JP2012116666A - Hydrogen generating apparatus and fuel cell system provided with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen generating apparatus that can suppress the deterioration of desulfurization performance of a hydrodesulfurizer even when oxygen concentration in a raw material gas varies, compared with the conventional hydrogen generator.SOLUTION: The hydrogen generating apparatus includes: a hydrogen generator 1 for generating a hydrogen-containing gas by a reforming reaction using the raw material gas; a raw material gas passage 51 configured to supply the raw material gas to the hydrogen generator 1; the hydrodesulfurizer 2 arranged at the raw material gas passage 51, which removes a sulfur compound in the raw material gas; an oxygen remover 3 arranged at an upstream of the hydrodesulfurizer 2 in the raw material gas passage 51, which removes oxygen in the raw material gas by a combustion reaction; and a cooler 4 which cools at least one of the oxygen remover 3 and the raw material gas passage 51 form the oxygen remover 3 to the hydrodesulfurizer 2.

Description

  The present invention relates to a hydrogen generator that generates a hydrogen-containing gas by reacting a raw material gas and water, and a fuel cell system including the hydrogen generator.

  Fuel cells that enable highly efficient power generation even with small devices are being developed as power generation systems for distributed energy sources. Hydrogen gas used as fuel for power generation is not established as general infrastructure. For example, raw gas supplied from existing fossil raw material infrastructure such as natural gas and LP gas is used. A hydrogen generator for generating a hydrogen-containing gas by the reforming reaction is also provided.

  The source gas supplied to the hydrogen generator usually contains a sulfur compound. Specifically, sulfur compounds such as sulfides and mercaptans are added to natural gas and LP gas as an odorant for the purpose of leakage detection in addition to the sulfur content derived from the raw material. On the other hand, such a sulfur compound is known to poison a reforming catalyst such as Ni-based or Ru-based used for the steam reforming reaction and deteriorate the catalyst.

  For this reason, when using gas containing sulfur compounds, such as natural gas and LP gas, as raw material gas, suitable desulfurization processing is performed before supplying these gas to a hydrogen generator. As a desulfurization treatment method, an adsorbent such as zeolite is used, and a sulfur compound is removed by adsorption at room temperature, and a sulfur compound contained in a raw material is about 300 ° C. to 400 ° C. using a hydrogenation catalyst. A method is known in which hydrogen sulfide is adsorbed at about 200 ° C. to 350 ° C. using an adsorbent catalyst to remove sulfur in the raw material after reaction with hydrogen to convert it to hydrogen sulfide.

  By the way, natural gas and LP gas may contain oxygen in order to adjust the calorific value, specific gravity, and the like. And in the method using a hydrodesulfurizer, there existed a subject that desulfurization performance fell by the oxygen contained in raw gas, such as natural gas.

  In order to solve such problems, a fuel cell power generation system is known in which an oxygen remover (combustion catalyst) is provided upstream of the hydrodesulfurizer to remove oxygen before hydrodesulfurization. (For example, see Patent Documents 1 to 3).

JP-A-9-27337 JP-A-9-27338 Japanese Patent No. 4264791

  However, the fuel cell power generation systems disclosed in Patent Documents 1 to 3 are configured not to recover heat generated when oxygen contained in the raw material gas is removed by the oxygen remover. For this reason, the temperature of the source gas discharged from the oxygen remover becomes higher than the temperature of the source gas supplied to the oxygen remover. Therefore, when the oxygen concentration in the raw material gas fluctuates, the temperature of the raw material gas discharged from the oxygen remover fluctuates, and the temperature of the hydrodesulfurizer disposed downstream of the oxygen remover fluctuates. Depending on the temperature of the hydrodesulfurizer, the sulfur compound in the raw material gas may not be sufficiently desulfurized (not removed).

  The present invention has been made in view of the above problems, and even if the oxygen concentration in the raw material gas fluctuates, it is possible to suppress a decrease in the desulfurization performance of the hydrodesulfurizer compared to the conventional hydrogen generator. An object of the present invention is to provide a hydrogen generator and a fuel cell system including the same.

  In order to solve the above problems, a hydrogen generator according to the present invention is configured to generate a hydrogen-containing gas by a reforming reaction using a raw material gas, and supply the raw material gas to the hydrogen generator. A raw material gas flow path configured, a hydrodesulfurizer provided in the raw material gas flow path for removing sulfur compounds in the raw material gas, and provided upstream of the hydrodesulfurizer in the raw material gas flow path. An oxygen remover that removes oxygen in the raw material gas by a combustion reaction; and at least one of the oxygen remover and the raw material gas passage from the oxygen remover to the hydrodesulfurizer is cooled and cooled. A cooler capable of controlling the amount.

  Thereby, even if the oxygen concentration in raw material gas fluctuates, the fall of the desulfurization performance of a hydrodesulfurizer can be suppressed compared with the conventional hydrogen generator.

  The hydrogen generator of the present invention and the fuel cell system including the hydrogen generator can suppress a decrease in the desulfurization performance of the hydrodesulfurizer as compared with the conventional hydrogen generator even if the oxygen concentration in the raw material gas fluctuates. It becomes.

