JP2002356305A - Reformer and start-up method for reformer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reformer and a start-up method for the reformer capable of starting up without impairing a durability. SOLUTION: By supplying a hydrocarbon raw fuel gas and steam, a treatment room 3 which reforms a raw fuel gas to gas containing hydrogen by steam is provided. The start-up method for the reformer is constituted so as to stop an operation in the condition of loading the raw fuel gas in the treatment room. Based on a start-up command, a heat treatment is started to heat the treatment room 3 by a heating section 4. When a temperature of the treatment room 3 rises to the temperature which can prevent a carbon precipitation by thermal cracking of the raw fuel gas and can prevent a dewing of steam, steam is fed into the treatment room 3. When a temperature of a steam substitution treatment substituting the raw fuel gas inside of the treatment room 3 by steam and of the treatment room 3 rises to the temperature capable of reforming, a treatment which feeds the raw fuel gas and steam into the treatment room 3 is processed in order.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a processing chamber for supplying a hydrocarbon-based raw fuel gas and water vapor and reforming the raw fuel gas into a hydrogen-containing gas with the water vapor. A method for starting the reformer configured to stop the operation with the fuel gas charged, and supplying a hydrocarbon-based raw fuel gas and steam to convert the raw fuel gas into a hydrogen-containing gas by the steam. The present invention relates to a reforming apparatus provided with a processing chamber for performing quality processing, and configured to stop operation when the processing chamber is filled with raw fuel gas.

[0002]

2. Description of the Related Art Such a reformer is for reforming a hydrocarbon-based raw fuel gas into a hydrogen-containing gas with water vapor in a processing chamber. Used as fuel gas for As a reforming catalyst for performing a reforming reaction between the raw fuel gas and steam in the processing chamber, a noble metal based catalyst such as nickel-based or ruthenium is used. If water vapor remains, the residual water vapor condenses due to a decrease in temperature, and the condensed water may be absorbed by the reforming catalyst, reducing the activity of the reforming catalyst. Then, the reforming catalyst may be oxidized and its activity may be reduced.

[0003] Therefore, in the reforming apparatus, when the processing chamber is stopped, the gas in the processing chamber is replaced with an inert gas such as nitrogen, carbon dioxide, or argon so that the processing chamber is filled with the inert gas. There was something to configure. However,
In this reforming apparatus, in order to fill the processing chamber with the inert gas, it is necessary to install an inert gas supply facility (for example, a gas cylinder) for supplying the inert gas. There is a problem that maintenance work related to maintenance is complicated. Therefore, in order to solve such a problem, when stopping in the reformer, the gas in the processing chamber is replaced with a raw fuel gas which is a raw material for generating a hydrogen-containing gas, and the raw fuel gas is introduced into the processing chamber. There is a configuration in which the operation is stopped when the battery is filled.
This reformer eliminates the need for inert gas supply equipment and eliminates the problems of the reforming catalyst absorbing dew water and oxidizing the reforming catalyst by infiltration of air from outside into the processing chamber. Becomes possible.

[0004] When a reformer configured to stop the operation in a state where the processing chamber is filled with the raw fuel gas is started, conventionally, the processing chamber is filled with the raw fuel gas. Then, the temperature of the processing chamber is raised to a temperature at which the raw fuel gas can be reformed, and then the raw fuel gas and steam are supplied to the processing chamber to start the reforming processing.

[0005]

However, in the prior art, while the processing chamber is filled with the raw fuel gas, the processing time is not increased until the processing chamber is heated to a temperature at which the raw fuel gas can be reformed. The raw fuel gas filled in the chamber thermally decomposes and deposits carbon, and the deposited carbon adheres to the reforming catalyst, resulting in deterioration of the reforming performance or blockage of the gas processing path in the reformer. Or malfunctions,
There was a problem that the durability of the reformer was low.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a starting method and a reforming apparatus for a reforming apparatus that can be started without impairing durability.

[0007]

Means for Solving the Problems [Invention according to claim 1]
A feature of the starting method of the reforming apparatus according to claim 1 is that, based on a start command, a heating section starts a heating process of heating the processing chamber, and the temperature of the processing chamber is reduced by the heat of the raw fuel gas. When the temperature is raised to a temperature at which carbon deposition due to decomposition can be prevented and condensation of water vapor can be prevented (hereinafter, sometimes referred to as non-condensing non-carbon deposition temperature), steam is supplied to the processing chamber,
When the temperature of the processing chamber is raised to a temperature at which the reforming process can be performed (hereinafter, sometimes referred to as a reforming processable temperature), and a steam replacement process of replacing the raw fuel gas inside the processing chamber with steam. And a step of sequentially supplying raw fuel gas and water vapor to the processing chamber. According to the starting method of the first aspect, based on the starting command, the heating unit starts the heating process of heating the processing chamber, and first, the temperature of the processing chamber is raised to the non-condensing non-carbon deposition temperature. Then, steam is supplied to the processing chamber to perform a steam replacement process in which the raw fuel gas inside the processing chamber is replaced with steam, and the raw fuel gas inside the processing chamber is separated from the dew condensation of the steam and the raw fuel gas. In a state in which the inside of the processing chamber is prevented from being condensed by the steam until the temperature of the processing chamber rises to a temperature at which the reforming process can be performed, while replacing the carbon with the steam while preventing the precipitation of carbon. Maintain filling state. Next, when the temperature of the processing chamber rises to the temperature at which the reforming process is possible, a process of supplying the raw fuel gas and the steam to the processing chamber is performed, and the raw fuel gas reforming process is started. In other words, when starting the reformer that is stopped by charging the raw fuel gas into the processing chamber, the temperature of the processing chamber is raised to a temperature at which the processing chamber can be reformed while the raw fuel gas is charged into the processing chamber. If this occurs, carbon will be deposited from the raw fuel gas, and before that, in order to prevent the deposition of carbon from the raw fuel gas, before the temperature of the processing chamber rises to the non-condensing non-carbon deposition temperature,
When the supply of water vapor is started, the water vapor condenses. Therefore, as described above, as a process of starting the reformer in which the processing chamber is filled with the raw fuel gas and stopped, by sequentially performing the respective processes, when the reformer is started, dew condensation of steam and condensation may occur. The reforming process can be started by starting the supply of the raw fuel gas and the steam to the processing chamber while preventing the deposition of carbon from the raw fuel gas charged at the time of the stop. Therefore, it is possible to provide a starting method of the reforming apparatus that can be started without impairing durability.

[0008] The invention of claim 2 is characterized in that the temperature of the processing chamber can prevent the deposition of carbon due to the thermal decomposition of the raw fuel gas and the generation of steam. Until the temperature rises to a level that prevents condensation, and
During the steam replacement process, the operation is performed so that the temperature of the heating unit is equal to or lower than a set temperature. Claim 2
According to the starting method described in the above, after the heating of the processing chamber is started by the heating unit, the temperature of the processing chamber is raised to the non-condensing non-carbon deposition temperature, and subsequently, the processing is performed by supplying steam to the processing chamber. Until the steam replacement process for replacing the raw fuel gas inside the chamber with steam is completed, the operation is performed so that the temperature of the heating unit becomes equal to or lower than the set temperature. That is, it is preferable to shorten the start-up time required for the start-up operation for raising the temperature of the processing chamber to the temperature at which the reforming process is possible. On the other hand, even when the processing chamber is heated by the heating unit, the responsiveness to the heating by the heating unit differs in each part of the processing chamber, so that the temperature in each part of the processing chamber tends to be different during the start-up operation. Further, the temperature of the processing chamber is detected in order to determine the time point at which the steam replacement processing is started. Even if the temperature of the processing chamber is detected in such a manner, it is not practical to detect the temperature of the entire processing chamber. Therefore, the temperature of a predetermined location in the processing chamber is detected. In order to shorten the start-up time, the operation is performed by increasing the heating power of the heating unit. In this case, only the temperature of the processing chamber is detected, and the temperature of the processing chamber is reduced to non-condensing non-carbon deposition. When the temperature is raised to the temperature, the steam replacement process is started.Because the heating power of the heating unit is large, the process is performed until the temperature at the temperature detection point in the processing chamber rises to the non-condensing non-carbon deposition temperature. There is a possibility that the temperature at a location other than the temperature detection location in the chamber may be higher than a temperature at which carbon deposition can be prevented (hereinafter, may be referred to as a non-carbon deposition temperature). On the other hand, while the temperature of the temperature detection point in the processing chamber rises to the non-condensing non-carbon deposition temperature, it is avoided that the temperature of the part other than the temperature detection point in the processing chamber becomes higher than the non-carbon deposition temperature. For this reason, if the operation is performed with the heating power of the heating unit reduced, the startup time becomes longer. Therefore, when the processing chamber is heated and started by the heating unit, the set temperature is appropriately set, and the temperature of the heating unit that is clearly higher than the highest temperature in the entire region of the processing chamber is detected. When the operation is performed by adjusting the heating power of the heating unit so that the temperature of the heating unit is equal to or lower than the set temperature, the heating unit is prevented from being higher than the non-carbon deposition temperature over the entire area or substantially the entire area of the processing chamber. By increasing the heating power as much as possible, it is possible to start the processing chamber so that the temperature of the processing chamber becomes a temperature at which the reforming process is possible. Therefore, it has become possible to provide a starting method of the reforming apparatus that can be started without deteriorating the durability and that can shorten the starting time.

