> to <5>,
<6> The transfer pipe causes at least the hydrogen-containing gas and the catalyst-containing liquid to flow out in a direction along the inner wall of the side portion of the hydrogen-generating means, thereby removing the hydrogen-containing gas and the catalyst-containing liquid from the hydrogen generating means. It is preferable to supply to.
A direction along which the hydrogen-containing gas and the catalyst-containing liquid (preferably a hydrogen-containing gas containing hydrogen and carbon dioxide and a catalyst-containing liquid containing catalyst and water) are transferred along the inner wall of the side of the hydrogen generating means. Therefore, a swirl flow is generated, giving a stirring effect, and a reduction effect against a rapid temperature rise is high. Furthermore, a heat exchange time with a gas phase liquid phase containing hydrogen that causes heat generation is also secured, which is effective in suppressing a significant temperature rise.

In the hydrogen supply device according to the first invention described in any one of <1> to <6>,
<7> The temperature after transfer in the hydrogen generating means to which at least the catalyst is transferred can be set to a range of 85 ° C. or lower.

Next, the second invention is:
<8> Supplying formic acid to the first hydrogen generating means, having at least a hydrogen supplying step of generating hydrogen by decomposing formic acid using a catalyst and supplying hydrogen to the outside, and the hydrogen supplying step is finished The hydrogen containing gas containing the hydrogen and the catalyst containing liquid containing the catalyst in the first hydrogen generating means are connected to the first hydrogen generating means from the hydrogen generating means that has completed the hydrogen supply step. In the hydrogen supply method, the hydrogen-containing gas is transferred to the generating means in contact with the catalyst-containing liquid.

Similarly to the first invention described above, the generated hydrogen-containing gas containing hydrogen is transferred in contact with the catalyst-containing liquid containing the catalyst, so that the temperature rise in the gas phase containing hydrogen is increased by the heat from the liquid phase. It can be mitigated by exchange. Thus, when hydrogen is continuously generated, a rapid temperature increase (for example, a temperature increase reaching 200 ° C.) in the hydrogen generating means to which the hydrogen has been transferred is effectively suppressed.
In the second invention, for example, in the hydrogen generating means scheduled to start the hydrogen generation other than the hydrogen generating means that has completed the reaction commensurate with the amount of formic acid, the hydrogen present in the hydrogen generating means that has completed the reaction and Effective use of hydrogen and continuous use of the catalyst are possible without wastefully discarding gas such as carbon dioxide.

In the hydrogen supply method according to the twelfth aspect of the invention described in <8>,
<9> As the hydrogen generation step, a first hydrogen generation step of supplying formic acid to the first hydrogen generation means, decomposing the formic acid using a catalyst to generate hydrogen, and supplying hydrogen to the outside; A second hydrogen generating step of supplying formic acid to the hydrogen generating means, decomposing formic acid using the catalyst to generate hydrogen and supplying hydrogen to the outside, and supplying formic acid to the third hydrogen generating means, A third hydrogen generation step of decomposing formic acid using hydrogen to generate hydrogen and supplying hydrogen to the outside, and
After the first hydrogen supply step is started, after the hydrogen supply step is finished, the hydrogen generation unit different from the first hydrogen generation unit and the second hydrogen generation unit is transferred to the second hydrogen generation unit. A hydrogen-containing gas is brought into contact with the catalyst-containing liquid and transferred to start a decomposition reaction, and the second hydrogen generation step is started;
After the second hydrogen generation step is started and after the first hydrogen supply step is completed, the hydrogen-containing gas is brought into contact with the catalyst-containing liquid from the first hydrogen generation unit to the third hydrogen generation unit. It is preferable that the decomposition reaction is started and the third hydrogen generation step is started.

When at least three of the first hydrogen generating means, the second hydrogen generating means, and the third hydrogen generating means are provided as the hydrogen generating means, for example, first, for example, the first hydrogen generating means When the formic acid decomposition reaction and hydrogen supply are started in step 1, for example, after the hydrogen supply step is completed on the condition that the hydrogen generation rate in the first hydrogen generation means is reduced or a certain time has elapsed from the start of hydrogen supply. The hydrogen-containing gas and the catalyst-containing liquid are transferred from the hydrogen generating means different from the first hydrogen generating means and the second hydrogen generating means to the second hydrogen generating means by bringing the hydrogen-containing gas into contact with the catalyst-containing liquid. Then, the decomposition reaction of formic acid is started, and hydrogen supply is started by the second hydrogen generating means instead of the first hydrogen generating means. Subsequently, for example, the hydrogen-containing gas and the catalyst-containing liquid in the first hydrogen generating unit are changed to hydrogen under the condition that a certain period of time has elapsed from the decrease in the hydrogen generation rate in the second hydrogen generating unit or the start of hydrogen supply. The contained gas is brought into contact with the catalyst-containing liquid and transferred to the third hydrogen generating means to start the formic acid decomposition reaction, and the hydrogen supply is started by the third hydrogen generating means instead of the second hydrogen generating means. Thereafter, for example, the hydrogen-containing gas and the catalyst-containing liquid in the second hydrogen generating means are supplied on the condition that a certain period of time has elapsed since the hydrogen generation rate in the third hydrogen generating means is reduced or the supply of hydrogen is started. Other hydrogen generating means (for example, first hydrogen generating means) different from the second hydrogen generating means and the third hydrogen generating means after contacting the hydrogen-containing gas with the catalyst-containing liquid and completing the hydrogen supply step Formic acid decomposition The hydrogen supply is started by another hydrogen generation means (for example, the first hydrogen generation means) different from the second hydrogen generation means and the third hydrogen generation means instead of the third hydrogen generation means. Start.
This makes it possible to effectively use the remaining hydrogen and the catalyst and the catalyst in the hydrogen generation means that has generated hydrogen by the decomposition reaction of formic acid in other hydrogen generation processes while suppressing a rapid temperature increase accompanying the transfer of hydrogen.

