JP2003277005A - Hydrogen manufacturing apparatus, system for generating electricity by using the same, and method for operating the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen manufacturing apparatus in which a plurality of reforming reactors are operated in combination with one another and the temperature of each of the reforming reactors in operation is kept optimum whether the amount of hydrogen to be manufactured is large or small. <P>SOLUTION: In a low-load operation mode of manufacturing a small amount of hydrogen, hydrogen is manufactured mainly in a group A of the reforming reactors and weak partial oxidation reaction is performed in a group B of the reforming reactors of stand-by states to restrain the temperature of the whole reforming system from being lowered. In a high-load operation mode of manufacturing a large amount of hydrogen, the manufacture of hydrogen is started by using the groups A and B at the same time and the ratio of exothermic reaction (partial oxidation reaction) is the group A is made low to restrain the excessive rise of the temperature. As mentioned above, a plurality of groups of the mutually heat-transferable reforming reactors are combined with one another, the amount of raw fuel to be supplied for specifying the ratio of the exothermic reaction in each group according to the requested amount of hydrogen to be manufactured can be controlled to be changed over. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrogen production apparatus, a power generation system using the hydrogen production apparatus, and an operating method thereof.

[0002]

2. Description of the Related Art Various methods are known for industrial hydrogen production processes. According to Hiroo Tominaga and Masakazu Tamaki, “Chemical Reaction and Reactor Design” (Maruzen Co., Ltd., 1996), page 221, electrolysis of water, gasification of coal / coke, steam reforming of hydrocarbons, and hydrocarbon fractions. Processes such as oxidation, hydrocarbon dehydrogenation are shown. Historically, the method was the forerunner of the process, but at present, the method of using petroleum and natural gas hydrocarbons as the raw material is the mainstream. These processes were developed mainly for the production of hydrogen for ammonia synthesis, but they are also considered to be applied as a basic process of hydrogen production in fuel cell power generation systems that generate electricity using hydrogen as one of the main raw materials. Has been done. In a power generation system typified by a fuel cell power generation system, it is desired that the hydrogen production apparatus be downsized, the apparatus startup time be shortened, and the load response be promptly changed. For this reason, it takes a sufficient time to raise the temperature of the apparatus, and it is necessary to devise a method different from the industrial hydrogen production process in which the operation is continued once the operation is started.

As an example of the above-mentioned device, Japanese Patent Laid-Open No. 2000-2
Japanese Patent Publication No. 85948 proposes a hydrogen production apparatus in which two or more series hydrogen production systems each having a capacity smaller than the maximum hydrogen production capacity of the system are provided in parallel. In the hydrogen production device, by combining the operation and stoppage of a plurality of hydrogen production systems each performing steam reforming,
The amount of hydrogen produced can be switched quickly. Here, in the steam reforming method, hydrogen is produced by a chemical reaction mainly composed of an endothermic reaction, so that each hydrogen production system requires a heating means (heat source). Alternatively, it is necessary to heat the entire reforming reactors with a heat source having a large capacity.

On the other hand, Japanese Patent Laid-Open No. 2001-114502
The publication discloses a combined hydrogen production apparatus in which a plurality of reforming reactors and a plurality of combustors are combined to enable mutual heat transfer. By adopting a hydrogen production process (combined reforming) that combines a steam reforming reaction and a partial oxidation reaction from a hydrocarbon-based substance such as methanol as a raw material, each reforming reactor is different from other reforming reactors. Can function as a heating means (heat source). In Japanese Patent Laid-Open No. 2001-114502, paying attention to this point, one reforming reactor is always supplied with a constant amount of raw fuel for hydrogen production operation, and heat generated by reaction and auxiliary heating by a combustor. A system in which other reforming reactors are held in a standby state (hot standby), and a predetermined amount of raw fuel is supplied to the reforming reactors in the hot standby state to start hydrogen production as needed. Is proposed. By combining the operation and shutdown of multiple hydrogen production systems that each perform simultaneous reforming, not only can the hydrogen production volume be switched quickly, but also the heat transfer between the reforming reactor and the combustor can be effectively utilized. The thermal efficiency.

The operation method of the hydrogen production device described in Japanese Patent Laid-Open No. 2001-114502 can be expected to be effective as a hydrogen production device for an on-vehicle fuel cell power generation system.
In the case of automobiles, the frequency of the output required for normal city driving is distributed so as to have a peak at 10 kW or less, so the amount of hydrogen produced during constant operation of hydrogen production should be adjusted to the peak output. If hydrogen production is started in a hot standby reforming reactor only when a higher output is set, a large reforming reactor that matches the capacity to the maximum output will not be wasted. It is possible to provide a hydrogen production device for a vehicle, which has excellent startability, responsiveness, and reaction stability as compared with the case where the temperature is raised to 0 or the reaction state is changed.

[0006]

However, in the hydrogen production apparatus disclosed in the above-mentioned Japanese Patent Laid-Open No. 2001-114502, during the low load mode operation in which the reforming reactor for varying the capacity is in the hot standby state, In some cases, the temperature of the entire manufacturing apparatus has dropped. This is due to heat release from the reforming reactor in the hot standby state, and the degree thereof depends on how to combine a plurality of reactors. Here, let's focus on the case where the temperature of the entire hydrogen production apparatus falls. In that case, there was a problem that the required reaction temperature could not be maintained, and the amount of hydrogen produced in the low load operation mode would decrease.

According to the steam reforming method described in JP-A-2000-285948, there is no problem of the temperature decrease. This is because the steam reforming system is provided with heating means (heat source) sufficient to maintain the reaction temperature of each reforming reactor. However, since there is the heating means (heat source), it is difficult to miniaturize the device, and there is a problem that heat transfer loss increases due to heating from the outside of the reactor.

[0008] Miniaturization and high efficiency of the hydrogen production device are necessary requirements for hydrogen production devices for fuel cells, including those for vehicles, and are important for practical use as well as weight reduction of the device.
Especially in the case of in-vehicle use, not only the fuel cell but also the engine system using hydrogen for direct combustion has the same demand.

An object of the present invention is to maintain an optimum temperature of the reforming reactor during operation in a hydrogen producing apparatus which operates by combining a plurality of reforming reactors, regardless of the amount of hydrogen produced. .

[0010]

In the present invention, the above-mentioned Japanese Patent Laid-Open No.
Similar to Japanese Patent Publication No. 001-114502, the operating states of a plurality of reforming reactors mainly for combined reforming are switched according to the required hydrogen production amount, but at that time, only the operation / stop of each reforming reactor is instructed. Instead, the ratio of the exothermic reaction was specified for each reforming reactor, and the ratio was switched according to the hydrogen production amount. To change the ratio of the exothermic reaction, the amount of raw fuel supplied to the reforming reactor may be changed. Practically, several reforming reactors are put together into one reforming reactor group,
It is easy to handle if the switching control of the raw fuel supply is performed for each reforming reactor group. Here, for simplification, the case of one reforming reactor will be included as a special case of the reforming reactor group.

In the hydrogen producing apparatus according to the present invention, a predetermined reforming reactor group can be switched and used as a heat source for another reforming reactor group in a predetermined operation mode. Therefore, the hydrogen production device having a plurality of reforming reactors can be efficiently operated in a plurality of operation modes, that is, over a wide range of hydrogen production amount. In fact, it has been found that the problem of the temperature drop in the low load operation mode described in the above problem can be easily solved by using a weak partial oxidation reaction together in the reforming reactor group in the hot standby state. There, the reforming reactor in the hot standby state is used as a heat source. In this sense
The reforming method of each reforming reactor according to the present invention is not limited to the combined reforming. Here, it is not always necessary to always use all of the reforming reactors in the hot standby state as heat sources, but at least a part of the reforming reaction tubes that had been standing by without causing a reaction causes an oxidation reaction and heats the reaction tubes. It is important to utilize as. Although part of the feed fuel is consumed due to the partial oxidation reaction, according to the simulation, the reaction temperature related to hydrogen production can be maintained at a high temperature, so that the reforming efficiency of the hydrogen production apparatus as a whole is improved. As a matter of course, in another operation mode, the supply amount of the raw fuel is switched and controlled so that the hydrogen production is actively started in the reforming reactor group in the hot standby state. It is important to switch and control the ratio of the raw fuel supply for each operation mode and each reforming reactor group while considering the heat exchange between the reforming reactor groups. At that time, it is important for effective heat exchange that the ratio of the supplied raw fuel is determined so that the reaction heat generation amounts of the respective reforming reactor groups satisfy mutually appropriate magnitude relationships.

[0012]

Embodiments of the present invention will be described in detail below with reference to the drawings.

FIG. 1 shows a hydrogen producing apparatus according to a first embodiment and a fuel cell power generation system using the hydrogen producing apparatus. Since it is a diagram for explaining the characteristics of the operation of the combined hydrogen production device, detailed portions of the configuration are omitted.

First, each part will be described.

In the two system configuration diagrams of FIG. 1, the upper stage shows the operation in the low load mode, and the lower stage shows the operation in the high load mode. Here, the low (high) load operation mode is representatively shown when the required hydrogen production amount is relatively small (large).

