JP2003212505A - Apparatus for producing hydrogen-containing gas and method of controlling quantity of production of hydrogen-containing gas - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To establish a technique to control the production quantity of a hydrogen-containing gas by which the quantity the hydrogen-containing gas is easily increased in a hydrogen-containing gas production apparatus provided with a steam production part for heating water by a steam production part heating means to produce steam and a reforming part for reforming the hydrocarbon-containing gas heated with a reforming part heating means by using steam produced in the steam production part. <P>SOLUTION: A treatment for increasing the quantity of the production of steam is carried out to increase the quantity of the production of steam in the steam production part before the supply quantity of the gaseous raw material to the reforming part is increased in order to increase the quantity of the production of the hydrogen-containing gas. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a steam generating section for heating water with a steam generating section heating means to generate steam.
Reformation processing unit: A reforming processing unit that is heated by a heating unit and reforms a hydrocarbon-based raw fuel gas using the steam generated in the steam generation unit to generate a hydrogen-containing gas; and the steam generation unit. Water vapor generation amount adjusting means for adjusting the water vapor generation amount, raw fuel gas supply amount adjusting means capable of adjusting the raw fuel gas supply amount to the reforming processing unit, and the water vapor generating unit by the water vapor generation amount adjusting means. The amount of water vapor produced in the reforming unit and the amount of raw fuel gas supplied to the reforming unit are adjusted by the raw fuel gas supply amount adjusting means to adjust the amount of hydrogen-containing gas produced in the reforming unit. The present invention relates to a hydrogen-containing gas generation apparatus including a hydrogen-containing gas generation amount adjusting means, and a hydrogen-containing gas generation amount adjusting method thereof.

[0002]

2. Description of the Related Art A hydrogen-containing gas generator as described above is
A reformer that generates hydrogen-containing gas containing hydrogen and carbon monoxide by performing a so-called steam reforming process in which steam is added to the raw fuel gas at a high temperature to cause a reaction by being heated by a reforming unit heating means such as a combustor. A quality processing unit is provided. Furthermore, the hydrogen-containing gas generation device is a shift treatment unit that shifts carbon monoxide in the hydrogen-containing gas generated in the reforming treatment unit to carbon dioxide, and the hydrogen-containing gas that has been subjected to the shift treatment. It is provided with a carbon monoxide selective oxidation treatment unit for selectively oxidizing carbon monoxide therein, and is configured to generate a hydrogen-rich hydrogen-containing gas having an extremely low carbon monoxide concentration (for example, 10 ppm or less). The generated hydrogen-containing gas is used, for example, as a fuel gas for a power generation reaction in a fuel cell. Further, the steam supplied to the reforming processing unit is generated in the steam generating unit, and the steam generating unit generates water by heat exchange with the combustion exhaust gas discharged from the combustor provided in the reforming processing unit. It is configured by a heat exchanger or the like that generates steam by heating (see, for example, Patent Document 1).

In such a hydrogen-containing gas generation device, in order to make the electric power output of the fuel cell follow the electric load, the hydrogen-containing gas generation is adjusted so that the amount of the hydrogen-containing gas produced by the fuel cell follows the electric load. It may be provided with a quantity adjusting means. Further, such a hydrogen-containing gas production amount adjusting means is a ratio of the number of moles of water molecules supplied as steam to the reforming processing section and the number of moles of carbon supplied as raw fuel gas,
While maintaining the so-called steam / carbon ratio at a predetermined value,
The raw fuel gas supply amount adjusting means composed of an adjusting valve or the like adjusts the raw fuel gas supply amount to the reforming processing unit, and the steam generation amount adjusting unit adjusts the steam generation amount in the steam generating unit. Then, the amount of steam supplied to the reforming treatment unit is adjusted, and as a result, the amount of hydrogen-containing gas produced in the reforming treatment unit is adjusted. By the way, the steam generation amount adjusting means is constituted by a water supply amount adjusting means capable of adjusting the water supply amount to the steam generating portion and a steam generating portion heating means configured so that the heat input amount can be adjusted. The supply amount adjusting means is specifically composed of an adjusting valve or the like.

[0004]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-83620

[0005]

In the hydrogen-containing gas generator as described above, the steam / carbon ratio is made as small as possible in order to reduce the amount of water vapor consumed in the reforming section as much as possible and improve the efficiency. However, if the steam / carbon ratio is extremely reduced, a sufficient amount of hydrogen will not be produced, or carbon monoxide that poisons platinum used in the fuel electrode of the fuel cell There is a problem that the production amount increases.

In particular, when the hydrogen-containing gas production amount adjusting means is used to increase the hydrogen-containing gas production amount in accordance with an increase in the electric power load of the fuel cell or the like, there is a delay in water vaporization in the water vapor production section, Due to a delay in the increase in heat input to the steam generation unit or a decrease in the temperature of the steam generation unit heating means due to an increase in the amount of water supplied to the steam generation unit, the steam supply amount to the reforming processing unit is temporarily transferred to the reforming processing unit. The amount of raw fuel gas supplied to the fuel cell may be smaller than that of the original fuel gas. For example, the hydrogen-containing gas supplied to the fuel cell cannot be made to follow the increase in the electric power load, or is supplied to the fuel cell. Carbon monoxide in the hydrogen-containing gas may increase to shorten the life of the fuel electrode.

[0007] When the amount of steam supplied to the reforming processing unit decreases with respect to the amount of raw fuel gas supplied, the point that carbon monoxide in the hydrogen-containing gas produced by the hydrogen-containing gas generator increases will be explained. Add. In the reforming processing section, when the raw fuel gas is, for example, methane gas, a reforming reaction is performed according to the reaction formula shown in [Chemical formula 1] below, and the methane gas is reformed into a hydrogen-containing gas containing hydrogen and carbon monoxide. However, since the reforming reaction in the reforming processing section is an equilibrium reaction, the higher the ratio of steam for reforming reaction is, the more hydrogen-containing gas is produced at the same reaction temperature and the same reaction pressure. The lower the proportion of carbon monoxide in the interior and, conversely, the lower the proportion of steam for the reforming reaction, the higher the proportion of carbon monoxide in the hydrogen-containing gas produced. Therefore, when the ratio of steam for the reforming reaction is temporarily reduced, the ratio of carbon monoxide in the hydrogen-containing gas produced in the reforming processing unit is also temporarily increased.

[0008]

[Chemical formula 1] CH ₄ + H ₂ O → CO + 3H ₂

In the shift conversion treatment section, a shift reaction is carried out according to the reaction formula shown in the following [Chemical formula 2], and carbon monoxide in the hydrogen-containing gas produced in the reforming treatment section is changed to carbon dioxide. However, since the shift reaction in the shift treatment section is an equilibrium reaction, at the same reaction temperature, the higher the ratio of water vapor in the hydrogen-containing gas, the higher the shift ratio to carbon dioxide, and vice versa. The lower the rate of water vapor in the hydrogen-containing gas, the lower the rate of conversion to carbon dioxide. Also, similarly,
At the same reaction temperature, the lower the ratio of carbon monoxide in the hydrogen-containing gas, the higher the conversion ratio to carbon dioxide,
Conversely, the higher the ratio of carbon monoxide in the hydrogen-containing gas,
The rate of conversion to carbon dioxide is low. Therefore, when the ratio of steam for the reforming reaction is temporarily decreased, the ratio of carbon monoxide in the hydrogen-containing gas generated in the reforming processing part is temporarily increased, as described above. At the same time, since the ratio of water vapor in the hydrogen-containing gas generated in the reforming processing unit temporarily decreases, the conversion ratio of carbon monoxide to carbon dioxide in the conversion processing unit temporarily decreases. Become.

