JP2003002605A - Method for operating and stopping steam reformer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the oxidation of a reforming catalyst for preventing its deterioration when starting to operate and stopping an apparatus for producing hydrogen. SOLUTION: This method for operating and stopping a steam reformer is that by using either one of reformer systems consisting of a reformer system (A) comprising a steam reformer and a carbon monoxide converter, a reformer system (B) comprising the steam reformer, the carbon monoxide converter and a carbon monoxide removal apparatus, and a reformer system (C) comprising the steam reformer and the carbon monoxide removal apparatus, and when the steam reformer is operated, the operation is started while preventing the oxidation of the reforming catalyst by setting the amount of air introduced into a combustion zone of the steam reformer less than the amount of air capable of completely burning a fuel gas and feeding a partially burning gas containing hydrogen and carbon monoxide produced by incomplete combustion of the fuel gas in the combustion zone into a reforming zone in the steam reformer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for starting and stopping a reformer by a steam reforming method for hydrocarbons and alcohols.

[0002]

2. Description of the Related Art Hydrogen is a basic raw material used for various purposes and is also used as a fuel for phosphoric acid fuel cells (PAEC) and polymer electrolyte fuel cells (PEFC). A steam reforming method is one of the methods for producing hydrogen. The steam reforming method uses methane, ethane, propane, butane, city gas, LP gas, natural gas, other hydrocarbon gas (including mixed gas of two or more kinds of hydrocarbons) and alcohols such as methanol and ethanol. This is a method of reforming with steam to generate a hydrogen-rich reformed gas. In the steam reforming method, those hydrocarbons and alcohols are converted into hydrogen-rich reformed gas by a catalytic reaction in a reformer, that is, a steam reformer.

FIG. 1 is a diagram schematically showing a steam reformer. In general, it is composed of a combustion section (heating section) in which a burner or a combustion catalyst is arranged and a reforming section in which a reforming catalyst is arranged. In the reforming section, hydrocarbons and alcohols react with steam to produce hydrogen-rich reformed gas. Since the reaction that takes place in the reforming section is accompanied by a large amount of heat absorption, heat is supplied from the outside for the progress of the reaction. When hydrocarbon is used as a raw material, a temperature of about 600 ° C. or higher is required, and when alcohol is used as a raw material, a temperature of about 250 to 400 ° C. is required. Therefore, the combustion heat (ΔH) generated by the combustion of the fuel gas in the combustion section by the air (combustion air) is supplied to the reforming section. A precious metal catalyst such as platinum is used as the combustion catalyst, and a Ni-based catalyst is used as the reforming catalyst.
A Ru-based catalyst or the like is used.

FIG. 2 is a diagram showing a mode example from hydrocarbon (raw material gas) to PEFC using the steam reformer as described above. Odorants such as mercaptans, sulfides, and thiophene are added to city gas and LP gas. Since the reforming catalyst is poisoned by these sulfur compounds and deteriorates in performance, they are introduced into the desulfurizer in order to remove the sulfur compounds. Next, steam from a separately provided steam generator is added, mixed and introduced into the reforming section of the steam reformer, and the hydrogen-rich reforming is performed by the reforming reaction of the raw material gas with steam in the reforming section. Gas is produced.

The reforming reaction when the source gas is methane is represented by "CH ₄ + 2H ₂ O → CO ₂ + 4H ₂ ". In the reformed gas produced, unreacted methane, unreacted water vapor, carbon dioxide produced, and carbon monoxide (CO) as a by-product are produced.
About 15% (volume%, the same applies below) is included. For this reason, the reformed gas is applied to a CO shift converter in order to remove by-product CO by converting it into carbon dioxide (CO ₂ ) and hydrogen. CO
In the shift converter, a catalyst such as a copper-zinc system or a platinum catalyst is used. Reaction in CO shifter "CO + H ₂ O → CO ₂ +
The unreacted residual steam in the reforming section is used as the steam necessary for "H ₂ ".

The reformed gas discharged from the CO shift converter is composed of hydrogen and carbon dioxide except for unreacted methane and surplus steam. Of these, hydrogen is the target component, but C
Also in the reformed gas obtained through the O-transformer, CO is not completely removed, but a slight amount of CO is still contained, although it is about 1% or less. For example, since the permissible concentration of CO in fuel hydrogen in PAFC is about 1%, the reformed gas that has passed through the CO shift converter can be used as it is as fuel hydrogen for PAFC.