  ADVANTAGE OF THE INVENTION According to this invention, the hydrogen supply apparatus and hydrogen supply method which perform supply of the high voltage | pressure hydrogen generated from the formic acid which is a hydrogen storage substance continuously, suppressing the remarkable temperature rise by Joule-Thompson effect are provided.

It is a schematic block diagram which shows the schematic structure of the hydrogen production apparatus which is 1st Embodiment. FIG. 2 is a diagram illustrating an example in which a hydrogen-containing gas is bubbled into a catalyst-containing liquid from one of hydrogen generation units in the hydrogen production apparatus of FIG. 1 and is transferred while creating a swirling flow. It is a figure which shows the example which has flowed out to the inner wall face of the side part curved surface of a hydrogen production | generation means so that a hydrogen containing gas and a catalyst containing liquid can be swirled. It is explanatory drawing for demonstrating the state change of each reaction tank accompanying a transfer. It is a schematic block diagram which shows the schematic structure of the hydrogen production apparatus which is 2nd Embodiment. It is a conceptual diagram for demonstrating the place which continuously produces | generates high pressure hydrogen using three reaction tanks by a ring number.

Hereinafter, an embodiment of a hydrogen supply device that generates high-pressure hydrogen from formic acid will be described in detail with reference to the drawings. In this description, an embodiment of a hydrogen supply method that generates high-pressure hydrogen using two reaction vessels is also described. This will be described in detail. However, the present invention is not limited to the embodiments shown below.
The high-pressure hydrogen refers to compressed hydrogen gas having a pressure of 10 MPa or more at normal temperature (35 ° C.).

(First embodiment)
1st Embodiment of the hydrogen supply apparatus of this invention is described with reference to FIGS. The hydrogen supply device of the first embodiment includes two reaction tanks as hydrogen generation means for generating hydrogen from formic acid, and generates and supplies hydrogen in a rotating manner in one of the two reaction tanks.

  As shown in FIG. 1, the hydrogen supply apparatus 100 of the present embodiment includes two reaction tanks 22 and 24 that are hydrogen generation means and two reaction tanks that are connected to each other and from one reaction tank to the other reaction tank. And a transfer pipe 35 for transferring the hydrogen-containing gas and the catalyst-containing liquid.

  In the present embodiment, a mode in which a mixed gas containing hydrogen gas generated by a decomposition reaction of formic acid and carbon dioxide gas flows as the hydrogen-containing gas is shown. Moreover, as a catalyst containing liquid, the aspect through which the liquid containing the catalyst used for the decomposition reaction of formic acid and water distribute | circulates is shown.

The reaction tanks 22 and 24 are stainless steel cylindrical containers, both of which have the same structure. The reaction tank 22 (first hydrogen generating means) and the reaction tank 24 (second hydrogen generating means) are supplied with formic acid through a supply pipe (not shown) so that the formic acid can be decomposed under heating and in the presence of a catalyst. It has become. The formic acid decomposition reaction proceeds according to the following reaction formula (decarboxylation reaction), and hydrogen and carbon dioxide are generated from formic acid.
HCOOH → CO ₂ + H ₂
Further, in the decomposition reaction of formic acid, the following dehydration reaction may occur as a competitive reaction. However, a catalyst (for example, a catalyst exemplified in Non-Patent Document 1) may be used so that the decarboxylation reaction proceeds preferentially. ) Is selected and allowed to react under heating and in the presence of a catalyst.
HCOOH → CO + H ₂ O
In this embodiment, heater units 12 and 14 as heating means are attached to the reaction tanks 22 and 24, respectively, and heating is possible from the cylindrical side curved surface of each reaction tank.

The heating temperature of the reaction tank is such that the temperature of the liquid phase in the tank is in the range of 20 ° C. to 120 ° C. from the viewpoint of increasing the hydrogen generation efficiency by promoting the decarboxylation reaction in preference to the dehydration reaction. Preferably, it is in the range of 60 ° C. to 100 ° C., more preferably in the range of 60 ° C. to 85 ° C.
The heating temperature of the reaction vessel can be measured by inserting a thermocouple into the reaction vessel and bringing it into contact with the liquid phase to be measured.

