JP2011195391A - On-start up operation method for hydrogen-containing gas producing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an on-start up operation method by which a hydrogen-containing gas producing apparatus is properly started while suppressing the cost thereof.SOLUTION: The on-start up operation method for the hydrogen-containing gas producing apparatus includes: a temperature rising step of combusting a raw fuel in a combustor 3 after a first valve Vb is closed, a second valve Ve is closed and a raw fuel distributary flow passage 12 is opened, upon starting up of the hydrogen-containing gas producing apparatus; a gas production starting step of starting the production of the hydrogen-containing gas in a reformer 4 by making the raw fuel flow in a desulfurizer 2 and the reformer 4 by opening the first valve Vb after raising the temperature of the reformer 4 to equal to or above set starting temperature by the temperature rising step; and a gas supply starting step of supplying the hydrogen-containing gas to the outside of the hydrogen-containing gas production apparatus by opening the second valve Ve after increasing the pressure of a hydrogen-containing gas supply passage 11 to a set operation starting pressure by the gas production starting step.

Description

  The present invention relates to a startup operation method for a hydrogen-containing gas generator having a desulfurizer that performs desulfurization treatment of sulfur components contained in raw fuel after adding hydrogen to the raw fuel.

There is a desulfurizer that can extend the life of a desulfurizing agent by adding hydrogen to a raw fuel containing hydrocarbons and then desulfurizing a sulfur component contained in the raw fuel. Patent Document 1 describes a hydrogen-containing gas generator having such a desulfurizer. For example, a hydrogen-containing gas generation device described in Patent Document 1 reforms a desulfurizer that performs desulfurization treatment of raw fuel supplied through a raw fuel supply path, and raw fuel desulfurized by the desulfurizer. The hydrogen-containing gas branch point in the middle of the reformer that generates hydrogen-containing gas mainly containing hydrogen and the hydrogen-containing gas supply path through which the hydrogen-containing gas generated by the reformer circulates and upstream of the desulfurizer A recycle gas supply path for connecting a portion of the hydrogen-containing gas in the middle of the raw fuel supply path on the side to flow a part of the hydrogen-containing gas generated by the reformer into the raw fuel supply path, Yes. In addition, it is described that the recycle gas supply path is provided with a shut-off valve, a control valve, a check valve, a blower, a metering pump, and the like. Therefore, the amount of hydrogen-containing gas added to the raw fuel is adjusted by controlling the operating state of the shutoff valve, control valve, check valve, blower, metering pump, etc. provided in the recycle gas supply path. It will be.
Furthermore, Patent Document 1 describes that when starting a hydrogen-containing gas generator, the hydrogen-containing gas having a low hydrogen concentration is hated from flowing into the desulfurizer and the recycling of the hydrogen-containing gas is suspended. .

JP2003-017109A (Claim 12, paragraph 0035, paragraph 0049)

  It is preferable from the viewpoint of cost reduction of the hydrogen-containing gas generator if it is not possible to provide the hydrogen-containing gas generator with an apparatus that opens and closes the recycle gas supply path as described above. However, in the case where an apparatus that opens and closes the recycle gas supply path as described above is not provided, the gas can always flow through the recycle gas supply path. Therefore, when the supply of raw fuel to the raw fuel supply path is started at the time of starting the hydrogen-containing gas generation device, the pressure at the hydrogen-containing gas confluence point becomes higher than the pressure at the hydrogen-containing gas diversion point. There is a possibility that the fuel flows backward through the recycle gas supply path. Then, raw fuel that has not been desulfurized flows into the downstream side of the reformer, and carbon monoxide as a reforming catalyst of the reformer or a carbon monoxide remover provided on the downstream side of the reformer. There may be a problem that the catalyst of the selective oxidizer is sulfur poisoned.

  In addition, when the hydrogen-containing gas generator is started, a combustor that releases combustion heat for heating the reformer is supplied through a raw fuel distribution channel branched from a raw fuel distribution point in the middle of the raw fuel supply channel. In the case of an apparatus configuration that combusts raw fuel, if the raw fuel flows toward the recycle gas supply path, the amount of raw fuel supplied to the combustor is relatively reduced. Can cause poor ignition and misfire.

  Furthermore, in the case where a check valve is provided in the recycle gas supply path, in addition to the above-mentioned problem of the apparatus cost, moisture contained in the generated hydrogen-containing gas is condensed while the operation of the hydrogen-containing gas generator is continued. The problem of blocking the check valve can also occur.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a start-up operation method capable of properly starting the hydrogen-containing gas generation device while suppressing the device cost of the hydrogen-containing gas generation device. In the point.