According to a third aspect of the present invention, there is provided a reforming apparatus according to the third aspect, wherein a processing chamber temperature detecting means for detecting a temperature of the processing chamber, and an intermittent supply of steam to the processing chamber. Steam intermittent means, and raw fuel gas intermittent means for intermittently supplying the raw fuel gas to the processing chamber are provided, and a control means for managing the operation of the reformer is provided to the heating unit based on the start command. A heating process for heating the processing chamber by heating, and based on the detection information of the processing chamber temperature detecting means, the temperature of the processing chamber can prevent the deposition of carbon due to the thermal decomposition of the raw fuel gas and the condensation of water vapor When the temperature is raised to a temperature at which the temperature of the processing chamber can be prevented, steam is supplied to the processing chamber to replace the raw fuel gas inside the processing chamber with steam. When the temperature rises, the fuel So as to sequentially perform a process of supplying the gas and water vapor, lies in that it is configured to control the operation of the steam and disconnecting means and the raw fuel gas interrupting means. According to the characteristic configuration of the third aspect, the control unit starts the heating process of heating the processing chamber in the heating unit based on the start command, and then, based on the detection information of the processing chamber temperature detection unit. When the temperature of the processing chamber rises to the non-condensing non-carbon deposition temperature, steam is supplied to the processing chamber to replace the raw fuel gas inside the processing chamber with steam. When the temperature rises to a temperature at which the reforming process is possible, the process of supplying the raw fuel gas and the steam to the processing chamber is sequentially performed, so that the raw fuel gas filled in the processing chamber is desorbed from the water vapor and the raw fuel gas. While the precipitation of carbon is prevented, the inside of the processing chamber is prevented from being dew-condensed by steam until the temperature of the processing chamber is raised to a temperature at which the reforming process can be performed, while the inside of the processing chamber is replaced by steam. The temperature of the processing chamber is When the temperature is raised to function temperature,
The raw fuel gas and the steam are supplied to the processing chamber, and the raw fuel gas reforming process is started. In other words, the supply of the raw fuel gas and the steam to the processing chamber is started, and the reforming process is started, while being filled during the condensation and stoppage of the steam to prevent the deposition of carbon from the raw fuel gas. Therefore, it has become possible to provide a reformer that can be started without impairing durability.

According to a fourth aspect of the present invention, there is provided the reformer according to the fourth aspect of the present invention, wherein a heating section temperature detecting means for detecting a temperature of the heating section is provided, and the control means is provided in the processing chamber. The temperature of the heating unit temperature detecting means is maintained until the temperature of the heating unit temperature is increased to a temperature at which carbon deposition due to thermal decomposition of the raw fuel gas can be prevented and condensation of steam can be prevented, and during the steam replacement process. It is configured to control the heating operation of the heating unit based on the detection information so that the temperature of the heating unit is equal to or lower than a set temperature. Claim 4
According to the characteristic configuration described in, the control unit, based on the detection information of the processing chamber temperature detection unit and the heating unit temperature detection unit,
After the heating of the processing chamber is started by the heating unit, the temperature of the processing chamber rises to the non-condensing non-carbon deposition temperature, and then steam is supplied to the processing chamber to convert the raw fuel gas inside the processing chamber into steam. The heating operation of the heating unit is controlled so that the temperature of the heating unit becomes equal to or lower than the set temperature until the steam replacement process for replacing by the process is completed. That is, it is preferable to shorten the start-up time required for the start-up operation for raising the temperature of the processing chamber to the temperature at which the reforming process is possible. On the other hand, even when the processing chamber is heated by the heating unit, the responsiveness to the heating by the heating unit differs in each part of the processing chamber, so that the temperature in each part of the processing chamber tends to be different during the start-up operation. Further, the temperature of the processing chamber is detected by the processing chamber temperature detecting means in order to determine the point in time at which the steam replacement processing is started. Since it is practically difficult to detect the temperature, the temperature at a predetermined location in the processing chamber is detected. And to shorten the startup time,
The heating operation of the heating unit is controlled so as to increase the heating power.In this case, if only the temperature of the processing chamber is detected and the temperature of the processing chamber is raised to the non-condensing non-carbon deposition temperature, steam When the replacement process is started, the heating power of the heating unit is large, so that the temperature of the temperature detection point in the processing chamber rises to the non-condensing non-carbon deposition temperature other than the temperature detection point in the processing chamber. Temperature may be higher than the non-carbon deposition temperature. On the other hand, while the temperature of the temperature detection point in the processing chamber rises to the non-condensing non-carbon deposition temperature, it is avoided that the temperature of the part other than the temperature detection point in the processing chamber becomes higher than the non-carbon deposition temperature. Therefore, if the heating operation of the heating unit is controlled so as to reduce the heating power, the startup time becomes longer. Therefore, when the processing chamber is heated by the heating unit and started, the set temperature is appropriately set, and the temperature of the heating unit, which is clearly higher than the highest temperature in the entire region of the processing chamber, is transmitted to the heating unit temperature detecting means. When the heating operation of the heating unit is controlled and operated so that the detected temperature is equal to or lower than the set temperature, it is possible to prevent the temperature from becoming higher than the non-carbon deposition temperature over the entire or almost the entire processing chamber. However, it is possible to increase the heating power of the heating unit as much as possible and start the processing chamber so that the temperature of the processing chamber becomes a temperature at which the reforming process is possible. Therefore, it has become possible to provide a reformer that can be started without deteriorating the durability and that can shorten the start-up time.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [First Embodiment] A first embodiment of the present invention will be described below. FIG. 1 shows a hydrogen-containing gas generator provided with a reformer R. The hydrogen-containing gas generator is provided with a desulfurization unit 1 for desulfurizing a supplied hydrocarbon-based raw fuel gas and a raw water feed. A steam generating section 2 that generates steam by heating, and a desulfurized raw fuel gas desulfurized in the desulfurizing section 1 is reformed into a gas containing hydrogen gas and carbon monoxide gas using the steam generated in the steam generating section 2. A reformer R for processing, a conversion unit 5 for converting carbon monoxide gas in a reforming gas supplied from the reformer R into carbon dioxide gas using steam, and a hydrogen-containing gas generator. A control unit C as a control means for managing the operation and an operation unit S for instructing the control unit C to give operation information are provided to generate a hydrogen-rich hydrogen-containing gas having a low carbon monoxide gas concentration. It is configured to do so.

The reforming apparatus R includes a reforming section 3 as a processing chamber which is filled with a reforming catalyst and reforms a desulfurized raw fuel gas using steam, and a reforming section 3 which burns gaseous fuel. And a combustion unit 4 (corresponding to a heating unit) that heats so as to be able to perform a reforming process.

In the desulfurization section 1, for example, a sulfur compound in the raw fuel gas is hydrogenated by a desulfurization catalyst at a reaction temperature of about 200 ° C., and the hydride is adsorbed by zinc oxide to be desulfurized. The desulfurization unit 1 is provided with a start heater 1h including an electric heater or the like for heating the desulfurization unit 1 to a desulfurization processing temperature at the time of start.

In the reforming section 3, when the city gas containing methane gas as the main component is the raw fuel gas, the methane gas and the water vapor are mixed under heating of, for example, about 650 to 750 ° C. by the catalytic action of the reforming catalyst. Undergoes a reforming reaction according to the following reaction formula, and is reformed into a gas containing hydrogen gas and carbon monoxide gas.

[0015]

Embedded image CH ₄ + H ₂ O → CO + 3H ₂

In the shift section 5, the carbon monoxide gas and steam in the reforming gas undergo a shift reaction by the catalytic action of the shift catalyst at a reaction temperature of, for example, about 200 ° C. by the following reaction formula. Thus, the carbon monoxide gas is converted into carbon dioxide gas. The metamorphic unit 5 is provided with a starting heater 5h including an electric heater or the like for heating the metamorphic unit 5 to the metamorphic processing temperature at startup.