[0010]

[Chemical formula 2] CO + H ₂ O → CO ₂ + H ₂

In the selective oxidation treatment section, the selective oxidation reaction is carried out according to the reaction formula shown in the following [Chemical formula 3], and carbon monoxide in the hydrogen-containing gas subjected to the shift treatment in the shift treatment section becomes carbon dioxide. Although it is selectively oxidized, more oxygen is required for the selective oxidation reaction as the amount of carbon monoxide in the hydrogen-containing gas increases. Therefore, when the ratio of the steam for the reforming reaction is temporarily decreased, the ratio of carbon monoxide in the hydrogen-containing gas subjected to the shift conversion treatment in the shift conversion treatment section is temporarily increased as described above. Therefore, the amount of oxygen required for the selective oxidation reaction is insufficient, so that the selective oxidation ratio of carbon monoxide in the selective oxidation treatment unit is temporarily reduced.

[0012]

[Chemical Formula 3] CO + (1/2) O ₂ → CO ₂

As described above, when the ratio of the steam for the reforming reaction is temporarily reduced, the ratio of carbon monoxide in the hydrogen-containing gas produced in the reforming treatment section is temporarily increased, and Since the conversion ratio in the shift conversion unit and the selective oxidation ratio in the selective oxidation unit are temporarily lowered, carbon monoxide in the hydrogen-containing gas generated by the hydrogen-containing gas generation device is temporarily increased. Become.

Therefore, in view of the above circumstances, the present invention aims to establish a hydrogen-containing gas production amount adjusting technique capable of satisfactorily increasing the hydrogen-containing gas production amount in a hydrogen-containing gas production apparatus. To aim.

[0015]

[Means for Solving the Problems] [Structure 1] According to the method for adjusting the amount of hydrogen-containing gas generation according to the present invention, as described in claim 1, in the hydrogen-containing gas generator, the amount of water vapor generation in the water vapor generation unit. And a raw fuel gas supply amount to the reforming processing unit, a hydrogen-containing gas generation amount adjusting method for adjusting the hydrogen-containing gas generation amount in the reforming processing unit,
In order to increase the hydrogen-containing gas generation amount, a steam generation amount increasing process for increasing the steam generation amount of the steam generation unit before the time of increasing the raw fuel gas supply amount to the reforming processing unit. It is characterized by performing.

[Operation and Effect] According to the hydrogen-containing gas production amount adjusting method of the present configuration, for example, when the hydrogen-containing gas production amount of the reforming processing unit is increased by following the increase of the electric power load of the fuel cell and the like. In the above, since the raw fuel gas supply amount to the reforming processing unit is increased after performing the steam generation amount increasing process for increasing the steam generation amount of the steam generating unit, the raw fuel gas to the reforming processing unit is increased. At the time of increasing the supply amount, the steam generation unit is already in a state where the steam supply amount to the reforming processing unit can be increased. Therefore, at the time when the supply amount of the raw fuel gas to the reforming processing unit is increased, the supply amount of steam to the reforming processing unit is also increased. Of the raw fuel gas to the reforming processing unit is prevented from becoming insufficient with respect to the supply amount of the raw fuel gas to the reforming processing unit, or the supply amount of steam to the reforming processing unit is temporarily changed to the raw fuel to the reforming processing unit. Even if the amount of gas supplied is insufficient, the amount can be made as small as possible, and the steam / carbon ratio can be prevented from temporarily decreasing extremely in the reforming treatment section, and the hydrogen-containing gas can be prevented. A decrease in the amount of hydrogen in the inside and an increase in carbon monoxide can be suppressed.

[Structure 2] The method for adjusting the amount of hydrogen-containing gas generation according to the present invention, as described in claim 2, has the structure 1 described above.
In addition to the configuration of the method for adjusting the amount of hydrogen-containing gas generation, the process for increasing the amount of steam generation, when increasing the amount of raw fuel gas supplied to the reforming processing unit, generates an amount of steam commensurate with the increase. It is characterized by performing as described above.

[Operation and Effect] According to the hydrogen-containing gas production amount adjusting method of the present configuration, the steam production amount increasing process is increased when increasing the raw fuel gas supply amount to the reforming processing unit. Therefore, when the amount of supply of the raw fuel gas to the reforming processing unit is increased, the amount of steam corresponding to the increased amount is supplied to the reforming processing unit. Therefore, it becomes possible to prevent the steam supply amount to the reforming processing unit from temporarily becoming insufficient with respect to the supply amount of the raw fuel gas to the reforming processing unit. Therefore, it is possible to further suppress the temporary decrease in the amount of hydrogen in the hydrogen-containing gas and the increase in carbon monoxide.

[Structure 3] The method for adjusting the amount of hydrogen-containing gas generation according to the present invention, as described in claim 3, has the structure 1 described above.
Or in addition to the configuration of the hydrogen-containing gas production amount adjustment method of 2,
As the steam generation amount increasing process, at least one of a process of increasing an amount of heat input to the steam generating unit heating unit and a process of increasing a water supply amount to the steam generating unit is performed.

[Operation and Effect] According to the hydrogen-containing gas production amount adjusting method of the present configuration, as the process for increasing the production amount of steam, the process of increasing the heat input to the steam producing unit heating means and the process of increasing the amount of heat input to the steam producing unit. Since at least one of the processes for increasing the water supply amount is performed, the steam generation unit may already increase the steam supply amount to the reforming treatment unit at the time of increasing the raw fuel gas supply amount to the reforming treatment unit. In this state, the same operational effects as those of the above-described configuration 1 are obtained, and it is possible to suppress a temporary decrease in the amount of hydrogen in the hydrogen-containing gas and an increase in carbon monoxide. By the way, as the process for increasing the steam generation amount, if both the process of increasing the heat input amount to the steam generating unit heating means and the process of increasing the water supply amount to the steam generating unit are performed, that is, the reforming processing unit Increase the amount of water supplied to the steam generator at a predetermined time before increasing the amount of raw fuel gas supplied to the steam generator, and heat the steam generator at a predetermined time before increasing the amount of water supply. If the amount of heat input to the means is increased, at the time of increasing the water supply amount, the steam generation unit is already in a state of being able to generate sufficient steam even if the water supply amount is increased. At the time of increasing the amount of raw fuel gas, the steam generator is in a state where it can supply a sufficient amount of steam to the increased amount of supply of raw fuel gas. Therefore, it is possible to further suppress the temporary decrease in the amount of hydrogen in the hydrogen-containing gas and the increase in carbon monoxide.

[Structure 4] A hydrogen-containing gas generation amount adjusting method according to the present invention is, in the hydrogen-containing gas generating device, as described in claim 4, wherein the steam generation amount in the steam generating unit and the reforming treatment unit are the same. A method for adjusting the amount of hydrogen-containing gas produced in the reforming processing unit by adjusting the amount of raw fuel gas supplied to the reforming treatment unit, in order to increase the amount of hydrogen-containing gas produced, A steam generation increasing process for increasing the steam generation amount of the steam generating unit, and a raw fuel gas supply amount increasing process for gradually increasing the raw fuel gas supply amount to the reforming processing unit. To do.