The heater units 12 and 14 are attached so as to surround the side curved surface of the cylindrical reaction tank, and the entire periphery of the reaction tank is heated.
A block heater is used as the heater unit of the present embodiment, and the reaction temperature can be stably maintained by heating the entire periphery of the cylindrical reaction tank. As the heater unit, in addition to the above, a ribbon heater, exhaust heat of a fuel cell, a gas burner, or the like may be used.

  One end of a transfer pipe 35 is connected to the bottom of the cylindrical reaction tank 22 (first hydrogen generating means), and the other end is connected to the bottom of the reaction tank 24. The reaction tank 22 and the reaction tank 24 are communicated with each other by the transfer pipe 35.

  The transfer pipe 35 has a valve V5 that is an on-off valve. In this embodiment, the valve V5 is opened and the hydrogen-containing gas and catalyst in the reaction tank 22 (first hydrogen generating means) after hydrogen supply is provided. The contained liquid is transferred from the reaction tank 22 to the reaction tank 24. Specifically, when hydrogen is supplied in the reaction tank 22 (first hydrogen generating means), the hydrogen-containing gas and the catalyst-containing liquid present in the reaction tank 22 after the hydrogen supply is finished are transferred to the reaction tank 24 through the transfer pipe 35. Transfer to

  The other end of the transfer pipe 35 is connected to the bottom of the cylindrical reaction tank 24 (second hydrogen generating means). The reaction tank 24 communicates with the reaction tank 22 by a transfer pipe 35.

  One end of a hydrogen supply pipe 32 having a valve V2 that is an on-off valve is connected to the top of the cylindrical reaction tank 22, and the valve is used when hydrogen is generated by decomposing formic acid in the reaction tank 22. Open V2. By opening the valve V <b> 2, hydrogen generated in the reaction tank 22 can be supplied to the outside through the hydrogen supply pipe 32.

  One end of a hydrogen supply pipe 34 provided with a valve V4 which is an on-off valve is connected to the top of the cylindrical reaction tank 24, and a valve is used when hydrogen is generated by decomposing formic acid in the reaction tank 24. Open V4. By opening the valve V4, hydrogen generated in the reaction tank 24 can be supplied to the outside through the hydrogen supply pipe 34.

  The other end of the hydrogen supply pipe 32 and the other end of the hydrogen supply pipe 34 are connected to the common pipe 30, and high-pressure hydrogen generated in each reaction tank is sent to the common pipe 30. The common pipe 30 is connected to the hydrogen discharge pipe 40. The hydrogen discharge pipe 40 is connected to a hydrogen storage tank (buffer tank) that stores high-pressure hydrogen (not shown) or a hydrogen using device that uses high-pressure hydrogen. The high-pressure hydrogen that circulates in the hydrogen discharge pipe 40 through the common pipe 30. Is available.

The hydrogen discharge pipe 40 may include an on-off valve. When the on-off valve is provided, the opening / closing of the on-off valve may be adjusted using a predetermined hydrogen pressure (for example, 80 MPa) as the gas pressure in the hydrogen discharge pipe 40 as a threshold value. For example, when the gas pressure in the hydrogen discharge pipe 40 exceeds a predetermined hydrogen pressure (for example, 80 MPa), the on-off valve may be opened so that high-pressure hydrogen is supplied to the outside through the hydrogen discharge pipe 40. . The on-off valve may be an automatic on-off valve that detects the pressure upstream of the on-off valve and is controlled to be opened when the pressure exceeds a threshold (for example, 80 MPa). A pressure valve may be used.
The threshold value may be a pressure at which hydrogen can be supplied to the outside as high-pressure hydrogen, can be 20 MPa or more, and is preferably 80 MPa or more.
Contrary to the above, when the gas pressure in the hydrogen discharge pipe 40 falls below the threshold value, the amount of high-pressure hydrogen that can be supplied to the outside, that is, the amount of hydrogen generated in the reaction vessel is reduced. The valve may be closed. Then, for example, when the high-pressure hydrogen is continuously generated by switching the reaction tank and the gas pressure in the hydrogen discharge pipe 40 exceeds the threshold again, the on-off valve is opened and the supply amount of high-pressure hydrogen to the outside is reduced. Can be increased.

Since the high-pressure hydrogen from the hydrogen discharge pipe 40 is supplied as a mixed gas mixed with carbon dioxide, it may be supplied to the outside as high-purity hydrogen gas through a separating means for separating carbon dioxide, if necessary.
As the carbon dioxide separation means, for example, a hydrogen separation membrane that selectively separates hydrogen, an adsorbent, cooling, or the like may be used.

  In the hydrogen supply apparatus of the present embodiment, an operation example in the case where the two reaction tanks 22 and 24 are operated by a wheel number to continuously generate high-pressure hydrogen will be described below.