[0017]

## STR2 ## CO + H ₂ O → CO ₂ + H ₂

The desulfurization section 1 is connected to a raw fuel gas supply path 7 for leading a raw fuel gas, and the desulfurized raw fuel gas desulfurized in the desulfurization section 1 is mixed with steam generated in the steam generation section 2. The desulfurization unit 1 and the reforming unit 3 are connected by a desulfurization gas passage 8 so as to supply the air-fuel mixture to the reforming unit 3, and a steam supply passage for guiding the steam generated by the steam generation unit 2. 9
Is connected to the desulfurization gas passage 8 and the reforming unit 3 and the shift unit 5 are connected by the reforming gas passage 10 so that the reforming gas is supplied from the reforming unit 3 to the shift unit 5. The metamorphic processing gas that has been subjected to the metamorphic processing in the section 5 is supplied to the gas consumer through the generated gas path 12 as a generated gas. For example, when the gas consumer is a fuel cell, the generated gas is supplied to the fuel cell as a fuel gas for cell reaction. Reference numeral 23 in FIG. 1 denotes a hydrogenation recycle path for supplying a part of the reforming gas discharged from the reforming section 3 to the desulfurizing section 1 as a hydrogen source for desulfurizing processing.

The combustion section 4 is connected to an air supply path 14 for guiding air from the blower 13 as combustion air and a gas fuel supply path 15 for guiding gas fuel. Incidentally, when the generated gas generated by the hydrogen-containing gas generator is consumed by the fuel cell as a fuel gas, the gas fuel guided through the gas fuel supply path 15 is the fuel gas discharged from the fuel cell. Use off-gas.

The raw fuel gas supply path 7 has a raw fuel gas opening / closing valve 16 as raw fuel gas connecting / disconnecting means for connecting / disconnecting the raw fuel gas to the desulfurizing section 1, ie, the reforming section 3, and a desulfurizing section. A raw fuel gas supply amount adjusting valve 17 for adjusting the supply amount of the raw fuel gas to the fuel cell 1 is provided. The steam supply path 9 is provided with a steam opening / closing means for interrupting the supply of steam to the reforming section 3. A valve 18 is provided, an air supply path 14 is provided with an air opening / closing valve 19 for interrupting the supply of air to the combustion section 4, and a gas fuel supply path 15 is provided with a gas for interrupting the supply of gas fuel to the combustion section 4. A fuel on-off valve 20 and a gas fuel flow control valve 25 for adjusting the supply amount of gas fuel are provided.
Is provided with a generated gas on-off valve 21 for interrupting the outflow of the generated gas from the hydrogen-containing gas generator.

Further, the reforming section 3 is provided with a reforming section temperature sensor 22 as a processing chamber temperature detecting means so as to detect the temperature of the highest temperature in the reforming reaction region inside the reforming section 3. is there. Incidentally, in the gas processing path including the desulfurization section 1, the desulfurization gas path 8, the reforming section 3, the reforming processing gas path 10, and the shift section 5, the temperature of the reforming section 3 becomes highest. 22 detects the temperature of the hottest part in the gas processing path.

The control section C is based on the control information from the operation section S and the detection information of the reforming section temperature sensor 22, the raw fuel gas on-off valve 16, the raw fuel gas supply amount regulating valve 17, The on-off valve 18, the on-off valve 19 for air, the on-off valve 20 for gas fuel, the gas fuel flow control valve 25, and the on-off valve 21 for generated gas are each controlled.

Next, an operation method of the hydrogen-containing gas generator configured as described above will be described. The hydrogen-containing gas generator performs a raw fuel gas replacement process to be described later, and stops in a state where the reforming unit 3 and the shift unit 5 are filled with the desulfurized raw fuel gas. When starting the hydrogen-containing gas generator that has been stopped by performing the processing, the desulfurizing unit 1 is heated by the starting heater 1h, and the reforming unit 4 is heated by the combustion unit 4 based on the start command. A heating process for heating the shift section 5 with the start-up heater 5h is started, and the temperatures of the reforming section 3 and the shift section 5 prevent the deposition of carbon due to the thermal decomposition of the desulfurized raw fuel gas and prevent the condensation of water vapor. When the temperature rises to a temperature that can be achieved, that is, a non-condensing non-carbon deposition temperature,
Steam is supplied to the reforming section 3 to perform a steam replacement process of replacing the desulfurization raw fuel gas inside the reforming section 3 and the shift section 5 with steam, and subsequently, the temperature of the reforming section 3 is reduced. When the temperature is raised to the processable temperature, a process gas supply process for supplying the desulfurization raw fuel gas and the steam to the reforming unit 3 is performed.

When shutting down the hydrogen-containing gas generator,
The supply of steam from the steam generation unit 2 to the reforming unit 3 is continued, and the supply of desulfurized raw fuel gas from the desulfurization unit 1 to the reforming unit 3 is stopped. A steam replacement process for replacing the gas with steam is performed.
When the temperature of the shift unit 5 drops to the non-condensing non-carbon deposition temperature, the supply of steam to the reforming unit 3 is stopped, and the desulfurizing raw fuel gas is supplied from the desulfurizing unit 1 to the reforming unit 3 to perform reforming. A raw fuel gas replacement process for replacing steam inside the section 3 and the shift section 5 with a desulfurized raw fuel gas is performed.

The non-condensing non-carbon deposition temperature is determined by conducting a test in advance. Hereinafter, a test for determining the non-condensing non-carbon deposition temperature will be described. In the test, the reforming section 3 was heated so that the temperature of the highest temperature section became various temperatures, city gas as a raw fuel gas was charged into the reforming section 3 at each temperature, and the charged state was changed. The relationship between the holding time (hereinafter sometimes abbreviated as the filling holding time) and the amount of deposited carbon was examined. FIG. 9 shows the result. The composition of city gas is methane 88 vo
1%, ethane 6 vol%, propane 3 vol%, butane 3 vol%. In the test, the minimum amount of the holding time was set to 20 hours, and the amount of deposited carbon was examined. The minimum time of 20 hours for the filling holding time is considerably longer than the time required for starting by the above-described method and the time required for stopping by the above-described method. If there is no carbon deposition in the gas processing path, it can be determined that carbon deposition does not occur in the gas processing path even if the method is started or stopped by the above method.

As shown in FIG. 9, as a result of examining the state of carbon deposition when the filling holding time was 20 hours, carbon deposition was observed when the temperature of the highest temperature was 500 ° C. As the temperature of the part became lower than 500 ° C., the amount of deposited carbon was reduced. At 450 ° C. or less, no carbon was deposited. Just in case, in the range of 450 ° or less, where no carbon precipitation occurred in the filling holding time of 20 hours,
As a result of examining the state of carbon deposition when the filling and holding time was 1000 hours, it was found that the carbon deposition amount was 0.4 when the temperature was 450 ° C.
At a temperature of 400 ° C. or less, no precipitation of carbon occurred.

Therefore, the non-condensing non-carbon deposition temperature is 450
It is preferable that the temperature be set to not more than 400C. The non-condensing non-carbon deposition temperature must be set to a temperature that can prevent condensation of water vapor. Naturally, the temperature at which water vapor is condensed is such that raw fuel gas is thermally decomposed and carbon is deposited. Since the temperature is lower than the temperature, the lower limit of the setting range of the non-condensing non-carbon deposition temperature is set to a temperature at which dew condensation of water vapor can be prevented.

In the configuration for starting or stopping by the above-described operation method, the temperature in the gas processing path is detected, and the temperature in the gas processing path is the non-condensing non-carbon deposition temperature. When configured to determine that, the temperature of the highest temperature part in the gas processing path is equal to or less than the temperature that can prevent the deposition of carbon from the raw fuel gas, and,
It is necessary to determine that the temperature of the lowest temperature portion is equal to or higher than the temperature at which condensation of water vapor can be prevented. In that case, to determine that the temperature in the gas processing path is the non-condensing non-carbon deposition temperature based on the temperature of the highest temperature part in the gas processing path, the temperature in the gas processing path must be the non-condensing non-carbon deposition temperature. The temperature of the hottest part in the gas processing path, which indicates the temperature, will be checked and set in advance, and the temperature is higher than the temperature at which the temperature of the lowest part of the gas processing path can prevent condensation of steam. In such a state, it is necessary to set the temperature at or below a temperature at which the deposition of carbon from the raw fuel gas can be prevented. Hereinafter, such a temperature set for the temperature of the highest temperature portion in the gas processing path is referred to as a replacement switching set temperature. Incidentally, since the relationship between the highest temperature part and the lowest temperature part in the gas processing path differs depending on the specifications of the hydrogen-containing gas generator, the replacement switching set temperature is set according to the specifications of the hydrogen-containing gas generator. However, for example, in general,
When the temperature of the highest temperature part in the gas processing path is 350 ° C., the temperature of the lowest temperature part is equal to or higher than the temperature at which dew condensation of water vapor can be prevented. , And more preferably in the range of 350 to 400 ° C. By the way, when the temperature of the highest temperature part is 400 ° C., the temperature of the lowest temperature part is about 120 ° C.