[Operation and Effect] According to the hydrogen-containing gas production amount adjusting method of this configuration, for example, when the hydrogen-containing gas production amount of the reforming processing unit is increased by following an increase in the electric power load of the fuel cell, etc. In the above, in the steam generation amount increasing process for increasing the steam generation amount of the steam generation unit, and
Since the raw fuel gas supply amount gradually increasing process for gradually increasing the raw fuel gas supply amount to the reforming processing unit is performed, an increase in the raw fuel gas supply amount to the reforming processing unit is not insufficient, or, It becomes possible to supply the steam to the reforming treatment unit while minimizing the deficiency. In addition, when the steam generation amount is increased by the steam generation amount increasing process, the steam generation amount is gradually increased. Therefore, the raw fuel gas supply amount to the reforming processing unit is gradually increased. This temporarily prevents the supply amount of steam to the reforming processing unit from becoming insufficient with respect to the supply amount of the raw fuel gas to the reforming processing unit, or temporarily prevents the supply of steam to the reforming processing unit. Even if the supply amount of water vapor is insufficient with respect to the supply amount of the raw fuel gas to the reforming processing unit, the insufficient amount can be minimized. Therefore, it is possible to suppress the steam / carbon ratio from temporarily decreasing extremely in the reforming treatment section, and to suppress the decrease in the amount of hydrogen in the hydrogen-containing gas and the increase in carbon monoxide.

[Structure 5] The hydrogen-containing gas generator according to the present invention, as described in claim 5, comprises: a steam generating part for heating water by the steam generating part heating means to generate steam; and a reforming process heating part. And a reforming treatment unit that reforms a hydrocarbon-based raw fuel gas using the steam produced in the steam producing unit to produce a hydrogen-containing gas, and a steam production amount of the steam producing unit. A steam generation amount adjusting unit for adjusting, a raw fuel gas supply amount adjusting unit capable of adjusting a raw fuel gas supply amount to the reforming processing unit, and a steam generation amount in the steam generating unit by the steam generation amount adjusting unit. And adjusting the raw fuel gas supply amount adjusting means to adjust the raw fuel gas supply amount to the reforming processing unit to adjust the hydrogen-containing gas generation amount in the reforming processing unit. Quantity adjustment means In the hydrogen-containing gas generation device, the hydrogen-containing gas generation amount adjusting means increases the hydrogen-containing gas generation amount by the raw fuel gas supply amount adjusting means to supply the raw fuel gas to the reforming processing unit. Before the time point of increasing the supply amount, it is configured to perform a steam generation amount increasing process for operating the steam generation amount adjusting means to increase the steam generation amount of the steam generation unit. .

[Operation and Effect] According to the hydrogen-containing gas generation apparatus of the present configuration, the hydrogen-containing gas generation amount adjusting means causes the hydrogen-containing gas in the reforming processing unit to follow the increase in the electric power load of the fuel cell, for example. When increasing gas production,
After performing the process for increasing the amount of steam generation by operating the steam generation amount adjusting means to increase the amount of steam generation of the steam generating part, the raw fuel gas supply amount adjusting means adjusts the raw fuel gas supply amount to the reforming processing part. Since it is increased, at least at the time when the raw fuel gas supply amount to the reforming processing unit is increased, the steam generating unit is already in a state where the steam supply amount to the reforming processing unit can be increased. Therefore, when the supply amount of the raw fuel gas to the reforming processing unit is increased, the supply amount of steam to the reforming processing unit is also increased, so that the steam supply to the reforming processing unit is temporarily performed. Of the raw fuel gas to the reforming processing unit is prevented from becoming insufficient with respect to the supply amount of the raw fuel gas to the reforming processing unit, or the supply amount of steam to the reforming processing unit is temporarily changed to the raw fuel to the reforming processing unit. Even if the amount of gas supplied is insufficient, the amount can be made as small as possible, and the steam / carbon ratio can be prevented from temporarily decreasing extremely in the reforming treatment section, and the hydrogen-containing gas can be prevented. A decrease in the amount of hydrogen in the inside and an increase in carbon monoxide can be suppressed.

[Structure 6] In the hydrogen-containing gas generator according to the present invention, as described in claim 6, in addition to the structure of the hydrogen-containing gas generator of Structure 5, the hydrogen-containing gas generation amount adjusting means is provided. In the process for increasing the amount of steam generation, when the amount of raw fuel gas supply to the reforming processing unit is increased by the raw fuel gas supply amount adjusting means, an amount of steam commensurate with the increase is generated. It is characterized in that it is configured to operate the water vapor production amount adjusting means.

[Operation and Effect] According to the hydrogen-containing gas generation apparatus of the present configuration, the hydrogen-containing gas generation amount adjusting means performs the steam generation amount increasing process and the raw fuel gas supply amount to the reforming processing unit. When the supply amount of the raw fuel gas to the reforming processing part is increased, the steam generation amount adjusting means is operated so that the amount of steam corresponding to the increase is generated when the supply amount is increased. The amount of steam commensurate with the increase will be supplied to the reforming processing unit, and the amount of steam supply to the reforming processing unit will temporarily be insufficient with respect to the amount of raw fuel gas supplied to the reforming processing unit. It is possible to prevent this.
Therefore, it is possible to further suppress the temporary decrease in the amount of hydrogen in the hydrogen-containing gas and the increase in carbon monoxide.

[Structure 7] In the hydrogen-containing gas generator of the present invention, as described in claim 7, in addition to the structure of the hydrogen-containing gas generator of Structure 5 or 6, the water vapor production amount adjusting means includes: The water supply amount adjusting means capable of adjusting the water supply amount to the steam generating portion and the steam generating portion heating means configured to be able to adjust the heat input amount, and the hydrogen-containing gas generation amount adjusting means. However, as the steam generation amount increasing process, at least a process of increasing the heat input amount to the steam generating unit heating unit, and a process of increasing the water supply amount to the steam generating unit by the water supply amount adjusting unit. It is characterized in that it is configured to perform one.

[Operation and Effect] According to the hydrogen-containing gas generator of the present invention, the hydrogen-containing gas production amount adjusting means increases the amount of heat input to the steam producing portion heating means as the steam production increasing treatment. Also, since at least one of the treatments for increasing the water supply amount to the steam generation unit is performed by the water supply amount adjusting means, at the time of increasing the raw fuel gas supply amount to the reforming treatment unit, the steam generation unit has already been modified. As a result, the amount of steam supplied to the quality treatment unit can be increased, and the same operational effect as that of the above-mentioned configuration 5 can be obtained, and the amount of hydrogen in the hydrogen-containing gas can be temporarily reduced and carbon monoxide can be reduced. The increase can be suppressed. By the way, as the process for increasing the amount of steam generation, if both the process of increasing the heat input to the steam generating unit heating means and the process of increasing the water supply amount to the steam generating unit are performed, that is, the raw fuel gas supply The amount of water supplied to the steam generation unit is increased at a predetermined time before the amount of raw fuel gas supplied to the reforming processing unit is increased by the amount adjusting means, and the amount of water supplied to the steam generation unit is increased from the time when the amount of water supply is increased to a predetermined amount. If the amount of heat input to the steam generator heating means is increased before the time, the steam generator can generate sufficient steam even when the water supply amount is already increased, at the time of increasing the water supply amount. In addition, when the raw fuel gas is increased, the steam generation unit can supply a sufficient amount of steam to the increased raw fuel gas supply amount. It made. Therefore, it is possible to further suppress the temporary decrease in the amount of hydrogen in the hydrogen-containing gas and the increase in carbon monoxide.

[Structure 8] In the hydrogen-containing gas generator according to the present invention, as described in claim 8, in addition to the structure of the hydrogen-containing gas generator in Structure 7, It is composed of a combustor that heats the reforming processing unit by combustion heat, and the steam generation unit heating means heats water by heat exchange with combustion exhaust gas discharged from the combustor, and an electric heater. The hydrogen-containing gas production amount adjusting means is configured to increase the output of the electric heater to increase the heat input amount to the steam generating part heating means.