On the other hand, C in fuel hydrogen supplied to PEFC
Allowable concentration of O is 100ppm (volume ppm, the same applies below)
Degree (10p depending on the constituent material of the fuel electrode, etc.)
pm), and if it exceeds this value, the battery performance will be significantly deteriorated, so the CO component must be removed as much as possible before being introduced into the PEFC. Therefore, after the CO concentration of the reformed gas is reduced to about 1% or less by the CO shifter,
It is applied to a CO remover (= CO selective oxidation reactor). C
In the O remover, an oxidizing agent such as air is added, and CO is removed by changing CO to CO ₂ by the oxidation reaction of CO (CO + 1 / 2O ₂ = CO ₂ ), and the CO concentration is 100 ppm or less, 10 ppm or less, or Reduce it to 5 ppm or less.

When alcohol is used as the raw material, the CO concentration in the reformed gas obtained by the steam reformer is 1
Since it is about 10% or less, when the reformed gas is used as fuel hydrogen for PAFC, it can be used as it is. However, when this reformed gas is used as fuel hydrogen for PEFC, it is applied to a CO remover in the same manner as above, and the CO concentration is 100 ppm or less, 10 ppm or less, or 5 p
It is supplied after being reduced to pm or less.

By the way, it is necessary to start and stop the steam reformer according to the demand of the obtained reformed gas. Along with this, it is necessary to start and stop the CO shifter connected to the steam reformer. When arranging the CO remover subsequent to the CO shifter, start and stop the CO shifter and the CO remover. There is a need to do. Further, when alcohol is used as a raw material in the steam reformer and the CO remover is connected to this, it is necessary to start and stop the CO remover.

In the present specification, a hydrogen production apparatus including a steam reformer and a CO shifter, a hydrogen production apparatus including a steam reformer, a CO shifter and a CO remover, a steam reformer and a CO remover. The hydrogen producing apparatus including the above will be referred to as a reformer system (A), a reformer system (B), and a reformer system (C), as appropriate.
These reformer systems may include a steam generator and the like. The combustion section and the reforming section mean the combustion section and the reforming section in the steam reformer, respectively. Combustion gas is supplied to the combustion section, and hydrocarbons and alcohols that are reformed by steam are supplied to the reforming section.The two are distinguished, and the combustion gas supplied to the combustion section is burned. As gas,
Hydrocarbons and alcohols supplied to the reforming section are called raw material gases.

For example, in a PEFC equipped with a reformer system,
Conventionally, at the time of the shutdown, in order to prevent the flammable gas from remaining in the reformer system and to maintain and protect the gas pressure balance on the fuel electrode side and the air electrode side of PEFC, the inside of the reformer system is protected with nitrogen. Purging using an inert gas such as. On the other hand, at the time of startup, it is necessary to raise the temperature of the reformer system to the operating temperature.
Therefore, the temperature is raised using an inert gas such as nitrogen or steam (steam) as a heat medium, except when an electric heater is attached. FIG. 2 is a diagram showing this aspect.

However, P used for general households
No inert gas can be used in EFC. That is, in order to use the inert gas, a separate facility for that purpose is required, and it is also necessary to manage the residual amount of the inert gas. Therefore, although it is unavoidable to use only steam as the heat medium at startup, when steam is used to raise the temperature,
A part of the reforming catalyst begins to be oxidized at around 400 ° C. When the reforming catalyst is oxidized, not only reduction treatment with hydrogen is required, but also redox is repeated to accelerate deterioration of the reforming catalyst, and frequent regeneration and replacement are required. .

In addition to this, it is also conceivable to raise the temperature of the CO shift converter by using the combustion exhaust gas in the combustion section of the steam reformer. FIG. 3 is a diagram showing this aspect. However, when the temperature of the combustion exhaust gas is increased as a heat medium when the steam reformer is started, oxygen in the combustion exhaust gas causes oxidation of the reforming catalyst. Therefore, not only reduction treatment with hydrogen is required, but also deterioration of the reforming catalyst is promoted by repeating oxidation and reduction.

[0014]

The inventors of the present invention have been studying and researching from various aspects in order to solve the above problems at the time of stopping and starting the steam reformer. And, at the time of stoppage, the combustion gas of the combustion part of the steam reformer is used, and at that time, by controlling the amount of combustion air (combustion air) relative to the amount of fuel gas supplied to the combustion part,
It has been found that oxidation of the reforming catalyst can be prevented. The present invention utilizes this fact to start and stop the
It is an object of the present invention to provide a starting method and a stopping method of a steam reformer which avoids oxidation of a reforming catalyst in a reforming section and prevents its deterioration.