In the figure, 11, 12 and 13 are raw fuels supplied to the reforming reactor, which are oxygen (air), methanol and water, respectively. Instead of methanol, city gas (methane), gasoline, or raw fuel chemically synthesized from natural gas may be used. However, the optimum reaction temperature differs depending on the type of raw fuel. 2 is a means for supplying raw fuel. The liquid supply means can be configured by combining a booster that boosts the primary pressure of the feed raw fuel, a solenoid valve for opening the boosted feed raw fuel to the secondary side, and starting the feed. The liquid fuel on the secondary side may be directly sprayed into the reforming reactor by an injector, or may be supplied to the reforming reactor after being vaporized by providing a vaporizer before charging the reforming reactor. Good. The supply amount of the liquid fuel can be controlled by the boosting amount on the primary side, but when the required hydrogen production amount is discretely set, the boosting amount is kept constant and the open / closed states of multiple solenoid valves are combined to supply the liquid fuel. The amount can be variable. The gas (air) supply means can be configured by using a blower or the like whose rotation speed can be variably controlled. When increasing the supply amount of the gaseous fuel, the rotation speed may be increased, and when decreasing, the rotation speed may be decreased. Of course, the number of rotations of the blower may be kept constant and a flow rate control means such as a butterfly valve may be provided in the subsequent stage.
Leakage can occur in the butterfly valve when it is closed, but the gas supply can be stopped by stopping the rotation of the blower. Of course, an on-off valve such as an electromagnetic valve may be combined with the control of the supply amount of the gaseous fuel. If there is no cost constraint, a more advanced flow rate controller may be provided as each raw fuel supply means.
4a and 4b show the reforming reactor groups A and B, respectively, as a representative of one reaction tube. As already mentioned,
Even when the reforming reactor used is only one reaction tube, it was decided to include it in the reforming reactor group. 7 is a reforming reactor group A, B
Is a power generation means for generating power using a reformed gas (hydrogen rich gas) manufactured by. As the power generation means 7, a fuel cell represented by a polymer electrolyte fuel cell (PEFC) can be used. Not limited to the fuel cell, a means for directly burning hydrogen to generate power may be considered. An external combustion engine or an internal combustion engine can be used for direct combustion of hydrogen. Instead of generating electricity
The system may be configured with 7 as the power generation means for obtaining power by direct combustion of hydrogen. In this case, an engine that directly burns hydrogen can be used as the power generation means. Reference numeral 81 is a processing means for giving the amount of supplied raw fuel. Reference numeral 82 is a storage means having information necessary for determining the amount of raw fuel supply. Reference numeral 9 denotes a combustor group (temperature adjusting means) that recirculates and combusts surplus hydrogen of the power generation means 7. In the combustor group, not only the surplus hydrogen but also a part of the raw fuel may be separately supplied and burned. White arrows in FIG. 1 indicate heat transfer in the reforming reactor group and the combustor group. The heat transfer required in the following description was extracted and schematically shown. Further, x 1 is an exothermic reaction ratio defined by Equation 1.

[0017]

[Equation 1] The types of exothermic reaction and endothermic reaction differ depending on what kind of reaction is used. Since chemical reactions generally occur through complicated reaction paths, when defining the exothermic reaction ratio, rather than discussing the exact description of the exothermic reaction and endothermic reaction, the main reactions are extracted and defined. Is convenient in design. Here, it is important that there is a strong correlation between the exothermic reaction ratio and the actual reaction temperature rather than the value of the defined exothermic reaction ratio itself.

Next, the operation of the hydrogen producing apparatus according to the first embodiment and the fuel cell power generation system using the hydrogen producing apparatus will be described.

First, the operation mode command 101 is given to the processing means 81. When there is a low load mode command, as shown in the upper part of FIG. 1, and when there is a high load mode command, as shown in the lower part of FIG. 1, the exothermic reaction ratio x of the reforming reactor group is determined to switch the amount of raw fuel supply. Control was implemented. This allows
A desired reaction temperature balance was provided between the reforming reactor groups. The operation mode command 101 may be externally given by a user, or may be automatically given in an internal sequence. In the latter case, if the operation mode is determined according to the magnitude of the load applied to the output end of the power generation means 7 and the free capacity of the power storage means (secondary battery) not shown in the figure, load follow-up and secondary battery The amount of hydrogen required for charging can be automatically produced without any external instruction.

The operation mode command 101 not only specifies a mode such as a low load or a high load, but also is specific numerical information such as, for example, how much volume the hydrogen production amount per unit time is in the standard state. Good. The processing means 81 reads a set of flow rate setting values from the storage means 82 in accordance with each operation mode command 101. The result is sent to the raw fuel supply means 2 as the fuel supply amount command 104. The raw fuel supply means 2 operates so as to realize a flow rate set value according to the fuel supply amount command 104. The specific operation content depends on the hardware configuration of the raw fuel supply means 2.
As an example, when the flow rate is set by combining the open / closed states of a plurality of valves, the processing means 81 changes the raw fuel supply means 2 from the processing means 81.
The opening and closing settings are transmitted to each valve. In this case, the solenoid valve may be directly driven to open or close, or only the command signal may be sent to a separately provided valve opening / closing means to open / close each valve by an air pressure signal generated by the valve opening / closing means. When the valve opening is adjusted to determine the flow rate, the processing unit 81 may provide the valve opening as an electric signal. When the flow rate is controlled by controlling the rotation speed of the blower, the processing unit 81 may give the set value of the rotation speed of the blower as an electric signal. Alternatively, the electric power necessary to drive the blower at the rotation speed may be directly supplied. Furthermore, when using a sophisticated flow rate controller, the flow rate set value of each raw fuel supply may be given from the processing means 81 to each flow rate controller.

When switching the feed raw fuel amount in accordance with the fuel feed amount command 104, the exothermic reaction ratio x _B of the reforming reactor group _B is set to 1 in the low load operation mode. The exothermic reaction ratio of 1 means that only the exothermic reaction occurs according to the definitional expression of Equation 1. If the exothermic reaction is a partial oxidation reaction, hydrogen can be obtained by the reaction, though it is less than the steam reforming reaction which is an endothermic reaction. If it is a complete oxidation reaction, hydrogen will not be generated as in a general combustor. In any case, the generated heat is used together with the heat of the combustor group 9 to heat the reforming reactor group A. Although the net heat generation is expected by the reforming reactor group A alone, the magnitude thereof is not always sufficient to raise the temperature of all the other reforming reactor groups in the operation stop state. Here, if the raw fuel is not supplied to the reforming reactor group B, the heat of the reforming reactor group A is taken to the reforming reactor group B, and the reforming reactor group A is practically used as the original heat. The reaction temperature may not be maintained in some cases. In the low load operation mode, the reforming reactor group B is heated by using the reforming reactor group B as an auxiliary heat source, thereby maintaining the reaction temperature required for hydrogen production of the reforming reactor group A. . In the low-load operation mode combined hydrogen production apparatus, most of the hydrogen is produced by the reforming reactor group A, but the exothermic reaction is carried out by the reforming reactor group B. Group B does not adversely affect the reaction temperature of reforming reactor group A.

On the other hand, in the high load operation mode, the exothermic reaction ratio of both the reforming reactor groups A and B is set to be between 0 and 1. In this case, since the reforming reactor groups A and B have both started the reaction for hydrogen production, the amount of hydrogen produced increases according to the total number of reforming reactors. In the high load operation mode combined hydrogen production apparatus, hydrogen is produced by both the reforming reactor groups A and B.

As a supplement, in the low load operation mode,
A method of completely stopping the supply of the raw fuel to the reforming reactor group B and maintaining the temperature only by the combustor group 9 can be considered as in the conventional case. However, note the following points. Combustor group 9
Then, the surplus hydrogen is combusted, but when the temperature of the reforming reactor group A decreases, the amount of generated hydrogen decreases, and the surplus hydrogen amount also decreases.
As a result, the heat generation of the combustor group 9 is reduced, which may lead to a vicious cycle in which the reaction temperature further decreases. In order to avoid this, in the low load operation mode, there is a method of supplying another fuel to the combustor group 9 to maintain heat generation, but a part of the heat generation is used for raising the temperature of the reforming reactor group B. There is always a loss of heat transfer. If the exothermic reaction is directly generated in the reforming reactor group B and the temperature is maintained as in the first embodiment of the present invention,
It is possible to eliminate unnecessary heat generation in the combustor group 9.

As another supplement, FIG. 1 shows only two types of reforming reactor groups, but similar switching control can be performed for a larger number of reforming reactor groups. For example, A, B, C
When three types of reforming reactor groups are provided, first, in the low load operation mode, hydrogen is produced by A, and B and C are used as heat sources. Next, in the medium load operation mode, hydrogen is produced by A and B, and C is used as a heat source. Finally, in the high load operation mode, hydrogen is produced in all of A, B and C. The reforming reactor group may be used in combination with the combustor group 9 which is an auxiliary heat source. It is important that the three types of reforming reactor groups of A, B, and C can exchange heat with each other. By this method, it is possible to make the step of switching the hydrogen production amount fine and to widen the dynamic range of the hydrogen production amount.

In the following examples, for simplicity, only the case of switching between the low load operation mode and the high load operation mode will be described. However, as described above, the switching control is performed for a larger number of reforming reactor groups. Of course, it is also possible.

According to the first embodiment described above, even if the hydrogen production apparatus comprising a plurality of reforming reactors is operated in the low load operation mode, the reforming reactor group in the standby state takes charge of hydrogen production. Does not lower the reaction temperature of the reforming reactor group.
As a result, the reforming efficiency in the low load operation mode can be maintained high.

Further, in the high load operation mode, the raw fuel supply amount is switched according to the command, and hydrogen production is started in the reforming reactor in the standby state. Therefore, a complex hydrogen producing system in which a plurality of reforming reactors are combined is produced. The device can be operated efficiently over a wide range of hydrogen production.

With the above effects, it is possible to provide the feature of the composite hydrogen production apparatus, which is excellent in startability and responsiveness, in a form for practical use.

FIG. 2 shows a system configuration example of a hydrogen production apparatus according to the second embodiment and a power generation system using the hydrogen production apparatus.

First, each part will be described.

In the figure, reference numeral 1 represents a supply source of various raw fuels. Air, methanol, and water were shown as raw fuels. The thick arrows in the figure collectively show independent flows related to a plurality of types of raw fuel. As the air supply source, the air can be used as it is, in addition to the air cylinder.
As an example of the supply source of methanol, a methanol storage tank can be used. For example, methanol can be taken out from the tank by pressurizing with nitrogen. Alternatively, it may be taken out by a transfer means such as a pump. A pure water tank may be used as the water supply source,
City water may be used as a supply source if ion exchange processing or evaporation processing that does not cause the mixture of droplets is performed in the subsequent stage. 2a and 2b are means for supplying raw fuel. Although a supply means is provided for each of the plurality of types of raw fuel, it is omitted here. The specific example of the supply means has been described in the first embodiment. 3a and 3b are pretreatment means for each raw fuel. The pretreatment means changes the state in advance so that each of the supplied raw fuels performs an appropriate reaction in the reforming reactor,
It is a means for removing foreign matter mixed in.
Pretreatment means suitable for each of a plurality of types of raw fuel are provided. The pretreatment means for air is composed of a filtering means for removing dust and dirt, a catalyst and activated carbon for removing sulfur compounds, and a heating means for raising the temperature. The actual configuration depends on the environment in which the device is used. As an example, in an automobile exhaust gas rich environment, it is desirable to have a process to remove the sulfur compounds that cause catalyst poisoning. The pretreatment means may be omitted in a relatively clean environment. The pretreatment means for methanol comprises means for vaporizing liquid fuel (vaporizer / evaporator), heating means for raising the temperature of vaporized methanol, and the like. Methanol and water may be mixed in advance and supplied as methanol water. In that case, a premixing means is provided as a pretreatment means. For methanol, the pretreatment means may be omitted and the liquid may be directly sprayed into the reforming reactor by an injector or the like. The pretreatment means for water can be configured in the same manner as in the case of methanol for vaporization and heating. However, when water is directly sprayed into the reforming reactor with an injector or the like as a liquid, a filtering means for removing impurity components contained in water or a means for ion exchange treatment may be required. . 4a, b
Is a group of reforming reactors that independently control fuel supply. It is important that heat can be exchanged between a plurality of reforming reactor groups. For example, the use of an insulating material does not completely eliminate the heat exchange, but the heat exchange possibility indicates a case where a significant temperature influence can be brought between the reforming reactor groups. The reforming reactor groups 4a and 4b are
It is arranged that heat can be exchanged with a combustor group (temperature adjusting means) 9 that generates heat by burning surplus hydrogen gas of the power generation means 7. Reference numeral 5 is a CO conversion means for reducing the CO concentration by using the shift equilibrium reaction. The CO conversion means is filled with a predetermined amount of a catalyst that promotes the reaction. The shift equilibrium reaction is shown in Equation 2.