[Operation and Effect] In the steam generating part heating means, the combustion exhaust gas and water discharged from the combustor as the reforming treatment part heating means are supplied to the heat exchanger to exchange heat with the combustion exhaust gas. If the heat input amount adjusting means capable of adjusting the heat input amount to the steam generating part heating means is configured as the heat amount of the combustion exhaust gas discharged from the combustor to be adjusted by the Along with the increase in the heat input to the steam generator heating means performed a predetermined time before the time when the raw fuel gas supply quantity is increased to increase the contained gas generation quantity, the reforming processing section heating means is provided. It is necessary to increase the amount of combustion in the combustor, and the temperature of the reforming processing part may rise abnormally.

Therefore, according to the hydrogen-containing gas generating apparatus of this configuration, the steam generating section heating means is set to a predetermined temperature as the temperature of the reforming processing section discharged from the combustor as the reforming processing section heating means. A heat exchanger that heats water by heat exchange with the subsequent combustion exhaust gas and an electric heater, and the heat input amount adjusting means adjusts the output of the electric heater to input heat amount to the steam generator heating means. Can be configured to be adjustable, in order to increase the production amount of hydrogen-containing gas,
Increasing the heat input to the steam generating part heating means without increasing the heat input to the reforming processing part heating means at a predetermined time before the time of increasing the water supply amount to the steam generating part. Therefore, it is possible to prevent abnormal temperature rise in the reforming processing section.

[Structure 9] A hydrogen-containing gas generator according to the present invention has a steam generating section for heating water by a steam generating section heating means to generate steam, and a heating for a reforming section. And a reforming treatment unit that reforms a hydrocarbon-based raw fuel gas using the steam produced in the steam producing unit to produce a hydrogen-containing gas, and a steam production amount of the steam producing unit. A steam generation amount adjusting unit for adjusting, a raw fuel gas supply amount adjusting unit capable of adjusting a raw fuel gas supply amount to the reforming processing unit, and a steam generation amount in the steam generating unit by the steam generation amount adjusting unit. And adjusting the raw fuel gas supply amount adjusting means to adjust the raw fuel gas supply amount to the reforming processing unit to adjust the hydrogen-containing gas generation amount in the reforming processing unit. Quantity adjustment means In the above hydrogen-containing gas generation device, the hydrogen-containing gas generation amount adjusting means increases the water-vapor generation amount of the water-vapor generating unit to increase the hydrogen-containing gas generation amount. It is configured to perform a steam generation amount increasing process to be operated and a raw fuel gas supply amount gradually increasing process to gradually increase the raw fuel gas supply amount to the reforming processing section by the raw fuel gas supply amount adjusting means. It is characterized by

[Operation and Effect] According to the hydrogen-containing gas generating apparatus of the present configuration, the hydrogen-containing gas generation amount adjusting means causes the hydrogen-containing gas in the reforming processing unit to follow the increase in the power load of the fuel cell, for example. When increasing gas production,
The hydrogen-containing gas production amount adjusting means operates the vapor production amount adjusting means to increase the vapor production amount of the water vapor producing portion, and the raw fuel gas supply amount adjusting means brings the reforming treatment portion to the reforming treatment portion. Since the raw fuel gas supply amount increasing process for gradually increasing the raw fuel gas supply amount is performed, the increase in the raw fuel gas supply amount to the reforming processing unit does not become insufficient, or the shortage amount is minimized. However, it becomes possible to supply the steam to the reforming processing section. In addition, when increasing the amount of steam generation in the steam generation unit by the steam generation amount increasing process by the steam generation amount adjusting means, the steam generation amount is gradually increased. By gradually increasing the amount of raw fuel gas supplied to the reforming processing unit, it is possible to temporarily prevent the amount of steam supplied to the reforming processing unit from becoming insufficient with respect to the amount of raw fuel gas supplied to the reforming processing unit. It is possible to prevent or even if the supply amount of steam to the reforming processing unit becomes temporarily short of the supply amount of the raw fuel gas to the reforming processing unit, the shortage amount can be minimized as much as possible. Becomes Therefore, it is possible to suppress the steam / carbon ratio from temporarily decreasing extremely in the reforming treatment section, and to suppress the decrease in the amount of hydrogen in the hydrogen-containing gas and the increase in carbon monoxide.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of a hydrogen-containing gas generator according to the present invention (hereinafter referred to as the present generator) will be described with reference to the drawings. As shown in FIG. 1, the present production apparatus P desulfurizes a hydrocarbon-based raw fuel gas such as natural gas which is supplied with a supply amount adjustment by an adjusting valve 11 (an example of a raw fuel gas supply amount adjusting means). Desulfurization treatment section 1 to be treated
A steam generator S for heating the supplied raw material water to generate steam, and a desulfurizer supplied from the desulfurization processor 1 after being heated by the combustor 4 as a combustion-type reforming processor heating means. A reforming process section 3 for reforming the raw fuel gas into a gas containing hydrogen gas and carbon monoxide gas using the steam produced in the steam producing section S, and a reforming process supplied from the reforming process section 3. Metamorphism processing unit 5 for performing metamorphism processing by converting carbon monoxide gas in the gas into carbon dioxide gas using steam.
A selective oxidation treatment unit 6 for selectively oxidizing the carbon monoxide gas in the transformation treatment gas supplied from the transformation treatment unit 5; and a control unit 20 for controlling the operation of the generator P. It is configured so as to generate a hydrogen-containing gas rich in hydrogen with a low carbon monoxide gas concentration (for example, 10 ppm or less).

In the desulfurization treatment section 1, for example, 150 to
At a desulfurization treatment temperature in the range of 300 ° C., the sulfur compound in the raw fuel gas is hydrogenated by the desulfurization catalyst, and the hydride is adsorbed by zinc oxide and desulfurized. By the way, the desulfurization reaction in the desulfurization treatment section 1 is an exothermic reaction. The desulfurization treatment section 1 is filled with a large number of granular molded bodies of a hydrodesulfurization catalyst such as a nickel-molybdenum system and a chromium-molybdenum system. The desulfurization treatment temperature is controlled by the controller 20.
The desulfurization treatment unit heater 32 that heats the desulfurization treatment unit 1 while detecting the desulfurization treatment temperature with the desulfurization treatment temperature sensor T1.
It is maintained by adjusting the output of.

In the reforming processing unit 3, when the natural gas containing methane gas as the main component is the raw fuel gas, the catalytic action of the reforming catalyst such as ruthenium, nickel, platinum, etc.
For example, under a reforming treatment temperature in the range of 600 to 700 ° C., methane gas and steam undergo a reforming reaction according to the following reaction formula [Chemical formula 4] to convert into a gas containing hydrogen gas and carbon monoxide gas. The quality is processed. By the way, the reforming reaction in the reforming processing section 3 is an endothermic reaction. Further, the reforming catalyst is held in a porous granular body made of ceramic, and the reforming treatment section 3 is filled with a large number of the porous granular bodies.

[0037]

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

Further, the combustor 4 provided in the reforming processing section 3
Is supplied with the fuel of off-gas discharged from the fuel cell G and the same natural gas as the raw fuel gas with the adjustment of the supply amount by the adjustment valve 13, and the combustion air for burning the fuel is adjusted by the adjustment valve. It is supplied with the supply amount adjustment by 14. The above-mentioned reforming treatment temperature is controlled by the control unit 20 while the reforming treatment temperature sensor T3 detects the reforming treatment temperature and the opening degree of the regulating valve 13 and the regulating valve 14 is adjusted to burn the combustor 4. It is maintained by adjusting the amount.