[0015]

The present invention is directed to a reformer system (A) including a steam reformer and a CO shifter, a steam reformer and a C.
Method of starting steam reformer in reformer system (B) including O shifter and CO remover, or reformer system (C) including steam reformer and CO remover At the time of startup, the amount of air introduced into the combustion section of the steam reformer is set to be smaller than the amount of air that completely burns the fuel gas, and the amount of air and hydrogen generated by incomplete combustion of the fuel gas in the combustion section are set equal to each other. Provided is a method for starting a steam reformer, which is characterized in that a partial combustion gas containing carbon oxide is supplied to a reforming section of a steam reformer to start while preventing oxidation of a reforming catalyst. .

The present invention relates to a reformer system (A) including a steam reformer and a CO shifter, a reformer system (B) including a steam reformer, a CO shifter and a CO remover, and a steam reformer. A method for starting a steam reformer in any one of the reformer systems (C) including a reformer system and a CO remover, the fuel gas being introduced into the combustion part of the steam reformer at the time of starting. After the ratio of air and air (air ratio λ) is set in the range of 1.0 to 2.0 and burned in the combustor to heat the reformer of the steam reformer to 400 ° C., the steam reformer is heated. The amount of air introduced into the combustion part is set to be less than the amount of air that completely burns the fuel gas, and the partial combustion gas containing hydrogen and carbon monoxide produced by incomplete combustion of the fuel gas in the combustion part is steam reformed. By supplying to the reforming section of the reactor, the water is characterized by starting while preventing the oxidation of the reforming catalyst. It provides a method of starting Kiaratame reformer.

The present invention relates to a reformer system (A) including a steam reformer and a CO shifter, a reformer system (B) including a steam reformer, a CO shifter and a CO remover, and a steam reformer. A method for stopping a steam reformer in any one of the reformer systems (C) including a reformer system and a CO remover, wherein the amount of air introduced into the combustion section of the steam reformer at the time of the stop Is set to less than the amount of air that completely burns the fuel gas, and the partial combustion gas containing hydrogen and carbon monoxide generated by incomplete combustion of the fuel gas in the combustion unit is supplied to the reforming unit of the steam reformer. By doing so, a method for stopping the steam reformer is provided, which comprises purging the combustible gas and steam in the reformer system.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The steam reformer is basically composed of a burner or a combustion section in which a combustion catalyst is arranged and a reforming section in which a reforming catalyst is arranged. A steam reformer is used. As the reforming catalyst, for example, a Ni-based (for example, a catalyst in which Ni is supported on alumina) or a Ru-based (for example, a catalyst in which Ru is supported on alumina) or the like is used. When arranging the combustion catalyst in the combustion section, for example, a noble metal catalyst such as platinum or a combustion catalyst such as alumina hexanate is used.

In the CO shift converter, for example, a platinum catalyst (platinum catalyst) or a copper-zinc shift catalyst (CO shift catalyst) is used. Alternatively, the catalyst layer may be composed of two stages of a high temperature CO shift catalyst containing Fe and Cr as main components and a low temperature CO shift catalyst containing Cu and Zn as main components. Among these, the high temperature CO shift catalyst containing Fe and Cr as main components is
Since it functions by itself, it may be used without being used in combination with the low temperature CO shift catalyst. Noble metal catalysts such as platinum and ruthenium are used in the CO remover.

Here, the steam reformer and CO shifter in the reformer system (A), the steam reformer and CO shifter and CO remover in the reformer system (B), and the reformer system (C ), The steam reformer and the CO remover are those steam reformer, C
In addition to the case where the O-transformer and the CO remover are separately arranged, the steam reformer, the CO shifter, and the CO remover may be integrally formed. The same applies to any of these reformer systems. Further, the steam reformer includes a type in which a steam generator is separately arranged and a type in which a steam generator is integrally configured. However, the present invention is applied to any of these steam reformers. It

<< Embodiment at Startup >> In the reformer systems (A) to (C), the present invention first (1)
Fuel gas in the combustion section of the steam reformer is air (combustion air)
To indirectly heat the reforming section of the steam reformer to preheat the reforming catalyst in the reforming section to 400 ° C. or lower. The combustion of the fuel gas here may be combustion according to the air amount (air ratio) of (2) below, and the air ratio λ = 1.0 to
The combustion may be set in the range of 2.0.