First, formic acid is decomposed in the reaction tank 22 to generate high-pressure hydrogen. In this case, as shown in FIG. 1, the hydrogen-containing gas and the catalyst-containing liquid are transferred to the reaction tank 22 through the transfer pipe 35 from the reaction tank 24 that has already completed the phase for generating high-pressure hydrogen, and Formic acid is supplied from a supply pipe (not shown).
As shown in FIG. 1, the reaction tank 22 is heated by a heater unit 12 surrounding the reaction tank 22, and a decomposition reaction of formic acid is performed using a catalytic action. At this time, the valve V2 is opened, and the other valves V4 and V5 are closed. When hydrogen is generated in the reaction tank 22, the generated hydrogen is sent to the common pipe 30 through the hydrogen supply pipe 32 and further flows through the hydrogen discharge pipe 40. Hydrogen distribute | circulates as a mixed gas containing the carbon dioxide produced | generated simultaneously. Although not shown, when the hydrogen discharge pipe 40 includes an on-off valve, the on-off valve is closed, so that the hydrogen pressure between the reaction tank 22 and the flow rate adjustment valve rises, and the hydrogen pressure in the hydrogen discharge pipe 40 is increased. When the pressure exceeds a predetermined threshold (for example, 80 MPa), it can be said that the high-pressure hydrogen is full. Therefore, the on-off valve is opened to supply high-pressure hydrogen to the outside.

  In the reaction tank 22, the hydrogen generation in the reaction tank 22 is terminated on the condition that a certain time has elapsed from the decrease in the hydrogen generation rate or the start of hydrogen generation. When the hydrogen generation in the reaction tank 22 is completed, as shown in FIG. 2, the valve V5 is opened in advance and the reaction from the reaction tank 22 to the standby tank is performed in preparation for switching the reaction tank that generates high-pressure hydrogen. The hydrogen-containing gas and the catalyst-containing liquid are transferred to the tank 24. After the transfer is completed, the valve V5 is closed.

When the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 22 are transferred from the reaction tank 22 to the reaction tank 24, the bottom of the reaction tank 22 and the bottom of the reaction tank 24 are communicated by the transfer pipe 35 and the reaction tank 24. 2 and 3, first, the catalyst-containing liquid flows out in the direction along the inner wall surface (inner circumferential surface) of the side curved surface of the reaction tank 24 and is then stored. The hydrogen-containing gas flows out while bubbling into the catalyst-containing liquid accommodated. Thereby, since heat exchange between gas and liquid is suitably performed, when the hydrogen-containing gas containing hydrogen is transferred, a rapid temperature increase in the gas phase in the reaction tank 24 that is likely to occur due to the Joule-Thompson effect is suppressed, and high-pressure hydrogen Generation and supply can be safely continued.
Further, in the present embodiment, when the hydrogen-containing gas and the catalyst-containing liquid flow out to the reaction vessel 24, the hydrogen-containing gas and the catalyst-containing liquid are flown out as shown in FIG. Therefore, a long time for the components to contact each other is ensured. Therefore, the temperature rise accompanying the transfer of the hydrogen-containing gas to the reaction tank 24 is effectively suppressed.
In addition, the bottom part in the reaction tank 24 on the side to be transferred is a place deeper than a depth sufficient to achieve the above object, specifically, the destination side of the transfer pipe when the gas phase part starts to be transferred. Is preferably at a position below at least the liquid surface of the liquid phase, that is, a position where the liquid is immersed in the liquid phase.

Here, when the system specifications are assumed as follows, changes in the volume and pressure of the transfer components when the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 22 are transferred to the reaction tank 24 are shown in FIG. It is assumed that the volume reduction capacity when water and formic acid are mixed is 5/6 times.
<System specifications>
・ Hydrogen supply pressure: 80 MPa
-Formic acid concentration: 15 mol / L
Catalyst concentration: 2.0 mmol / L (value at the beginning of the reaction)
-Heater unit: Electric type, 80 ° C (Gas type or fuel cell exhaust heat is also possible)
-Container capacity: 1000ml (height 100mm)
・ Ambient temperature: Room temperature (30 ℃)
・ Reactor shape: Cylindrical

As shown in FIG. 4, the pressure change reaches 40 MPa when the reaction tank 24 is communicated until the reaction tank 24 has the same pressure as the reaction tank 22. The communication may be continued until the same pressure, that is, the differential pressure between the reaction tank 22 and the reaction tank 24 becomes 0 MPa. However, in order to shorten the communication time, the initial differential pressure is preferably set before the differential pressure becomes 0 MPa. Communication may be terminated when it reaches within 10%. The temperature change also depends on the heat exchange efficiency between the gas and liquid in the tank and the heat insulation of the tank, but if the heat exchange is performed uniformly in a completely insulated environment, the adiabatic compression and joule Considering the Thomson effect, it is considered that the temperature rises to 67 ° C.
Thus, it is preferable that the temperature in the reaction tank to which the catalyst or the like is transferred is suppressed to 85 ° C. or lower. When the temperature inside the reaction tank after the transfer is 85 ° C. or less, the safety is high and it is suitable for continuous supply of high-pressure hydrogen. The lower the temperature inside the reaction tank after the transfer, the better as long as it does not affect the decarboxylation reaction of formic acid, and more preferably 80 ° C. or lower.