In order to achieve the above object, the hydrogen-containing gas generator according to the present invention has a start-up operation method characterized in that a desulfurizer that performs desulfurization treatment of raw fuel supplied through a raw fuel supply path, and desulfurization using the desulfurizer A reformer that reforms the treated raw fuel to generate a hydrogen-containing gas containing hydrogen as a main component, and a raw fuel branch channel that branches from a raw fuel branch point in the middle of the raw fuel supply channel. Combusting raw fuel to release combustion heat for heating the reformer, and hydrogen in the middle of a hydrogen-containing gas supply path through which the hydrogen-containing gas generated by the reformer flows. Recycle gas supply in which a part of the hydrogen-containing gas flows into the raw fuel supply path by connecting the containing gas branch point and a hydrogen-containing gas confluence part in the middle of the raw fuel supply path upstream of the desulfurizer A hydrogen-containing gas comprising A startup operating method of forming apparatus,
When starting up the hydrogen-containing gas generator,
Close the first valve provided in the raw fuel supply path downstream of the hydrogen-containing gas joining point and the raw fuel branching point and upstream of the desulfurizer, and the hydrogen-containing gas branching point And closing the second valve provided in the hydrogen-containing gas supply path on the downstream side, and opening the raw fuel distribution flow path to supply the raw fuel to the combustor and supplying the raw fuel with the combustor. A temperature raising step for burning;
After the temperature of the reformer is raised to a set start temperature or higher by the temperature raising step, the first valve is opened to flow the raw fuel into the desulfurizer and the reformer, and the reformer A gas generation start step for starting generation of a hydrogen-containing gas;
After increasing the pressure of the hydrogen-containing gas supply path to a set start pressure by the gas generation start step, the gas supply starts to supply the hydrogen-containing gas to the outside of the hydrogen-containing gas generator by opening the second valve And a process.

If the recycle gas supply path is not equipped with a device that can adjust the gas flow (for example, a shut-off valve, a control valve, a check valve, a blower, a pump, etc.), the raw fuel is supplied only to the combustor during the heating process. When gas is circulated through the raw fuel supply path so as to be supplied, there is a possibility that the gas flows from the hydrogen-containing gas distribution point of the raw fuel supply path into the recycle gas supply path and flows back through the recycle gas supply path. When the raw fuel flows back through the recycle gas supply path, the raw fuel that has not been desulfurized flows into the reformer and removes the carbon monoxide provided on the reformer's reforming catalyst and downstream of the reformer. The problem may be that the catalyst of the vessel is sulfur poisoned.
However, in the temperature raising process of this feature configuration, the hydrogen-containing gas junction and the fuel split flow are supplied while the raw fuel distribution flow path is opened and the raw fuel is supplied to the combustor in order to burn the raw fuel in the combustor. The first valve provided in the raw fuel supply path downstream from the location and upstream from the desulfurizer is closed, and the first valve provided in the hydrogen-containing gas supply path downstream from the hydrogen-containing gas distribution location. Two valves are closed. In other words, by closing the first valve provided in the raw fuel supply path upstream of the desulfurizer, the desulfurizer and the necessary temperature rise from the upstream side of the desulfurizer are not yet sufficiently performed. It can be prevented from flowing into the organ. Further, by closing the second valve, it is possible to prevent the gas from flowing out of the hydrogen-containing gas generator (for example, the fuel cell). Furthermore, by closing the first valve and the second valve, the raw fuel supply path upstream of the hydrogen-containing gas distribution point to which the recycle gas supply path is connected is closed by the first valve, and the downstream side The hydrogen-containing gas supply path is closed by the second valve. That is, the gas cannot flow toward the upstream side from the hydrogen-containing gas distribution point, and the gas cannot flow toward the downstream side from the hydrogen-containing gas distribution point. Therefore, the gas does not flow (that is, reversely flow) through the recycle gas supply path connected to the hydrogen-containing gas distribution point, and the raw fuel that has not been desulfurized flows into the reformer or the carbon monoxide remover. Nor.
Furthermore, since the raw fuel to be supplied to the combustor does not flow toward the recycle gas supply path in the temperature raising step, the supply amount of the raw fuel to the combustor is relatively reduced. Such a problem does not occur. As a result, a sufficient amount of raw fuel can be supplied to the combustor so that ignition failure and misfire do not occur in the combustor.
Therefore, it is possible to provide a start-up operation method that can properly start the hydrogen-containing gas generation device while suppressing the device cost of the hydrogen-containing gas generation device.