[0032]

[Equation 2] As an example, when a suitable catalyst is used and the ambient temperature is set to about 200 to 250 ° C., CO reacts with water by the shift equilibrium reaction and is converted into carbon dioxide and hydrogen.
As a result, the CO concentration can be reduced to about 1% or less. Reference numeral 6 denotes a CO removing means for newly introducing air, oxygen, or an oxidant from the outside to oxidize and remove CO. The CO removing means is filled with a predetermined amount of a catalyst that promotes the oxidation reaction. Since the generated hydrogen is also oxidized in the oxidation reaction at the same time, it is desirable that the catalyst has a selectivity to selectively oxidize only CO. As a result, the CO concentration can be reduced to about several ppm or less. The reduction of CO concentration is particularly important when a polymer electrolyte fuel cell (PEFC) is used as the power generation means 7. This is because the platinum catalyst used for the electrode of the polymer electrolyte fuel cell is poisoned by even a small amount of CO, and the catalytic action necessary for ionization of hydrogen cannot be obtained. On the other hand, when a solid oxide fuel cell (SOFC) operating at a higher temperature is used as the power generation means 7,
The problem of CO poisoning is relatively small. In this case, the CO conversion means 5 and the CO removal means 6 may be omitted. SOFC
Has a high reaction temperature and is relatively resistant to the inclusion of impurities, the pretreatment means 3a and 3b can be simplified or omitted. Reference numeral 81 is a processing means for giving the amount of raw fuel supply according to the operation mode. Reference numeral 82 is a storage means (memory) for storing the amount of each raw fuel to be supplied according to the operation mode. 101 is the operation mode command described in the embodiment of FIG. Reference numeral 102 is information relating to the hydrogen production reaction, such as the reaction temperature of each reforming reactor group. 10
3 is operation information of the power generation means 7. The driving information is
Not only the information on the operating state such as the operating temperature of the power generation means 7 (the information on the reaction state in the case of a fuel cell), but also the information on the load state on the output side may be used. 104a,
b is a fuel supply amount command for setting the supply of the raw fuel according to the operation mode. Reference numeral 200 denotes a composite reactor in which a plurality of reforming reactor groups and a combustor group (temperature adjusting means) capable of mutually heat transfer are combined. As described above, the composite hydrogen production apparatus and the entire power generation system using the hydrogen production apparatus were configured.

Next, the function of the system configuration shown in FIG. 2 will be described.

The processing means 81 issues a fuel supply instruction 104 to each raw fuel supply means 2 in response to the operation mode instruction 101. The fuel supply command 104 sets the required amount of raw fuel supply. The optimum amount of raw fuel supply for each operation mode is
It is stored in the storage means 82 in advance. Processing means 81
Reads out the optimum supply raw fuel amount from the storage means 82 in accordance with the operation mode command 101. Fuel supply amount command 104
Accordingly, the raw fuel supply means 2 switches the amount of raw fuel supplied to each reforming reactor group. In this way, the exothermic reaction ratio is selected for each reforming reactor group so that heat generation is prioritized or hydrogen production (endotherm) is prioritized. To what extent the exothermic reaction or endothermic reaction is preferentially performed in each reforming reactor group is determined by the selected operation mode and the arrangement relationship of each reforming reactor group. For specific examples,
This will be described in the following examples. The reformed gas generated as a result of the reaction is improved to have a gas composition suitable for the power generation means 7 in the CO shift conversion means 5 and the CO removal means 6 in the subsequent stage. As mentioned above, depending on what kind of means is selected for the power generation means 7,
It is also possible to omit these latter-stage processes. Power generation means 7
The remaining hydrogen-containing gas is combustor group (temperature control means) 9
It was used as a fuel to help maintain the temperature of the hydrogen production reaction. When the hydrogen-containing gas is insufficient at the time of starting hydrogen production, a combustion fuel, such as methanol, may be separately supplied to the combustor group (temperature adjusting means).

In the hydrogen production reaction, it is ideally desirable to be able to continue the same reaction repeatedly, but in reality, it usually changes over time due to deterioration of the catalyst and the like. Therefore, the operating state of each reforming reactor group is monitored as the operation information 103. As an example, after switching the operation mode, even if a predetermined time has elapsed, a predetermined operating temperature (reaction temperature)
In the case of not being obtained, it can be seen that the catalyst involved in the exothermic reaction has deteriorated. In that case, the processing means 81 reads the raw fuel supply amount suitable for catalyst deterioration from the storage means 82. As the amount of raw fuel supply suitable for catalyst deterioration,
For example, when it is necessary to correct the shortage of heat generation, the raw fuel supply amount is set so as to increase the exothermic reaction ratio. Further, the operation information 102 provides information on the operating state and output of the power generation means 7, for example, information on output voltage and current. If the output of the power generation means 7 becomes insufficient due to deterioration over time as compared with the initial characteristics, the raw fuel supply amount that similarly corrects the deterioration of the power generation means is read from the storage means 82. When it is necessary to correct the decrease in output as a raw fuel supply amount suitable for deterioration of the power generation means, reduce the exothermic reaction ratio of the reforming reactor group that contributes to hydrogen production and increase the hydrogen production amount. You can By providing a plurality of data sets (maps) in the storage means 82 and adjusting the exothermic reaction ratio of each reforming reactor group, it is possible to correct the changes over time in the reforming reactor groups 4a, 4b and the power generation means 7. I chose

As a supplement, the CO shift conversion means and the CO removal means may be provided independently for each reforming reactor group, instead of collectively treating the outlet gases of a plurality of reforming reactors. When the CO conversion means and the CO removal means are independently provided for each reforming reactor group, an abnormality occurs in a specific reforming reactor group, and as a result, the gas composition changes to change the CO conversion means and CO
Even in a situation where the catalyst of the removal means is deactivated, the CO conversion means and the CO removal means of the other reforming reactor groups do not have to be adversely affected, so that the hydrogen production operation can be continued.

According to the second embodiment described above, the exothermic reaction ratio of each of the plurality of reforming reactor groups capable of transferring heat to each other can be independently set for each operation mode, so that the hydrogen producing apparatus as a whole is efficient. In addition to the operation, the pretreatment means 2 for the supplied raw fuel can supply the raw fuel suitable for the reaction of the reforming reactor group, and can suppress the deterioration of the catalyst with time.

Further, the post-treatment means such as the CO shift conversion means 5 and the CO removal means 6 can realize the composition of the supply gas suitable for the power generation means 7, and suppress the deterioration of the power generation means 7 with time.

Further, processing means 81 stores temperature information 102 of the reforming reactor group and operation information (output information) 103 of the power generation means 7.
Even if there is a change over time in the system operation, the raw fuel supply amount can be selected so as to be corrected by feedback.

With the above effects, it is possible to provide a system with improved reliability in practical use.

Here, a typical exothermic reaction and endothermic reaction relating to hydrogen production will be described. These reactions will be needed in the following description.

FIG. 3 shows an example of a typical exothermic reaction and hydrogen production reaction (endothermic reaction) using methanol, water, and oxygen as raw fuels. The partial oxidation reaction is an exothermic reaction between methanol and oxygen. The steam reforming reaction is an endothermic reaction between methanol and water. The steam reforming reaction can generate 3 moles of hydrogen from 1 mole of methanol, but requires an external heating because it is an endothermic reaction. On the other hand, since the partial oxidation reaction is an exothermic reaction, it does not require heating, but 2 mol of hydrogen can be produced from 1 mol of methanol, which is relatively small. When these two reactions are combined so that the oxidation reaction ratio becomes x and the total reaction amount is designated by y, the combined reforming reaction formula of FIG. 3 is obtained. Here, E is the steam excess rate. It shows that extra water is added to suppress the carbon precipitation reaction. If the amount of hydrogen produced per unit time is Y, there is a relationship of equation 3.

[0043]

[Equation 3] In the composite hydrogen production apparatus according to the present invention, a plurality of reforming reactor groups are used in combination so that heat can be mutually transferred. In each reforming reactor group, what kind of endothermic / exothermic reaction is used? In terms of thermal design, it is important to combine them in proportion. Therefore, the oxidation reaction ratio x is selected for each reforming reactor group, and the reaction ratio of heat generation and heat absorption is specified. Hydrogen is also generated in the partial oxidation reaction which is an exothermic reaction, so how much hydrogen is used may be determined by y or Y.

As a supplement, raw fuels that can be used in the hydrogen production apparatus and the power generation system using the hydrogen production apparatus are:
It is not limited to methanol, water and air (oxygen). A liquid raw fuel other than methanol, such as dimethyl ether, may be used as the main raw fuel for reforming. Pressurization is usually required to keep dimethyl ether in a liquid state, but there is no problem in applying the present invention. As another example, a gaseous raw fuel such as methane may be used as a main raw fuel for reforming. As an example, a typical exothermic reaction when methane is the main raw material is shown in Equation 4, and a typical endothermic reaction for hydrogen production is shown in Equation 5.

[0045]

[Equation 4]

[Equation 5] By extracting typical exothermic reaction and endothermic reaction and designating the mixing ratio of both, the exothermic / endothermic state of each reforming reactor group can be specified in correlation with the ratio.

In the following, description will be given taking as an example a case of a raw fuel composition mainly containing methanol.

FIG. 4 shows an example of raw fuel supply amount data stored in the storage means 82 according to the first and second embodiments.