When starting or stopping by the above-described operation method, it is performed based on the detected temperature of the highest temperature portion of the gas processing path and the set temperature for replacement switching.

In the present invention, the control unit C is used to automatically perform the above-described operation method. Hereinafter, the control operation of the control unit C for controlling the operation of the hydrogen-containing gas generator will be described based on a time chart shown in FIG. The control unit C includes a replacement switching set temperature set at a non-condensing non-carbon deposition temperature (for example, 400 ° C.) and a reforming set temperature set at a reformable processing temperature at which raw fuel gas can be reformed. Set temperature for processing start (for example,
650 ° C.). The control unit C stores a first set time and a second set time set as described later.

Although the details will be described later, when the hydrogen-containing gas generator is stopped, the raw fuel gas on-off valve 16, the steam on-off valve 18, the air on-off valve 19, the gas fuel on-off valve 2
0 and the on-off valve 21 for product gas are all closed, and the desulfurization raw fuel gas is kept sealed in the gas processing path including the reforming section 3 and the shift section 5 as described above.
When a start command is issued from the operation unit S, the air on-off valve 1
9 and the gas fuel on-off valve 20 are opened to burn the combustion part 4, and the gas fuel flow control valve 25 is adjusted to a predetermined opening. That is, the combustion section 4 is burned at a predetermined set combustion amount, and the heating of the reforming section 3 is started. Note that, based on the start command, the start heater 1h is operated to heat to start heating the desulfurization unit 1, and the start heater 5h is operated to heat to start heating the shift unit 5. 1h and 5h are stopped when the temperature detected by the reforming section temperature sensor 22 rises to the reforming processing start set temperature and the start-up operation ends.

Then, when the temperature detected by the reforming section temperature sensor 22 rises to the set temperature for replacement switching, the steam on-off valve 18 and the generated gas on-off valve 21 are opened. The temperature is maintained until the temperature detected by the internal temperature sensor 22 rises to the reforming process start set temperature. In other words, the desulfurization raw fuel gas in the gas processing path is converted to steam by the generated gas path 1
2, a steam replacement process is performed in which the desulfurization raw fuel gas inside the gas treatment path including the reforming unit 3 and the shift unit 5 is replaced with steam. Is continued until the temperature detected by the reforming section temperature sensor 22 rises to the set temperature for starting the reforming process. In the start-up operation, the time when the steam replacement process is started is determined based on the temperature detected by the reforming unit temperature sensor 22, but the temperature detected by the reforming unit temperature sensor 22 rises to the replacement switching set temperature. Previously, the desulfurization unit 1 was already heated to the desulfurization processing temperature by the start-up heater 1h, and the shift unit 5 was already heated to the shift-processing temperature by the start-up heater 5h, and was heated to a temperature at which dew condensation of water vapor was prevented. are doing. Therefore, even if the steam replacement process is performed,
Water vapor does not condense in each of the desulfurization unit 1 and the shift unit 5.

When the temperature detected by the reforming section temperature sensor 22 rises to the set temperature for starting the reforming process, the raw fuel gas on-off valve 1
The valve 6 is opened, and thereafter, the state is maintained until a stop command is issued from the operation unit S. That is, the raw fuel gas is supplied to the desulfurizing section 1, and the desulfurized raw fuel gas desulfurized in the desulfurizing section 1 is mixed with the steam generated in the steam generating section 2, and the resulting mixture is reformed into the reforming section 3. And the reforming process is started to start the generation of the hydrogen generation gas. Thereafter, the generation of the hydrogen generation gas is continued until a stop command is issued from the operation unit S. Therefore, while preventing the deposition of carbon and the deposition of carbon from the desulfurized raw fuel gas that was charged at the time of the condensation and stoppage of the steam, the desulfurized raw fuel gas and the steam were supplied to the reforming unit 3 to start the reforming process, The generation of the contained gas can be started.

When a stop command is issued from the operation unit S, the on-off valve 19 for air and the on-off valve 20 for gas fuel are closed, and the on-off valve 16 for raw fuel gas is also closed. , Until the temperature detected by the reforming section temperature sensor 22 drops to the replacement switching set temperature. That is, while the combustion in the combustion unit 4 is stopped, the steam in the gas processing path is replaced with steam, and the steam replacement processing is performed. The process is continued until the temperature detected by the temperature sensor 22 decreases to the replacement switching set temperature.

Subsequently, when the temperature detected by the reforming section temperature sensor 22 drops to the replacement switching set temperature, the steam opening / closing valve 18 is closed, and the raw fuel gas opening / closing valve 16 is opened. When the first set time elapses, the generated gas on-off valve 21 is closed, and thereafter, when the second set time elapses, the raw fuel gas on-off valve 16 is closed. During the first set time period, after the steam valve 18 is closed and the raw fuel gas valve 16 is opened, all of the steam in the gas treatment path is pushed out of the apparatus, and the gas treatment is started. The time is set to be longer than the time required for the inside of the passage to be replaced with the desulfurization raw fuel gas. Further, the second set time is set in the gas processing path so that the desulfurization raw fuel gas can be maintained in a state in which the desulfurization raw fuel gas is sealed at a pressure higher than the outside pressure even in a state where the temperature in the gas processing path is reduced to room temperature. The time is set to be longer than the time that the desulfurization raw fuel gas can be charged. That is, the steam in the gas processing path is pushed out of the apparatus by the desulfurization raw fuel gas, and
A raw fuel gas replacement process is performed in which steam inside the gas processing path including the shift unit 5 is replaced with the desulfurized raw fuel gas, and the desulfurized raw fuel gas has a temperature in the gas processing path. Even when the temperature is lowered to room temperature, the air is sealed in a state maintained at the atmospheric pressure or higher, so that air is prevented from entering the gas processing path.

Therefore, poisoning of the reforming catalyst by the sulfur component,
It is possible to prevent the absorption of water by the reforming catalyst and the shift catalyst and the oxidation of the reforming catalyst and the shift catalyst, thereby preventing the reforming and shift performance from lowering.

Hereinafter, second to eighth embodiments of the present invention will be described. In each embodiment, the same components and components having the same functions as those of the first embodiment will be described.
In order to avoid repetition, the description will be omitted by assigning the same reference numerals, and a configuration different from the first embodiment will be mainly described.

[Second Embodiment] Hereinafter, a second embodiment of the present invention will be described. In the second embodiment, the configuration of the hydrogen-containing gas generator is the same as that of the above-described first embodiment, an operation method for operating the hydrogen-containing gas generator, and control for executing the operation method. The control operation of the unit C is different from that of the first embodiment.

Hereinafter, a method of operating the hydrogen-containing gas generator will be described. The hydrogen-containing gas generator is stopped by performing a raw fuel gas replacement process described later, and when starting the hydrogen-containing gas generator stopped by performing the raw fuel gas replacement process as described above, As in the first embodiment, when the temperature of the reforming unit 3 and the shift unit 5 rises to the non-condensing non-carbon deposition temperature, steam is supplied to the reforming unit 3 and the inside of the reforming unit 3 and the shift unit 5 are changed. A steam replacement process of replacing the desulfurized raw fuel gas with steam is performed. Subsequently, when the temperature of the reforming unit 3 is raised to a temperature at which the reforming process can be performed, the desulfurized raw fuel gas and the steam are supplied to the reforming unit 3. The processing target gas supply processing is performed.

When shutting down the hydrogen-containing gas generator,
When the temperatures of the reforming section 3 and the shift section 5 decrease to the non-condensing non-carbon deposition temperature, the supply of the desulfurization raw fuel gas from the desulfurizing section 1 to the reforming section 3 is continued. The supply of steam is stopped, and a raw fuel gas replacement process for replacing the gas inside the reforming unit 3 and the shift unit 5 with the desulfurized raw fuel gas is performed.

Hereinafter, the control operation of the control unit C will be described with reference to a time chart shown in FIG. It should be noted that, similarly to the first embodiment, the control unit C has a set temperature for replacement switching,
A set temperature for starting the reforming process, a first set time, and a second set time are stored.

Since the control operation at the time of starting is the same as that of the first embodiment, the description is omitted. When a stop command is issued from the operation unit S, the air on-off valve 19 and the gas fuel on-off valve 20 are closed, and this state is thereafter changed to the detection temperature of the reforming unit temperature sensor 22 and the set temperature for replacement switching. Keep it down to. That is, the state in which the combustion of the combustion unit 4 is stopped and the mixture of the desulfurization raw fuel gas and the steam flows in the gas processing path until the temperature detected by the reforming unit temperature sensor 22 reaches the replacement switching set temperature. Continued until lowered.