In the shift treatment section 5, the carbon monoxide gas and the steam in the reforming treatment gas are subjected to the shift action temperature in the range of 150 to 300 ° C. by the catalytic action of the shift catalyst of iron oxide or copper zinc. Under the conditions, the carbon monoxide gas is converted into carbon dioxide gas by the conversion reaction according to the following reaction formula [Chemical formula 5]. By the way, the shift reaction in the shift processing unit 5 is an exothermic reaction. The transformation processing section 5 is filled with a large number of granular molded bodies. Further, the above-mentioned shift treatment temperature is maintained by adjusting the output of the shift treatment heater 33 that heats the shift treatment unit 5 while the control unit 20 detects the shift treatment temperature by the shift treatment temperature sensor T5. Has been done.

[0040]

[Chemical formula 5] CO + H ₂ O → CO ₂ + H ₂

In the selective oxidation treatment section 6, the catalytic treatment of the noble metal selective oxidation catalyst such as platinum, ruthenium, rhodium, etc., in the shift treatment gas under the selective oxidation treatment temperature in the range of 80 to 120 ° C. The remaining carbon monoxide gas is selectively oxidized. By the way, the selective oxidation treatment unit 6
The oxidation reaction in is an exothermic reaction. Also, the selective oxidation catalyst is retained in a porous granular body made of ceramic,
The selective oxidation treatment section 6 is filled with a large number of the porous particles.

Then, the hydrogen-containing gas produced by the production apparatus P is supplied to the fuel cell G as a fuel gas.
Although the detailed description is omitted, the fuel cell G is a solid polymer type having a polymer membrane as an electrolyte, and is supplied from hydrogen in the fuel gas supplied from the generator P and a blower (not shown). Power is generated by an electrochemical reaction with oxygen in the reaction air.

Further, a steam production amount adjusting means V for adjusting the steam production amount of the steam production unit S is provided, and the steam production unit S is provided with combustion exhaust gas having a temperature higher than the reforming treatment temperature supplied from the combustor 4. And a heat exchanger 8 for generating water vapor by exchanging heat with the supplied water while adjusting the supply amount by the adjusting valve 10 (an example of water supply amount adjusting means). In addition, the steam generator S is provided with an electric heater 7 capable of preheating the water supplied to the heat exchanger 8. The heat exchanger 8 and the electric heater 7 are referred to as a steam generating unit heating means 9 for heating water in the steam generating unit S. The heat input to the steam generator heating means 9 can be adjusted by intermittently supplying power to the electric heater 7 or adjusting the heat quantity of the combustion exhaust gas supplied to the heat exchanger 8. Has been done. Further, the steam generation amount adjusting means V is a control valve 10 as a water supply amount adjusting means capable of adjusting the water supply amount to the steam generating portion S, and the steam configured to be able to adjust the heat input amount as described above. It is composed of the generator heating means 9.

The present generator P configured as described above is
The fuel cell G is configured to include a hydrogen-containing gas production amount adjusting means 21 capable of adjusting the hydrogen-containing gas production amount so as to follow the electric power load of the fuel cell G. That is, the hydrogen-containing gas production amount adjusting means 21 of the control unit 20 operates the adjustment valve 11 to adjust the raw fuel gas supply amount to the desulfurization processing unit 1 based on the power load information input from the fuel cell G side or the like. The amount of steam-containing gas produced by the production apparatus P is adjusted so as to follow the power load on the fuel cell G side. Further, when adjusting the amount of raw fuel gas supplied to the desulfurization processing unit 1 in this way, the hydrogen-containing gas production amount adjusting means 21 activates the adjustment valve 10 to generate steam based on the amount of raw fuel gas supplied. The amount of water supplied to the part S is adjusted so that the ratio of the amount of raw fuel gas supplied to the amount of steam generated in the steam generating part S becomes a predetermined steam / carbon ratio.

More specifically, when the electric power load on the fuel cell G side increases, the hydrogen-containing gas production amount adjusting means 21 increases the raw fuel gas supply amount to the desulfurization treatment section 1, and
The amount of water supplied to the steam generation unit S is increased to increase the amount of steam generation of the steam generation unit S, the amount of hydrogen-containing gas generation of the present generation device P is increased, and the output of the fuel cell G is increased. On the contrary, when the electric power load on the fuel cell G side decreases, the hydrogen-containing gas production amount adjusting means 21 reduces the raw fuel gas supply amount to the desulfurization treatment unit 1 and supplies the raw fuel gas to the steam generation unit S. The amount of water supply is reduced to reduce the amount of water vapor produced by the water vapor producing unit S, the amount of hydrogen-containing gas produced by the production apparatus P is reduced, and the output of the fuel cell G is reduced.

Further, when the raw fuel gas supply amount is changed by the hydrogen-containing gas production amount adjusting means 21, the processing load on the reforming processing unit 3 changes, so the reforming processing temperature sensor T
The opening degree of the adjusting valves 13 and 14 adjusted by the control unit 20 based on the detection result of No. 3 changes, and the fuel amount of the combustor 4 also changes. That is, when the raw fuel gas supply amount is increased, the combustion amount of the combustor 4 also increases, and conversely, when the raw fuel gas supply amount decreases, the combustion amount of the combustor 4 also decreases. Furthermore, when the combustion amount of the combustor 4 changes, the heat amount of the combustion exhaust gas discharged from the combustor 4 also changes, so the heat input amount to the steam generating unit heating means 9 to which the combustion exhaust gas is supplied also changes. To do.

The hydrogen-containing gas production amount adjusting method in the hydrogen-containing gas production amount adjusting means 21 of the present production apparatus P, which has been described so far, is characterized by the control procedure for increasing the hydrogen-containing gas production amount. Detailed examples will be described below. 2, FIG. 3, FIG. 4, and FIG. 5 show an increasing state (a) of the raw fuel gas supply amount and an increasing state of the water supply amount to the steam generation part S when increasing the hydrogen-containing gas generation amount. (B) is a diagram showing an increasing state (c) of the heat input to the steam generating part heating means 9 and an increasing state (d) of the steam generating amount of the steam generating part S, and is directed to the right in the figure. Time has passed.

[Embodiment 1] In Embodiment 1, the hydrogen-containing gas production amount adjusting means 21 increases the hydrogen-containing gas production amount in order for the production apparatus P to increase the hydrogen-containing gas production amount. , Increasing the amount of steam generation by operating the steam generation amount adjusting means V to increase the amount of steam generation of the steam generation unit P before the time when the amount of raw fuel gas supplied to the reforming processing unit 3 is increased by the adjustment valve 11. And a hydrogen-containing gas production amount adjusting means 2
When the control valve 11 increases the amount of raw fuel gas supplied to the reforming processing unit 3 by the steam generation amount increasing process,
It is configured to operate the steam generation amount adjusting means V so that the amount of steam corresponding to the increase is generated.

As an example of the case where the hydrogen-containing gas production amount adjusting means 21 is configured as described above, as shown in FIG. 2, the hydrogen-containing gas production amount adjusting means 21 uses the adjustment valve 11 to supply the raw fuel gas. A case will be described in which the control valve 10 increases the water supply amount to the water vapor generation unit S a predetermined time before the point at which the raw fuel gas supply amount increases. In such a case, the amount of heat input to the steam generator heating means 9 at the time of increasing the amount of water supplied to the steam generator S, that is, the amount of heat in the combustion exhaust gas supplied from the combustor 4 to the heat exchanger 8. When the amount of heat is sufficient to heat the supplied water to steam, as shown in FIG. 2 (d), at the time when the raw fuel gas supply amount is increased, the steam generator is already in use. The steam generation amount of S is increased, and sufficient steam can be supplied to the reforming processing unit 3 with respect to the increased raw fuel gas. Further, in this case, the heat input amount of the steam generating unit heating means 9 increases as the fuel amount of the combustor 4 increases and the heat amount in the combustion exhaust gas supplied to the heat exchanger 8 increases. It will increase when the gas supply increases.