FIG. 1 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to the first embodiment. FIG. 2 is a block diagram schematically showing a schematic configuration of the hydrogen generator of the first modification. FIG. 3 is a block diagram schematically showing a schematic configuration of the hydrogen generator of the second modification. FIG. 4 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention. FIG. 5 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention. FIG. 6 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 4 of the present invention. FIG. 7 is a block diagram schematically showing a fuel cell system according to Embodiment 5 of the present invention.

  Hereinafter, embodiments of the present invention will be exemplified with reference to the drawings. In all the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, in all the drawings, only components necessary for explaining the present invention are extracted and illustrated, and other components are not illustrated. Furthermore, the present invention is not limited to the following embodiment.

(Embodiment 1)
A hydrogen generator according to Embodiment 1 of the present invention includes a hydrogen generator, a raw material gas channel, a hydrodesulfurizer, an oxygen remover, and a cooler provided in the raw material gas channel. And the cooler cools the oxygen remover.

[Configuration of hydrogen generator]
FIG. 1 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to the first embodiment.

  As shown in FIG. 1, the hydrogen generator 100 according to the first embodiment includes a hydrogen generator 1, a raw material gas passage 51, a hydrodesulfurizer 2, an oxygen remover 3, and a cooler 4. The vessel 4 can control the amount of cooling, and is configured to cool the oxygen remover 3. Thereby, even if the oxygen concentration in the raw material gas fluctuates, the temperature of the raw material gas after flowing through the oxygen remover 3 can be kept at a predetermined temperature, and hydrodesulfurization is possible as compared with the conventional hydrogen generator. A decrease in the desulfurization performance of the vessel 2 can be suppressed.

  Here, the raw material gas only needs to contain a hydrocarbon component, oxygen, and a sulfur compound. For example, natural gas, LP gas, or the like can be used.

  Moreover, a sulfur compound means sulfur components derived from raw materials, such as odorants, such as sulfides and mercaptans, and natural gas, such as hydrogen sulfide.

  Furthermore, the cooler 4 may have any configuration as long as the oxygen remover 3 can be cooled. For example, the cooler 4 supplies a cooling medium supply device (for example, a pump) and the oxygen remover 3. And a heat exchanging part (for example, fins) for exchanging heat with each other. In the first embodiment, the cooler 4 is provided with a heat exchanging unit so as to surround the oxygen remover 3, and the cooling medium is supplied to the heat exchanging unit by the cooling medium supply unit. The remover 3 is configured to be cooled. The cooler 4 can change (control) the cooling amount by changing the operation amount of the cooling medium supply device.

  The upstream end of the source gas channel 51 is connected to a source gas supply source (for example, a gas infrastructure such as natural gas), and the downstream end thereof is connected to the reformer 1 </ b> A of the hydrogen generator 1. An oxygen remover 3 and a hydrodesulfurizer 2 are arranged in this order in the middle of the raw material gas passage 51.

  Further, the downstream end of the recycle channel 53 is connected to the upstream side of the source gas channel 51 from the oxygen remover 3. The recycle channel 53 is configured to supply hydrogen generated by the hydrogen generator 1 to the oxygen remover 3. Further, the first valve 5 is provided in the middle of the recycle channel 53. As the first valve 5, an open / close valve such as an electromagnetic valve that allows / blocks the flow of the hydrogen-containing gas in the recycle flow path 53 may be used. A flow rate adjusting valve for adjusting the flow rate may be used, and both an on-off valve and a flow rate adjusting valve may be used.

  Further, a raw material gas supply device is provided in the middle of the raw material gas channel 51 (not shown). The raw material gas supply unit is configured to supply the raw material from the raw material supply source to the reformer 1A of the hydrogen generator 1 while adjusting the flow rate thereof. As a raw material gas supply device, for example, it may be configured by a flow rate adjusting valve alone, or may be configured by a combination of a booster pump and a flow rate adjusting valve. The source gas supply unit is provided in a part of the source gas channel 51 on the downstream side of the connection part at the downstream end of the recycle channel 53 and in the part of the upstream side of the arrangement part of the oxygen remover 3. It is preferable.

  The oxygen remover 3 is configured to remove oxygen contained in the source gas flowing through the source gas channel 51 by a combustion reaction. Specifically, for example, the oxygen remover 3 includes a combustion catalyst, and combusts a combustible gas such as a raw material gas or hydrogen and oxygen contained in the raw material gas with the combustion catalyst. In addition, as a combustion catalyst, a Pt-type catalyst etc. can be used, for example.

  The hydrodesulfurizer 2 may have any configuration as long as it can convert the sulfur compound contained in the raw material into hydrogen sulfide and adsorb the converted hydrogen sulfide (hereinafter referred to as hydrodesulfurization). The hydrodesulfurizer 2 includes, for example, a CoMo catalyst for converting a sulfur compound in a raw material gas into hydrogen sulfide as a hydrodesulfurization catalyst, and a ZnO or CuZn catalyst that is a sulfur adsorbent for adsorbing and removing hydrogen sulfide downstream thereof. May be used.