Subsequently, when the temperature detected by the reforming section temperature sensor 22 drops to the replacement switching set temperature, the steam opening / closing valve 18 is closed. The valve 21 is closed, and thereafter, when the second set time has elapsed, the raw fuel gas on-off valve 16 is closed. That is, the gas in the gas processing path is pushed out of the apparatus by the desulfurization raw fuel gas, and the steam in the gas processing path including the reforming section 3 and the shift section 5 is replaced by the desulfurization raw fuel gas. Fuel gas replacement processing is performed, and the desulfurization raw fuel gas is sealed in the gas processing path in a state where the temperature in the gas processing path is maintained at an external pressure or higher even when the temperature in the gas processing path is reduced to room temperature. Air is prevented from entering the path.

Therefore, the poisoning of the reforming catalyst by the sulfur component,
It is possible to prevent the absorption of water by the reforming catalyst and the shift catalyst and the oxidation of the reforming catalyst and the shift catalyst, thereby preventing the reforming and shift performance from lowering.

[Third Embodiment] Hereinafter, a third embodiment of the present invention will be described. First, the configuration of the hydrogen-containing gas generator will be described. As shown in FIG. 2, in addition to the configuration of the hydrogen-containing gas generation device of each of the first and second embodiments, the hydrogen-containing gas generation device includes A selective oxidizing unit 6 for selectively oxidizing the remaining carbon monoxide gas is provided. This third
The hydrogen-containing gas generator of the embodiment can generate a hydrogen-containing gas having a lower carbon monoxide concentration (for example, 10 ppm or less) than the hydrogen-containing gas generators of the first and second embodiments. It is. As shown in FIG. 2, the shift unit 5 and the selective oxidation unit 6 are connected by a shift process gas path 11 so that a shift process gas is supplied from the shift unit 5 to the selective oxidation unit 6. Connect to the selective oxidation unit 6,
The shift processing gas after the selective oxidation in the selective oxidation section 6 is supplied as a product gas to a gas consumer (for example, a fuel cell) through a product gas passage 12.

In the selective oxidation section 6, the carbon monoxide gas remaining in the shift gas is selectively oxidized by, for example, the catalytic action of ruthenium. The selective oxidizing section 6 is provided with a starting heater 6h including an electric heater or the like for heating the selective oxidizing section 6 to a selective oxidizing temperature at the time of activation.

Next, a method of operating the hydrogen-containing gas generator configured as described above will be described. The hydrogen-containing gas generator performs a raw fuel gas replacement process described below, and stops in a state where the reforming unit 3, the shift unit 5, and the selective oxidizing unit 6 are filled with the desulfurized raw fuel gas. When starting the hydrogen-containing gas generator that has been stopped by performing the raw fuel gas replacement process, the desulfurization unit 1 is heated by the start heater 1h based on the start command, and the reforming unit is heated by the combustion unit 4. 4, the heating unit 5h is heated by the starting heater 5h, and the heating process of heating the selective oxidizing unit 6 by the starting heater 6h is started, and the reforming unit 3, the converting unit 5, and the selective oxidizing unit 6 are heated. When the temperature rises to the non-condensing non-carbon deposition temperature, steam is supplied to the reforming section 3 to convert the desulfurized raw fuel gas inside the reforming section 3, the shift section 5 and the selective oxidizing section 6 with steam. A steam replacement process for replacement is performed, and then the temperature of the reforming section 3 rises to a temperature at which the reforming process is possible. Then, perform the untreated gas supply process for supplying the desulfurized raw fuel gas and steam to the reforming unit 3.

When shutting down the hydrogen-containing gas generator,
The supply of steam from the steam generation unit 2 to the reforming unit 3 is continued, and the supply of desulfurized raw fuel gas from the desulfurization unit 1 to the reforming unit 3 is stopped. A steam replacement process is performed to replace the gas inside the section 6 with steam, and subsequently, when the temperatures of the reforming section 3, the shift section 5 and the selective oxidizing section 6 decrease to the non-condensing non-carbon deposition temperature, the reforming section The supply of steam to the fuel cell 3 is stopped, and the desulfurization raw fuel gas is supplied from the desulfurization unit 1 to the reforming unit 3, and the steam inside the reforming unit 3, the shift unit 5, and the selective oxidation unit 6 is removed. A raw fuel gas replacement process for replacement is performed.

Next, a control operation of the control unit C for executing the above-described operation method will be described. The control unit C performs the same control operation as the control operation described in the first embodiment based on the time chart shown in FIG. However, the method of setting the replacement switching set temperature, the first set time, and the second set time is different from the first embodiment.

In the start-up operation, the point in time when the steam replacement process is started is determined based on the temperature detected by the reforming unit temperature sensor 22. Desulfurization unit 1 before rising to
Are already heated to the desulfurization processing temperature by the start-up heater 1h, the shift converter 5 is already heated to the shift-processing temperature by the start-up heater 5h, and the selective oxidizing section 6 is already heated to the selective oxidation processing temperature by the start-up heater 6h. Therefore, the temperature is raised to a temperature at which condensation of water vapor is prevented. Therefore, even if the steam replacement process is performed, the steam does not condense in each of the desulfurization unit 1, the shift unit 5, and the selective oxidation unit 6.

In the third embodiment, the gas processing paths are the desulfurization section 1, the desulfurization gas path 8, the reforming section 3, the reforming gas path 10, the shift section 5, the shift processing gas path 11, and the selective oxidizing section 6.
Consists of Therefore, the set temperature for replacement switching is:
Since the temperature is set with respect to the temperature of the hottest part in the gas processing path, the replacement switching set temperature is set at the lowest part of the gas processing path including the reforming unit 3, the shift unit 5, and the selective oxidizing unit 6 as described above. In a state where the temperature is equal to or higher than the temperature at which condensation of water vapor can be prevented, the temperature is set to a temperature equal to or lower than the temperature at which carbon deposition of the raw fuel gas can be prevented. Incidentally, as in the first embodiment described above, the set range of the replacement switching set temperature is, for example, preferably in the range of 350 to 450 ° C., and in the range of 350 to 4 ° C.
The range of 00 ° C is more preferable.

During the first set time, after the steam on-off valve 18 is closed and the raw fuel gas on-off valve 16 is opened,
As described above, all of the steam in the gas processing path including the reforming section 3, the shift section 5, and the selective oxidizing section 6 is pushed out of the apparatus, and the gas processing path is replaced with the desulfurization raw fuel gas. Is set longer than the time required for The second set time is set such that the gas processing path can be maintained in a state in which the desulfurization raw fuel gas is sealed at a pressure equal to or higher than the outside pressure in the gas processing path even when the temperature in the above-described gas processing path is lowered to room temperature. It is set to be longer than the time in which the desulfurization raw fuel gas can be sealed.

[Fourth Embodiment] Hereinafter, a fourth embodiment of the present invention will be described. In the fourth embodiment, the configuration of the hydrogen-containing gas generator is the same as that of the third embodiment.

Next, an operation method of the hydrogen-containing gas generator configured as described above will be described. The hydrogen-containing gas generator is stopped after performing a raw fuel gas replacement process described below, and when starting the hydrogen-containing gas generator stopped by performing the raw fuel gas replacement process as described above,
As in the third embodiment, when the temperatures of the reforming unit 3, the shift unit 5, and the selective oxidizing unit 6 rise to the non-condensing non-carbon deposition temperature,
Steam is supplied to the reforming unit 3 to perform a steam replacement process of replacing the desulfurized raw fuel gas inside the reforming unit 3, the shift unit 5, and the selective oxidation unit 6 with steam. When the temperature rises to the temperature at which the reforming process is possible, a process gas supply process for supplying the desulfurization raw fuel gas and the steam to the reforming unit 3 is performed.

When shutting down the hydrogen-containing gas generator,
When the temperatures of the reforming section 3, the shift section 5 and the selective oxidizing section 6 decrease to the non-condensing non-carbon deposition temperature, the reforming is performed in a state where the supply of the desulfurized raw fuel gas from the desulfurizing section 1 to the reforming section 3 is continued. The supply of steam to the reforming unit 3 is stopped, and a raw fuel gas replacement process is performed to replace the gas inside the reforming unit 3, the shift unit 5, and the selective oxidizing unit 6 with the desulfurized raw fuel gas.

Next, a control operation of the control unit C for executing the above-described operation method will be described. The control unit C executes a control operation similar to the control operation described in the above-described second embodiment based on the time chart shown in FIG. However, the replacement switching set temperature, the first set time, and the second set time are different from the second embodiment, and are set in the same manner as the third embodiment.

[Fifth Embodiment] Hereinafter, a fifth embodiment of the present invention will be described. First, the configuration of the hydrogen-containing gas generator will be described. As shown in FIG. 3, in the hydrogen-containing gas generator, the desulfurizer 1 is omitted and the raw fuel gas supply path 7 is directly connected to the configuration of the hydrogen-containing gas generator of the first and second embodiments. The steam supply path 9 is connected to the raw fuel gas supply path 7 so that the raw fuel gas flowing through the raw fuel gas supply path 7 is mixed with the steam generated by the steam generation section 2. Connected.