In FIG. 4, when the operation mode and the reforming reactor group are designated, a specific exothermic reaction ratio x is determined.
Although the exothermic reaction ratio x is described for explanation, the value of x itself does not necessarily need to be stored. When the exothermic reaction ratio is determined, it is uniquely determined whether the reforming reactor group is a net exothermic reaction or an endothermic reaction. It is important for the thermal structural design of the composite hydrogen production device to properly select whether each reforming reactor group generates heat or absorbs heat in each operation mode, or a combination thereof. Therefore, the supply flow rates Q of methanol, water, and air are set so as to satisfy the respective exothermic reaction ratios. Here, the supply flow rate Q is the main data to be stored. Specific values are shown in FIG.
Can be determined according to the formula for combined reforming. When the steam excess ratio E is set to a value of, for example, about 1.2 to 1.6, the carbon deposition reaction can be suppressed. Further, the hydrogen production amount Y per unit time may be determined so that the hydrogen production amount required for each reforming reactor group can be obtained for each operation mode. The details of how much heat is actually transferred can be adjusted by the value of the parameter Y (or y) as well as the magnitude of the value of x. This should be determined in consideration of the specific layout and structure of the composite reformer.

The storage means 82 stores the respective feed fuels Q _AM1 shown in FIG.
~ The value of Q _BA2 is stored corresponding to the operation mode and the reforming reactor group. For example, methanol, water, and air supply raw fuels are stored in the form of a map according to two parameters of an operation mode and a reforming reactor group. Alternatively, one parameter may be called by designating three parameters of the operation mode, the reforming reactor group, and the raw fuel name (for example, methanol). Alternatively, the operation mode and the index of the reforming reactor group may be replaced with appropriate numerical values and then stored in the form of a function. The stored value of the raw fuel supply amount may not only be constant but may be changed with time. In such a case, as described with reference to FIG. 2, for example, a map of the raw fuel supply amount suitable for a slightly deteriorated state of the catalyst may be stored separately. In this way, it is possible to deal with the time-dependent change of the reaction only by changing the map to be called.

As a supplement, the value of Q may be given as a supply amount per reforming reactor or as a supply amount to the entire reforming reactor group. The processing means 81 determines the fuel supply amount command 104 to be sent to the raw fuel supply means 2 based on these pieces of information.

As another supplement, again, the actual reaction path is complicated, and reactions other than the extracted endothermic reaction / exothermic reaction may occur. However, specifying the representative reaction and quantifying the raw fuel supply amount as described above is effective as one design method. As a result of the experiment, when the selected endothermic reaction / exothermic reaction is not sufficient to describe the phenomenon, the raw fuel supply amount may be corrected and the value may be adjusted.

Storage means 8 according to the first and second embodiments
According to the method of specifying the raw fuel supply amount data stored in 2, it is possible to supply the raw fuel by specifying the endothermic / exothermic state of each reforming reactor group for each operation mode. Will be easier.

By selecting the value of the parameter Y (or y) together with the size of the parameter x, the amount of heat transfer between the reforming reactor groups is adjusted according to the specific structure of the composite hydrogen production apparatus. it can.

FIG. 5 shows an example of selecting the value of Y, which is the hydrogen production amount per unit time.

The value of Y is shown in correspondence with the supply raw fuel amount list of FIG. However, in the case of a reforming reactor group in which a plurality of reforming reactors are combined, the total hydrogen production amount is shown. When using a partial oxidation reaction as an exothermic reaction,
Even if x = 1, Y = 0 does not hold. This is shown in Figure 3.
This is because hydrogen is generated in the partial oxidation reaction, as described in Section 2. Here, x _A1 <x _B1 . This means that the reforming reactor group A is caused to react with exothermic priority in the reforming reactor group B. At this time, the condition Y _BL shown in FIG.
<Y _AL indicates the case where the reforming reactor group B is used together with the weak partial oxidation reaction. “Weak” means that the total hydrogen production amount Y _BL of the reforming reactor group B is sufficiently smaller than the total hydrogen production amount Y _{AL of} the reforming reactor group A. That is, the reforming reactor group A produces most of the hydrogen required in the low load operation mode, while the reforming reactor group B in the same operation mode gives priority to heat generation and produces only a small amount of hydrogen. I assumed to do. The heat generated in the reforming reactor group B is used for maintaining the reaction temperature of the reforming reactor group A by heat transfer, and is useful for maintaining the temperature of the entire complex hydrogen production apparatus. Further, the hydrogen produced in the reforming reactor group B can contribute to the hydrogen production as it is, though it is a small amount.

According to the parameter selection such that x _A1 <x _B1 and Y _BL <Y _AL , the reforming reactor group B in the low load operation mode (mode 1) is in a state of performing a weak partial oxidation reaction, so At the same time, hydrogen can be produced. This is a distinct operation from a conventional combustor that completely oxidizes the fuel and produces heat. From the viewpoint of the reforming reactor group, the reaction states such as an exothermic reaction and an endothermic reaction can be switched by simply switching the amount of raw fuel supplied, even though the catalytic reaction is the same.

In order to explain the setting example of the raw fuel supply amount in more detail, it is easy to identify the structure / function of the combined hydrogen production system. This will be described below.

FIG. 6 shows a composite hydrogen production system according to the third embodiment.

First, each part will be described.

In the figure, 2a and b are raw fuel supply means, 4a and
Reference numeral b represents a reforming reactor (group), 9 represents a combustor group (temperature adjusting means), and 201 represents a unit structure of a composite reactor. Here, the unit configuration means that a plurality of combined hydrogen reactors can be combined to form an entire combined hydrogen production apparatus. Of course, the composite hydrogen production apparatus may be configured by combining configurations that are slightly different from the unit configuration, or the hydrogen production apparatus may be configured by only the unit configuration. In the unit structure 201, the reforming reactor A has 1
The book is located in the center of multiple reformer reactors and combustors. The reforming reactor A was adopted for base load operation related to hydrogen production from low load to high load. Here, the expression “base load” is used in the sense of being related to hydrogen production in all operation modes, and does not indicate that the hydrogen production amount is constant. Around the reforming reactor A, six combustor groups 9 were arranged. In addition, six reforming reactor groups B were arranged around it. The reforming reactor group B is
Used for variable capacity. That is, it is a group of reforming reactors in which the hydrogen production is started in the high load operation mode while the standby state that does not contribute to the main hydrogen production in the low load operation mode is set. According to the conventional method, the reforming reactor group B in the low load operation mode is
It was in a hot standby state with operation stopped. However, when the operation of the reforming reactor group B is stopped, it contributes exclusively to heat radiation to the outside and may lower the temperature of the reforming reactor A, which is not preferable. Therefore, it was tried to cause a weak partial oxidation reaction in the reforming reactor group B in the low load operation mode. By controlling the switching of the raw fuel supply amount in this way, it becomes easier to maintain the reaction temperature and the reforming efficiency is improved. In order to obtain the effect of improving the reforming efficiency, it is premised that heat can be transferred between the reforming reactor and the combustor. For example, in a composite hydrogen production device in which heating means (heaters) are provided in individual reforming reactors, since thermally independent reforming reactors are installed in parallel, the efficiency improvement effect due to mutual heat transfer is I can't expect. In order to effectively obtain heat transfer between the reforming reactors, it is preferable that the reforming reactor groups A and B are adjacent to each other. Figure 6
In this embodiment, the reforming reactor group B is adjacent to the periphery of the reforming reactor A, and the combustor is arranged between them.

As a supplement, the structure of the composite reactor of FIG. 6 is given priority for simplicity of explanation, but in order to construct this as a prototype, it is easy to construct it with a metal material resistant to corrosion such as stainless steel. The plurality of reforming reactors and the combustor may be connected by welding or the like. Further, the plurality of reforming reactors and the combustor joined to each other may be immersed in a liquid having a good heat transfer property to improve the heat transfer property to each other. Alternatively, it may be integrally configured by digging out a space corresponding to a reactor or a combustor from a bulk metal material.

According to the composite hydrogen production apparatus according to the third embodiment of the present invention, the reforming reactor A that contributes to hydrogen production in all operation modes and the hydrogen production mainly in the high load operation mode. By combining the reforming reactor group B,
Hydrogen production with a wide dynamic range can be realized with good startup and responsiveness. In particular, by controlling the amount of raw fuel to be supplied so that a weak partial oxidation reaction occurs in the reforming reactor group B in the low load operation mode, the temperature drop in the reforming reactor A can be suppressed, and a plurality of reaction tubes can be combined. Comprising a composite hydrogen production device,
It is possible to operate efficiently from the low load operation mode.

FIG. 7 shows an example of setting the raw fuel supply amount of the hydrogen producing apparatus according to the third embodiment of the present invention.

The raw fuel supply amount shown in FIG. 7 is a value per reforming reactor in each operation mode. In the low load operation mode, the reforming reactor A is supposed to produce about 7 L / min of hydrogen. The net heating value due to the reaction in the reforming reactor A is about 69W. The net calorific value is an approximate calorific value obtained by subtracting the heat of vaporization of the raw fuel supplied as a liquid. Here, the partial oxidation ratio was set to x _{A L} = 0.65. On the other hand, in the reactor of the reforming reactor group B, a weak partial oxidation reaction was performed to take out heat. In the reforming reactor group B, the net calorific value per reactor is 8W. The partial oxidation ratio is x _BL = 1 but hydrogen is also generated because of the partial oxidation reaction. About 1 L / min of hydrogen was produced in the entire reforming reactor group B (6 pieces). On the other hand, in the high load operation mode, all reforming reactors are supposed to produce about 7 L / min of hydrogen. In this case, the temperature of the entire hydrogen production device may rise excessively. Therefore, with respect to exothermic reaction ratio x _BL = 0.65 of the reforming reaction unit group B, and exothermic reaction ratio of the reforming reactor A was set as small as x _AL = 0.63. At this time, the net calorific value of the reforming reactor group B is about 69 W per one, and the net calorific value of the reforming reactor A is about 56 W. The net calorific value of the reforming reactor A was suppressed to about 80% of that of the reforming reactor B. By such a method, it is possible to suppress a rapid increase in the device temperature in the high load operation mode.

The characteristics of the setting of the raw fuel supply amount are summarized as follows.

First, x _AL <x _BL was set in the low load operation mode. This is because the reforming reactor A, which is mainly responsible for hydrogen production,
In the reforming reactor group B, it means that a reaction mainly involving heat generation is performed.

Next, regarding the reforming reactor group B, x _BL > x _BH was set for the ratio in the high load operation mode. This means that hydrogen production is started in the reforming reactor group B in the high load operation mode by switching the mode. According to the required hydrogen production amount, the switching control of the raw fuel to the plurality of reforming reactor groups is performed.