  In order to perform heat exchange, the position of the connection part at one end of the transfer pipe is preferably set to a position lower than the liquid level (for example, 73.2 mm from the bottom) in the transferred reaction tank. It is more preferable to set to a position lower than the height of the liquid level in the reaction tank (for example, 50.5 mm from the bottom). In this embodiment, it is connected to a position 10.0 mm from the bottom.

  When the formic acid decomposition reaction proceeds in the reaction tank 22 and the formic acid concentration in the tank decreases and the hydrogen production rate decreases, the hydrogen pressure in the hydrogen discharge pipe 40 decreases. Stop hydrogen production. Here, when the hydrogen discharge pipe 40 is provided with an on-off valve, the on-off valve is closed and the supply of hydrogen in the reaction tank 22 is stopped.

  The catalyst used in the decomposition reaction of formic acid is a catalyst that promotes the decomposition reaction of formic acid, and is not particularly limited as long as it is a catalyst that diffuses uniformly into the liquid phase. The catalyst described in Patent Document 1 can be used. Examples of the metal species in the transition metal complex include platinum group metals such as ruthenium, rhodium and iridium, manganese, chromium, cobalt, and zinc chloride.

Subsequently, formic acid is decomposed in the reaction tank 24 to generate high-pressure hydrogen.
Similarly to the reaction tank 22 described above, the reaction tank 24 is heated by the heater unit 14 surrounding the reaction tank 24, and hydrogen generation and hydrogen supply are performed using catalytic action. At this time, the valve V4 is opened, and the other valves V2 and V5 (and the opening / closing valve provided in the hydrogen discharge pipe 40 if necessary) are closed. When hydrogen is generated in the reaction tank 24, the generated hydrogen is sent to the common pipe 30 through the hydrogen supply pipe 34 and further flows through the hydrogen discharge pipe 40. As described above, when the hydrogen discharge pipe 40 includes an on-off valve (not shown), the on-off valve is closed, so that the hydrogen pressure between the reaction tank 24 and the on-off valve increases. When the hydrogen pressure in the hydrogen discharge pipe 40 exceeds a predetermined threshold value (for example, 80 MPa), it can be said that the high-pressure hydrogen is full. Therefore, the on-off valve is opened and high-pressure hydrogen is supplied to the outside.

  In the reaction tank 24, the hydrogen generation in the reaction tank 24 is terminated on the condition that a certain time has elapsed from the decrease in the hydrogen generation rate or the start of hydrogen generation. When the hydrogen generation in the reaction tank 24 is completed, the hydrogen-containing gas and the catalyst-containing liquid are transferred through the transfer pipe 35 in the direction opposite to the flow direction shown in FIG. To do. That is, the valve V5 of the transfer pipe 35 is opened, and the hydrogen-containing gas and the catalyst-containing liquid are transferred from the reaction tank 24 to the reaction tank 22 that is a standby tank. After the transfer is completed, the valve V5 is closed again.

Even when the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 24 are transferred from the reaction tank 24 to the reaction tank 22, the transfer pipe 35 that communicates the bottom of the reaction tank 24 and the bottom of the reaction tank 22 with FIG. Similarly, the hydrogen-containing gas and the catalyst-containing liquid flow out in a direction along the inner wall surface (inner peripheral surface) of the side curved surface of the reaction tank 22.
When transferring to the reaction tank 22, as in FIGS. 2 and 3, first, the catalyst-containing liquid flows out and is stored in the direction along the inner wall surface (inner peripheral surface) of the side curved surface of the reaction tank 22. Thereafter, the hydrogen-containing gas flows out while bubbling into the catalyst-containing liquid contained therein. Thereby, when the hydrogen-containing gas containing hydrogen is transferred, a rapid temperature increase in the reaction tank 22 that is likely to occur due to the Joule-Thompson effect is suppressed, and generation and supply of high-pressure hydrogen can be safely continued.
Furthermore, in this embodiment, when the hydrogen-containing gas and the catalyst-containing liquid flow out to the reaction tank 22, the hydrogen-containing gas and the catalyst-containing liquid are flown out as shown in FIG. Therefore, a long time for the components to contact each other is ensured. Therefore, the temperature rise accompanying the transfer of the hydrogen-containing gas to the reaction tank 22 is effectively suppressed.

  When the formic acid decomposition reaction proceeds in the reaction tank 24 and the formic acid concentration in the tank decreases and the hydrogen production rate decreases, the hydrogen pressure in the hydrogen discharge pipe 40 decreases. Stop the hydrogen supply. Here, when the hydrogen discharge pipe 40 includes a flow rate adjustment valve, the on-off valve is closed, and the hydrogen supply in the reaction tank 24 is stopped.

  By repeating the above-described operation, high-pressure hydrogen can be continuously generated and supplied while suppressing an abrupt increase in temperature accompanying the transfer of hydrogen.

  In the above embodiment, two reaction tanks are used as the hydrogen generation means, and the description has focused on the case where two reaction tanks are operated in a rotating manner to continuously generate and supply high-pressure hydrogen. Even when a tank is used, it may be operated by a ring number in the same manner as described above.

