JP2000220805A - Catalyst combustion heating device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To start catalyst combustion appropriately by rapidly starting a device without increasing heater power and device size even if the fresh air temperature is low in a catalyst combustion heating device using methanol as a fuel for starting. SOLUTION: A device is provided with a first fuel gas supply means for supplying methanol from a methanol supply path 31 to a heat exchanger 2 with a catalyst along with a burning-supporting gas from a burning-supporting gas supply path 7 by vaporizing the methanol and a second fuel gas supply means for supplying hydrogen in a hydrogen storage container 81 to the heat exchanger 2 with a catalyst along with the burning-supporting gas from the burning-supporting gas supply path 7 from a hydrogen supply path 8. When the fresh air temperature is low on starting, first the second fuel gas supply means is operated for increasing the temperature of the catalyst on the surface of a fin 23 due to the catalyst combustion heat of hydrogen where a temperature for burning the catalyst is low and switching is made to the first fuel gas supply means when a temperature for burning the catalyst of methanol is reached, thus starting the device at an early stage.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for heating methanol supplied to a reformer for obtaining hydrogen from methanol, for example, in a fuel cell system used for a household or automobile generator. The present invention relates to a catalytic combustion heating apparatus that heats an aqueous methanol solution to high-temperature methanol steam using heat of oxidation reaction by a catalyst.

[0002]

2. Description of the Related Art In recent years, fuel cells have been attracting attention as a clean energy source with increasing interest in environmental issues. In a fuel cell, a method of supplying hydrogen required for power generation has been an issue, and a method of obtaining hydrogen by reforming methanol or natural gas with a reforming catalyst has been studied. Among them, a fuel cell system using methanol is said to have high potential for practical use because methanol is liquid and easy to handle. A mixed solution of methanol and water (hereinafter referred to as an aqueous methanol solution) is heated to methanol steam at a temperature of several hundred degrees Celsius and sent to a reformer. The gas reformed into hydrogen, carbon dioxide, and water by the reformer is used as a fuel. Supply battery.
Normally, in this fuel cell system, one mole of methanol is reformed to obtain three moles of hydrogen, and about one mole is obtained from the fuel cell.
An off-gas containing moles of hydrogen is exhausted.

Here, as a prior art of a catalytic combustion heating device, there is one described in, for example, Japanese Patent Application Laid-Open No. 6-249414. In this device, a ceramic body carrying a catalyst is disposed in a combustion cylinder, and a mixed gas of a fuel and a supporting gas vaporized in a vaporization chamber is supplied to perform catalytic combustion. Thus, the fluid to be heated can be heated. In addition, by forming the combustion cylinder as an extension of the constituent members of the vaporization chamber, the radiant heat radiated from the catalyst layer during steady combustion is fed back to the vaporization chamber via the combustion cylinder wall, so that good fuel vaporization is achieved. In addition, the fuel and the supporting gas can be uniformly mixed.

[0004]

However, when the above-mentioned conventional catalytic combustion heating device is applied to a fuel cell system, there are the following problems, particularly at the time of starting the fuel cell system. In a fuel cell system, usually, a part of methanol to be reformed is heated and vaporized by an electric heater and used as a starting fuel for a catalytic combustion heating device. When the battery starts generating electricity,
It is common to switch the fuel to off-gas containing hydrogen from the fuel cell. However, when the catalyst is extremely cooled, such as when used on a winter day or a cold place where the outside air temperature is low, it is the lower limit temperature at which methanol starts catalytic combustion.
It is necessary to raise the temperature of the catalyst to around 0 ° C. The most common method is to heat the supporting gas with an electric heater for vaporizing methanol and heat the catalyst using the supporting gas as a medium.However, the heat transfer coefficient between the metal and the gas is extremely high. Because of its low power, it has a considerable amount of heater power. Further, the storage battery capacity for that purpose becomes excessive, and the weight and the physique increase. Alternatively, there is a means for providing a pilot burner, but there is a problem that exhaust gas containing NOx or the like is discharged.

Accordingly, the present invention provides a method for quickly starting an apparatus even when the outside air temperature is low, for example, at a low temperature of, for example, -40 ° C., without increasing the heater power or increasing the size of the apparatus. An object of the present invention is to provide a catalytic combustion heating device capable of starting combustion.