  Another characteristic configuration of the start-up operation method of the hydrogen-containing gas generation device according to the present invention is to stay upstream from the second valve during the gas generation start step prior to the gas supply start step. A gas discharge step of discharging the gas being discharged from a gas discharge point provided in the hydrogen-containing gas supply path upstream of the second valve.

In the stage before the execution of the gas supply start process, not only the hydrogen-containing gas generated by the reformer during the execution of the gas generation start process but also the upstream side of the second valve before the execution of the gas generation start process. Gas that was already present in the hydrogen-containing gas generator at the stage (gas used to seal the inside of the hydrogen-containing gas generator while the hydrogen-containing gas generator was shut down) Is present. Therefore, when the gas generation start process is directly shifted to the gas supply start process, there is a possibility that a hydrogen-containing gas having a low hydrogen purity is supplied to the downstream side of the hydrogen-containing gas generation apparatus. As a result, when a fuel cell is connected downstream of the hydrogen-containing gas generator, the fuel cell may be poisoned by sulfur compounds or carbon monoxide.
However, according to this characteristic configuration, hydrogen having a low hydrogen purity stays upstream from the second valve during the gas generation start step by performing the gas discharge step prior to the gas supply start step. The contained gas is discharged from the gas discharge point. That is, when the gas supply start process is performed, a hydrogen-containing gas having a high hydrogen purity can be supplied to the downstream side of the hydrogen-containing gas generator.

  Still another characteristic configuration of the start-up operation method of the hydrogen-containing gas generation device according to the present invention is that gas discharged from the gas discharge point is supplied to the combustor.

  According to the above characteristic configuration, since the gas discharged from the gas discharge location contains hydrogen and the like, it can be effectively used for combustion in the combustor.

  Still another characteristic configuration of the startup method of the hydrogen-containing gas generation device according to the present invention is that the hydrogen-containing gas generation device removes carbon monoxide contained in the hydrogen-containing gas generated by the reformer. The hydrogen-containing gas branch point is provided in the middle of the hydrogen-containing gas supply path that connects between the reformer and the carbon monoxide remover.

It is not necessary to selectively oxidize carbon monoxide contained in the gas supplied to the desulfurizer through the recycle gas supply path. In other words, if the carbon monoxide selective oxidizer is selectively oxidized up to the carbon monoxide contained in the gas supplied to the desulfurizer through the recycle gas supply path, the life of the carbon monoxide selective oxidizer becomes shorter than necessary. End up.
However, according to this characteristic configuration, the hydrogen-containing gas distribution point to which the recycle gas supply path is connected is provided in the middle of the hydrogen-containing gas supply path that connects between the reformer and the carbon monoxide selective oxidizer. That is, the gas supplied to the desulfurizer through the recycle gas supply path does not pass through the carbon monoxide selective oxidizer. As a result, the lifetime of the carbon monoxide selective oxidizer can be avoided from being unnecessarily shortened.

It is a figure which shows the structure of the hydrogen containing gas production | generation apparatus of 1st Embodiment. It is a figure which shows the structure of the hydrogen containing gas production | generation apparatus of 2nd Embodiment. It is a figure which shows the structure of the hydrogen containing gas production | generation apparatus of 3rd Embodiment.

<First Embodiment>
Hereinafter, a start-up operation method of the hydrogen-containing gas generator of the first embodiment will be described with reference to the drawings. FIG. 1 is a diagram illustrating a configuration of a hydrogen-containing gas generation device according to a first embodiment in which a startup operation method of a hydrogen-containing gas generation device according to the present invention is performed. As shown in the figure, in the hydrogen-containing gas generation device S1 (S), raw fuel is supplied to the reformer 4 through the raw fuel supply path 10, and the raw fuel is a gas containing hydrogen as a main component in the reformer 4 ( Reformed to hydrogen-containing gas). Then, the hydrogen-containing gas generated by the reformer 4 is supplied to the fuel cell 1 through the hydrogen-containing gas supply path 11.