  The hydrodesulfurizer 2 is known to exhibit desulfurization performance at a relatively high temperature of about 300 to 400 ° C. In the hydrogen generator 100 according to the first embodiment, the hydrodesulfurizer 2 is a hydrogen generator. It is configured to be able to exchange heat with the generator 1. Specifically, the hydrodesulfurizer 2 is configured to be heated by heat transfer from a hydrogen-containing gas generated in the reformer 1A, for example. Further, the hydrodesulfurizer 2 may be configured such that, in addition to heat transfer from the hydrogen generator 1, a heater such as an electric heater is separately provided and the hydrodesulfurizer 2 is heated by the heater. Good.

  The hydrogen generator 1 has a reformer 1A and a combustor 1B. In the reformer 1A, a hydrogen-containing gas is generated by a reforming reaction between the raw material gas desulfurized in the hydrodesulfurizer 2 and separately supplied water (steam). The generated hydrogen-containing gas is supplied to a hydrogen-using device (for example, a fuel cell or a hydrogen storage tank) 101 via a hydrogen-containing gas supply path 52. An upstream end of the recycle channel 53 is connected to the hydrogen-containing gas supply channel 52 in the middle.

  Combustor 1B is supplied with combustion fuel (for example, raw material, hydrogen-containing gas discharged from reformer 1A or hydrogen-containing gas not used in hydrogen-using device 101) and combustion air, and these are combusted. A combustion exhaust gas is generated. The generated combustion exhaust gas heats the reformer 1A and the like, then flows through the combustion exhaust gas passage (not shown in FIG. 1) and is discharged out of the hydrogen generator 100.

  In the hydrogen generator 100 according to the first embodiment, the hydrogen-containing gas generated by the reformer 1A is sent to the hydrogen utilization device 101. However, the present invention is not limited to this. For example, the hydrogen generator 100 has a shift catalyst (for example, a copper-zinc catalyst) for reducing carbon monoxide in the hydrogen-containing gas sent from the reformer 1A in the hydrogen generator 1. And a carbon monoxide remover having an oxidation catalyst (for example, ruthenium-based catalyst) and a methanation catalyst (for example, ruthenium-based catalyst), and the hydrogen-containing gas after passing through these devices uses hydrogen. A configuration for sending to the device 101 may be adopted.

  Further, the hydrogen generator 100 has a controller 20. The controller 20 may be in any form as long as it is a device that controls each device constituting the hydrogen generation apparatus 100. For example, the controller 20 may be an arithmetic processing unit exemplified by a microprocessor, a CPU, etc. A storage unit configured by a memory or the like that stores a program for executing the operation is provided. Then, in the controller 20, the arithmetic processing unit reads out a predetermined control program stored in the storage unit and executes it, thereby processing the information and the hydrogen generator 100 including these controls. Various controls are performed.

  Note that the controller 20 is not only configured as a single controller, but also configured as a controller group in which a plurality of controllers cooperate to execute control of the hydrogen generator 100. I do not care. The controller 20 may be configured by a microcomputer, and may be configured by an MPU, a PLC (Programmable Logic Controller), a logic circuit, or the like.

  In the first embodiment, a mode in which the hydrogen-containing gas flowing through the hydrogen-containing gas supply path 52 is supplied to the hydrodesulfurizer 2 is adopted, but the present invention is not limited to this. The hydrodesulfurizer 2 may be supplied with a gas containing hydrogen. Therefore, for example, when the hydrogen generator 100 is provided with a transformer or the like that reduces carbon monoxide in the hydrogen-containing gas produced by the reformer 1A, the gas after passing through the transformer or the like is treated with water. You may employ | adopt the form supplied to the addition desulfurizer 2. FIG. Moreover, you may employ | adopt the form which supplies the hydrogen containing gas which was not used with the hydrogen utilization apparatus 101 to the hydrodesulfurizer 2. FIG.

[Operation of hydrogen generator]
Next, the operation of the hydrogen generator 100 according to Embodiment 1 will be described with reference to FIG.

  First, when an activation command for the hydrogen generator 100 is input to the controller 20, the controller 20 outputs an activation start command to each device constituting the hydrogen generator 100. In addition, as a start-up command of the hydrogen generator 100, for example, when a user of the hydrogen generator 100 instructs to start the hydrogen generator 100 by operating a remote controller (not shown) or a preset hydrogen generation The case where it becomes the operation start time of the apparatus 100 etc. is mentioned.

In particular,
The controller 20 supplies combustion fuel (for example, raw material gas) and combustion air to the combustor 1B. In the combustor 1B, the supplied combustion fuel and combustion air are combusted to generate combustion exhaust gas. The generated flue gas is discharged outside the hydrogen generator 100 by heating the reformer 1A and the like while flowing through the flue gas passage (not shown in FIG. 1). The reformer 1A (hydrogen generator 1) heated by the combustion exhaust gas heats the hydrodesulfurizer 2 by its heat transfer.

  Next, the controller 20 operates a source gas supply unit (not shown) to cause the source gas to flow through the source gas channel 51. In addition, the controller 20 opens the first valve 5. As a result, the hydrogen-containing gas remaining in the hydrogen-containing gas supply path 52 and the recycle path 53 is supplied to the source gas path 51 and mixed with the source gas flowing through the source gas path 51. Then, the source gas supplied (mixed) with the hydrogen-containing gas flows through the source gas channel 51 and is supplied to the oxygen remover 3.