In the fifth embodiment, since the desulfurization unit 1 is not provided, the raw fuel gas is directly supplied to the reforming unit 3, so that the raw fuel gas contains no sulfur component. Alternatively, it is preferable to use a hydrocarbon-based gas which has a low sulfur component content and does not poison the reforming catalyst.

Next, a method of operating the hydrogen-containing gas generator configured as described above will be described. The hydrogen-containing gas generator performs a raw fuel gas replacement process described below, and stops in a state where the reforming unit 3 and the shift unit 5 are filled with the raw fuel gas. When starting the hydrogen-containing gas generator stopped by performing
On the basis of the start command, the reforming section 4 is heated by the combustion section 4,
When a heating process for heating the shift section 5 by the start-up heater 5h is started and the temperatures of the reforming section 3 and the shift section 5 rise to the non-condensing non-carbon deposition temperature, steam is supplied to the reforming section 3. Then, a steam replacement process for replacing the raw fuel gas inside the reforming section 3 and the shift section 5 with steam is performed. Subsequently, when the temperature of the reforming section 3 is raised to a reformable temperature, the reforming is performed. A processing target gas supply process for supplying the raw fuel gas and the steam to the unit 3 is performed.

When shutting down the hydrogen-containing gas generator,
The supply of steam from the steam generation unit 2 to the reforming unit 3 is continued and the supply of the raw fuel gas to the reforming unit 3 is stopped, and the gas inside the reforming unit 3 and the shift unit 5 is converted to steam. When the temperature of the reforming section 3 and the shift section 5 is reduced to the non-condensing non-carbon deposition temperature, the supply of steam to the reforming section 3 is stopped and the steam is replaced to the reforming section 3. The raw fuel gas is supplied, and a raw fuel gas replacement process for replacing the steam inside the reforming unit 3 and the shift unit 5 with the raw fuel gas is performed.

Next, the control operation of the control unit C for executing the above-described operation method will be described. The control unit C performs the same control operation as the control operation described in the first embodiment based on the time chart shown in FIG. However, the method of setting the replacement switching set temperature, the first set time, and the second set time is different from the first embodiment.

In the third embodiment, the gas processing path includes the reforming section 3, the reforming gas path 10, and the shift section 5. Therefore, the replacement switching set temperature is set for the temperature of the highest temperature part in the gas processing path. Therefore, the replacement switching set temperature is such that the temperature of the lowest part of the gas processing path is equal to the condensation of water vapor. The temperature is set to be equal to or higher than the temperature at which the deposition of carbon in the raw fuel gas can be prevented. Incidentally, similarly to the first embodiment, the setting range of the replacement switching set temperature is as follows.
For example, a range of 350 to 450 ° C. is preferable,
The range of -400 ° C is more preferable.

For the first set time, after the steam on-off valve 18 is closed and the raw fuel gas on-off valve 16 is opened,
The time is set to be equal to or longer than the time required for all of the water vapor in the gas processing path to be pushed out of the apparatus and replaced in the gas processing path with the raw fuel gas. The second set time is set so that the desulfurization raw fuel gas can be maintained in a state in which the desulfurization raw fuel gas is sealed in the gas processing path at an atmospheric pressure or higher even when the temperature in the gas processing path is lowered to room temperature. The time is set to be longer than the time that the desulfurization raw fuel gas can be sealed in the passage.

[Sixth Embodiment] Hereinafter, a sixth embodiment of the present invention will be described. In the sixth embodiment, the configuration of the hydrogen-containing gas generator is the same as that of the fifth embodiment.

Next, a method of operating the hydrogen-containing gas generator configured as described above will be described. The hydrogen-containing gas generator is stopped after performing a raw fuel gas replacement process described below, and when starting the hydrogen-containing gas generator stopped by performing the raw fuel gas replacement process as described above,
As in the fifth embodiment, when the temperatures of the reforming section 3 and the shift section 5 rise to the non-condensing non-carbon deposition temperature, steam is supplied to the reforming section 3 and the reforming section 3 and the shift section 5 are supplied. When a steam replacement process is performed to replace the raw fuel gas in the inside with steam, and then the temperature of the reforming unit 3 is raised to a temperature at which the reforming process is possible,
A processing target gas supply process for supplying raw fuel gas and steam to the reforming unit 3 is performed.

When shutting down the hydrogen-containing gas generator,
When the temperatures of the reforming section 3 and the shift section 5 decrease to the non-condensing non-carbon deposition temperature, the supply of steam to the reforming section 3 is stopped while the supply of the raw fuel gas to the reforming section 3 is continued. Then, a raw fuel gas replacement process for replacing the gas inside the reforming unit 3 and the shift unit 5 with the raw fuel gas is performed.

Next, the control operation of the control unit C for executing the above-described operation method will be described. The control unit C executes a control operation similar to the control operation described in the above-described second embodiment based on the time chart shown in FIG. However, the replacement switching set temperature, the first set time, and the second set time are different from the second embodiment and are set in the same manner as the fifth embodiment.

[Seventh Embodiment] Hereinafter, a seventh embodiment of the present invention will be described. As shown in FIG. 6, in the seventh embodiment, the hydrogen-containing gas generator includes, in addition to the configuration of the hydrogen-containing gas generator of the first embodiment, a combustion part temperature for detecting the temperature of the combustion part 4. A sensor 24 is provided, and the reforming unit temperature sensor 22 detects a temperature occupying the widest range in the temperature distribution in the reforming reaction region inside the reforming unit 3, that is, a temperature at which the reforming process is mainly performed. It is provided. Incidentally, the combustion part temperature sensor 24 detects, for example, a temperature as close as possible to the highest temperature in the reforming reaction region of the reforming part 3, for example, combustion on a heat transfer wall dividing the reforming part 3 and the combustion part 4. It is provided so as to detect the temperature and the like on the part 4 side.

Hereinafter, an operation method of the hydrogen-containing gas generator will be described. The hydrogen-containing gas generator is stopped by performing a raw fuel gas replacement process described later, and when starting the hydrogen-containing gas generator stopped by performing the raw fuel gas replacement process as described above, As in the first embodiment, based on the start command, the desulfurization unit 1 is heated by the start heater 1h, the reforming unit 4 is heated by the combustion unit 4, and the shift unit 5 is heated by the start heater 5h. When the temperature of the reforming unit 3 and the shift unit 5 rises to the non-condensing non-carbon deposition temperature, steam is supplied to the reforming unit 3 and the inside of the reforming unit 3 and the shift unit 5 is started. A steam replacement process of replacing the desulfurized raw fuel gas with steam is performed. Subsequently, when the temperature of the reforming unit 3 is raised to a temperature at which the reforming process can be performed, the desulfurized raw fuel gas and the steam are supplied to the reforming unit 3. The processing target gas supply processing is performed. Further, in the seventh embodiment, the temperature of the combustion unit 4 is increased until the temperature of the reforming unit 3 rises to the non-condensing non-carbon deposition temperature and during the steam replacement process. Operate so that the temperature is lower than the set temperature.

When shutting down the hydrogen-containing gas generator,
As in the first embodiment, the supply of steam from the steam generation unit 2 to the reforming unit 3 is continued, and the supply of desulfurization raw fuel gas from the desulfurization unit 1 to the reforming unit 3 is stopped. 3. Metamorphic part 5
And performing a steam replacement process of replacing the gas inside the selective oxidation unit 6 with steam, and subsequently, when the temperatures of the reforming unit 3, the shift unit 5, and the selective oxidation unit 6 decrease to the non-condensing non-carbon deposition temperature, The supply of steam to the reforming unit 3 is stopped, and the desulfurizing raw fuel gas is supplied from the desulfurizing unit 1 to the reforming unit 3 to desulfurize the steam inside the reforming unit 3, the shift unit 5, and the selective oxidizing unit 6. A raw fuel gas replacement process for replacing the raw fuel gas is performed.

Hereinafter, the control operation of the control unit C will be described with reference to a time chart shown in FIG. The control unit C has a set temperature for heating at startup, a set temperature for switching at startup, a set temperature for replacement at stop, a set temperature for reforming processing, a first set time, a second set time, and The third set time set to perform the setting is stored.

In the seventh embodiment, when the temperature detected by the reforming section temperature sensor 22 is 250 ° C., the temperature of the lowest temperature section in the gas processing path is higher than the temperature at which dew condensation of water vapor can be prevented. The startup replacement switching set temperature set to the non-condensing non-carbon deposition temperature is, for example, 250 to
It is preferable to set the temperature in the range of 450 ° C.
It is more preferable to set the temperature in the range of 00 ° C, and in the seventh embodiment, the temperature is set to 300 ° C. Incidentally, when the temperature detected by the reforming section temperature sensor 22 is 250 ° C., the temperature of the lowest temperature section is about 105 ° C. The set temperature for replacement switching at stop is the same as in the first embodiment.
The temperature is set to 400 ° C., that is, the non-condensing non-carbon deposition temperature, and the set temperature for heating at the time of startup is also set to the non-condensing non-carbon deposition temperature, for example, 400 ° C.