Next, (2) the amount of air introduced into the combustion section of the steam reformer as a heat transfer medium to the reforming catalyst in the reforming section of the steam reformer is determined from the amount of air that completely burns the fuel gas. A small partial combustion gas containing hydrogen and carbon monoxide generated by incompletely combusting the fuel gas in the combustion section is supplied to the reforming section of the steam reformer. Thus, the reforming catalyst can be prevented from oxidizing, and the partial combustion gas can be used as a heat medium to rapidly start the reformer system.

As described in (2) above, in the present invention,
It is important to set less than the amount of air that completely burns the fuel gas. The amount of air is preferably the air ratio λ (= the amount of dry air actually supplied to the theoretically minimum amount of air required to completely burn the fuel gas in the combustion section of the steam reformer). Ratio) of 0.8 to less than 1.0, and sufficient mixing is required.

If incomplete combustion is started in the combustion section of the steam reformer while the temperature is not sufficiently raised, soot may be generated in the partial combustion gas. Further, thermal NOx may be generated due to the high temperature of the combustion part. When such a partial combustion gas containing soot is circulated to the reforming section, soot may be deposited (adhered) on the reforming catalyst to deteriorate the reforming catalyst. In this case, the steam generated from the steam generator for reforming attached to the steam reformer is added to the combustion section, or the feed water is dropped directly into the combustion section to remove the soot in the partial combustion gas. Suppression and reduction of thermal NOx due to reduction of combustion temperature can be achieved. Further, if the fuel and the air are preheated to 200 ° C. or higher, the generation of soot can be suppressed from the partial combustion gas having the air ratio set to 0.8 to less than 1.0.

In the present invention, in addition to the above basic configurations (1) and (2) at the time of startup, the following (3) to
Various modes such as (9) can be adopted. (3) In the reformer system (B) including the steam reformer, the CO shifter, and the CO remover, and the reformer system (C) including the steam reformer and the CO remover, the partial combustion gas contains Of the reducing gas contained, CO selectively reacts with the oxidant introduced into the CO remover to become an inactive component (CO ₂ ), and thus may be discharged outside the reformer system. Further, when the PEFC is connected to the reformer system, the PEFC may be discharged after being circulated in the PEFC, or hydrogen in the partial combustion gas may be used as a fuel for power generation. The oxidizing agent is air, oxygen-enriched air,
Oxygen or the like is used.

(4) In the mode in which hydrogen in the partial combustion gas that has passed through the CO remover is used as fuel for power generation, the steam and the raw material gas from the steam generator of the reformer system are introduced into the reforming section for reforming. By causing the reaction, more reformed gas can be introduced into the PEFC to generate power. In this case, by introducing a large amount of water vapor, the precipitation of carbon (soot) on the reforming catalyst can be suppressed. In addition, the CO conversion reaction (CO + H ₂ O → H ₂ + CO ₂ ) is promoted, and the steam reacts with the unreacted methane to reform, so that the amount of hydrogen in the reformed gas can be increased.

The combustion gas partially combusted in the combustion section of the steam reformer may contain a small amount of unburned oxygen. When the partial combustion gas containing oxygen is passed through the reforming section to the CO shift converter, the shift catalyst filled therein may be oxidized and deteriorated. In this case,
(5) A combustion catalyst layer is arranged after the reforming catalyst layer in the reforming section of the steam reformer, whereby unburned oxygen is reacted with hydrogen and CO in the partial combustion gas to be removed, and CO conversion is performed. It is possible to start while preventing oxidation of the CO shift catalyst filled in the vessel. (6) A bypass path is provided in a line (conduit) from the reforming section of the steam reformer to the CO shift converter, and the partial combustion gas flowing through the reforming section is discharged through the bypass path. It can also be made to flow through the bypass path to the CO remover. Figure 4
[Fig. 3] is a diagram showing this aspect.

Further, (7) after the partial combustion gas is circulated in the reforming section of the steam reformer, the discharged gas may be oxidized by air in a separately installed processing device. In this case, the heat generated by the oxidation treatment is
It can be heat-exchanged with water and stored as hot water in a hot water tank, or can be used for heating water required for a process such as heating water supplied to a steam generator. In addition, in the oxidation treatment, even if it is simply mixed with air and burned, it may be out of the burning range depending on the conditions, but in this case, fuel for support may be added separately and burned, A combustion catalyst may be used.
The problem of combustible range is cleared by using a combustion catalyst.