[0006]

In order to solve the above problems, a catalytic combustion heating device according to claim 1 of the present invention comprises:
The fuel gas flow path through which the fuel gas flows and the heated fluid flow path through which the heated fluid flows are provided in contact with each other, and an oxidation catalyst layer that contacts the fuel gas to generate an oxidation reaction is provided in the fuel gas flow path. A heat exchanger with a catalyst is provided, and the fluid to be heated is heated by the heat of oxidation reaction of the fuel gas. Then, the methanol storage means, the heated fluid supply means for mixing the methanol from the methanol storage means with water and supplying it as an aqueous methanol solution into the heated fluid flow path, and the methanol from the methanol storage means being vaporized and supported. First fuel gas supply means for supplying the fuel gas flow path together with the gas,
It has a hydrogen storage means and a second fuel gas supply means for supplying a small amount of hydrogen from the hydrogen storage means together with the supporting gas to the fuel gas flow path.

According to the present invention, hydrogen can be catalyzed at about -40 ° C., and catalytic combustion does not have a flammable concentration unlike flame combustion, and can burn even dilute fuel having a very low concentration. Focusing on such factors, hydrogen is used as fuel for starting at low temperatures. That is, in the heat exchanger with a catalyst, when the temperature of the oxidation catalyst layer is lower than the temperature at which the catalytic combustion of methanol is possible, the second fuel gas supply means is operated to reduce a small amount of hydrogen to the supporting gas. At the same time, the fuel gas is supplied to the fuel gas flow path to cause catalytic combustion. When the fluid to be heated is not flowing in the fluid passage to be heated, the heat transfer resistance into the fluid passage to be heated is relatively large, and the heat transfer coefficient from the metal surface to the gas is small. Since the heat generated on the surface is not easily taken away by the combustion gas, the catalyst temperature rises quickly. When the temperature of the oxidation catalyst layer reaches a temperature at which catalytic combustion of methanol is possible, the apparatus can be easily started by switching to the first fuel gas supply means. Therefore, even at a low temperature, the catalyst can be activated early while suppressing the heater power,
A compact, low-power, catalytic combustion heating device with a short start-up time can be obtained.

[0008] In the configuration of the second aspect, the first and the second
Control means for controlling the operation of the fuel gas supply means,
When the temperature of the oxidation catalyst layer is lower than a predetermined temperature when the apparatus is started, a small amount of hydrogen is supplied to the fuel gas flow path together with the supporting gas by the second fuel gas supply means, and When the temperature reaches the predetermined temperature, the second fuel gas supply means is stopped, and the first fuel gas supply means is operated.

[0009] More specifically, the temperature of the oxidation catalyst is set to a predetermined temperature, for example, when the apparatus is started, by the control means.
When the temperature is lower than about 20 ° C., which is a temperature at which catalytic combustion of methanol is possible, the second fuel gas supply means is operated.
The heat generated by catalytic combustion of hydrogen increases the temperature of the oxidation catalyst layer, and when the temperature reaches the predetermined temperature, stops the second fuel gas supply means and activates the first fuel gas supply means. Switch fuel from hydrogen to methanol. Thus, the catalyst can be activated early and easily to start catalytic combustion.

[0010] In the structure of the third aspect, a small-sized pressure vessel, a cold storage vessel, or a hydrogen storage alloy is used as the hydrogen storage means. In the present invention, the amount of hydrogen required is very small, since hydrogen is used only to raise the catalyst temperature to about 20 ° C. at which methanol can be catalyzed.
Therefore, the container for storing hydrogen may be small, and by using a cartridge-type small pressure container or a hydrogen storage alloy, it is possible to prevent the entire apparatus from becoming large. Liquid hydrogen may be stored in a cool container.

According to the fourth aspect of the present invention, the third gas for supplying a gas containing hydrogen discharged from the fuel cell to the fuel gas flow path is provided.
When the fuel cell starts power generation by the control means, the first fuel gas supply means is stopped and the third fuel gas supply means is operated.