As will be described in detail later, when the hydrogen-containing gas generator is shut down, the on-off valve 16 for raw fuel gas, the on-off valve 18 for steam, the on-off valve 19 for air, and the on-off valve 2 for gas fuel
0 and the on-off valve 21 for product gas are all closed, and the desulfurization raw fuel gas is kept sealed in the gas processing path including the reforming section 3 and the shift section 5 as described above.
When a start command is issued from the operation unit S, the air on-off valve 1
9 and the gas fuel on-off valve 20 are opened to burn the combustion part 4, and the generated gas on-off valve 21 is opened.
The gas fuel flow control valve 25 is controlled so that the temperature detected by the combustion section temperature sensor 24 becomes the set temperature for heating at startup.
Note that, based on the start command, the start heater 1h is operated to heat to start heating the desulfurization unit 1, and the start heater 5h is operated to heat to start heating the shift unit 5. 1h and 5h are stopped when the temperature detected by the reforming section temperature sensor 22 rises to the reforming processing start set temperature and the start-up operation ends.

When the temperature detected by the reforming section temperature sensor 22 rises to the start-time replacement switching set temperature, the steam open / close valve 18 is opened, and thereafter, until the third set time elapses. The gas fuel flow control valve 2 is controlled so that the temperature detected by the combustion part temperature sensor 24 is maintained at the set heating start temperature.
5 is continued, and after the third set time has elapsed, the gas fuel flow control valve 25 is controlled so that the temperature detected by the reforming unit temperature sensor 22 becomes the set temperature for starting the reforming process, and the reforming is performed. When the temperature detected by the temperature sensor 22 rises to the set temperature for starting the reforming process, the raw fuel gas on-off valve 16 is opened, and thereafter, the state is maintained until a stop command is issued from the operation unit S. .

It should be noted that the third set time is set to the steam on-off valve 18.
After the valve is closed, all of the desulfurization raw fuel gas in the gas processing path is pushed out of the apparatus, and the time is set to be equal to or longer than the time required for the gas processing path to be replaced with steam. In short, during the elapse of the third set time, the desulfurization raw fuel gas in the gas processing path is pushed out of the apparatus through the generated gas path 12 by steam, and the gas processing path including the reforming section 3 and the shift section 5 A steam replacement process is performed in which the desulfurization raw fuel gas inside the fuel cell is replaced by steam.

That is, in the seventh embodiment, until the temperature detected by the reforming section temperature sensor 22 rises to the set temperature for replacement switching at the time of starting, and while the steam replacement processing is performed, the combustion section 4 The temperature is controlled so as to be equal to or lower than the set temperature for starting heating set at the non-carbon deposition temperature. Therefore, even if there is a temperature distribution in the reforming section 3, the entire area in the reforming section 3 is controlled so as to be lower than the non-carbon deposition temperature.
Supplying the desulfurized raw fuel gas and steam to the reforming unit 3 while preventing carbon deposition from the desulfurized raw fuel gas charged at the time of stoppage more reliably than in the first to sixth embodiments. Then, the reforming process can be started, and the generation of the hydrogen-containing gas can be started.

When a stop command is issued from the operation unit S, the on-off valve for air 19 and the on-off valve 20 for gas fuel are closed, and the on-off valve 16 for raw fuel gas is also closed. , Until the temperature detected by the reforming section temperature sensor 22 falls to the set temperature for switching at the time of stoppage. That is,
The combustion in the combustion unit 4 is stopped, and a steam replacement process is performed in which the gas in the gas processing path is replaced with steam. This is continued until the detected temperature of 22 drops to the set temperature for switching at the time of stoppage. Subsequently, when the temperature detected by the reforming unit temperature sensor 22 decreases to the set temperature for switching at the time of stoppage, the steam on-off valve 18 is closed, and the raw fuel gas on-off valve 16 is opened. First
When the set time has elapsed, the generated gas on-off valve 21 is closed, and thereafter, when the second set time has elapsed, the raw fuel gas on-off valve 16 is closed.

That is, the steam in the gas treatment path is pushed out of the apparatus by the desulfurization raw fuel gas, and the steam in the gas treatment path including the reforming section 3 and the shift section 5 is replaced by the desulfurization raw fuel gas. The raw fuel gas replacement process is performed, and the desulfurized raw fuel gas is sealed in the gas processing path in a state in which the temperature in the gas processing path is maintained at or above the atmospheric pressure even when the temperature in the gas processing path is lowered to room temperature. In addition, air is prevented from entering the gas processing path.

[Eighth Embodiment] An eighth embodiment of the present invention will be described below. In the eighth embodiment, the configuration of the hydrogen-containing gas generator is the same as that of the above-described seventh embodiment, an operation method for operating the hydrogen-containing gas generator, and control for executing the operation method. The control operation of the unit C is different from that of the seventh embodiment.

Hereinafter, an operation method of the hydrogen-containing gas generator will be described. The hydrogen-containing gas generator is stopped after performing a raw fuel gas replacement process described below, and a startup method for starting the hydrogen-containing gas generator stopped by performing the raw fuel gas replacement process as described above includes: The description is omitted because it is the same as the seventh embodiment.

When shutting down the hydrogen-containing gas generator,
As in the second embodiment, when the temperatures of the reforming section 3 and the shift section 5 decrease to the non-condensing non-carbon deposition temperature, the supply of the desulfurized raw fuel gas from the desulfurizing section 1 to the reforming section 3 is continued. Then, the supply of steam to the reforming unit 3 is stopped, and a raw fuel gas replacement process for replacing the gas inside the reforming unit 3 and the shift unit 5 with the desulfurized raw fuel gas is performed.

Hereinafter, the control operation of the control unit C will be described with reference to a time chart shown in FIG. Note that, similarly to the seventh embodiment, the control unit C includes a set temperature for heating at startup, a set temperature for replacement switching at startup, a set temperature for replacement switching at stop, a set temperature for reforming process start, a first set temperature for reforming processing, Time, second
The set time and the third set time are stored.

The control operation at the time of starting is the same as that of the above-described seventh embodiment, and the description is omitted. When a stop command is issued from the operation unit S, the air on-off valve 19 and the gas fuel on-off valve 20 are closed. Maintain until the temperature drops to the set temperature. That is, the state in which the combustion of the combustion unit 4 is stopped and the mixture of the desulfurization raw fuel gas and the steam flows in the gas processing path depends on the detection temperature of the reforming unit temperature sensor 22 being the stop replacement set temperature. It continues until it falls to.

Subsequently, when the temperature detected by the reforming section temperature sensor 22 decreases to the set temperature for switching at the time of stoppage, the on-off valve 18 for steam is closed. Valve 21 is closed, and then the second
When the set time has elapsed, the raw fuel gas on-off valve 16 is closed. That is, the gas in the gas processing path is pushed out of the apparatus by the desulfurization raw fuel gas, and the steam in the gas processing path including the reforming section 3 and the shift section 5 is replaced by the desulfurization raw fuel gas. Fuel gas replacement processing is performed, and the desulfurization raw fuel gas is sealed in the gas processing path in a state where the temperature in the gas processing path is maintained at an external pressure or higher even when the temperature in the gas processing path is reduced to room temperature. Air is prevented from entering the path.

[Another Embodiment] Next, another embodiment will be described. (A) In each of the above embodiments, after the steam replacement process at the time of startup and before the reforming process is started, the on-off valve 21 for generated gas is maintained in the open state to flow steam. Although the case of continuing is illustrated, when the steam replacement processing is completed, the steam on-off valve 18 and the production gas on-off valve 21 are once closed to maintain the steam in a sealed state, and at the start of the reforming process, Alternatively, the on-off valve 18 for steam and the on-off valve 21 for generated gas may be opened. In each of the first and third embodiments, the generated gas on-off valve 21 is maintained in an open state after the steam replacement process at the time of stoppage and before the raw fuel gas replacement process is started. Although the case where the steam is continued to flow has been exemplified, once the steam replacement process is completed, the steam-operated on-off valve 18 and the production gas on-off valve 21 are once closed to maintain the steam in a sealed state, and the raw fuel gas At the start of the replacement process, the steam on-off valve 18 and the generated gas on-off valve 21 may be opened again.

(B) In each of the above embodiments, when the raw fuel gas replacement processing is completed at the time of stoppage, the production gas on-off valve 21 and the raw fuel gas on-off valve 16 are closed, and the gas processing path is changed. Although the case where the desulfurized raw fuel gas is sealed in the gas processing path in a state where the pressure does not become negative even when the temperature drops to room temperature has been described as an example, the generated gas on-off valve 21 and the raw fuel gas By maintaining the valve 16 in the open state and adjusting the raw fuel gas supply amount adjusting valve 17, a small amount of desulfurized raw fuel gas is kept flowing so that air does not enter from outside into the gas processing path. May be.