[Configuration of hydrogen-containing gas generator]
The raw fuel supply path 10 is provided with a flow rate adjusting valve Va, which adjusts the flow rate of gas flowing into the system of the hydrogen-containing gas generating device S1. For example, the control unit 20 controls the opening of the electric flow control valve Va to adjust the flow rate of the raw fuel flowing into the system of the hydrogen-containing gas generation device S1 through the raw fuel supply path 10.
A booster pump 5 is provided in the raw fuel supply path 10 on the downstream side of the flow rate control valve Va. That is, the raw fuel that has flowed into the system from the flow rate adjusting valve Va is sucked and boosted by the booster pump 5, and then sent to the downstream side of the booster pump 5.
The desulfurizer 2 is provided in the raw fuel supply passage 10 downstream of the booster pump 5. The desulfurizer 2 is filled with a desulfurizing agent, and performs desulfurization processing of raw fuel such as hydrocarbon and alcohol supplied through the raw fuel supply passage 10. In the present embodiment, the raw fuel is a raw fuel gas mainly composed of hydrocarbons such as methane and propane. Methane, propane and the like used as these raw fuels are generally city gas and LPG, and a sulfur compound such as dimethyl sulfide (DMS) is included as an odorant. Therefore, the sulfur compound is removed by the desulfurizer 2 in order to avoid deterioration of the reforming catalyst charged in the reformer 4 at the subsequent stage and the anode constituting the cell of the fuel cell 1 due to the sulfur compound. Further, the life of the desulfurizing agent can be extended by performing hydrodesulfurization in which hydrogen is added to the raw fuel gas. The configuration of the recycle gas supply path 13 used for adding hydrogen to the raw fuel gas will be described later.

  The reformer 4 is filled with a reforming catalyst, and steam reforming of the raw fuel after the desulfurization treatment is performed in the presence of steam to generate a hydrogen-containing gas containing hydrogen as a main component. The reformer 4 is provided with a combustor 3 for heating the reformer 4. The combustor 3 burns the raw fuel supplied through the raw fuel branch channel 12 branched from the raw fuel branch point 17 in the middle of the raw fuel supply channel 10 and releases combustion heat for heating the reformer 4. To do. An open / close valve Vc for opening and closing the flow path is provided in the middle of the raw fuel distribution flow path 12. Although not shown in FIG. 1, the reformer 4 is supplied with raw fuel gas mixed with water vapor. The reformer 4 reforms the raw fuel gas into a reformed gas containing hydrogen as a main component and carbon monoxide as a by-product. Since carbon monoxide as a by-product deteriorates the anode constituting the cell of the fuel cell 1, a carbon monoxide conversion treatment by a carbon monoxide converter (not shown) may be performed as necessary. In this carbon monoxide converter, carbon monoxide contained in the hydrogen-containing gas reacts with moisture, and carbon monoxide is converted into carbon dioxide.

  The hydrogen-containing gas generated by the reformer 4 is supplied to the fuel cell 1 through the hydrogen-containing gas supply path 11. However, not all carbon monoxide is converted to carbon dioxide by the carbon monoxide transformer. Accordingly, in the carbon monoxide selective oxidizer (an example of the “carbon monoxide remover” of the present invention) 6 provided on the downstream side of the reformer 4, the hydrogen-containing gas (or Carbon monoxide contained in the hydrogen-containing gas after being subjected to the transformation treatment by the carbon oxide transformer is selectively oxidized. That is, the carbon monoxide selective oxidizer 6 oxidizes carbon monoxide to carbon dioxide. By the oxidation treatment in the carbon monoxide selective oxidizer 6, the concentration of carbon monoxide contained in the hydrogen-containing gas supplied to the fuel cell 1 can be very low.

The recycle gas supply path 13 used for adding hydrogen to the raw fuel gas includes a hydrogen-containing gas branch point 18 in the middle of the hydrogen-containing gas supply path 11 through which the hydrogen-containing gas generated in the reformer 4 flows, A hydrogen-containing gas confluence 16 in the middle of the raw fuel supply path 10 upstream of the desulfurizer 2 is connected. Specifically, the hydrogen-containing gas branch point 18 is provided in the middle of the hydrogen-containing gas supply path 11 connecting the reformer 4 and the carbon monoxide selective oxidizer 6. As a result, a part of the hydrogen-containing gas generated in the reformer 4 flows into the raw fuel supply path 10, and the raw fuel to which hydrogen is added is supplied to the desulfurizer 2. As described above, the gas supplied to the desulfurizer 2 through the recycle gas supply path 13 does not pass through the carbon monoxide selective oxidizer 6. Accordingly, since the amount of gas selectively oxidized in the carbon monoxide selective oxidizer 6 is suppressed, the life of the carbon monoxide selective oxidation catalyst charged in the carbon monoxide selective oxidizer 6 is unnecessarily shortened. Can be avoided.
In this embodiment, the recycle gas supply path 13 is not provided with a shut-off valve, a control valve, a check valve, a blower, a pump, or the like.

  On the downstream side of the booster pump 5 in the raw fuel supply passage 10 and upstream of the desulfurizer 2, an on-off valve (“first valve” in the present invention) Vb is provided. An open / close valve (“second valve” in the present invention) Ve is also provided in the hydrogen-containing gas supply path 11 downstream of the hydrogen-containing gas branch point 18. In addition, a gas discharge path 14 is connected to the gas discharge point 19 of the hydrogen-containing gas supply path 11 upstream of the on-off valve Ve. The gas discharge path 14 on the downstream side of the on-off valve Vd is open to the atmosphere.