(8) When partial combustion is performed in the combustion section of the steam reformer, the unburned fuel may be generated due to non-uniform mixing of fuel gas and air. When such a partial combustion gas containing fuel (hydrocarbon-based fuel) is circulated in the reforming section, soot may be deposited (adhered) to the reforming catalyst. In this case, it is possible to prevent the precipitation by generating steam from a steam generator for reforming attached to the steam reformer and introducing the steam into the reforming section together with the partial combustion gas.

(9) At the time of starting the steam reformer, the fuel introduced into the combustion part of the steam reformer is circulated in the desulfurizer in advance, and the sulfur component (sulfur compound) contained in the fuel is removed to start the steam reformer. At times, it is possible to prevent the reforming catalyst from being poisoned by the sulfur component contained in the partial combustion gas. This point is similarly applied when stopping the steam reformer described below.

<< Embodiment at the time of stop >> In the present invention, the combustion gas from the combustion part of the steam reformer is used for purging the reformer system when the steam reformer is stopped. Also in this case, it is important to set the amount of air introduced into the combustion section of the steam reformer to be smaller than the amount of air that completely burns the fuel gas. The amount of air is preferably in the range of 0.8 to less than 1.0 in terms of the air ratio λ in the combustion section of the steam reformer. The partial combustion gas generated in the combustion section is a reducing gas containing hydrogen and carbon monoxide, so by supplying this to the reforming section, the reforming catalyst can be prevented from being deteriorated by oxidation while reforming. Combustible gases such as methane, hydrogen and carbon monoxide, carbon dioxide, water and water vapor remaining in the system can be purged and stopped.

The amount of air introduced into the combustion section is smaller than the amount of air which completely burns the fuel gas, for example 0.8 at an air ratio λ.
In the range of 1.0 to less than 1.0, the dew point of water in the partial combustion gas to be generated is about 50 to 60 ° C. Therefore, after the partial combustion gas is stopped flowing, steam reforming is performed so that the catalyst does not become a dew condensation atmosphere. It is necessary to keep the reforming section of the vessel warm. When the PEFC is connected to the reformer system, the temperature of the battery cooling water is about 60 to 80 ° C., and thus the battery cooling water is used for maintaining the temperature in the reformer system including the heat retention. can do.

When the steam reformer is stopped for a relatively long time, hot water from the hot water tank can be used. FIG. 5A to FIG. 5C are diagrams showing examples of these modes. FIG. 5 (a) shows an example in which hot water, for example, a battery cooling water pipe such as PEFC, is kept warm by winding it in a steam reformer, and FIG. 5 (b) shows a pipe in which the steam reformer is wound from a hot water tank An example of keeping warm by circulating hot water, FIG.
(C) is an example in which a steam reformer is arranged in a hot water tank to integrally keep the temperature. The warm water obtained in the above (7) can also be used as the warm water. Furthermore, by heating the reforming section with a heater from time to time, it is possible to control the temperature inside the reformer system to be kept at a temperature at which water does not condense.

[0034]

The present invention will be described in more detail based on the following examples, but it goes without saying that the present invention is not limited to these examples. City gas (13A) was used as the raw material gas and the fuel gas, and air was used as the oxidant supplied to the CO remover.

6 to 10 show a steam reformer and a C according to the present invention.
It is an example applied to a reformer system (B) including an O shifter and a CO remover. PEFC is connected to the reformer system. A burner is used as the combustion section of the steam reformer, a catalyst in which Ni is supported on alumina is used in the reforming section, a copper-zinc catalyst (Cu / Zn catalyst) is used in the CO shift converter, and a CO remover is used. Then, a catalyst in which Pt was supported on alumina was used. A temperature sensor was arranged in the reformer system according to a conventional method. In FIGS. 6 to 9, solid lines (pipes) marked with arrows indicate that the corresponding gas is flowing, and dotted lines without arrows and solid lines without arrows correspond. It shows that no gas is flowing.

<Starting operation = starting operation to normal operation state> At the time of starting, the fuel gas is first burned with air in the combustion section of the steam reformer (air ratio λ = 1.1), and the reforming section is indirectly operated. By heating, the reforming catalyst in the reforming section was preheated to 400 ° C. Even in an oxidizing atmosphere such as a steam atmosphere, the reforming catalyst hardly oxidizes up to 400 ° C. FIG. 6 shows this state.