  In the oxygen remover 3, hydrogen and oxygen contained in the source gas are burned by the combustion catalyst filled in the oxygen remover 3, and the oxygen concentration contained in the source gas is reduced. At this time, heat is generated by the combustion of hydrogen and oxygen, and the source gas is heated. When the heated source gas is supplied to the hydrodesulfurizer 2, the temperature of the hydrodesulfurizer 2 may fluctuate, and the sulfur compound in the source gas may not be sufficiently removed by the hydrodesulfurizer 2. There is.

  However, in the hydrogen generator 100 according to Embodiment 1, the controller 20 can cool the oxygen remover 3 by operating the cooler 4. Further, the controller 20 controls the cooler 4 so as to increase the cooling amount (so as to increase the operation amount of the cooling medium supply device) when the oxygen concentration in the raw material gas increases, When the oxygen concentration decreases, the cooler 4 is controlled so that the cooling amount is decreased (so that the operation amount of the cooling medium supply device is decreased). Thereby, the source gas flowing through the oxygen remover 3 can be maintained at a predetermined temperature. For this reason, the temperature of the hydrodesulfurizer 2 can be maintained at a temperature suitable for easy hydrodesulfurization, and the degradation of the desulfurization performance of the hydrodesulfurizer 2 is suppressed as compared with the conventional hydrogen generator. be able to.

  Note that the oxygen concentration in the raw material gas may be detected directly or may be detected indirectly. Examples of the method for directly detecting the oxygen concentration include a method using a gas detector. Moreover, as a method of indirectly detecting the oxygen concentration, for example, there is a method of detecting the temperature of the oxygen remover 3 with a temperature detector.

  By the way, for example, the pressure of the raw material gas such as natural gas supplied to the pipeline of the gas infrastructure may decrease due to a decrease in the outside air temperature. In order to compensate for the pressure drop of the raw material gas, a hydrocarbon (for example, propane) different from the hydrocarbon (for example, methane) as the main component of the raw material gas and oxygen may be supplemented. In such a case, the controller 20 is provided with a pressure detector in the source gas passage 51, the pressure of the source gas flowing through the source gas passage 51 is once reduced, and then the pressure is increased. The cooler 4 may be controlled to increase the cooling amount in the case of returning to the original pressure.

  In addition, when the outside temperature rises after the outside air temperature decreases and the propane and oxygen are replenished, when the replenishment of hydrocarbons and oxygen is stopped, the pressure of the raw material gas flowing through the raw material gas passage 51 is reduced. It decreases once, and then the pressure increases (returns to the original pressure). For this reason, the controller 20 increases the cooling amount of the cooler 4 and then sets the cooler 4 so that the cooling amount is decreased when the pressure detector detects a pressure fluctuation in the source gas flow path 51. You may control.

  Furthermore, since the component of the raw material gas is changed by replenishing propane, a raw material gas composition detector (frame rod) is provided in the combustor 1B, and the controller 20 detects the raw material gas detected by the frame rod. When the composition changes, the cooling amount of the cooler 4 may be varied. That is, when the propane is detected by the frame rod, the controller 20 determines that oxygen has been replenished, and increases the cooling amount of the cooler 4, and when no propane is detected, the replenishment of oxygen is stopped. It may be determined that the cooling amount of the cooler 4 is decreased.

  Then, the raw material gas that has flowed through the oxygen remover 3 is supplied to the hydrodesulfurizer 2. In the hydrodesulfurizer 2, the sulfur compound contained in the raw material gas reacts with hydrogen to be converted into hydrogen sulfide, and the converted hydrogen sulfide is adsorbed by the catalyst and removed from the raw material gas. In this way, the sulfur compound in the raw material gas is desulfurized. Since oxygen in the raw material gas is sufficiently reduced by the oxygen remover 3, the hydrogen generator 100 according to the first embodiment sufficiently reduces the deterioration of the desulfurization performance of the hydrodesulfurizer 2. be able to.

  The raw material gas desulfurized by the hydrodesulfurizer 2 (hereinafter referred to as post-desulfurized raw material gas) flows through the raw material gas passage 51 and is supplied to the reformer 1A of the hydrogen generator 1. Further, water (steam) is supplied to the reformer 1A from a water supply device (not shown in FIG. 1). The raw material gas after desulfurization and steam supplied to the reformer 1A undergo a reforming reaction to generate a hydrogen-containing gas. The generated hydrogen-containing gas is supplied to the hydrogen-containing gas supply path 52.

  The hydrogen-containing gas supplied to the hydrogen-containing gas supply path 52 flows through the hydrogen-containing gas supply path 52 and is supplied to the hydrogen utilization device 101. Further, a part of the hydrogen-containing gas flowing through the hydrogen-containing gas supply passage 52 flows through the recycle passage 53 and is supplied from the source gas passage 51 to the oxygen remover 3 and the hydrodesulfurizer 2.