Further, x _AL > x _AH . In the high load operation mode, the temperature of the entire hydrogen production device may rise excessively, which means that the heat generation amount of the reforming reactor A is suppressed. Although there is a method of suppressing the heat generation of the reforming reactor group B, here, the heat generation amount of the reforming reactor A located in the center where the heat radiation to the surroundings is small is suppressed.

Further, x _BL = 1 was set. This means that a partial oxidation reaction (partial oxidation reforming) is performed in the reforming reactor group B in the low load operation mode. In the setting of FIG. 7, the hydrogen production amount in the low load operation mode is about 1 in the entire reforming reactor group B.
L / min. This is sufficiently smaller than the hydrogen production amount in the reforming reactor A of about 7 L / min. Heat was generated by a weak partial oxidation reaction that did not place importance on hydrogen production.

According to the setting example of the raw fuel supply amount of the hydrogen producing apparatus according to the third embodiment of the present invention, methanol, water,
It is possible to easily maintain the temperature of the combined hydrogen production device using air.

Reforming reactor group B arranged in the peripheral portion (FIG. 6)
In the low load operation mode, the operation was performed with weak partial oxidation reaction in combination, and in the high load operation mode, the raw fuel supply was switched so that hydrogen was produced by combined reforming, so the reaction temperature decreased. Even in the low-load operation mode of the easy-to-use composite hydrogen production apparatus, wasteful hydrogen production can be performed with good responsiveness.

Further, regarding the reforming reactor A arranged in the central portion (FIG. 6), hydrogen is produced by the combined reforming in the low load operation mode, and the oxidation reaction of the reforming reactor is carried out in the high load operation mode. Since the ratio is reduced to suppress heat generation, it is possible to suppress an excessive temperature rise in the high load operation mode.

As a supplement, the above-mentioned hydrogen production amount is shown as an example, and is not particularly limited to the size. When a larger amount of hydrogen is required, the type and amount of catalyst can be selected so as to increase the hydrogen production amount per reforming reactor. Further, the composite reformer may be used as a unit structure and the number thereof may be increased while maintaining the hydrogen production amount.

FIG. 8 shows an example of using the heat insulating material according to the third embodiment of the present invention.

In this embodiment, in addition to the structure of the composite reformer shown in FIG. 6, a heat insulating material 41 for suppressing heat radiation to the outside is provided. Although not shown in the figure, when flanges are provided at the inlet and outlet of the reforming reactor, it is effective for heat insulation to use a packing or gasket having good heat insulating properties for the flanges. Further, when the pipe is formed by welding or the like, the pipe portion may be surrounded by a heat insulating material. It is preferable to configure the composite reformer 202 in this manner, because it is possible to suppress the temperature decrease in the low load operation mode. However, as a result of simulation on reaction and heat transfer, it was found that it may be difficult to maintain the reaction temperature by the method using only the heat insulating means. Because,
This is because the heat insulating effect is limited in consideration of the types and thicknesses of heat insulating materials that can be practically used. Therefore, also in the present embodiment, in the low load operation mode, it is desirable to switch the raw fuel supply amount so that the weak partial oxidation reaction is also used in the reforming reactor group B. On the contrary, in the high load operation mode, the temperature of the entire reforming reactor is likely to rise by using the heat insulating material, but as described above, the temperature of the reforming reactor A (or the reforming reactor group B) is increased. If the raw fuel supply amount is controlled so as to suppress the exothermic reaction ratio, the heat generation amount can be easily adjusted.

According to the composite reformer combined with the heat insulating material shown in FIG. 8, the reaction temperature can be adjusted and maintained by using the heat insulating material as a structural measure for controlling the switching of the raw fuel supply amount. It will be easier. On the other hand, in a combined hydrogen production system with a wide range of temperature change, it is possible to suppress the temperature rise in the high load operation mode by using the above-mentioned raw fuel supply amount switching control together, so it is possible to operate in a wide range of operations without attaching or removing a heat insulating material. Hydrogen can be produced in mode.

FIG. 9 shows an example of the temperature adjusting means according to the third embodiment.

In the figure, 4a is a reforming reactor A for base load operation. 9 is a temperature adjusting means (combustor group) provided around the reforming reactor A. Reforming reactors and combustors
It can be easily constructed by processing a metal material resistant to corrosion such as stainless steel as described above. Reference numeral 91 denotes a heat generating portion of the temperature adjusting means 9, which is filled with a combustion catalyst for an exothermic reaction. In the heat generating part 91, excess hydrogen in the power generation means (7),
In addition, the fuel for combustion is burned to obtain heat. As the catalyst to be filled, alumina particles supporting platinum can be used. A honeycomb catalyst may be used instead of the granular catalyst. Reference numeral 92 is a non-heat generating portion of the temperature adjusting means 9. The non-heat generating portion 92 is filled with a member having no catalytic action, such as ceramic pellets, to prevent combustion reaction. The non-heat generating portion 92 may be left as a space instead of being filled with a specific member. The temperature of the non-heat generating portion 92 is determined solely by heat transfer with the surroundings. Therefore, a part of the non-heat generating portion 92 becomes lower than the temperature of the reforming reactor A in which the reaction occurs, and can function as a heat absorbing portion for the reforming reactor A. That is, it can be said that the temperature adjusting means 9 is a temperature adjusting means in which the heating means (heat generating portion 91) and the heat absorbing means (a part of the non-heat generating portion 92) are combined.

FIG. 10 shows a temperature distribution (simulation result) in the flow direction of the reforming reactor A.

The upper part of FIG. 10 shows the case where the temperature adjusting means of FIG. 9 is not used, and the lower part of FIG. 10 shows the comparison of the case where the temperature adjusting means of FIG. 9 is used. The raw fuel is supplied to the reforming reactor A and the temperature adjusting means from the same direction. It can be seen that by using the temperature adjusting means, the temperature on the outlet side of the reforming reactor rises and the localization of the maximum temperature is alleviated. The rise in the outlet temperature reflects the heat generation effect of the heat generating portion of the temperature adjusting means. In contrast,
The relaxation of the maximum temperature localization is due to the endothermic effect of the non-heat generating portion of the temperature adjusting means. Due to the endothermic effect, the temperature of the reforming reactor A in the flow direction could be made uniform.

As a supplement, a gas may flow through the temperature adjusting means in the direction opposite to that of the reforming reactor A. Since the catalytic combustion of the exothermic part has a relatively high reaction rate, the peak of the exothermic part appears at the gas inlet part of the combustion catalyst. This allows
The temperature distribution in the flow direction of the reforming reactor can be changed.
Further, the temperature distribution can be adjusted by the temperature of the supplied gas together with the selection of the flow direction.

According to the temperature adjusting means of the third embodiment, the reformer outlet temperature can be maintained high and the temperature distribution in the reforming reactor flow direction can be made uniform. The homogenization of the reaction temperature is preferable for the hydrogen production device. If the local temperature rise is suppressed, the local thermal deterioration of the catalyst can be suppressed. Further, if the temperature can be maintained uniform, the reaction can be stably maintained when the combustion position is displaced due to the change of the gas flow velocity.

FIG. 11 shows a fourth embodiment.

In this embodiment, the case where the composite reactor 203 similar to that of the third embodiment is constituted by pressing or welding a thin metal plate such as stainless steel is shown.

Reference numeral 21 in the drawing denotes a raw fuel supply section. 22
Is an outlet for the reformed gas (hydrogen rich gas).
These correspond to the flange portions omitted in FIG. Four
a and b are reforming reactors for base load operation,
Although it is a reforming reactor for varying the capacity, unlike the case of FIG. 6, the unevenness portion of a metal thin plate processed into a rectangular corrugated plate serves as the reforming reaction portion (including this reforming reaction portion as well. Collectively referred to as the reforming reactor). Reforming reactor group A and reforming reactor group B
In order to maintain good mutual heat transfer, they are arranged adjacent to each other. The corrugated plate structure was sandwiched by the temperature adjusting means 9. By doing so, the reforming reactor groups A and B and the temperature adjusting means 9 can be arranged adjacent to each other. Of course, the arrangement of the reforming reactor groups A and B and the temperature adjusting means 9 is not limited to the structure shown in FIG. Here, the temperature adjusting means 9 worked a thin metal plate so as to form a tunnel structure having a rectangular cross section. The temperature adjusting means adjusts the position of the combustion catalyst arranged inside the tunnel structure,
Not only heat-generating part but also non-heat-generating part (heat absorbing part) in the gas flow direction
Can be provided. The gas inlet piping can be configured so that the raw fuel is supplied collectively by a manifold for each reforming reactor group. Further, not only the gas outlet pipes are output in parallel, but also after being combined into one by the manifold, the subsequent stage processing such as CO shift conversion and CO removal as described in the system configuration example of FIG. 2 may be performed. .

As a supplement, the reforming reactor of the hydrogen producing apparatus need not necessarily have an independent structure as a reaction tube as shown in FIG. In other words, the complex hydrogen production device targeted by the present invention is not only a hydrogen production device in which independent reforming reactors are integrated and combined, but also a plurality of reforming devices separated by partition walls capable of mutual heat transfer. It may be a hydrogen production device having a reaction part.

According to the fourth embodiment, as compared with the case of FIG. 6 in which a plurality of metal reaction tubes are combined, the composite reactor is easier to process and the heat transfer between the reforming reaction parts is also improved. Therefore, a structure preferable for practical use can be provided as the composite hydrogen production apparatus.

FIG. 12 shows a structural example of the electronic control unit according to the present invention. One of the features of the present invention is to control the supply amount of a plurality of raw fuels for each operation mode targeting a plurality of reforming reactor groups. The operation becomes complicated as the number of reforming reactor groups increases, but the supply amount can be controlled relatively easily by using a commercially available one-chip microcomputer.

Reference numeral 105 in the figure denotes a signal given from the outside, such as an operation mode command. Reference numeral 83 is a pre-processing unit for enabling the microcomputer 105 to process the signal 105, and includes processing such as voltage conversion by an analog circuit. 8
Reference numeral 4 is an input processing means for A / D converting the input signal. Reference numeral 810 is a signal processing unit for determining the supply amount of raw fuel based on the input signal. The signal processing unit 810 is configured to include functions such as a timer necessary for signal processing. 82
0 is the program or data (map) required for the process
A ROM (read only memory) for storing information such as. Reference numeral 821 denotes a RAM (ra) for temporarily storing an intermediate result of the processing and storing data (map) that needs updating.
ndom access memory). Here, the data that needs to be updated is, for example, numerical data as shown in FIG.
The data that can be used for the learning function that can be corrected or updated at any time depending on the operating conditions such as the reaction temperature of the hydrogen production device is shown. Alternatively, when the hydrogen production equipment is stopped, the state of the equipment is memorized, and when the equipment is started up next time with reference to this when starting up, it is temporarily stored, and the data updated every time the equipment is stopped include. Reference numeral 85 is an output processing means for D / A converting the processing result. Reference numeral 86 denotes post-processing means for instructing the raw fuel supply means of the raw fuel supply amount obtained as a result of the processing, and includes analog processing such as a driver circuit. Reference numeral 106 is an output signal such as a fuel supply command obtained as a result of the processing.