[Operation method at startup of hydrogen-containing gas generator (temperature raising process)]
In the temperature raising step, the on-off valve (first valve) Vb provided in the raw fuel supply passage 10 downstream of the hydrogen-containing gas confluence 16 and the raw fuel branch 17 and upstream of the desulfurizer 2 is closed. And the on-off valve (second valve) Ve provided in the hydrogen-containing gas supply path 11 downstream from the hydrogen-containing gas distribution point 18 is closed, and the raw fuel distribution path 12 is opened to combustor 3. The raw fuel is supplied to the fuel and the combustor 3 burns the raw fuel.

  Specifically, when starting the hydrogen-containing gas generation device S1, the control unit 20 opens the flow rate control valve Va and operates the booster pump 5 to supply raw fuel into the system of the hydrogen-containing gas generation device S1. Inflow. At this time, the control unit 20 opens the on-off valve Vc, and closes the on-off valve (first valve) Vb, the on-off valve (second valve) Ve, and the on-off valve Vd. And since the control part 20 carries out the combustion operation of the combustor 3 to which raw fuel is supplied, the heating of the reformer 4 by the combustor 3 is started.

That is, the on-off valve (first valve) Vb provided in the raw fuel supply passage 10 upstream of the desulfurizer 2 is closed, so that the raw fuel is desulfurized from the upstream side of the desulfurizer 2 and the necessary temperature rise. Can be prevented from flowing into the reformer 4 which has not been sufficiently performed. Further, by closing the on-off valve (second valve) Ve, raw fuel can be prevented from flowing out of the hydrogen-containing gas generation device S1 (for example, the fuel cell 1). Further, by closing the on-off valve Vb and the on-off valve Ve, the raw fuel supply path 10 upstream of the hydrogen-containing gas distribution point 18 to which the recycle gas supply path 13 is connected is closed by the on-off valve Vb. The downstream hydrogen-containing gas supply path 11 is closed by the on-off valve Ve. That is, the gas cannot flow toward the upstream side from the hydrogen-containing gas distribution point 18, and the gas cannot flow toward the downstream side from the hydrogen-containing gas distribution point 18. Therefore, gas does not flow (that is, reversely flow) through the recycle gas supply path 13 connected to the hydrogen-containing gas branch point 18, and the raw fuel that has not been desulfurized is converted into the reformer 4 or the carbon monoxide selective oxidizer. 6 does not flow.
Further, since the raw fuel to be supplied to the combustor 3 does not flow toward the recycle gas supply path 13 in the temperature raising process, the supply amount of the raw fuel to the combustor 3 is relatively reduced. There will be no problem. As a result, it is possible to supply a sufficient amount of raw fuel to the combustor 3 so that ignition failure and misfire do not occur in the combustor 3.

[Operation method when starting hydrogen-containing gas generator (gas generation start process)]
In the gas generation start step, the temperature of the reformer 4 is raised to the set start temperature or higher by the temperature raising step, and then the on-off valve (first valve) Vb is opened to feed the raw fuel to the desulfurizer 2 and the reformer 4. The generation of hydrogen-containing gas is started in the reformer 4 by flowing in.

  Specifically, after starting the temperature raising step, the control unit 20 determines that the temperature of the reformer 4 is equal to or higher than the set startup temperature based on the detection result of the temperature sensor T that detects the temperature of the reformer 4. It is determined whether or not. Then, when the control unit 20 determines that the temperature of the reformer 4 is equal to or higher than the set activation temperature, the control unit 20 starts generating the hydrogen-containing gas in the reformer 4. Specifically, the control unit 20 controls the raw fuel to flow into the desulfurizer 2 and the reformer 4 by opening the on-off valve (first valve) Vb. Further, the raw fuel continues to be supplied to the combustor 3 during the gas generation start process. As a result, a gas mainly composed of hydrogen is generated by the reforming reaction in the reformer 4.