After that, the air ratio λ in the combustion section of the steam reformer was changed to 0.95, and the partial combustion gas generated here was introduced into the reforming section. This partial combustion gas is used to heat the reforming catalyst, the CO shift catalyst, the CO selective oxidation catalyst (in the CO remover), the reformer system furnace material, the partition wall, etc. as a heat transfer medium. It was discharged, that is, purged through the reforming section of the quality control device, the CO shift converter, and the CO remover. Due to chemical equilibrium, soot is not generated from the partial combustion gas having an air ratio λ = 0.8 to less than 1.0.

CO and hydrogen in the partial combustion gas are CO
It is treated by reacting with air in the remover. The CO selective oxidation catalyst is heated faster by the heat generated at this time. Figure 7
Indicates this state. The purge gas may be discharged as it is, but by oxidizing it with air, it is possible to exchange the generated heat with water to store it as warm water, and to heat the water supplied to the steam generator. It can also be used to heat water required in the process such as by using it.

In this way, the temperature of the CO shift catalyst (Cu / Zn catalyst: low temperature CO shift catalyst) at which the activity appears (CO shift inlet temperature 200 to 350 ° C.), the CO shift catalyst was heated sufficiently. At that time, water was introduced into the steam generator to generate steam. At the same time, the supply of partial combustion gas from the combustion section of the steam reformer to the reforming section is stopped, and the air ratio λ
Is changed to a value during normal combustion (air ratio λ = 1.1), the raw material gas is introduced into the reforming section for steam reforming, and a CO converter,
The hydrogen-rich reformed gas that passed through the CO remover was introduced into PEFC to start power generation. The reformed gas remaining in the PEFC was used as the anode off gas in the combustion section of the steam reformer. Thus, the normal operation state was set. FIG. 8 shows this state.

<Operation Stop> After the above-mentioned normal operation, the reformer system was purged by using the partial combustion gas from the combustion part of the steam reformer, and the reformer system was stopped. That is, when the operation was stopped, the air ratio λ in the combustion section was set to a low range of 0.95 and the generated partial combustion gas was introduced into the reforming section to confirm the purging of the residual gas in the reformer system. Then, the combustion in the combustion section was stopped, and the temperature was lowered by natural cooling. 9 to 10 show this state.

The above startup, normal operation, and stop were repeated 30 times. At this time, the dew point of water in the partial combustion gas used when the operation was stopped is about 50 to 60 ° C., so that the temperature of the reforming catalyst does not fall below that temperature by natural cooling after the flow of the partial combustion gas is stopped. I rebooted. As a result, it was confirmed that there was no change in the composition of the reformed gas obtained from the CO remover during normal operation, and there was no performance deterioration of the reforming catalyst.

During the period from the stop to the restart, that is, during the stop of operation, the PEFC battery cooling water or hot water from the hot water tank is used to keep the temperature (see FIG. 5). When the temperature in the reformer system falls below 60 ° C. due to a long stoppage, the inside of the reformer system may be purged with a raw material gas, or the reformed gas may be stored in a tank during operation of the reformer system. It is also possible to store the reformed gas in the reformer system for purging.

[0043]

According to the present invention, a reformer system including a steam reformer and a CO shifter, a steam reformer, a CO shifter, and a CO shifter are provided.
In the reformer system including the reformer system including the remover and the reformer system including the steam reformer and the CO remover, the oxidation of the reforming catalyst is prevented at the time of starting and stopping, It is possible to prevent deterioration.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a steam reformer.

FIG. 2 is a diagram showing an example of a conventional method for starting a reformer system.

FIG. 3 is a diagram showing an example of a method of starting and stopping another reformer system that is conventionally conceivable.

FIG. 4 is a diagram showing an embodiment of the present invention.

FIG. 5 is a diagram showing an embodiment of the present invention.

FIG. 6 is a diagram showing an embodiment of the present invention (startup).

FIG. 7 is a diagram showing an embodiment of the present invention (startup).

FIG. 8 is a diagram showing an embodiment of the present invention (normal operation state).

FIG. 9 is a diagram showing an embodiment of the present invention (stop).