If a commercially available one-chip microcomputer is used, FIG.
The part surrounded by the dotted line can be functionally integrated into one chip. An electronic control unit for raw fuel switching control can be configured by including peripheral analog circuits. The power supply circuit and the clock oscillation circuit for driving the one-chip microcomputer can be configured by analog circuits.
Is omitted.

As a supplement, when a large voltage or a large current is required for driving the external actuator as the signal 106, an overvoltage / overcurrent protection circuit may be provided separately for the one-chip microcomputer. Good. In other cases, a simple protection function may be added by a Zener diode or a capacitor.

According to the above electronic control unit of the present invention, the raw fuel supply control of the composite hydrogen production system composed of a plurality of reforming reactor groups can be easily implemented in terms of software.

Particularly, if a one-chip microcomputer in which a plurality of functions are integrated is used, the control unit can be downsized and the productivity can be improved.

If a general-purpose one-chip microcomputer is used, it is possible to easily perform sophisticated control such as detecting the malfunction of the reforming reactor and switching the raw fuel supply amount. This will be described next.

FIG. 13 shows an example of the flow of processing for switching to the failure mode. Since the combined hydrogen production system is composed of multiple reformer reactor groups, if one reformer reactor group, such as a frequently used reformer reactor group, malfunctions, it will control the supply of raw fuel. The raw fuel supply amount can be reassigned to another reforming reactor group. As a result, the minimum operation of the hydrogen production device can be continued.

In the example of FIG. 13, the change in the electrical output of the power generation means (7) is referred to in determining whether or not the hydrogen production device is in failure. More generally, it is possible to refer to the output of the operation detecting means by using the operation detecting means for detecting the temperature related to the hydrogen production process or the amount related to the energy output obtained by using the hydrogen. Examples of the operation detecting means include a temperature sensor and means for measuring current and voltage. Instead of using an advanced detection means, a thermocouple or an electric resistance may be used as the operation detection means. To determine whether or not the electrical output such as the voltage value or the current value detected by the operation detecting means follows the load command, for example, the following may be performed. At the time of switching a predetermined operation mode, the signal processing unit (810, 81) determines whether or not the expected output is obtained in a predetermined time. To implement this easily, start counting from the time when the operation mode is switched based on the clock built in the 1-chip microcomputer, and the detected value obtained after a predetermined count (time) reaches the predetermined output value. Whether or not it is normal can be determined. The predetermined output value serving as a criterion for determination includes a fluctuation during normal operation as a margin in order to prevent malfunction. Alternatively, the predetermined output value may be changed according to the change of the season or the environment, or the change of the device over time. On the other hand, in the case of steady operation in the predetermined operation mode, the signal processing unit (810, 81) determines whether or not the detection value detected periodically is within a predetermined range. In order to easily carry out this, it suffices to carry out a comparison process between the upper and lower limit values of the predetermined output and the detected value. The upper and lower limits of the output should include fluctuations during normal operation as a margin to prevent malfunction. Alternatively, the predetermined upper and lower limits may be changed according to changes in seasons and environments, and changes in the device over time. Both of the above diagnoses may be performed, or only one of them may be performed. When the normal output followability cannot be confirmed by the above diagnosis and it is determined that there is a failure, the mode is switched to the failure mode. In the failure mode, the signal processing unit (810, 81) selects and reads the raw fuel supply amount according to the failure mode from the storage means (82, 821, or 820), and based on the result, reads the raw fuel supply means (2 ) Command (104). In the case of the composite hydrogen generator shown in FIG. 6, the following measures can be taken.
As an example, the reforming reactor A used for base load operation
When a failure occurs and the predetermined hydrogen production amount cannot be obtained in the low load operation mode, the output of the power generation means (7) does not reach the predetermined value, so that it can be determined as a failure. In this case, in failure mode,
The raw fuel supply to the reforming reactor A is stopped, a predetermined one of the reforming reactor groups B provided for variable capacity is selected, and the same raw fuel supply as the reforming reactor A is started. . Although the output of the power generation means (7) does not reach the predetermined value, but when the degree is small, the heating value of the reforming reactor group B is increased while the raw fuel supply to the reforming reactor A is maintained. Alternatively, the parameter y may be adjusted. As another example, if one of the reforming reactor groups fails and a predetermined amount of hydrogen production cannot be obtained in the high load operation mode, the output of the power generation means (7) does not reach the predetermined value, so the failure occurs. I can judge. In this case, the exothermic reaction ratio of the reforming reactor group B is lowered to increase the hydrogen production amount. Here, if the reforming reactor A is out of order, it can be compensated by hydrogen production in the reforming reactor group B. Further, if any one of the reforming reactor group B is out of order, hydrogen production can be continued in the reforming reactor A and the reforming reactor group B which operates normally. As yet another example, when the output of the power generation means (7) rises abnormally and becomes equal to or higher than a predetermined value, it can be similarly judged as a failure. When the output increase is small, the raw fuel supply amount is changed so as to suppress the hydrogen production amount. When the degree of increase in the output is large, the supply of raw fuel to all reforming reactors is stopped. As described above, in the failure mode, the content can be changed based on the degree of abnormality. In order to speed up the transition to the failure mode, the raw fuel supply amount data can be stored in advance for each of the abnormal modes that are expected.

When the effect cannot be obtained by one raw fuel supply control, another process may be added in cascade. Alternatively, when an auxiliary power source such as a secondary battery can be used as the system, the auxiliary power source is driven before the raw fuel supply amount control as shown by the portion surrounded by a dotted line in FIG. You may be allowed to do. When dealing with an abnormal increase in output, it may be necessary to skip the processing indicated by the dotted line and stop the supply of raw fuel to the reforming reactor group.

In the flow of FIG. 13, a warning of failure is issued after the emergency response to the failure. When the degree of failure is slight, it may be as simple as turning on a lamp indicating the start of deterioration of the catalyst. In some cases, the warning may be omitted. If the degree of failure is severe, hydrogen production is being continued as an emergency evacuation, but an appropriate indication that repair is necessary is required at an early stage. The display may be changed according to the degree of failure. The degree of failure can be quantitatively determined based on, for example, how much the output of the power generation means (7) deviates from a predetermined threshold value. Alternatively, even in the case of a minor malfunction, the frequency of occurrence of the malfunction may be recorded and weighted based on the frequency.

According to the process for switching to the failure mode according to the present invention, the feed amount of the raw fuel for each reforming reactor group can be independently controlled in the combined hydrogen production apparatus, so that the malfunctioning reforming reactor can be controlled. The process of replacing the role with another reforming reactor can be facilitated. By doing this, for example, the frequency of use is high, such as in a reforming reactor used for base load operation,
Even in a system including a reforming reactor with a high possibility of catalyst deterioration, the entire system does not fail even if the reforming reactor fails. For equipment failure,
Even if complete restoration is not possible in a short time, necessary emergency measures such as moving the vehicle to a repair shop can be performed.

A fuel cell power generation system is an application example of the hydrogen production apparatus according to the present invention and a power generation system using the hydrogen production apparatus.

As an example, the case of a moving body, particularly a vehicle, equipped with a fuel cell power generation system using the hydrogen production apparatus according to the present invention will be described.

FIG. 14 shows a comparison of efficiency between a PEFC-equipped vehicle using methanol as a main raw fuel and a gasoline engine vehicle to which engine combustion technology is applied. The horizontal axis is the output [kW]
And the vertical axis represents thermal efficiency [%]. Compared with the engine, the fuel cell is more efficient in the low output range, so it is suitable for applications that are frequently used in the low output range. On the other hand, when the vehicle is normally driven in the city, the peak of the output frequency is often 10 kW or less. This is illustrated as a "frequently used output area". That is, it can be seen that the vehicle equipped with the fuel cell is suitable for normal city driving. Taking the hydrogen production device shown in Fig. 6 as an example, hydrogen is mainly produced in the base load reforming reactor A in the low output region where it is frequently used, and the capacity is variable only during sudden acceleration or heavy load operation. If hydrogen is produced in the reforming reactor B, it is possible to operate the hydrogen production apparatus without waste. The features are summarized below. (1) Start-up time Since the small base-load reforming reactor A may be started first for traveling in the city, the start-up time can be shortened. The variable capacity reforming reactor group B, which is less frequently used, may be warmed up over a longer period of time. (2) Response time Since it corresponds to operating by reforming one large reforming reactor into a plurality of reforming reactors, the gas flow velocity (linear velocity) in each reaction tube does not decrease even in low output operation. Therefore, the responsiveness can be improved. (3) Controllability Since one large reforming reactor is divided into a plurality of reforming reactors, it is possible to perform optimum raw material supply control for each reforming reactor. The uniformity and response of the reaction may be realized for each divided reforming reactor, which is advantageous for stable control. (4) Reliability Even if the frequently used reforming reactor fails for some reason, hydrogen supply can be continued in the remaining reforming reactors.

Of course, the operation mode can be set to low load and high load.
There is no need to limit to two kinds. It is also possible to divide the hydrogen production operation mode more finely to cover the required output range.

According to the hydrogen production apparatus and the fuel cell power generation system using the hydrogen production apparatus, not only is it easy to produce hydrogen suitable for the operation pattern of the vehicle, but also the reforming reactor B during base load operation. Since the exothermic reaction (weak partial oxidation reaction) is also used in the above, the temperature decrease of the reforming reactor A can be suppressed. Further, since the exothermic reaction ratio of the reforming reactor is controlled for each operation mode, it is possible to suppress excessive temperature rise in the high load operation mode.

The above-described features of the composite reformer are also effective for a hydrogen production apparatus mounted on an internal combustion engine that directly burns hydrogen instead of the power generation means. This is because it is particularly important for a moving body such as a vehicle, a ship, and an aircraft to obtain a quick output response according to an operating state, and therefore high responsiveness to hydrogen production is required. If the response of the hydrogen production device is unavoidable due to the length of the gas pipe, etc., the system may be configured with an electric power storage means such as a secondary battery, but even in such a case, the hydrogen production device according to the present invention may be used. By using, it is possible to reduce the capacity of the power storage means, which contributes to the reduction in size and cost of the system.