  In the hydrogen generator 100 according to Embodiment 1 configured as described above, even if the oxygen concentration in the raw material gas varies, the raw material gas supplied to the hydrodesulfurizer 2 is maintained at a predetermined temperature. Can do. For this reason, the hydrodesulfurizer 2 can be maintained at a predetermined temperature, and a decrease in the desulfurization performance of the hydrodesulfurizer can be suppressed as compared with a conventional hydrogen generator.

[Modification 1]
Next, Modification 1 of the hydrogen generator 100 according to Embodiment 1 will be described.

  The hydrogen generator of Modification 1 in Embodiment 1 exemplifies a mode in which the cooler is provided in the raw material gas flow path from the oxygen remover to the hydrodesulfurizer.

  FIG. 2 is a block diagram schematically showing a schematic configuration of the hydrogen generator of the first modification.

  As shown in FIG. 2, the hydrogen generator 100 of the first modification has the same basic configuration as the hydrogen generator 100 according to the first embodiment, but the cooler 4 includes oxygen in the source gas flow channel 51. The difference is that it is provided between the remover 3 and the hydrodesulfurizer 2. Specifically, the cooler 4 is provided with a heat exchange part so as to surround, for example, piping constituting the source gas flow path 51. And when a cooling medium flows through a heat exchange part, it heat-exchanges with the source gas which flows through the source gas flow path 51, and cools source gas.

  In the hydrogen generator 100 of the first modification, the heated raw material gas is discharged from the oxygen remover 3 to the raw material gas flow path 51, but is disposed between the oxygen remover 3 and the hydrodesulfurizer 2. The raw material gas is cooled by the cooler 4. Thereby, since source gas is maintained at predetermined temperature, the hydrodesulfurizer 2 can be easily maintained at an appropriate temperature. For this reason, the hydrogen generator 100 of the first modification has the same operational effects as the hydrogen generator 100 according to the first embodiment.

[Modification 2]
Next, Modification 2 of the hydrogen generator 100 according to Embodiment 1 will be described.

  The hydrogen generator of Modification 2 in Embodiment 1 exemplifies a form in which the oxygen remover is configured to burn the source gas and oxygen in the source gas.

  Here, “burning the source gas and oxygen contained in the source gas” refers to burning hydrocarbons such as methane, which are combustible gases in the source gas, and oxygen in the source gas.

  FIG. 3 is a block diagram schematically showing a schematic configuration of the hydrogen generator of the second modification.

  As shown in FIG. 3, the hydrogen generator 100 according to the second modification has the same basic configuration as the hydrogen generator 100 according to the first embodiment, but the oxygen remover 3 includes a source gas and a source gas. It is different in that it is configured to burn oxygen. Specifically, the difference is that the downstream end of the recycle channel 53 is connected between the oxygen remover 3 and the hydrodesulfurizer 2 in the source gas channel 51.

  Thereby, the hydrogen-containing gas (hydrogen) generated by the hydrogen generator 1 is not supplied to the oxygen remover 3. For this reason, in the oxygen remover 3, hydrocarbons such as methane and oxygen in the raw material gas burn.

  Even the hydrogen generator 100 of the second modification configured as described above has the same operational effects as the hydrogen generator 100 according to the first embodiment.

(Embodiment 2)
A hydrogen generator according to Embodiment 2 of the present invention includes a combustor configured to supply heat for a reforming reaction to a hydrogen generator, an air supply device that supplies combustion air to the combustor, And the cooler is configured to cool the oxygen remover with combustion air.

  FIG. 4 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention.

  As shown in FIG. 4, the hydrogen generator 100 according to Embodiment 2 of the present invention has the same basic configuration as the hydrogen generator 100 according to Embodiment 1, but the combustor 1 </ b> B of the hydrogen generator 1. Is provided with an air supply device 6 for supplying combustion air, and the cooler 4 is configured to cool the oxygen remover 3 with combustion air. Specifically, the air supply unit 6 is connected to the combustor 1 </ b> B via the combustion air supply path 54. The air supply device 6 may be in any form as long as the flow rate of the combustion air can be adjusted and supplied to the combustor 1B. For example, a fan such as a blower or a sirocco fan can be used.

  A cooler 4 is disposed in the middle of the combustion air supply path 54. More specifically, the heat exchanging part of the cooler 4 is disposed in the middle of the combustion air supply path 54, and the air passing through the combustion air supply path 54 is supplied to the heat exchanging part of the cooler 4. It is configured as follows.

  That is, in the hydrogen generator 100 according to Embodiment 2, combustion air is used as the cooling medium of the cooler 4. The air supplier 6 is also configured to serve as a cooling medium supplier for the cooler 4.

  Thus, when the air supply device 6 is activated, the combustion air flows through the combustion air supply path 54 and is supplied to the cooler 4 (more precisely, the heat exchange section of the cooler 4). The combustion air supplied to the cooler 4 cools the raw material gas flowing through the oxygen remover 3 while flowing through the cooler 4. And the combustion air which flowed through the cooler 4 flows through the combustion air supply path 54, and is supplied to the combustor 1B.

  Even the hydrogen generator 100 according to the second embodiment configured as described above has the same effects as the hydrogen generator 100 according to the first embodiment.

(Embodiment 3)
The hydrogen generator according to Embodiment 3 of the present invention includes a water supply device that supplies water for a reforming reaction to the hydrogen generator, and the cooler is configured to cool the oxygen remover with water. This is an example of the embodiment.