FIG. 10 is a diagram showing an embodiment of the present invention (stop)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01M 8/04 H01M 8/04 Y 8/06 8/06 G 8/10 8/10 (72) Inventor Naohiko Fujiwara 1-5-20 Kaigan, Minato-ku, Tokyo F-term in Tokyo Gas Co., Ltd. (reference) 4G040 EA02 EA03 EA06 EB01 EB12 EB31 EB32 EB42 EB43 EC03 5H026 AA04 AA06 5H027 AA04 AA06 BA01 BA17

Claims (19)

[Claims] 1. A reformer system (A) including a steam reformer and a CO shifter, a reformer system (B) including a steam reformer, a CO shifter and a CO remover, and a steam reformer. A method for starting a steam reformer in any reformer system of a reformer system (C) including a CO remover, wherein the amount of air introduced into a combustion part of the steam reformer is set as fuel when starting the steam reformer system. Supplying a partial combustion gas containing hydrogen and carbon monoxide generated by incomplete combustion of fuel gas in the combustion section to the reforming section of the steam reformer by setting the amount of air less than the amount of air that completely burns the gas. The method for starting a steam reformer is characterized by starting the reforming catalyst while preventing oxidation of the reforming catalyst. 2. A reformer system (A) including a steam reformer and a CO shifter, a reformer system (B) including a steam reformer, a CO shifter and a CO remover, and a steam reformer. A method for starting a steam reformer in any reformer system of a reformer system (C) including a CO remover, the fuel gas and air being introduced into a combustion part of the steam reformer at the time of starting. Ratio (air ratio λ) is set in the range of 1.0 to 2.0 and burned in the combustion section to heat the reforming section of the steam reformer to 400 ° C., and then the combustion section of the steam reformer. The amount of air introduced into the steam reformer is set to be less than the amount of air that completely burns the fuel gas, and the partial combustion gas containing hydrogen and carbon monoxide generated by incomplete combustion of the fuel gas in the combustion section is fed to the steam reformer. Steam reformer characterized by starting while preventing oxidation of the reforming catalyst by supplying to the reforming section How to start. 3. The method for starting a steam reformer according to claim 1, wherein the reformer system includes a steam reformer and a CO shifter, and a steam reformer system (A). CO transformer and C
The reformer system of any one of the reformer system (B) including the O remover, wherein the combustion catalyst layer is arranged at a subsequent stage in the reforming section of the steam reformer, and is passed through the reforming section. The steam reforming is characterized in that after the combustion gas is passed through the combustion catalyst layer, it is passed through a CO shifter subsequent thereto to start while preventing the oxidation of the CO shift catalyst filled in the CO shifter. How to start the pawn. 4. The method for starting a steam reformer according to claim 1, wherein the reformer system includes a steam reformer and a CO shifter, and a steam reformer system (A). CO transformer and C
A reformer system of any one of the reformer system (B) including an O remover, wherein a CO shifter arranged at a subsequent stage of the reforming section of the steam reformer is composed of a platinum-based catalyst layer, A method for starting a steam reformer, which is started by causing the partial combustion gas to flow through a reforming section of the steam reformer and a CO shift converter. 5. The method for starting a steam reformer according to claim 1, wherein the reformer system includes a steam reformer and a CO shifter, and a steam reformer system (A). CO transformer and C
It is one of the reformer systems of the reformer system (B) including the O remover, and the CO shifter arranged in the latter stage of the reforming section of the steam reformer has a high temperature mainly composed of Fe and Cr. CO shift catalyst and C
A low-temperature CO shift catalyst containing u and Zn as main components is constituted by two stages of catalyst layers, and the partial combustion gas is circulated through the reforming section of the steam reformer and the CO shifter to fill the CO shift converter. A method for starting a steam reformer, which is started while preventing oxidation of the existing CO shift catalyst. 6. The method for starting a steam reformer according to claim 1 or 2, wherein the reformer system includes a steam reformer and a CO shifter, and a steam reformer system (A). CO transformer and C
A reformer system of any one of the reformer system (B) including an O remover, wherein a bypass path is provided in a line from the reforming section of the steam reformer to the CO shift converter, and the bypass section is circulated to the reforming section. A method for starting a steam reformer, characterized in that the partial combustion gas is started by circulating the partial combustion gas in a bypass path and releasing the partial combustion gas. 7. The method for starting a steam reformer according to claim 1 or 2, wherein the reformer system is a reformer system (B) including a steam reformer, a CO shift converter, and a CO remover. A steam is characterized in that a bypass path is provided in a line from the reforming section of the steam reformer to the CO shift converter, and the partial combustion gas flowing through the reforming section is passed through the bypass path to the CO remover. How to start the reformer. 8. The method for starting a steam reformer according to claim 1, wherein the reformer system includes a steam reformer, a CO shifter, and a CO remover, and a steam reformer system (B). Reformer and C