The above-mentioned features of the composite reformer are
It is useful not only for in-vehicle use, but also for power generation systems that use ordinary fuel cells. Examples of the fuel cell power generation system include a distributed power source for home use, an industrial distributed power source used in hotels and convenience stores, and a portable power source in the event of a disaster and a backup power source for medical facilities.

FIG. 15 shows an example in which the hydrogen production apparatus and the power generation system using the hydrogen production apparatus are applied to a stationary type distributed power source arranged in each home.

In the figure, reference numeral 204 designates a stationary type distributed power source, which includes a hydrogen production apparatus according to the present invention and a fuel cell as a power generation system as at least a part of its constituent elements. The hydrogen production device produces hydrogen using gas and air supplied from the outside and pure water generated as a result of power generation in a fuel cell as raw materials. As a raw material gas, for example, natural gas containing methane as a main component can be used. Here, a feature of using a fuel cell in the power generation system is that not only power generation but also hot water obtained by exhaust heat of the fuel cell can be provided. In the case of a solid polymer combustion battery, the temperature during power generation is about 80 ° C., and the temperature inside the battery is adjusted using cooling water or the like. Therefore, hot water can be obtained by collecting excess heat generated by internal resistance of the battery by cooling. However, if the water supplied from the outside is directly used for cooling the fuel cell, impurities contained in the water may adversely affect the fuel cell. In that case, the temperature of the water supplied from the outside may be indirectly increased by using a means having a heat exchange function.
The temperature of the heated hot water is, for example, about 60 ° C. Therefore, if the hot water is stored in the hot water storage tank, hot water used in the kitchen, bath or hand washing can be provided instead of the water heater. In addition, since the electric power obtained by the power generation can be used together with the electric power supplied from the outside to drive various electric appliances in the home, the amount of electric power supplied from the outside can be reduced. Of course, if the power generation capacity is sufficient, the power can be supplied without the power supplied from the outside.

When the temperature of the water supplied from the outside is low and the temperature rise is insufficient, or when the temperature of the water in the hot water storage tank decreases, for example, heating means is provided at the inlet or outlet of the hot water storage tank or inside. May be. The heating means burns a part of the raw material gas supplied from the outside to raise the temperature of the hot water.
If feedback control for detecting the temperature is also used, the amount of heating and the flow rate of hot water can be adjusted to raise and maintain the supply water temperature at a predetermined temperature.

When the power generation amount of the fuel cell fluctuates, auxiliary power storage means may be used together. A rechargeable secondary battery can be used as the power storage means.

According to the above hydrogen production apparatus, the startup time of the apparatus can be shortened, and the hydrogen production amount can be swiftly switched according to the usage status of hot water or electric power. Since an efficient hydrogen production operation can be performed for a wide range of hydrogen production, a power generation system for practical use can be provided.

As described above, according to the present embodiment, in a hydrogen production apparatus having a plurality of reforming reactors capable of mutually transferring heat, the plurality of reforming reactors are connected to at least two reforming reactor groups (A, B). , ...), and switching control of the feed fuel is performed so that at least one of the reforming reactor groups (B) performs a partial oxidation reaction or an oxidation reaction in a predetermined operation mode,
The heat generated as a result of the exothermic reaction is transferred to another reforming reactor group (A).
The structure was used for hydrogen production.

In the hydrogen production apparatus, a part of the reforming reactor group is operated in a predetermined operation mode by switching to a reaction in which heat generation is more important than hydrogen production. By utilizing the heat exchange between the reforming reactor groups to avoid lowering the reaction temperature of the reforming reactor group (A) during hydrogen production operation, it is possible to improve the reforming efficiency of the entire hydrogen producing device. And
It has become possible to avoid lowering the reaction temperature in the low load operation mode of the combined hydrogen production system.

Further, another means has a plurality of reforming reactors capable of mutually transferring heat, and each reforming reactor has an exothermic reaction and an endothermic reaction in the ratio x: (1-x) ( x is an exothermic reaction ratio) to produce hydrogen in combination, and the plurality of reforming reactors are classified into at least two reforming reactor groups, and at least two of the reforming reactor groups are combined. Exothermic reaction ratios x _{A ,} x _{B , of} each reforming reactor group (A, B, ...)
It is a hydrogen production device that controls the switching of the raw fuel supply amount so that any one of (0 ≤ x _A ≤ 1, 0 ≤ x _B ≤ 1, ...) becomes a different value for each operation mode. In addition, the above operation mode is a low load operation mode in which the hydrogen production amount is relatively small (exothermic reaction ratio x _{AL ,} x _{BL of} each of the reforming reactor groups A and B)
And a high load operation mode in which the hydrogen production amount is relatively large (exothermic reaction ratio x _{A H,} x _{B H of} each of the reforming reactor groups A and B), and the exothermic reaction ratio is x _AL <x _BL In addition, it is a hydrogen production device that switches and controls the amount of raw fuel supply so that x _BL > x _BH, and that controls hydrogen supply so that x _AL > x _AH. Manufacturing equipment,
Furthermore, it is a hydrogen production device in which the amount of raw fuel supply is switched and controlled so that x _BL = 1.
The total amount of hydrogen produced per unit time for each of the two reforming reactor groups (A, B) is calculated by Y _{A L,}
If the Y _{B L,} a hydrogen production apparatus and Y _AL> Y _BL and Y _BL ≠ 0.

In the hydrogen producing apparatus, the ratio of the raw fuel to be supplied is switched and controlled for each reforming reactor group.
At that time, the ratio of the supplied raw fuel was determined so that the exothermic reaction ratio x designating the ratio of the exothermic reaction and the endothermic reaction would be a predetermined value. The exothermic reaction ratio of each reforming reactor group was switched for each operation mode so that an appropriate reaction temperature could be maintained in the entire combined hydrogen production system. Particularly, when x = 1, only the exothermic reaction proceeds in the reforming reactor group that operates so as to satisfy the exothermic reaction ratio. In this case, the effect of using the reforming reactor group as a heat source is great. In addition, the above 2
The total amount of hydrogen produced per unit time for each of the two reforming reactor groups (A, B) is calculated by Y _{A L,}
Y _{B L} , Y _AL > Y _BL and Y _BL ≠
When it is set to 0, the reforming reactor group B is an exothermic reaction, but produces a slight amount of hydrogen. As a specific example, in the reforming reactor B, a weak partial oxidation reaction is performed in which importance is not placed on the hydrogen production amount.

Another means is to arrange each reforming reactor of the reforming reactor group B in the above hydrogen producing apparatus so as to be adjacent to at least one reforming reactor of the reforming reactor group A. Thus, the hydrogen production apparatus capable of mutually heat transfer, and in the hydrogen production apparatus, a hydrogen production apparatus having a heating means for heating at least a part of the reforming reactor group, Further, in the hydrogen production device,
A hydrogen producing apparatus having an endothermic means for cooling at least a part of the reforming reactor group, and further comprising a heat insulating means for thermally insulating the entire reforming reactor group from the outside in the hydrogen producing apparatus. The hydrogen production device is configured as described above, and further, the reaction devices of the plurality of reforming reactors are separated by a partition wall capable of mutually conducting heat.

In the hydrogen producing apparatus, the reforming reactor groups are arranged so that heat can be efficiently transferred between the reforming reactor groups. Moreover, temperature control is facilitated by using a heating means such as a combustor together. If the surplus hydrogen in the fuel cell is supplied to the combustor as fuel, the thermal efficiency of the system can be improved. Further, by partially providing a non-heat generating portion in the heating means such as the combustor, the local temperature rise of the reforming reactor is suppressed by using this as a heat absorbing means. By combining the heating means and the endothermic means, an optimum temperature profile in the gas flow direction of the reforming reactor group is provided. Moreover, the reaction temperature is easily maintained by insulating the entire reforming reactor group from the outside. Furthermore, by constructing at least a part of the hydrogen production device by pressing or welding a thin metal plate such as stainless steel, it is possible to reduce the size and weight of the entire structure while combining a plurality of reforming reactors. .

Further, another means has an electronic control unit (ECU) for controlling the switching of the raw fuel supply amount in the hydrogen production apparatus, and the ECU carries out the processing for the switching control by a one-chip microcomputer. The hydrogen production device is designed to operate, and when one reforming reactor group malfunctions, it detects it and switches the role to the other reforming reactor group. It is a hydrogen production device that is controlled.

In the hydrogen production apparatus, switching of the raw fuel supply amount for each operation mode for a plurality of reforming reactor groups is performed.
It is controlled by a microcomputer. If the general-purpose one-chip microcomputer is used as the microcomputer, various switching controls can be implemented at a relatively low cost. Since the combined hydrogen production system has many reforming reactors, it is important for practical use that various switching control of the raw fuel supply amount can be easily performed. At the same time, it is possible to easily perform advanced control such as detecting a malfunction of the reformer and switching the raw fuel supply amount. When one reforming reactor group of the composite hydrogen production device, for example, a frequently used reforming reactor group, malfunctions,
By controlling the supply of raw fuel, the required amount of raw fuel supply was reassigned to another reforming reactor group so that the hydrogen production device could continue to operate. Even if the device cannot be completely restored in a short time due to a failure of the device, for example, in the case of in-vehicle application, necessary emergency measures such as moving the vehicle to a repair shop can be performed. Such an emergency response is of course important for other moving bodies such as ships and airplanes.

Furthermore, as an application of the hydrogen production apparatus, there is a fuel cell power generation system using the hydrogen production apparatus as an internal hydrogen supply source.

In the fuel cell power generation system, it is possible to enhance the startability / responsiveness of hydrogen production. We are trying to provide a fuel cell power generation system that is easy to use from the user side and has good controllability from the manufacturer side.

[0122] The demand for hydrogen production startability and responsiveness is particularly great in applications to moving bodies such as vehicles. This is because it is necessary to supply the raw material hydrogen in an environment where load changes are large, such as when the vehicle starts or accelerates or decelerates. As a means for solving this, the hydrogen production device is provided on a moving body such as a vehicle, a ship, or an aircraft.

In the mobile unit equipped with the hydrogen producing apparatus, the reforming reactor group A is used for the base load operation for producing hydrogen from a low load to a high load, and the reforming reactor group B is used. It provides a moving body that has excellent startability and responsiveness and uses less thermal waste for each operation mode by using it for variable capacity, which starts the main hydrogen production only during relatively large acceleration. be able to.