  FIG. 5 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention.

  As shown in FIG. 5, the hydrogen generator 100 according to Embodiment 3 of the present invention has the same basic configuration as the hydrogen generator 100 according to Embodiment 1, but the reformer of the hydrogen generator 1. The difference is that a water supply device 7 for supplying water to 1A is provided, and the cooler 4 is configured to cool the oxygen remover 3 with water. Specifically, the water supply unit 7 is connected to the reformer 1 </ b> A via the water supply path 55. The water supply device 7 may be in any form as long as it can supply water while adjusting the flow rate. For example, the water supply device 7 may be constituted by a single flow rate adjustment valve, or a pump, a flow rate adjustment valve, It may be configured by a combination of The water supplied to the reformer 1A is heated by the heat transfer of the combustion exhaust gas generated by the combustor 1B and supplied as water vapor.

  A cooler 4 is disposed in the middle of the water supply path 55. More specifically, the heat exchanging part of the cooler 4 is disposed in the middle of the water supply path 55, and the heat exchanging part of the cooler 4 is supplied with water flowing through the water supply path 55. It is configured.

  That is, in the hydrogen generator 100 according to Embodiment 3, water is used as the cooling medium of the cooler 4. The water supplier 7 is also configured to serve as a cooling medium supplier of the cooler 4.

  Thus, when the water supply unit 7 is activated, water flows through the water supply path 55 and is supplied to the cooler 4 (more precisely, the heat exchange part of the cooler 4). The water supplied to the cooler 4 cools the raw material gas flowing through the oxygen remover 3 while flowing through the cooler 4. The water flowing through the cooler 4 flows through the water supply path 55 and is supplied to the reformer 1A.

  Even the hydrogen generator 100 according to the third embodiment configured as described above has the same effects as the hydrogen generator 100 according to the first embodiment.

(Embodiment 4)
A hydrogen generator according to Embodiment 4 of the present invention includes a combustor configured to supply heat for a reforming reaction to a hydrogen generator, and combustion in which combustion exhaust gas generated by the combustor flows. An exhaust gas flow path, a first heat medium flow path through which the first heat medium flows, a first heat exchanger configured to exchange heat between the combustion exhaust gas and the first heat medium, and an exhaust gas from the hydrogen generator A first heat accumulator that stores the first heat medium that has recovered the heat, a cooler is provided downstream of the first heat exchanger in the first heat medium flow path, and the oxygen remover is provided by the first heat medium. It illustrates an embodiment configured to cool.

  FIG. 6 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 4 of the present invention.

  As shown in FIG. 6, the hydrogen generating apparatus 100 according to the fourth embodiment has the same basic configuration as the hydrogen generating apparatus 100 according to the first embodiment, but the combustion exhaust gas generated in the combustor 1B is the same. The point which is provided with the flue gas flow path 56 which flows, the 1st heat-medium flow path 57, the 1st heat exchanger 8, and the hot water storage tank (1st heat storage) 9, and the cooler 4 by the 1st heat medium It differs from the point which is comprised so that the oxygen remover 3 may be cooled.

  Specifically, the combustion exhaust gas flow path 56 is connected to the combustor 1B. The combustion exhaust gas channel 56 is configured to discharge the combustion exhaust gas generated by the combustor 1 </ b> B to the outside of the hydrogen generator 100. A first heat exchanger 8 is provided in the middle of the combustion exhaust gas passage 56.

  In the fourth embodiment, the hot water storage tank 9 is formed so as to extend in the vertical direction, and a so-called stacked boiling type hot water storage tank is used. A first heat medium flow path 57 is connected to the hot water storage tank 9. More specifically, the upstream end of the first heat medium flow path 57 is connected to the lower part of the hot water storage tank 9, and the downstream end of the first heat medium flow path 57 is connected to the upper part of the hot water storage tank 9. .

  In the middle of the first heat medium flow path 57, a delivery device such as a pump for passing the first heat medium in the first heat medium flow path 57 is provided (not shown). A first heat exchanger 8 is provided in the middle of the first heat medium flow path 57. That is, the first heat exchanger 8 is provided so as to straddle the combustion exhaust gas passage 56 and the first heat medium passage 57. The first heat exchanger 8 exchanges heat between the flue gas flowing through the flue gas passage 56 and the first heat medium (here, water) flowing through the first heat medium passage 57. Any configuration may be used as long as it is configured. As the first heat exchanger 8, various heat exchangers such as a total heat exchanger can be used.

  In addition, the cooler 4 is provided on the downstream side of the first heat exchanger 8 in the first heat medium flow path 57. More specifically, the heat exchanging part of the cooler 4 is disposed in the middle of the first heat medium flow path 57, and the heat exchanging part of the cooler 4 flows through the first heat medium flow path 57. One heat medium is configured to be supplied. That is, in the hydrogen generator 100 according to Embodiment 4, the first heat medium is used as the cooling medium of the cooler 4. The delivery device also serves as a cooling medium feeder for the cooler 4.