Therefore, the hydrogen-containing gas production amount adjusting means 21 of the present production apparatus P increases the hydrogen-containing gas production amount, after increasing the water supply amount to the steam production unit S, and after a predetermined time elapses. By increasing the raw fuel gas supply amount, it is possible to suppress an increase in the carbon monoxide production amount due to the insufficient steam supply amount to the reforming processing unit 3. On the other hand, FIG.
As shown by the broken line in (b), when the water supply amount is increased as in the conventional case at the time when the raw fuel gas supply amount is increased, as shown by the broken line in FIG. Since the steam generation amount gradually increases from the time when the gas supply amount is increased, the steam amount is temporarily insufficient in the reforming processing unit 3 at the time when the raw fuel gas supply amount is increased, and the carbon monoxide is temporarily increased. The production amount increases. Then, in the hydrogen-containing gas production amount adjusting means 21 of the present production apparatus P as described above, for example, as shown in FIG. 7, the raw fuel gas supply amount and the water supply amount are simultaneously increased as in the conventional case. (Fig. 7
Comparative Example), the carbon monoxide production amount increases when the water supply amount is increased 30 seconds before the raw fuel gas supply amount is increased (Example 1a in FIG. 7). Experiments have shown that when the time is halved and the water supply amount is increased 1 minute before the raw fuel gas supply amount is increased (Example 1b in FIG. 7), almost no carbon monoxide is produced. Confirmed by. In addition, in FIG. 7, the rated load is 4.2 L / min.
(Normal) (natural gas city gas 13A) hydrogen-containing gas generator, load from 50% to 100%
It is the result of measuring the carbon monoxide concentration in the hydrogen-containing gas generated when the gas was instantaneously increased to.

[Embodiment 2] In this Embodiment 2 as well, the hydrogen-containing gas production amount adjusting means 21 increases the hydrogen-containing gas production amount by using the adjusting valve 11 to feed the raw fuel gas to the reforming treatment section 3. Before the time point of increasing the supply amount, it is configured to perform a steam generation amount increasing process for operating the steam generation amount adjusting means V to increase the steam generation amount of the steam generation unit P. Quantity adjusting means 2
When the control valve 11 increases the amount of raw fuel gas supplied to the reforming processing unit 3 by the steam generation amount increasing process,
It is configured to operate the steam generation amount adjusting means V so that the amount of steam corresponding to the increase is generated.

As an example of the case where the hydrogen-containing gas production amount adjusting means 21 is configured as described above, as shown in FIG. 3, the hydrogen-containing gas production amount adjusting means 21 of the present production apparatus P is shown.
However, in order to increase the raw fuel gas supply amount by the adjustment valve 11, the adjustment valve 10 increases the water supply amount to the water vapor generation unit S by a predetermined time before the raw fuel gas supply amount is increased. A case will be described in which the heat input to the steam generator heating means 9 is increased a predetermined time before the time of increasing the water supply. In such a case, the heat input amount to the steam generating unit heating means 9 at the time of increasing the water supply amount to the steam generating unit S, that is, the heat amount in the combustion exhaust gas supplied to the heat exchanger 8 is supplied. When the amount of water to be generated is not sufficient to heat it into steam, as shown in FIG. 6 (a), the amount of fuel in the combustor 4 is increased from a predetermined time before the time of increasing the amount of water supply. Is increased and the heat quantity in the combustion exhaust gas supplied to the heat exchanger 8 is shown in FIG.
As shown in (b), the electric heater 7 is turned on until the time of increase, and the amount of heat input to the steam generator heating means 9 is increased a predetermined time before the time when the raw fuel gas supply amount is increased. That is, the hydrogen-containing gas production amount adjusting means V increases the amount of heat input to the steam producing portion heating means 9 as the vapor production amount increasing processing, and supplies water to the steam producing portion P by the adjusting valve 10. It will be configured to perform the process of increasing the amount.

In this case, as shown in FIG. 3 (d), at the time when the water supply amount is increased, the steam generator S must generate sufficient water vapor even if the water supply amount is already increased. The steam generation amount of the steam generation unit S is rapidly increased, and at the time of increasing the raw fuel gas, the steam generation amount of the steam generation unit S has already been increased. And sufficient steam can be supplied to the reforming processing unit 3.

Therefore, the hydrogen-containing gas production amount adjusting means 21 of the present production apparatus P increases the hydrogen-containing gas production amount in order to increase the amount of heat input to the steam producing portion heating means 9 and supply water to the steam producing portion S. By sequentially increasing the amount and the raw fuel gas supply amount through a predetermined time interval, it is possible to suppress the increase in the carbon monoxide production amount due to the insufficient steam supply amount to the reforming processing unit 3.

Further, the heat input to the steam generating section heating means 9 and the water supply to the steam generating section S may be simultaneously increased at a predetermined time before increasing the raw fuel gas supply rate.
Even in this case, when the raw fuel gas supply amount is increased, the steam generation amount of the steam generation unit S has already been increased, and sufficient steam is supplied to the reforming processing unit 3 with respect to the increased raw fuel gas. can do. Then, the hydrogen-containing gas production amount adjusting means 21 of the present production apparatus P as described above.
For example, as shown in FIG. 7, compared with the case where the increase in the raw fuel gas supply amount and the increase in the water supply amount are simultaneously increased as in the conventional case (comparative example of FIG. 7), the raw fuel gas supply is increased. When the water supply amount and the heat input amount are increased 10 seconds before the amount increase time (Example 2a in FIG. 7), only a very small amount of carbon monoxide is produced, and further, the raw fuel gas supply amount is increased. It was confirmed by experiments that when the water supply amount and the heat input amount were increased 30 seconds before the increasing time (Example 2b in FIG. 7), almost no carbon monoxide was produced.

[Third Embodiment] In the third embodiment,
In order to increase the hydrogen-containing gas production amount, the hydrogen-containing gas production amount adjusting means 21 uses the adjustment valve 11 to modify the reforming processing unit 3.
Before the time point of increasing the raw fuel gas supply amount to the steam generator, the steam generation amount increasing process for activating the steam generation amount adjusting means V to increase the steam generation amount of the steam generation unit P is performed. .

As an example of the case where the hydrogen-containing gas production amount adjusting means 21 is configured as described above, as shown in FIG. 4, the hydrogen-containing gas production amount adjusting means 21 of the present production apparatus P is shown.
However, in order to increase the raw fuel gas supply amount by the adjustment valve 11, the adjustment valve 10 increases the water supply amount to the steam generation unit S at the same time when the raw fuel gas supply amount is increased, and the steam generation unit heating means 9 is supplied. A case will be described in which the heat input amount is configured to be increased a predetermined time before the raw fuel gas supply amount is increased, as in the second embodiment.

In such a case, as in the second embodiment,
As shown in FIG. 6, from a time point before a predetermined time before the raw fuel gas supply amount increases, the fuel amount in the combustor 4 increases and the heat amount in the combustion exhaust gas supplied to the heat exchanger 8 increases. Until then, the electric heater 7 is turned on and the heat input to the steam generator heating means 9 is increased a predetermined time before the raw fuel gas supply amount is increased.