  However, at this time, the control unit 20 is provided in the on-off valve Ve provided in the hydrogen-containing gas supply path 11 downstream of the reformer 4 and the gas discharge path 14 branched from the hydrogen-containing gas supply path 11. The open / close valve Vd is closed. Therefore, since the gas generated in the reformer 4 is blocked from flowing by the on-off valve Ve and the on-off valve Vd, the pressure of the hydrogen-containing gas supply path 11 on the upstream side of the on-off valve Ve gradually increases. By carrying out this gas generation start step, when the gas pressure in the hydrogen-containing gas supply path 11 upstream from the on-off valve Ve increases, the pressure of the hydrogen-containing gas diversion point 18 is higher than the pressure of the hydrogen-containing gas junction point 16. Also gets higher. As a result, the hydrogen-containing gas generated in the reformer 4 flows from the hydrogen-containing gas distribution point 18 through the recycle gas supply path 13 to the hydrogen-containing gas junction 16 and flows into the raw fuel supply path 10. Then, hydrodesulfurization is performed in the desulfurizer 2.

[Operation method for starting hydrogen-containing gas generator (gas supply start process)]
In the gas supply start step, the pressure of the hydrogen-containing gas supply path 11 is increased to the set start pressure in the gas generation start step, and then the on-off valve (second valve) Ve is opened to the outside of the hydrogen-containing gas generation device S1. Supplying a hydrogen-containing gas is performed. Prior to the gas supply start step, the gas staying upstream from the second valve during the gas generation start step is provided in the hydrogen-containing gas supply path 11 upstream from the second valve. A gas discharge step of discharging from the gas discharge point 19 is performed. Further, the raw fuel continues to be supplied to the combustor 3 during the gas supply start process.

  Specifically, the control unit 20 starts the gas generation start step, and then the internal pressure of the hydrogen-containing gas generation device S1 (that is, the gas pressure of the hydrogen-containing gas supply path 11 on the upstream side of the on-off valve Ve). ) Rises to the set starting pressure, it is determined that it is time to supply the hydrogen generated in the hydrogen-containing gas generator S1 to the fuel cell 1. In the present embodiment, the pressure sensor P that detects the pressure of the raw fuel supply passage 10 upstream of the desulfurizer 2 is used to increase the pressure inside the hydrogen-containing gas generator S1 (that is, upstream of the on-off valve Ve). The gas pressure of the hydrogen-containing gas supply path 11 is detected. However, the gas remaining in the hydrogen-containing gas supply path 11 on the upstream side of the on-off valve Ve at this time is low-purity hydrogen. Therefore, the control unit 20 opens the on-off valve Vd provided in the gas discharge passage 14 for a predetermined period, and the gas staying upstream from the on-off valve (second valve) Ve During the valve-opening period, a gas discharge step of discharging from a gas discharge point 19 provided in the hydrogen-containing gas supply path 11 upstream of the on-off valve (second valve) Ve is executed. Thereafter, the control unit 20 opens the on-off valve Ve provided in the hydrogen-containing gas supply path 11, and the hydrogen generated in the hydrogen-containing gas generation device S 1 is supplied to the fuel cell 1 as the hydrogen-containing gas supply path 11. To be supplied through.

  As described above, in the temperature raising step, while the raw fuel distribution channel 12 is opened and the raw fuel is supplied to the combustor 3 in order to burn the raw fuel in the combustor 3, The on-off valve (first valve) Vb provided in the raw fuel supply passage 10 downstream of the raw fuel branching point 17 and upstream of the desulfurizer 2 is closed, and more than the hydrogen-containing gas branching point 18. The on-off valve (second valve) Ve provided in the downstream hydrogen-containing gas supply path 11 is closed. That is, the on-off valve Vb provided in the raw fuel supply passage 10 upstream of the desulfurizer 2 is closed, so that the raw fuel is still sufficiently heated from the upstream side of the desulfurizer 2 and the necessary temperature rise. Inflow to the reformer 4 which is not broken can be prevented. Further, by closing the on-off valve Ve, it is possible to prevent gas from flowing out of the hydrogen-containing gas generation device S1 (for example, the fuel cell 1). Further, by closing the on-off valve Vb and the on-off valve Ve, the raw fuel supply path 10 upstream of the hydrogen-containing gas distribution point 18 to which the recycle gas supply path 13 is connected is closed by the on-off valve Vb. The downstream hydrogen-containing gas supply path 11 is closed by the on-off valve Ve. That is, the gas cannot flow toward the upstream side from the hydrogen-containing gas distribution point 18, and the gas cannot flow toward the downstream side from the hydrogen-containing gas distribution point 18. Therefore, the gas does not flow back into the recycle gas supply path 13 connected to the hydrogen-containing gas branch point 18.

Second Embodiment
The hydrogen-containing gas generator S2 of the second embodiment is different from the hydrogen-containing gas generator S1 of the first embodiment in that the anode exhaust gas of the fuel cell is supplied to the combustor. Hereinafter, the hydrogen-containing gas generation device S2 of the second embodiment will be described, but the description of the same configuration as that of the first embodiment will be omitted.