  As a result, the first heat medium having a low temperature in the lower part of the hot water storage tank 9 is heated by the first heat exchanger 8 and the cooler 4 while flowing through the first heat medium flow path 57, so that the hot water storage tank Stored at the top of 9. The first heat medium supplied to the cooler 4 cools the source gas flowing through the oxygen remover 3 while flowing through the cooler 4.

  Even the hydrogen generator 100 according to the fourth embodiment configured as described above has the same effects as the hydrogen generator 100 according to the first embodiment.

(Embodiment 5)
The fuel cell system according to Embodiment 5 of the present invention exemplifies an aspect including a hydrogen generator and a fuel cell that generates power using a hydrogen-containing gas supplied from the hydrogen generator.

  FIG. 7 is a block diagram schematically showing a fuel cell system according to Embodiment 5 of the present invention.

  As shown in FIG. 7, the fuel cell system 200 according to the fifth embodiment includes a hydrogen generator 100 according to the first embodiment, a fuel cell 101 as a hydrogen utilization device, an oxidant gas supplier 102, Is provided. The fuel cell 101 may be a fuel cell such as a polymer electrolyte fuel cell or a phosphoric acid fuel cell. As the oxidant gas supply device 102, for example, fans such as a blower and a sirocco fan can be used.

The fuel cell system 200 according to Embodiment 5 includes an off fuel gas channel 59, a second heat medium channel 61, a second heat exchanger 11, and a hot water storage tank (second heat accumulator) 9. And
The cooler 4 is provided downstream of the second heat exchanger 11 in the second heat medium flow path 61 and is configured to cool the oxygen remover 3 with the heat medium.

  A hydrogen generator 100 (hydrogen generator 1) is connected to the fuel cell 101 via a hydrogen-containing gas supply path 52, and a hydrogen-containing gas (fuel gas) is connected to an anode (not shown) of the fuel cell 101. Is supplied. Further, an oxidant gas supply device 102 is connected to the fuel cell 101 through an oxidant gas supply path 58, and an oxidant gas (for example, air) is connected to a cathode (not shown) of the fuel cell 101. Is supplied.

  In the fuel cell 101, the hydrogen-containing gas supplied to the anode and the oxidant gas supplied to the cathode react electrochemically to generate water, and electricity and heat are generated. The generated power is supplied to an external power load (for example, a power device used at home) by a power controller (not shown).

  The fuel gas that has not been used in the fuel cell 101 (hereinafter referred to as “off fuel gas”) flows through the off fuel gas passage 59 and is discharged outside the fuel cell system 200. The oxidant gas that has not been used in the fuel cell 101 flows through the oxidant gas discharge path 60 and is discharged out of the fuel cell system 200. In the fifth embodiment, the off fuel gas is discharged to the outside of the fuel cell system 200. However, the present invention is not limited to this, and the off fuel gas is supplied to the combustor 1B and used as the combustion fuel. You may comprise as follows. A second heat exchanger 11 is provided in the middle of the off-fuel gas flow path 59.

  In the fifth embodiment, the hot water storage tank 9 is formed so as to extend in the vertical direction, and a so-called stacked boiling type hot water storage tank is used. A second heat medium flow path 61 is connected to the hot water storage tank 9. More specifically, the upstream end of the second heat medium flow path 61 is connected to the lower part of the hot water storage tank 9, and the downstream end of the second heat medium flow path 61 is connected to the upper part of the hot water storage tank 9. .

  In the middle of the second heat medium flow path 61, a delivery device such as a pump for passing the second heat medium in the second heat medium flow path 61 is provided (not shown). A second heat exchanger 11 is provided in the middle of the second heat medium flow path 61. That is, the second heat exchanger 11 is provided so as to straddle the off-fuel gas passage 59 and the second heat medium passage 61. The second heat exchanger 11 exchanges heat between the off-fuel gas flowing through the off-fuel gas flow path 59 and the second heat medium (here, water) flowing through the second heat medium flow path 61. Any configuration is possible as long as it is configured as described above. As the second heat exchanger 11, various heat exchangers such as a total heat exchanger can be used.

  Further, the cooler 4 is provided on the downstream side of the second heat exchanger 11 in the second heat medium passage 61. More specifically, the heat exchanging part of the cooler 4 is disposed in the middle of the second heat medium flow path 61, and the heat exchanging part of the cooler 4 flows through the second heat medium flow path 61. Two heat media are configured to be supplied. That is, in the fuel cell system 200 according to Embodiment 5, the second heat medium is used as the cooling medium of the cooler 4. The delivery device also serves as a cooling medium feeder for the cooler 4.

  As a result, the second heat medium having a low temperature in the lower part of the hot water storage tank 9 is heated by the second heat exchanger 11 and the cooler 4 while flowing through the second heat medium flow path 61, so that the hot water storage tank Stored at the top of 9. The second heat medium supplied to the cooler 4 cools the raw material gas flowing through the oxygen remover 3 while flowing through the cooler 4.

  In the fifth embodiment, the controller 20 is configured to control not only the hydrogen generator 100 but also other devices that constitute the fuel cell system 200. The controller 20 is configured to perform the operation of the hydrogen generator 100 as described in the first embodiment in the operation of the fuel cell system 200.