[0124]

EFFECTS OF THE INVENTION According to the present invention, in a hydrogen production apparatus in which a plurality of reforming reactors are operated in combination, the reforming reactor temperature during the operation can be optimally maintained regardless of the amount of hydrogen production. You can

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a hydrogen production apparatus according to a first embodiment of the present invention and a power generation system using the hydrogen production apparatus.

FIG. 2 is an explanatory diagram of a hydrogen producing apparatus according to a second embodiment of the present invention and a power generation system using the hydrogen producing apparatus.

FIG. 3 is an explanatory diagram of an exothermic reaction using methanol as a main raw fuel, an endothermic reaction, and a combined reaction of both.

FIG. 4 is an explanatory diagram of raw fuel supply amount data according to the second embodiment of the present invention.

FIG. 5 is an explanatory diagram of the hydrogen production amount according to the second embodiment of the present invention.

FIG. 6 is an explanatory diagram of a hydrogen production device according to a third embodiment of the present invention.

FIG. 7 is an explanatory diagram of raw fuel supply amount data according to the third embodiment of the present invention.

FIG. 8 is an explanatory diagram of a heat insulating material according to a third embodiment of the present invention.

FIG. 9 is an explanatory view of temperature adjusting means according to a third embodiment of the present invention.

FIG. 10 is an example of a simulation result showing the effect of the temperature adjusting means according to the third embodiment of the present invention.

FIG. 11 is an explanatory diagram of a hydrogen production device according to a fourth embodiment of the present invention.

FIG. 12 is an explanatory diagram of a configuration of an electronic control unit for controlling raw fuel supply according to the present invention.

FIG. 13 is an example of a failure mode switching flow according to the present invention.

FIG. 14 shows the relationship between the output and efficiency of a fuel cell vehicle and a gasoline engine vehicle, and how to operate each reforming reactor group.

FIG. 15 is an explanatory diagram of a household stationary distributed power supply (hot water supply source) using a power generation system using a hydrogen production device according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Raw fuel of a reforming reactor, 11 ... Oxygen (air, oxidizer), 12 ... Methanol, 13 ... Water, 2, 2a, b ... Raw fuel supply means, 21 ... Raw fuel supply part, 22 ... Reforming Gas extraction section 3a, b ... Pretreatment means, 4a, b ... Reforming reactor (group), 5 ... CO shift conversion means, 6 ... CO removal means, 7 ...
Power generation means (or may be power generation means using hydrogen), 81 ... Processing means, 82 ... Storage means, 83 ...
Pre-processing means (analog processing), 84 ... Input processing means (A
/ D conversion), 85 ... Output processing means (D / A conversion), 86
... post-processing means (analog processing), 800 ... 1-chip microcomputer, 810 ... signal processing section (including functions such as clock), 820 ... storage means (RAM), 821 ... storage means (ROM), 9 ... combustor group (Temperature control means), 91 ... Heat generation part of temperature control means, 92 ... Non-heat generation part (including heat absorption part) of temperature control means, 101 ... Operation mode command, 102 ...
Reformation reactor temperature information, 103 ... Operation information of power generation means (including information on output / load), 104, 104
a, b ... Fuel supply amount command, 105 ... Input signal to electronic control unit, 106 ... Output signal from electronic control unit, 200 ... Composite reactor, 201 ... Unit configuration example of composite reactor, 202 ... Adiabatic Unit configuration example of a composite reactor having a material, 203 ... Unit configuration example of a composite reactor configured by forming each thin metal plate, 204 ... Household stationary type by a power generation system using the hydrogen production device according to the present invention Distributed power source (hot water source).

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yuichi Kamo             7-1-1, Omika-cho, Hitachi-shi, Ibaraki Prefecture             Inside the Hitachi Research Laboratory, Hitachi Ltd. F term (reference) 4G140 EA02 EA03 EA06 EA07 EB12                       EB42 EB43 EB44                 5H027 AA02 BA01 BA13

Claims (20)

[Claims] 1. A hydrogen generator having a plurality of reforming reactors, wherein the plurality of reforming reactors are classified into at least two reforming reactor groups (A, B, ...) And the reforming is performed. At least one of the reactor groups (B) controls the switching of the raw feed fuel so that the partial oxidation reaction or the oxidation reaction is performed in a predetermined operation mode,
The heat generated as a result of the exothermic reaction is transferred to another reforming reactor group (A).
A hydrogen production device having a structure for use in hydrogen production. 2. A plurality of reforming reactors capable of mutually transferring heat, each reforming reactor having a predetermined exothermic reaction and endothermic reaction.
A hydrogen production apparatus for producing hydrogen by combining at a ratio of x: (1-x) (x is referred to as an exothermic reaction ratio), wherein the plurality of reforming reactors are at least two reforming reactors. Exothermic reaction ratios x _{A and} x _B of at least two reforming reactor groups (A, B, ...) Of the reforming reactor groups.
_, (0 ≤ x _A ≤ 1, 0 ≤ x _B ≤ 1, ...) is controlled so that the raw fuel supply amount is switched so as to have a different value for each operation mode. Hydrogen production equipment. 3. The reforming reactor group according to claim 2, wherein the reforming reactor group includes two reforming reactor groups A and B, and the operation mode includes a low load operation mode (a modified Exothermic reaction ratio of quality reactor groups A and B
x _{AL ,} x _BL ) and the high load operation mode in which the hydrogen production amount is relatively large (exothermic reaction ratio x for each of the reforming reactor groups A and B)
_{A H,} there are two operation modes of the _{x B H), x AL <} x BL and x _BL> hydrogen generating device being characterized in that so as to switch between control of the raw fuel supply amount so that the x _BH . 4. The hydrogen generator according to claim 3, further comprising switching control of the raw fuel supply amount so that x _AL > x _AH . 5. The hydrogen generator according to claim 3 or 4, further comprising switching control of the raw fuel supply amount so that x _BL = 1. 6. The total hydrogen production amount per unit time of each of the two reforming reactor groups (A, B) according to any one of claims 2 to 5, which is Y in the low load operation mode. _{In case of A L,} Y _{B L} , in the low load operation mode
A hydrogen production apparatus characterized in that Y _AL > Y _BL and Y _BL ≠ 0. 7. The reforming reactor of the reforming reactor group B according to claim 1 or 2, is arranged adjacent to at least one reforming reactor of the reforming reactor group A,
A hydrogen production device characterized in that they can mutually transfer heat. 8. The hydrogen production apparatus according to claim 7, wherein the hydrogen production apparatus has heating means for heating at least a part of the reforming reactor group. 9. The hydrogen producing apparatus according to claim 7, wherein the hydrogen producing apparatus has a heat absorbing means for cooling at least a part of the reforming reactor group. 10. The hydrogen producing apparatus according to claim 7, wherein the hydrogen producing apparatus has heat insulating means for thermally insulating the entire reforming reactor group from the outside. 11. The hydrogen production apparatus according to claim 7, wherein the reaction sections of the plurality of reforming reactors are separated by partition walls that can transfer heat to each other. 12. The hydrogen producing apparatus according to claim 1 or 2, further comprising an electronic control unit (ECU) for controlling switching of a raw fuel supply amount, and the ECU is 1
A hydrogen production device characterized in that a processing for the switching control is performed by a chip microcomputer. 13. A hydrogen generator having a plurality of reforming reactor groups, wherein when one reforming reactor group of the reforming reactor groups malfunctions, this is detected and other The hydrogen production apparatus is characterized in that the control of switching the supply amount of the raw fuel is performed so as to switch the role to the reforming reactor group. 14. A fuel cell power generation system comprising the hydrogen production device according to claim 1. 15. A hydrogen production device-equipped mobile body, comprising the hydrogen production device according to any one of claims 1 to 13 provided on a mobile body such as a vehicle, a ship, or an aircraft. 16. A method for operating a hydrogen production apparatus, comprising at least two sets of reforming reactor groups A and B, wherein the operating states of the respective reforming reactor groups are switched according to the required hydrogen production amount. In the low load operation mode where the production amount is relatively small, hydrogen is produced by the combined reforming in the reforming reactor group A, and the partial oxidation reaction is caused in the reforming reactor group B in the standby state to lower the temperature of the entire apparatus. A method for operating a hydrogen production apparatus, which is characterized in that 17. A method of operating a hydrogen production apparatus, comprising at least two sets of reforming reactor groups A and B, wherein the operating states of the respective reforming reactor groups are switched according to the required hydrogen production amount. In the high load operation mode in which the production amount is relatively large, the hydrogen production by the combined reforming is started in the reforming reactor group B in the standby state, and the reforming reactor group A which has already started the hydrogen production is started. A method for operating a hydrogen production device, characterized in that the partial oxidation ratio is reduced to suppress the temperature rise of the entire device. 18. A method of operating a hydrogen generator having at least two sets of reforming reactor groups A and B, wherein methanol is added to the reforming reactor group A in a low load operation mode in which hydrogen production is relatively small. For example, in the high load operation mode in which the hydrogen production amount is relatively large, a predetermined amount of hydrocarbon fuel and water and air are supplied to the reforming reactor group B, and only the hydrocarbon fuel and air are supplied to the reforming reactor group B. Both the reforming reactor group A and the reforming reactor group B are configured so that the feed raw fuel amount is switched according to the operation mode so as to supply a predetermined amount of hydrocarbon fuel, water and air, respectively. Characteristic hydrogen production equipment operating method. 19. A method of operating a hydrogen production apparatus having at least two sets of reforming reactor groups A and B, wherein the unit of the reforming reactor group A is used in a low load operation mode in which the hydrogen production amount is relatively small. The hydrogen production amount per hour is set to be larger than the hydrogen production amount per unit time of the reforming reactor group B. In the high load operation mode where the hydrogen production amount is relatively large, the unit time of the reforming reactor group B is set. The hydrogen production amount per unit time is set to be larger than the hydrogen production amount per unit time of the reforming reactor group A. 20. A plurality of reforming reactor groups, control means for controlling the raw fuel supply amount to the plurality of reactor groups, and the raw fuel supply amount in advance in a normal operation mode and an emergency operation mode. A hydrogen production apparatus and a hydrogen production apparatus provided with a storage means for storing the temperature and an operation detection means for detecting a temperature related to the hydrogen production process or an amount related to an energy output obtained by using the hydrogen. A method of operating a power generation system used, wherein the control means compares the detection value of the operation detection means with at least one preset setting value, and compares the magnitude relationship obtained as a result of the comparison processing. Based on the judgment result, the raw fuel supply amount corresponding to each operation mode is read from the storage means, A method for operating a hydrogen production apparatus and a power generation system using the hydrogen production apparatus, characterized in that the amount of raw fuel supplied to each reforming reactor group is controlled.