The catalytic combustion heating device of the present invention is suitably used in a fuel cell system using hydrogen obtained by reforming methanol steam in a reformer as a fuel, and heating a methanol aqueous solution supplied to the reformer. Used as a device.
In this fuel cell system, a gas containing hydrogen is discharged from the fuel cell. Therefore, when the fuel cell starts generating power, the supply of methanol from the first fuel gas supply means to the fuel gas flow path is stopped. Then, the gas is switched to a gas containing hydrogen from the third fuel gas supply means. As described above, by using surplus hydrogen discharged from the fuel cell as fuel, consumption of methanol can be suppressed, and heater power for methanol vaporization can be suppressed to reduce cost.

According to a fifth aspect of the present invention, in the configuration of the fourth aspect, the hydrogen-containing gas discharged from the fuel cell is supplied to the fuel gas flow path in the middle of a flow path for supplying the hydrogen-containing gas to the fuel gas flow path. A storage unit for storing gas is provided to serve as the hydrogen storage means. As a result, part of the hydrogen generated by the fuel cell can be used as fuel at the start of the device, and there is no need to provide another hydrogen storage container, so that the entire device can be made smaller.

[0014]

FIG. 1 shows a first embodiment of the present invention, and is a view showing the entire configuration of a fuel cell system provided with a catalytic combustion heating device of the present invention. In the figure, the catalytic combustion heating device includes a heat exchanger with catalyst 2 for heating a fluid to be heated by heat of oxidation reaction of a fuel gas, and a methanol vaporizer 3 connected to a lower end portion thereof. In the heat exchanger with catalyst 2, an aqueous methanol solution is used as a fluid to be heated. The aqueous methanol solution is heated by high-temperature methanol steam and sent to the reformer 4. The methanol steam is reformed into hydrogen in the reformer 4 and then supplied to the fuel cell 5.

The heat exchanger with catalyst 2 is provided so as to cross a fuel gas flow path 21 provided in the container 1 and has a plurality of tubes 22a through which an aqueous methanol solution flows. Both ends of the plurality of tubes 22a are joined to the U-turn tube 22b by a method such as welding, and constitute a continuous heated fluid flow path connected to each other by the tubes 22a and 22b. At one end of the continuous fluid passage, a heated fluid introduction passage 22c serving as a heated fluid supply means is provided, and methanol is supplied via a reforming methanol supply pump P1 and a water supply pump P2. They are connected to a methanol storage tank T1 and a water storage tank T2 as storage means, respectively.

In the heat exchanger with catalyst 2, a number of ring-shaped fins 23 are integrally joined to the outer periphery of each tube 22a by a method such as brazing, and the surface of the fins 23 is made of platinum or palladium. Such an oxidation catalyst is carried to form an oxidation catalyst layer. When the fuel gas comes into contact with the surfaces of the fins 23, an oxidation reaction occurs, and the heat generated at that time heats the aqueous methanol solution in the tubes 22a, 22b. The combustion exhaust gas after the catalytic combustion is discharged to the outside through an exhaust gas port 24 provided at a downstream end (upper end in the figure) of the fuel gas flow path 21.

The methanol vaporizer 3 is for vaporizing methanol which is a main fuel at the start of the system.
Methanol is supplied from the methanol storage tank T1 via a methanol supply pump P3 for combustion and a methanol supply path 31. An electric heater 32 for vaporizing methanol is installed at the bottom of the methanol vaporizer 3. The vaporized methanol is mixed with the supporting gas supplied from the supporting gas supply pump P4 through the supporting gas supply passage 7. The fuel gas is mixed and supplied to the fuel gas passage 21 as a fuel gas. The methanol vaporizer 3, the methanol supply path 31, and the support gas supply path 7 constitute first fuel gas supply means for starting. In general, air is suitably used as the supporting gas.

A hydrogen supply path 8 for supplying hydrogen as auxiliary fuel at the start of the system is connected in the middle of the support gas supply path 7. The hydrogen supply passage 8 communicates with a hydrogen storage container 81 serving as hydrogen storage means, and by opening and closing a valve 82 provided in the hydrogen supply passage 8, hydrogen can be supplied to the support gas supply passage 7. The hydrogen supply path 8 and the supporting gas supply path 7 constitute a second fuel gas supply means, and are used prior to the first fuel gas supply means when the outside air temperature is lower than a predetermined temperature. Then, a small amount of hydrogen is supplied to the fuel gas passage 21 together with the supporting gas to generate heat, and the temperature of the oxidation catalyst is quickly raised to a temperature at which methanol can be combusted. If the hydrogen storage container 81 uses, for example, a cartridge-type small pressure container that stores compressed hydrogen, no space is required for installation and the handling is easy. Alternatively, hydrogen can be stored using a hydrogen storage alloy.