  FIG. 2 is a diagram illustrating a configuration of the hydrogen-containing gas generation device S2 of the second embodiment. Each step (temperature raising step, gas generation start step, gas supply start step, gas discharge step) of the startup operation method of the hydrogen-containing gas generation device S2 is the same as in the first embodiment. However, in the present embodiment, as illustrated, an anode exhaust gas passage 15 through which anode exhaust gas discharged from the anode of the fuel cell 1 flows is connected to the raw fuel distribution passage 12. As a result, when the hydrogen-containing gas is supplied to the fuel cell 1 in a stage after the gas supply start process, the anode exhaust gas of the fuel cell 1 passes through the anode exhaust gas passage 15 and the raw fuel distribution channel 12 and the combustor 3. Flow into. Since the anode exhaust gas contains hydrogen that has not been used for the power generation reaction in the fuel cell 1, the hydrogen is used for combustion in the combustor 3.

  In addition, in the present embodiment, the gas discharge path 14 is connected in the middle of the anode exhaust gas path 15. As a result, the gas staying upstream from the on-off valve (second valve) Ve during the gas generation start process opens the on-off valves Vd and Ve, thereby opening the gas discharge path from the gas discharge point 19. 14, the anode exhaust gas passage 15, and the raw fuel distribution passage 12, and flows into the combustor 3. Since the gas discharged from the gas discharge point 19 contains hydrogen and the like, it can be effectively used for combustion in the combustor 3.

<Third Embodiment>
The hydrogen-containing gas generation device S3 of the third embodiment is different from the above-described embodiment in that the carbon monoxide selective oxidizer 6 is not provided. Hereinafter, the hydrogen-containing gas generation device S3 according to the third embodiment will be described.

  FIG. 3 is a diagram illustrating a configuration of the hydrogen-containing gas generation device S3 of the third embodiment. Each process (temperature raising process, gas generation start process, gas supply start process, gas discharge process) of the startup operation method of the hydrogen-containing gas generation device S3 is the same as in the first embodiment. When the fuel cell 1 is a solid oxide fuel cell, since the operating temperature is high, the electrode reaction proceeds quickly without using a noble metal catalyst such as a platinum catalyst, and the electrode poisoning by carbon monoxide is caused. Does not occur. Therefore, the hydrogen-containing gas generation device S3 of this embodiment does not include the carbon monoxide selective oxidizer 6 as described above. Therefore, the device configuration of the hydrogen-containing gas generation device S3 can be simplified.

<Another embodiment>
<1>
In the said embodiment, although the case where the valve Va was comprised with the flow control valve was illustrated, you may change the structure of the valve Va. For example, the valve Va may be composed of a valve having a raw fuel cutoff function. In that case, the flow rate of the gas flowing into the system of the hydrogen-containing gas generator S can be adjusted using the booster pump 5 and a flow meter (not shown) connected in series with the booster pump 5. .

<2>
In the above embodiment, the arrangement of the valves may be changed. For example, in the third embodiment (FIG. 3), it is not necessary to provide the on-off valve Vd in the gas discharge path 14.

<3>
In the above embodiment, the carbon monoxide selective oxidizer 6 is shown as an example of the “carbon monoxide remover” of the present invention, but other types of carbon monoxide removers may be used. For example, a carbon monoxide selective methanator that selectively methanates carbon monoxide may be used as the carbon monoxide remover.

<4>
In the said embodiment, you may implement another process before the temperature rising process mentioned above. For example, the raw fuel gas may be supplied into the hydrogen-containing gas generation device S and the pressure in the hydrogen-containing gas generation device S may be increased before the start of the temperature raising step described above.
Specifically, using the hydrogen-containing gas generation device S1 in FIG. 1, the control unit 20 performs the pressure-increasing step of the hydrogen-containing gas generation device S1 before the temperature raising step.
The boosting process will be described below. The flow rate adjustment valve Va is opened, the booster pump 5 is operated, and the raw fuel is caused to flow into the system of the hydrogen-containing gas generator S1 for a predetermined time. At this time, the control unit 20 opens the on-off valve (first valve) Vb, and closes the on-off valve Vc, the on-off valve (second valve) Ve, and the on-off valve Vd. As a result, the pressure upstream of the on-off valve Vb and the on-off valve Vc in the hydrogen-containing gas generator S, the pressure between the on-off valve Vb and the on-off valve (second valve) Ve, and the on-off valve Vd, and The pressure of the recycle gas supply path 13 increases. After the pressure at the relevant point increases, the on-off valves Vb and Va are closed. That is, the hydrogen-containing gas generator S1 is held in a state where the pressure is increased. The above is the boosting step.
After the boosting step, the control unit 20 opens the on-off valve Vc (the on-off valve (first valve) Vb, the on-off valve (second valve) Ve, and the on-off valve Vd remain closed), Combustion operation of the combustor 3 to which fuel is supplied is performed (temperature raising step). As a result, even if the pressure in the hydrogen-containing gas generation device S is lower than the raw fuel supply pressure before the start of the pressurization process, the pressure at the hydrogen-containing gas confluence 16 is increased by performing the pressurization process. Since the pressure does not become higher than the pressure at the containing gas branch point 18, it is possible to reliably prevent the raw fuel from flowing (reversely flowing) into the recycle gas supply path 13 at the stage where the supply of the raw fuel to the combustor 3 is started ( That is, since the raw fuel can be reliably supplied to the combustor 3), the ignition failure or ignition failure of the combustor 3 can be prevented from occurring.