Alternatively, a pressure sensor for detecting the pressure in the gas processing path is provided, and the pressure sensor detects the pressure in the gas processing path in a state in which the desulfurization raw fuel gas is sealed, and detects the detected pressure. However, when the pressure drops to a set pressure which is set to a pressure slightly higher than the outside air pressure in advance, the raw fuel gas on-off valve 1
By opening the valve 6 and additionally supplying the desulfurization raw fuel gas, the inside of the gas treatment path may be maintained at a negative pressure. In this case, since the pressure at which the desulfurization raw fuel gas is sealed in the gas processing path can be reduced, the pressure resistance specification of the hydrogen-containing gas generator can be reduced, and the cost can be reduced.

(C) As a specific configuration for determining that the temperature in the gas processing path is the non-condensing non-carbon deposition temperature, the configuration exemplified in the above embodiment, that is, the highest temperature part in the gas processing path However, the present invention is not limited to the configuration in which the determination is made based on the temperature. For example, the determination may be made based on the temperature of the lowest temperature part in the gas processing path, or the determination may be made based on the temperature of both the highest temperature part and the lowest temperature part in the gas processing path. good. Alternatively, at the time of startup, the determination may be made based on the lapse of time after the combustion of the combustion unit 3 is started, and at the time of shutdown, the determination may be made based on the lapse of time after the combustion of the combustion unit 3 is stopped. May be configured.

(D) In the first to sixth embodiments, the air opening / closing valve 21 is maintained in the closed state based on the start command from the operating section S, and the air opening / closing valve 21 is maintained in the closed state. The case where the valve 19 and the gas fuel on-off valve 20 are opened to burn the combustion unit 4 and control the temperature of the reforming unit 3 to be increased to the replacement switching set temperature is illustrated. Alternatively, based on a start command from the operation unit S, the on-off valve 21 for product gas is opened, and the on-off valve 19 for air and the on-off valve 20 for gas fuel are opened to burn the combustion unit 4. Then, control may be performed so as to start raising the temperature of the reforming section 3. In this case, it is possible to lower the pressure resistance specification of the hydrogen-containing gas generator, so that the cost can be reduced.

(E) In the above embodiment, the hydrogenation recycle path 23 is connected to the reforming gas path 10,
As a hydrogen source for desulfurization treatment in the desulfurization unit 1, the reforming unit 3
Although a case where a part of the reforming gas discharged from the fuel cell is used has been described as an example,
May be connected to the production gas path 12, and a part of the shift gas discharged from the shift unit 5 may be used as a hydrogen source for the desulfurization process in the desulfurization unit 1.

(F) In executing the operation method of the present invention, in the above embodiment, the raw fuel gas on-off valve 16, the steam on-off valve 18, the air on-off valve 19, the gas fuel on-off valve 20, The operation of the gas fuel flow control valve 25 and the production gas on-off valve 21 has been described as being configured to be automatically operated using the control unit C, but may be configured to be performed manually.

(G) The operation method described in each of the seventh and eighth embodiments is provided with a selective oxidation unit 6 in addition to the configuration exemplified in the third embodiment, that is, the configuration of the seventh embodiment. May be executed in the hydrogen-containing gas generator having the above-described configuration, or the configuration illustrated in the fifth embodiment, that is, the hydrogen-containing gas generator having the configuration in which the desulfurization unit 1 is omitted from the configuration of the seventh embodiment. .

(H) In each of the above-described seventh and eighth embodiments, the temperature detection locations of the reforming section temperature sensor 22 and the combustion section temperature sensor 24 can be changed. For example, the reforming unit temperature sensor 22 is, as in the first embodiment,
The temperature of the portion where the temperature is highest in the reforming reaction region of the reforming section 3 or the temperature of the portion exhibiting the temperature corresponding to the average temperature in the reforming reaction region may be detected. Further, the combustion section temperature sensor 24 may detect the temperature in the combustion chamber of the combustion section 3.

(I) In the above embodiment, the case where the reformer R of the present invention is used to constitute the hydrogen-containing gas generator is illustrated. However, the reformer R may be used alone. It is. When the reformer R is used alone, in the above embodiment, the desulfurization unit 1, the shift unit 5, and the selective oxidation unit 6 are omitted, and the raw fuel gas supply path 7 and the product gas path 12 are directly connected to each other. What is necessary is just to connect to the reforming part 3, and the control part C should be comprised so that the control operation similar to each said embodiment may be performed.

(G) Specific examples of the raw fuel gas are not limited to the city gas exemplified in the above embodiment, and various hydrocarbon-based gases such as propane and butane can be used. is there.

[Brief description of the drawings]

FIG. 1 is a system diagram of a hydrogen-containing gas generator according to first and second embodiments.

FIG. 2 is a system diagram of a hydrogen-containing gas generator according to third and fourth embodiments.

FIG. 3 is a system diagram of a hydrogen-containing gas generator according to fifth and sixth embodiments.

FIG. 4 is a diagram showing a time chart of a control operation of the hydrogen-containing gas generator according to the first, third, and fifth embodiments.

FIG. 5 is a diagram showing a time chart of a control operation of the hydrogen-containing gas generator according to the second, fourth, and sixth embodiments.

FIG. 6 is a system diagram of a hydrogen-containing gas generator according to seventh and eighth embodiments.

FIG. 7 is a diagram showing a time chart of a control operation of the hydrogen-containing gas generator according to the seventh embodiment.

FIG. 8 is a time chart of a control operation of the hydrogen-containing gas generator according to the eighth embodiment.

FIG. 9 is a graph showing the relationship between temperature, filling retention time, and carbon deposition amount.

[Explanation of symbols]

 Reference Signs List 3 processing chamber 4 heating section 16 raw fuel gas intermittent means 18 steam intermittent means 22 processing chamber temperature detecting means 24 heating section temperature detecting means C control means

Claims (4)

[Claims] 1. A processing chamber for supplying a hydrocarbon-based raw fuel gas and steam and reforming the raw fuel gas into a hydrogen-containing gas by the steam is provided, and the processing chamber is filled with the raw fuel gas. A starting method for heating the processing chamber in a heating unit based on a start command, wherein the temperature of the processing chamber is reduced to an original value. When the temperature is raised to a temperature that can prevent carbon deposition due to thermal decomposition of the fuel gas and prevent dew condensation of the steam, steam is supplied to the processing chamber, and the raw fuel gas inside the processing chamber is replaced with the steam. A method for activating a reformer, which sequentially performs a steam replacement process and a process of supplying raw fuel gas and steam to the process chamber when the temperature of the process chamber rises to a temperature at which the reforming process is possible. 2. A process in which the temperature of the processing chamber rises to a temperature at which carbon deposition due to thermal decomposition of the raw fuel gas can be prevented and condensation of steam is prevented, and during the steam replacement process. The method according to claim 1, wherein the operation is performed such that the temperature of the heating unit is equal to or lower than a set temperature. 3. A processing chamber for supplying a hydrocarbon-based raw fuel gas and steam and reforming the raw fuel gas into a hydrogen-containing gas by the steam is provided, and the processing chamber is filled with the raw fuel gas. A processing chamber temperature detecting means for detecting a temperature of the processing chamber, a steam interrupting means for interrupting the supply of steam to the processing chamber, A raw fuel gas interrupting means for interrupting the supply of the raw fuel gas to the chamber; and a control means for managing the operation of the reformer, wherein the heating unit heats the processing chamber in the heating unit based on the start command. When processing is started, and based on the detection information of the processing chamber temperature detecting means, the temperature of the processing chamber is raised to a temperature at which carbon deposition due to thermal decomposition of the raw fuel gas can be prevented and condensation of water vapor can be prevented. Supplies steam to the processing chamber And a steam replacement process for replacing the raw fuel gas inside the processing chamber with steam, and when the temperature of the processing chamber is raised to a temperature at which the reforming process can be performed, the raw fuel gas and the steam are transferred to the processing chamber. A reformer configured to control the operations of the steam intermittent means and the raw fuel gas intermittent means so as to sequentially perform the supplying process. 4. A heating section temperature detecting means for detecting a temperature of the heating section, wherein the control means is capable of preventing the temperature of the processing chamber from depositing carbon due to thermal decomposition of a raw fuel gas and condensing water vapor. Until the temperature is raised to a temperature at which the temperature can be prevented, and during the steam replacement process, based on the detection information of the heating unit temperature detection means, the temperature of the heating unit is set to be equal to or less than a set temperature. The reforming apparatus according to claim 3, wherein the reforming apparatus is configured to control a heating operation of the heating unit.