(Second Embodiment)
A second embodiment of the hydrogen supply apparatus of the present invention will be described with reference to FIGS. The hydrogen supply apparatus according to the second embodiment includes three reaction tanks as hydrogen generation means for generating hydrogen from formic acid, and generates and supplies hydrogen in one of the three reaction tanks.
In addition, the same referential mark is attached | subjected to the component similar to 1st Embodiment, and the detailed description is abbreviate | omitted.

  As shown in FIG. 5, the hydrogen supply apparatus 200 of the second embodiment includes three reaction vessels 22, 24, and 26 that are hydrogen generation means and two reaction vessels that are connected to each other, and thus one reaction vessel. And transfer pipes 35, 38, and 33 for transferring components such as a catalyst to the other reaction tank.

  Similar to the reaction tanks 22 and 24, the reaction tank 26 is a cylindrical container made of a stainless alloy, both of which have the same structure. The reaction tank 22 (first hydrogen generation means), the reaction tank 24 (second hydrogen generation means), and the reaction tank 26 (third hydrogen generation means) are supplied with formic acid through a supply pipe (not shown) and heated. In addition, formic acid can be decomposed in the presence of a catalyst. As described above, the formic acid decomposition reaction generates hydrogen and carbon dioxide from formic acid.

Further, heater units 12, 14, and 16 as heating means are attached to the reaction tanks 22, 24, and 26, respectively, and heating is possible from the cylindrical side curved surface of each reaction tank.
About the heating temperature of a reaction tank, and the measuring method, it is the same as that of 1st Embodiment.
Similarly to the heater units 12 and 14, the heater unit 16 is attached so as to surround the periphery of the side curved surface of the cylindrical reaction tank 26, and the entire periphery of the reaction tank 26 is heated. .

One end of a transfer pipe 35 (first transfer pipe) is connected to the bottom of the cylindrical reaction tank 22, and the other end is connected to the bottom of the reaction tank 24.
One end of the second transfer pipe 38 is connected to the bottom of the cylindrical reaction tank 24, and the other end is connected to the bottom of the reaction tank 26. The reaction tank 24 and the reaction tank 26 are communicated with each other by the second transfer pipe 38.

  The second transfer pipe 38 has a valve V7 that is an on-off valve. In the present embodiment, the valve V7 is opened, and the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 26 after hydrogen supply are reacted. Transfer from the tank 26 to the reaction tank 24. Specifically, when hydrogen is supplied in the reaction tank 22 (first hydrogen generating means), the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 26 after the completion of the hydrogen supply are passed through the second transfer pipe 38 to the reaction tank 24. Transfer to

  One end of a third transfer pipe 33 is connected to the bottom of the cylindrical reaction tank 26 (third hydrogen generating means), and the other end is connected to the bottom of the reaction tank 22. The reaction tank 26 and the reaction tank 22 are communicated with each other by the third transfer pipe 33.

  The third transfer pipe 33 has a valve V3 that is an on-off valve, and in this embodiment, the valve V3 is opened, and the hydrogen content in the reaction tank 22 (first hydrogen generating means) after hydrogen supply is provided. The gas and catalyst-containing liquid are transferred from the reaction vessel 22 to the reaction vessel 26. Specifically, when hydrogen is supplied in the reaction tank 24 (second hydrogen generating means), the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 22 after completion of the hydrogen supply are passed through the third transfer pipe 33 to the reaction tank 26. Transfer to

  One end of a hydrogen supply pipe 36 having a valve V6 that is an open / close valve is connected to the top of the cylindrical reaction tank 26, and when formic acid is decomposed and reacted in the reaction tank 26 to generate hydrogen and supply hydrogen. Then, the valve V6 is opened. By opening the valve V6, hydrogen generated in the reaction tank 26 can be supplied to the outside through the hydrogen supply pipe 36.

The other end of the hydrogen supply pipe 32, the other end of the hydrogen supply pipe 34, and the other end of the hydrogen supply pipe 36 are all connected to the common pipe 30L, and the high-pressure hydrogen generated in each reaction tank is the common pipe. Sent to 30L. The common pipe 30L is connected to the hydrogen discharge pipe 40. The hydrogen discharge pipe 40 is connected to a hydrogen storage tank (buffer tank) that stores high-pressure hydrogen (not shown) or a hydrogen using device that uses high-pressure hydrogen, and the high-pressure hydrogen that circulates in the hydrogen discharge pipe 40 through a common pipe 30L. Is available.
The hydrogen discharge pipe 40 may be provided with an on-off valve, and details of the case where the on-off valve is provided are the same as in the first embodiment.

In the hydrogen supply apparatus of the present embodiment, the operation of continuously generating high-pressure hydrogen by operating the three reaction tanks 22, 24, and 26 with a wheel number may be controlled as shown in FIG.
Hereinafter, the operation of generating high-pressure hydrogen in the order of phase 2 → phase 3 → phase 1 from the end state of phase 1 in which high-pressure hydrogen is generated in the reaction tank 26 will be described with reference to FIG.