Also in this case, as shown in FIG.
As shown in, when the raw fuel gas supply amount and the water supply amount are increased, the steam generator heating means 9 is already in a state of being able to generate sufficient steam even if the water supply amount is increased. The amount of steam generated in the steam generator S is increased in a shorter time than before. Therefore, even if the increase in the steam generation in the steam generating unit S is slightly delayed with respect to the increase in the raw fuel gas supply amount, it is possible to increase the steam generating amount in the steam generating unit S in a shorter time than in the conventional case. Therefore, it becomes possible to minimize the delay in the increase in steam generation with respect to the increase in the raw fuel gas supply amount, and it is possible to suppress the increase in the carbon monoxide production amount due to the insufficient steam supply amount to the reforming processing unit 3. .

[Embodiment 4] In this Embodiment 4, the hydrogen-containing gas production amount adjusting means 21 generates steam to increase the production amount of the hydrogen-containing gas in order to increase the production amount of the steam in the steam production unit P. It is configured to perform a steam generation amount increasing process for operating the amount adjusting means V and a raw fuel gas supply amount gradually increasing process for gradually increasing the raw fuel gas supply amount to the reforming processing unit 3 by the adjusting valve 11. .

As an example of the case where the hydrogen-containing gas production amount adjusting means 21 is configured as described above, as shown in FIG. 5, the hydrogen-containing gas production amount adjusting means 21 uses the adjustment valve 11 to supply the raw fuel gas. Is gradually increased so as to reach a predetermined target raw fuel gas supply amount over a predetermined period of time, and at the same time when the gradual increase is started, the water supply amount to the steam generating unit S is increased by the adjusting valve 10 and the steam generating unit is increased. A case in which the heat input to the heating means 9 is increased will be described.

That is, the amount of heat input to the steam generator heating means 9 at the time of increasing the amount of water supplied to the steam generator S, that is, the amount of heat in the combustion exhaust gas supplied to the heat exchanger 8 is supplied. When the amount of water is not sufficient to heat it to steam, the amount of raw fuel gas supplied increases from the start of the gradual increase of the amount of raw fuel gas supplied, and the amount of combustion exhaust gas supplied to the heat exchanger 8 increases. The electric heater 7 is turned on until the amount of heat increases to an amount sufficient to heat the supplied water to steam.
In the N state, the amount of heat input to the steam generator heating means 9 is increased.

Then, as shown in FIGS. 5 (b) and 5 (d), even if the amount of water supplied to the steam generator S is increased, the amount of steam generated in the steam generator S immediately increases to a predetermined amount. However, as shown in FIG. 5A, since the raw fuel gas supply amount is gradually increased, the water supply amount to the steam generator S is increased at the same time when the raw fuel gas supply amount is gradually increased. Even if the amount is increased, the ratio of water vapor to the raw fuel gas does not decrease, so it is possible to suppress an increase in the amount of carbon monoxide produced due to the insufficient amount of water vapor supplied to the reforming processing unit 3. On the other hand, as shown by the broken line in FIG. 5B, when the water supply amount is increased as in the conventional case when the raw fuel gas supply amount reaches the target raw fuel gas supply amount, As indicated by the broken line in d), since the steam generation amount gradually increases from the time when the raw fuel gas supply amount reaches the target raw fuel gas supply amount, in the reforming processing unit 3, the raw fuel gas is temporarily changed. When the supply amount is increased, the amount of water vapor is insufficient and the amount of carbon monoxide produced is temporarily increased.

In the present production apparatus P, the desulfurization raw fuel gas from the desulfurization treatment section 1 and the high temperature reforming treatment gas from the reforming treatment section 3 are heat-exchanged and supplied to the reforming treatment section 3. The desulfurization raw fuel gas heat exchanger Ep for preheating the desulfurization raw fuel gas, and the high temperature reforming treatment gas from the reforming treatment unit 3 and the raw fuel gas supplied to the desulfurization treatment unit 1 are heat-exchanged to obtain the raw fuel. A raw fuel gas heat exchanger Ea for preheating the gas is provided. A heat exchanger 17 for preheating raw material water is provided to preheat the raw material water by exchanging heat with the raw material water supplied to the steam generating section S and the metamorphic processing gas discharged from the metamorphic processing section 5.

At the time of start-up, a desulfurization treatment section heater 32 for heating the desulfurization treatment section 1 so that it can be desulfurized, and two transformation treatment section heaters 33 for heating the transformation processing section so that they can be subjected to transformation processing are provided. The heaters 32 and 33 are electric heaters.

Further, a desulfurization treatment temperature sensor T1 for detecting the temperature of the desulfurization treatment section 1 and a selective oxidation treatment temperature sensor T5 for detecting the temperature of the selective oxidation treatment section 6 are provided.

Another Embodiment Next, another embodiment will be described. (A) In order to increase the hydrogen-containing gas production amount, the hydrogen-containing gas production amount adjusting means 21 generates steam before the time when the raw fuel gas supply amount to the reforming processing unit 3 is increased by the adjustment valve 11. In a case where the steam generation amount increasing means for activating the steam generation amount adjusting means V is operated to increase the steam generation amount of the part P, the hydrogen containing gas generation amount adjusting means V is used for increasing the steam generation amount. In the process of increasing the heat input amount to the steam generating unit heating means 9 and the process of increasing the water supply amount to the steam generating unit P by the adjusting valve 10, the heat input amounts are changed. The timing of performing the increasing treatment and the increasing water supply amount can be variously changed.
For example, as illustrated in Example 2 above, the process of increasing the heat input amount is performed before the process of increasing the water supply amount, or the process of increasing the heat input amount and the process of increasing the water supply amount are performed at the same time. In addition to the process, the process of increasing the water supply amount may be performed before the process of increasing the heat input amount.

(B) Hydrogen-containing gas production amount adjusting means 21
To increase the amount of hydrogen-containing gas produced, to increase the amount of produced steam in the water vapor production unit P, to operate the amount of vapor production adjusting means V to increase the amount of produced water vapor;
In the case where the adjustment valve 11 is configured to perform the raw fuel gas supply amount gradually increasing process for gradually increasing the raw fuel gas supply amount to the reforming processing unit 3, in the above-described fourth embodiment, the steam generation amount increasing process is not performed. The case where it is performed at the same time when the fuel gas supply amount is gradually increased has been described, but the steam generation amount increasing process may be performed before the raw fuel gas supply amount is gradually increased.

When the process for increasing the amount of steam generation is performed at the same time as the start of gradually increasing the supply amount of raw fuel gas, and when the process for increasing the amount of steam generation is performed before the start time of gradually increasing the supply amount of raw fuel gas. In any of the above, both the process of increasing the heat input amount to the steam generating part heating means 9 and the process of increasing the water supply amount to the steam generating part P by the adjusting valve 10 as the process for increasing the steam generating amount. May be performed, or either one of them may be performed.

(C) Hydrogen-containing gas production amount adjusting means 21
To increase the amount of hydrogen-containing gas produced, to increase the amount of produced steam in the water vapor production unit P, to operate the amount of vapor production adjusting means V to increase the amount of produced water vapor;
When the raw fuel gas supply amount gradually increasing process for gradually increasing the raw fuel gas supply amount to the reforming processing unit 3 by the adjusting valve 11 is performed, the steam generating unit heating means 9 is used as the steam generation amount increasing process. In the configuration for performing both the process of increasing the heat input amount to the steam generation unit and the process of increasing the water supply amount to the steam generation unit P by the adjustment valve 10, the process of increasing the heat input amount and the water supply amount. The timing for performing the process of increasing the can be variously changed.
For example, the process of increasing the water supply amount may be performed at the same time when the raw fuel gas supply amount is gradually increased, and the process of increasing the heat input amount may be performed before the process of increasing the water supply amount.