A reformer system of any one of the reformer systems (C) including an O remover, wherein the partial combustion gas that has been made to flow to the reforming section of the steam reformer is made to flow to the CO remover and at the same time CO A method for starting a steam reformer, which comprises introducing an oxidizer into a remover and reacting carbon monoxide contained in a partial combustion gas with oxygen to remove the carbon monoxide. 9. The method for starting a steam reformer according to claim 1, wherein the partial combustion gas is passed through the reforming section of the steam reformer, and at the same time, the reformer system is provided. A method for starting a steam reformer, characterized in that the steam generated by the steam generator is circulated. 10. The method for starting a steam reformer according to claim 8 or 9, wherein the reformer system includes a steam reformer, a CO shifter, and a CO remover, and a steam reformer system (B). A reformer system (C) that includes a reformer and a CO remover, in which a fuel cell is connected to a subsequent stage of the CO remover, and carbon monoxide is used as a fuel in the CO remover. A method for starting a steam reformer, comprising supplying a partial combustion gas, which has been removed to an allowable value or less in a battery, to a fuel cell to generate power. 11. A reformer system (A) including a steam reformer and a CO shifter, a reformer system (B) including a steam reformer, a CO shifter and a CO remover, and a steam reformer. A method for stopping a steam reformer in any reformer system of a reformer system (C) including a CO remover, the method comprising: Supplying a partial combustion gas containing hydrogen and carbon monoxide generated by incomplete combustion of fuel gas in the combustion section to the reforming section of the steam reformer by setting the amount of air less than the amount of air that completely burns the gas. The method for shutting down a steam reformer is characterized by purging combustible gas and steam in the reformer system. 12. The method for stopping a steam reformer according to claim 11, wherein the reformer system includes a steam reformer, a CO shifter and a CO remover, and a steam reformer. Vessel and CO
A reformer system of any one of the reformer system (C) including a remover, and when the partial combustion gas which has been made to flow to the reforming section of the steam reformer is made to flow to the CO remover when the reformer system is stopped. at the same time,
A method for stopping a steam reformer, which comprises introducing an oxidant into a CO remover and reacting carbon monoxide contained in a partial combustion gas with oxygen to remove the carbon monoxide. 13. The method for stopping a steam reformer according to claim 12, wherein the reformer system includes a steam reformer, a CO shifter, and a CO remover, and a steam reformer. Vessel and CO
A reformer system (C) including a remover, wherein a fuel cell is connected to a subsequent stage of the CO remover, and when the fuel cell is stopped, carbon monoxide is removed from the CO remover. A method for stopping a steam reformer, which comprises purging combustible gas in a fuel cell with the partially burned gas. 14. A method for stopping a steam reformer according to claim 11, wherein after the stop, the temperature of the reforming catalyst of the steam reformer is maintained at a dew point temperature of the partial combustion gas or higher. The method for stopping a steam reformer is characterized by preventing the steam in the partial combustion gas contained in the reforming section from condensing. 15. The method for stopping a steam reformer according to claim 14, wherein the reformer system includes a steam reformer, a CO shifter and a CO remover, and a steam reformer. Vessel and CO
A reformer system (C) that includes a eliminator, and a fuel cell is connected to the latter stage of the CO eliminator. A method for stopping a steam reformer, characterized in that the temperature of a reforming catalyst in a reforming section of a steam reformer is maintained at a dew point temperature of a partial combustion gas or higher. 16. The method for stopping a steam reformer according to claim 11, wherein the temperature of the catalyst in the reforming section of the steam reformer is a partial combustion gas after the stop until restarting. A method for stopping a steam reformer, characterized in that the reformer is heated by a heater so that the temperature does not drop below the dew point temperature. 17. The method for starting or stopping the steam reformer according to claim 1, wherein the reforming catalyst arranged in the reforming section is a Ni-based or Ru-based reforming catalyst. A method characterized by the following. 18. The method for starting or stopping the steam reformer according to claim 1, wherein the fuel introduced into the combustion section of the steam reformer is preliminarily circulated to the desulfurizer and contained in the fuel. The method is characterized by removing the sulfur component that is generated. 19. The method for starting or stopping the steam reformer according to claim 1, wherein the partial combustion gas is circulated through the reforming section of the steam reformer and then discharged. A method in which the oxidation treatment is performed with air in a treatment device separately installed.