In phase 2, hydrogen is generated by performing a decomposition reaction of formic acid in the reaction tank 22. In this case, the reaction tank 22 is in a state where the hydrogen-containing gas and the catalyst-containing liquid are transferred from the reaction tank 24 in which the phase for supplying high-pressure hydrogen has already been completed, and formic acid is supplied from a supply pipe (not shown). Yes. At this time, the valve V2 is opened, and the other valves V4 and V6 (and the opening / closing valve provided in the hydrogen discharge pipe 40 as necessary) are closed. When hydrogen is generated in the reaction tank 22, the generated hydrogen is sent to the common pipe 30 </ b> L through the hydrogen supply pipe 32 and further flows through the hydrogen discharge pipe 40. When the hydrogen discharge pipe 40 includes an on-off valve, the on-off valve is closed, so that the hydrogen pressure between the reaction tank 22 and the on-off valve increases. When the hydrogen pressure in the hydrogen discharge pipe 40 exceeds a predetermined threshold (for example, 80 MPa), the high-pressure hydrogen is filled, so the high-pressure hydrogen is supplied to the outside by opening the on-off valve.
Here, the valve V7 shown in FIG. 5 is opened in preparation for switching the reaction tank for generating high-pressure hydrogen on condition that the hydrogen generation rate in the reaction tank 22 is reduced or a certain time has elapsed since the start of hydrogen generation. Then, the hydrogen-containing gas and the catalyst-containing liquid are transferred from the reaction tank 26 that has already stopped producing high-pressure hydrogen to the reaction tank 24 that is a standby tank. After the transfer is finished, the valve V7 is closed.

  When transferring the hydrogen-containing gas and the catalyst-containing liquid in the reaction vessel 26 from the reaction vessel 26 to the reaction vessel 24, the bottom of the reaction vessel 26 and the bottom of the reaction vessel 24 are communicated by the second transfer pipe 38, and When transferred to the reaction tank 24, the hydrogen-containing gas and the catalyst-containing liquid are discharged in a direction along the inner wall surface (inner peripheral surface) of the side curved surface of the reaction tank 24, as in FIG. 3. Since the hydrogen-containing gas and the catalyst-containing liquid are swirled while the hydrogen-containing gas is bubbled through the catalyst-containing liquid, the hydrogen-containing gas and the catalyst-containing liquid are accommodated in a stirred state. Therefore, when the hydrogen-containing gas is transferred to the reaction vessel 24, there is an effect of suppressing a temperature rise that is likely to occur due to the Joule-Thompson effect.

When the formic acid decomposition reaction proceeds in the reaction tank 22 and the formic acid concentration in the tank decreases and the hydrogen production rate decreases, the hydrogen pressure in the hydrogen discharge pipe 40 decreases. Stop the hydrogen supply. Here, when the hydrogen discharge pipe 40 is provided with an on-off valve, the on-off valve is closed and the hydrogen supply in the reaction tank 22 is stopped.
In addition, the detail of the catalyst used for the decomposition reaction of formic acid is synonymous with 1st Embodiment, and its preferable aspect is also the same.

Subsequently, the process proceeds to phase 3 shown in FIG. In phase 3, hydrogen is supplied by performing a formic acid decomposition reaction in the reaction vessel 24. In this case, the valve V4 is opened, and the other valves V2, V6 (and the opening / closing valve provided in the hydrogen discharge pipe 40 as necessary) are closed. When hydrogen is generated in the reaction tank 24, the generated hydrogen is sent to the common pipe 30 </ b> L through the hydrogen supply pipe 34 and further circulates in the hydrogen discharge pipe 40. The operation when the hydrogen discharge pipe 40 includes an on-off valve is the same as described above.
Here, on the condition that the hydrogen generation rate in the reaction tank 24 is reduced or a certain time has elapsed since the start of hydrogen generation, the valve V3 is opened to switch the reaction tank for generating high-pressure hydrogen. The catalyst and the like are transferred from the reaction tank 22 that has been stopped after the generation of the catalyst to the reaction tank 26 that is a standby tank. After the transfer is finished, the valve V3 is closed.

  Even when the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 22 are transferred from the reaction tank 22 to the reaction tank 26, the bottom of the reaction tank 22 and the bottom of the reaction tank 26 are communicated by the third transfer pipe 33. And when transferring to the reaction tank 26, similarly to FIG. 3, the hydrogen-containing gas and the catalyst-containing liquid flow out in a direction along the inner wall surface (inner peripheral surface) of the side curved surface of the reaction tank 26. As a result, similarly to the above, the hydrogen-containing gas and the catalyst-containing liquid are accommodated in a stirred state by creating a swirling flow while the hydrogen-containing gas is bubbled through the catalyst-containing liquid. Therefore, the temperature rise that is likely to occur when hydrogen is transferred to the reaction vessel 26 is suppressed.

  When the formic acid decomposition reaction proceeds in the reaction tank 24 and the formic acid concentration in the tank decreases and the hydrogen production rate decreases, the hydrogen pressure in the hydrogen discharge pipe 40 decreases. Stop the hydrogen supply. Here, when the hydrogen discharge pipe 40 includes an on-off valve, the on-off valve is closed and the supply of hydrogen in the reaction tank 24 is stopped.