(D) When the steam generation amount increasing process is carried out by increasing the heat input amount to the steam generating part heating means 9, a specific configuration for adjusting the heat input amount to the steam generating part heating means 9 However, the configuration is not limited to the configuration in which the electric heater 7 is turned on and off as illustrated in the above embodiment. For example, it may be configured to adjust the amount of power supplied to the electric heater 7 or to adjust the amount of combustion exhaust gas supplied to the heat exchanger 8.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a hydrogen-containing gas generation device.

FIG. 2 is a diagram showing various states when increasing the amount of hydrogen-containing gas produced.

FIG. 3 is a diagram showing various states when increasing the amount of hydrogen-containing gas produced.

FIG. 4 is a diagram showing various states when increasing the amount of hydrogen-containing gas produced.

FIG. 5 is a diagram showing various states when increasing the amount of hydrogen-containing gas produced.

FIG. 6 is a diagram showing a state in which the heat input amount of the steam generator heating means is increased.

FIG. 7 is a graph showing the concentration of carbon monoxide produced as the amount of hydrogen-containing gas produced increases.

[Explanation of symbols]

1 Desulfurization unit 3 Modification processing section 4 Combustor (heating means for reforming process part) 5 Metamorphic processing section 6 Selective oxidation treatment section 7 Electric heater 8 heat exchanger 9 Steam generator heating means 10 Adjustment valve (water supply amount adjustment means) 11 Regulator valve (raw fuel gas supply amount adjustment means) 20 Control unit 21 Hydrogen-containing gas production amount adjusting means P Hydrogen-containing gas generator S Steam generator G fuel cell V Water vapor production amount adjusting means

Claims (9)

[Claims] 1. A steam producing part for producing water vapor by heating water with a steam producing part heating means and a reforming treatment part heating means to produce a hydrocarbon-based raw fuel gas in the steam producing part. In a hydrogen-containing gas generation apparatus including a reforming processing unit that reforms using steam to generate a hydrogen-containing gas, a steam generation amount in the steam generating unit and a raw fuel gas to the reforming processing unit A hydrogen-containing gas production amount adjusting method of adjusting a supply amount and adjusting a hydrogen-containing gas production amount in the reforming treatment unit, wherein the reforming treatment unit is used to increase the hydrogen-containing gas production amount. A method for adjusting a hydrogen-containing gas production amount, which comprises performing a steam production amount increasing process for increasing a steam production amount of the steam production unit before a time point of increasing a raw fuel gas supply amount to the steam generation unit. 2. The process for increasing the amount of steam generation is performed so that when the amount of raw fuel gas supplied to the reforming processing unit is increased, an amount of steam corresponding to the increase is generated. Method for adjusting the amount of hydrogen-containing gas produced. 3. A process for increasing the heat input to the steam generator heating means as the process for increasing the steam generation amount,
The method for adjusting the hydrogen-containing gas production amount according to claim 1 or 2, wherein at least one of the treatments for increasing the water supply amount to the water vapor production unit is performed. 4. A steam producing part for producing water vapor by heating water with a steam producing part heating means and a reforming treatment part heating means to produce a hydrocarbon-based raw fuel gas in the steam producing part. In a hydrogen-containing gas generation apparatus including a reforming processing unit that reforms using steam to generate a hydrogen-containing gas, a steam generation amount in the steam generating unit and a raw fuel gas to the reforming processing unit A method for adjusting a hydrogen-containing gas generation amount by adjusting a supply amount and adjusting a hydrogen-containing gas generation amount in the reforming processing unit, wherein the hydrogen-containing gas generation amount is increased by increasing the hydrogen-containing gas generation amount. A method for adjusting a hydrogen-containing gas generation amount, comprising: a process for increasing a steam generation amount for increasing a steam generation amount; and a raw fuel gas supply amount gradually increasing process for gradually increasing a raw fuel gas supply amount to the reforming processing section. 5. A steam producing section for producing water vapor by heating water with a steam producing section heating means and a reforming treatment section heating means to produce a hydrocarbon-based raw fuel gas in the steam producing section. A reforming processing unit that reforms using steam to generate a hydrogen-containing gas, a steam generation amount adjusting unit that adjusts the steam generation amount of the steam generating unit, and a raw fuel gas supply to the reforming unit. The raw fuel gas supply amount adjusting means capable of adjusting the amount, and the steam producing amount adjusting means to adjust the steam producing amount in the steam producing part, and the raw fuel gas supplying amount adjusting means to the reforming processing part. A hydrogen-containing gas generation apparatus comprising: a hydrogen-containing gas generation amount adjusting unit that adjusts a raw fuel gas supply amount to adjust the hydrogen-containing gas generation amount in the reforming processing unit. Production amount adjustment means In order to increase the hydrogen-containing gas production amount, the steam production amount of the steam production unit is changed before the time point of increasing the raw fuel gas supply amount to the reforming processing unit by the raw fuel gas supply amount adjusting means. A hydrogen-containing gas generator configured to perform a process for increasing the amount of steam generation, which operates the steam generation amount adjusting means to increase the amount. 6. The hydrogen-containing gas production amount adjusting means, when increasing the raw fuel gas supply amount to the reforming processing section by the raw fuel gas supply amount adjusting means, performs the water vapor production amount increasing process. The hydrogen-containing gas generator according to claim 5, wherein the hydrogen-containing gas generator is configured so as to operate the steam generation amount adjusting means so that an amount of steam corresponding to the increase is generated. 7. The water vapor production amount adjusting means, which is capable of adjusting the water supply amount to the water vapor producing portion, and the water vapor producing portion heating means, which is configured to be able to adjust the heat input amount. The hydrogen-containing gas production amount adjusting means, as the water vapor production amount increasing processing, a treatment for increasing the heat input amount to the water vapor producing section heating means, and the water vapor by the water supply amount adjusting means. The hydrogen-containing gas generation device according to claim 5 or 6, which is configured to perform at least one of treatments for increasing the amount of water supplied to the generation unit. 8. The reforming treatment section heating means is composed of a combustor for heating the reforming treatment section with combustion heat, and the steam generation section heating means is used for combustion exhaust gas discharged from the combustor. It is composed of a heat exchanger that heats water by heat exchange and an electric heater, and the hydrogen-containing gas production amount adjusting means increases the output of the electric heater to increase the heat input amount to the steam producing part heating means. The hydrogen-containing gas generator according to claim 7, which is configured as described above. 9. A steam producing part for producing water vapor by heating water with a steam producing part heating means and a reforming treatment part heating means to produce a hydrocarbon-based raw fuel gas in the steam producing part. A reforming processing unit that reforms using steam to generate a hydrogen-containing gas, a steam generation amount adjusting unit that adjusts the steam generation amount of the steam generating unit, and a raw fuel gas supply to the reforming unit. The raw fuel gas supply amount adjusting means capable of adjusting the amount, and the steam producing amount adjusting means to adjust the steam producing amount in the steam producing part, and the raw fuel gas supplying amount adjusting means to the reforming processing part. A hydrogen-containing gas generation apparatus comprising: a hydrogen-containing gas generation amount adjusting unit that adjusts a raw fuel gas supply amount to adjust the hydrogen-containing gas generation amount in the reforming processing unit. Production amount adjustment means A process for increasing the amount of generated steam that increases the amount of generated hydrogen-containing gas, the steam generation amount adjusting unit operates to increase the amount of steam generation of the steam generation unit; and the raw fuel gas supply amount adjusting unit. The hydrogen-containing gas generation device configured to perform the raw fuel gas supply amount gradually increasing process for gradually increasing the raw fuel gas supply amount to the reforming processing unit.