  In the start-up operation method of the hydrogen-containing gas generator according to the present invention, a device (for example, a shutoff valve, a control valve, a check valve, a blower, a pump, etc.) capable of adjusting the gas flow is provided in the recycle gas supply path. It can be used in a hydrogen-containing gas generator that has not been used.

DESCRIPTION OF SYMBOLS 1 Fuel cell 2 Desulfurizer 3 Combustor 4 Reformer 6 Carbon monoxide selective oxidizer 10 Raw fuel supply path 11 Hydrogen-containing gas supply path 12 Raw fuel distribution path 13 Recycle gas supply path 14 Gas discharge path 15 Anode exhaust gas path 16 Hydrogen-containing gas junction point 17 Raw fuel branch point 18 Hydrogen-containing gas branch point 19 Gas discharge point S (S1, S2, S3) Hydrogen-containing gas generator Vb valve (first valve)
Ve valve (second valve)

Claims (4)

A desulfurizer that performs desulfurization treatment of the raw fuel supplied through the raw fuel supply path, and a reformer that reforms the raw fuel desulfurized by the desulfurizer to generate a hydrogen-containing gas mainly containing hydrogen. A combustor that burns raw fuel supplied through a raw fuel branch channel branched from a raw fuel branch point in the middle of the raw fuel supply channel and releases combustion heat for heating the reformer; A hydrogen-containing gas distribution point in the middle of the hydrogen-containing gas supply path through which the hydrogen-containing gas generated in the reformer flows and a hydrogen-containing gas junction in the middle of the raw fuel supply path upstream of the desulfurizer And a recycle gas supply path for allowing a part of the hydrogen-containing gas to flow into the raw fuel supply path, and a startup method of a hydrogen-containing gas generation device comprising:
When starting up the hydrogen-containing gas generator,
Close the first valve provided in the raw fuel supply path downstream of the hydrogen-containing gas joining point and the raw fuel branching point and upstream of the desulfurizer, and the hydrogen-containing gas branching point And closing the second valve provided in the hydrogen-containing gas supply path on the downstream side, and opening the raw fuel distribution flow path to supply the raw fuel to the combustor and supplying the raw fuel with the combustor. A temperature raising step for burning;
After the temperature of the reformer is raised to a set start temperature or higher by the temperature raising step, the first valve is opened to flow the raw fuel into the desulfurizer and the reformer, and the reformer A gas generation start step for starting generation of a hydrogen-containing gas;
After increasing the pressure of the hydrogen-containing gas supply path to a set start pressure by the gas generation start step, the gas supply starts to supply the hydrogen-containing gas to the outside of the hydrogen-containing gas generator by opening the second valve And a start-up operation method of the hydrogen-containing gas generator.   Prior to the execution of the gas supply start step, the gas that has accumulated in the upstream side of the second valve during the execution of the gas generation start step is transferred to the hydrogen-containing gas supply path upstream of the second valve. The operation method at the time of starting of the hydrogen containing gas production | generation apparatus of Claim 1 including the gas discharge process discharged | emitted from the gas discharge location provided in this.   The operation method at the time of starting of the hydrogen-containing gas generation device according to claim 2, wherein the gas discharged from the gas discharge point is supplied to the combustor.   The hydrogen-containing gas generating device includes a carbon monoxide remover that removes carbon monoxide contained in the hydrogen-containing gas generated by the reformer, and the hydrogen-containing gas branch point is the reformer and The operation method at the time of starting of the hydrogen containing gas production | generation apparatus as described in any one of Claims 1-3 provided in the middle of the said hydrogen containing gas supply path connecting between the said carbon monoxide removers.

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