Next, the process proceeds to phase 1 shown in FIG. In phase 1, hydrogen is supplied by performing a decomposition reaction of formic acid in the reaction vessel 26. In this case, similarly to the above, the reaction vessel 26 is heated by the heater unit 16 surrounding the reaction vessel 26, and the decomposition reaction of formic acid is performed using the catalytic action. At this time, the valve V6 is opened, and the other valves V2 and V4 (and the open / close valve provided in the hydrogen discharge pipe 40 as necessary) are closed. When hydrogen is generated in the reaction tank 26, the generated hydrogen is sent to the common pipe 30 </ b> L through the hydrogen supply pipe 36 and further flows through the hydrogen discharge pipe 40. The operation when the hydrogen discharge pipe 40 includes an on-off valve is the same as described above.
Here, on the condition that the hydrogen generation rate in the reaction tank 26 is reduced or a certain time has elapsed from the start of hydrogen generation, the valve V5 is opened to switch the reaction tank for generating high-pressure hydrogen, and the high pressure has already been reached. A catalyst or the like is transferred from the reaction tank 24 which has been stopped after the generation of hydrogen to the reaction tank 22 which is a standby tank. After the transfer is completed, the valve V5 is closed.

  Even when the hydrogen-containing gas and the catalyst-containing liquid in the reaction tank 24 are transferred from the reaction tank 24 to the reaction tank 22, the bottom of the reaction tank 24 and the bottom of the reaction tank 22 are communicated by the first transfer pipe 35. And when transferring to the reaction tank 22, similarly to FIG. 3, the hydrogen-containing gas and the catalyst-containing liquid flow out in a direction along the inner wall surface (inner peripheral surface) of the side curved surface of the reaction tank 22. As a result, similarly to the above, the hydrogen-containing gas and the catalyst-containing liquid are accommodated in a stirred state by creating a swirling flow while the hydrogen-containing gas is bubbled through the catalyst-containing liquid. Therefore, the temperature rise that is likely to occur when hydrogen is transferred to the reaction vessel 22 is suppressed.

  When the formic acid decomposition reaction proceeds in the reaction tank 26 and the formic acid concentration in the tank decreases and the hydrogen production rate decreases, the hydrogen pressure in the hydrogen discharge pipe 40 decreases. Stop hydrogen production. Here, when the hydrogen discharge pipe 40 is provided with an on-off valve, the on-off valve is closed and the production of hydrogen in the reaction tank 26 is stopped.

  Thereafter, the process proceeds to phase 2 again and the same operation as described above is repeated. Thereby, high-pressure hydrogen can be continuously generated and supplied.

12, 14, 16 ... heater unit (heating means)
22, 24, 26 ... Reaction tank (hydrogen generating means)
33, 35, 38 ... transfer pipes 100, 200 ... hydrogen supply devices V2-V7 ... on-off valve

Claims (6)

At least two hydrogen generating means to which formic acid is supplied, hydrogen is generated by a formic acid decomposition reaction using a catalyst and hydrogen is supplied to the outside;
A heating unit disposed in each of the hydrogen generation units and heating the hydrogen generation unit;
The hydrogen-containing gas containing the hydrogen and the catalyst-containing liquid containing the catalyst in the hydrogen-generating means that has been connected to at least two of the hydrogen-generating means and from which the hydrogen supply has ended are supplied from the hydrogen-generating means that has ended the hydrogen supply. A transfer pipe for transferring the hydrogen-containing gas in contact with the catalyst-containing liquid to a hydrogen generator other than the hydrogen generator;
A hydrogen supply device comprising:   As the hydrogen generation means, at least a first hydrogen generation means and a second hydrogen generation means are provided, at least one of the transfer pipes has an on-off valve, and the first hydrogen generation means and the first hydrogen generation means The hydrogen supply device according to claim 1, wherein the two hydrogen generation means communicate with each other.   3. The hydrogen supply device according to claim 1, wherein one end of the transfer pipe is connected to a bottom of a hydrogen generation unit to which the hydrogen-containing gas and the catalyst-containing liquid are transferred.   The transfer pipe supplies the hydrogen-containing gas and the catalyst-containing liquid to the hydrogen generating means by flowing at least the hydrogen-containing gas and the catalyst-containing liquid in a direction along the inner wall of the side portion of the hydrogen generating means. The hydrogen supply device according to any one of claims 1 to 3.   The hydrogen supply apparatus according to any one of claims 1 to 4, wherein a temperature after the transfer inside the hydrogen generating means to which the hydrogen-containing gas and the catalyst-containing liquid are transferred is 85 ° C or lower. At least a hydrogen supply step of supplying formic acid to the first hydrogen generating means, decomposing formic acid using a catalyst to generate hydrogen, and supplying hydrogen to the outside;
The hydrogen-containing gas containing hydrogen and the catalyst-containing liquid containing the catalyst in the first hydrogen generation unit that has completed the hydrogen supply step are transferred from the hydrogen generation unit that has completed the hydrogen supply step to the first hydrogen generation unit. A hydrogen supply method for transferring the hydrogen-containing gas in contact with the catalyst-containing liquid to a second hydrogen generating means communicated with the catalyst.