  For this reason, the fuel cell system 200 according to the fifth embodiment has the same effects as the hydrogen generator 100 according to the first embodiment.

  The fuel cell system 200 according to the fifth embodiment employs a mode that uses the hydrogen generator 100 according to the first embodiment. However, the present invention is not limited to this, and the first modification or the first modification of the first embodiment is not limited thereto. 2 may be used, or any one of the hydrogen generators 100 according to Embodiments 2 to 4 may be employed.

  From the foregoing description, many modifications and other embodiments of the present invention are obvious to one skilled in the art. Accordingly, the foregoing description is to be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the scope of the invention. Moreover, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment.

  The hydrogen generator according to the present invention and the fuel cell system including the hydrogen generator can suppress a decrease in the desulfurization performance of the hydrodesulfurizer compared to the conventional hydrogen generator even when the oxygen concentration in the raw material gas fluctuates. It is useful because it can.

DESCRIPTION OF SYMBOLS 1 Hydrogen generator 1A Reformer 1B Combustor 2 Hydrodesulfurizer 3 Oxygen remover 4 Cooler 5 1st valve 6 Air supply 7 Water supply 8 First heat exchanger 9 Hot water storage tank 11 2nd heat exchanger 20 controller 51 source gas channel 52 hydrogen-containing gas supply channel 53 recycle channel 54 combustion air supply channel 55 water supply channel 56 combustion exhaust gas channel 57 first heat medium channel 58 oxidant gas supply channel 59 off fuel gas flow Path 60 Oxidant gas discharge path 61 Second heat medium flow path 100 Hydrogen generator 101 Hydrogen utilization equipment (fuel cell)
102 Oxidant gas supply device 200 Fuel cell system

Claims (10)

A hydrogen generator for generating a hydrogen-containing gas by a reforming reaction using a raw material gas;
A source gas flow path configured to supply the source gas to the hydrogen generator;
A hydrodesulfurizer provided in the source gas flow path to remove sulfur compounds in the source gas;
An oxygen remover that is provided upstream of the hydrodesulfurizer in the source gas flow path and removes oxygen in the source gas by a combustion reaction;
A hydrogen generator comprising: the oxygen remover; and a cooler capable of cooling at least one of the source gas flow paths from the oxygen remover to the hydrodesulfurizer and controlling a cooling amount.   The hydrogen generation apparatus according to claim 1, further comprising a controller configured to control a cooling amount of the oxygen remover by the cooler according to an oxygen concentration in the source gas. Comprising a recycle channel configured to supply hydrogen generated by the hydrogen generator to the source gas;
The hydrogen generator according to claim 1 or 2, wherein the oxygen remover is a device that burns using oxygen in the source gas and the hydrogen supplied via the recycle channel.   The hydrogen generator according to claim 1 or 2, wherein the oxygen remover is a device that burns oxygen in the source gas and the source gas. A combustor configured to supply heat for a reforming reaction to the hydrogen generator;
An air supply for supplying combustion air to the combustor,
The said cooler is an apparatus which cools at least any one of the said raw material gas flow path from the said oxygen remover and the said oxygen remover to the said hydrodesulfurizer with the said combustion air. A hydrogen generator according to claim 1. A water supply for supplying water for the reforming reaction to the hydrogen generator;
The said cooler is an apparatus which cools at least any one of the said raw material gas flow path from the said oxygen remover and the said oxygen remover to the said hydrodesulfurizer with the said water. The hydrogen generator described in 1. A first heat accumulator for storing a first heat medium recovered from the exhaust heat of the hydrogen generator;
The said cooler is an apparatus which cools at least any one of the said raw material gas flow path from the said oxygen remover and the said oxygen remover to the said hydrodesulfurizer with the said 1st heat medium. The hydrogen generator according to any one of the above. A combustor configured to supply heat for a reforming reaction to the hydrogen generator;
A combustion exhaust gas passage through which the combustion exhaust gas generated in the combustor flows;
A first heat medium flow path through which the first heat medium flows;
A first heat exchanger configured to exchange heat between the combustion exhaust gas and the first heat medium;
A first heat accumulator for storing the first heat medium recovered from the exhaust heat of the hydrogen generator,
The cooler is provided downstream of the first heat exchanger in the first heat medium flow path, and is at least one of the oxygen remover and the source gas flow path from the oxygen remover to the hydrodesulfurizer. The hydrogen generator according to claim 1, which is a device that cools one of them with the first heat medium. A hydrogen generator according to any one of claims 1 to 8,
And a fuel cell that generates electricity using the hydrogen-containing gas supplied from the hydrogen generator. An off fuel gas passage through which off fuel gas discharged from the fuel cell flows;
A second heat medium flow path through which the second heat medium flows;
A second heat exchanger configured to exchange heat between the off-fuel gas and the second heat medium;
A second heat accumulator for storing the second heat medium that has recovered the exhaust heat of the fuel cell system,
The cooler is provided downstream of the second heat exchanger in the second heat medium flow path, and is at least one of the oxygen remover and the source gas flow path from the oxygen remover to the hydrodesulfurizer. The fuel cell system according to claim 9, wherein the fuel cell system is a device that cools one of them with the second heat medium.

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