The reformer 4 has a known structure, and converts the high-temperature methanol steam sent from the heat exchanger with catalyst 2 into
The fuel is reformed into hydrogen by a reforming catalyst, and
Supplied to Normally, in this system, one mole of methanol is reformed to generate three moles of hydrogen. In the fuel cell 5, about ／ of the reformed hydrogen is consumed, and the remaining hydrogen is used for the power generation reaction. Emitted with unused carbon dioxide and water. That is, off-gas containing about 1 mol of hydrogen is discharged. The off-gas is introduced into the fuel mixing section 25 upstream of the fuel gas flow path by the off-gas introduction path 6 serving as a third fuel gas supply means.
Used as the main fuel of the catalytic combustion heating device 1. The tip of the off-gas introduction path 6 extends into the fuel mixing section 25, and the off-gas introduced from the plurality of off-gas introduction ports 61 provided in the pipe wall on the upstream side is supplied to the above-described supporting gas supply path 7 through the above-mentioned methanol vaporization. After being mixed with the supporting gas supplied through the inside of the vessel 3, it is supplied to the fuel gas passage 21.

On the other hand, a temperature sensor S for detecting the temperature of the oxidation catalyst layer on the surface of the outer fins 23 is provided in the tube 22a located at the most upstream part of the fuel gas flow path 21. The detection result of the temperature sensor S is input to the control device 9 as a control means. In the present invention, based on the result, the reforming methanol supply pump P1,
Water supply pump P2, combustion methanol supply pump P3,
By operating the support gas supply pump P4 and the valve 82 of the hydrogen supply path 8, the supply of methanol, water, support gas, and hydrogen is controlled. Hereinafter, the control method will be described.

A feature of the present invention resides in that a small amount of hydrogen supply means is provided in addition to ordinary methanol as a fuel gas for starting the system, and when the outside air temperature is extremely low (for example, 0 ° C. or less). First, a small amount of hydrogen is supplied to raise the catalyst temperature, and then, is switched to methanol. That is,
As shown in the flowchart of FIG. 2, when a start command is issued to the fuel cell system, the temperature sensor S detects the catalyst temperature T.
Is detected (step 1), and it is determined whether or not the catalyst temperature T is equal to or higher than the combustion start temperature Ta (about 20 ° C.) of methanol (step 2). If the temperature of the catalyst is lower than the combustion start temperature Ta, the valve 82 of the hydrogen supply path 8 is opened to open the storage container 81.
Is supplied to the combustion gas supply passage 7 and the combustion gas is supplied from the combustion gas supply pump P4 to the combustion gas supply passage 7 (steps 3 and 4).

Since hydrogen can be catalytically burned at a low temperature of about -40 ° C., a fuel gas obtained by mixing hydrogen and a supporting gas is used.
When the fuel gas is introduced into the fuel gas flow path 21 through the methanol vaporizer 3, catalytic combustion easily starts on the surface of the fin 23. At this time, the heated fluid methanol and water are not supplied, and the heat generated by the catalytic combustion is used to raise the catalyst temperature as much as possible. At this time, the supply amounts of hydrogen and the supporting gas are 1/10 to 1 in the steady state.
/ 100 and a very small amount, it is possible to prevent the heat generated on the catalyst surface from being carried away by the combustion gas. Therefore, the catalyst temperature T can be efficiently raised in a short time.

Subsequently, the catalyst temperature T is detected again by the temperature sensor S (step 5), and the heat generated by catalytic combustion of hydrogen is
The catalyst temperature T is the combustion start temperature Ta of methanol (about 20
C.) or more (step 6), the electric heater 32 of the methanol vaporizer 3 is energized (step 7). Then, methanol is supplied from the combustion methanol supply pump P3 to the methanol vaporizer 3 through the methanol supply path 31 to vaporize the methanol, and the supply of hydrogen is stopped by closing the valve 82 of the hydrogen supply path 8 ( Step 8). Next, the flow rate of the supporting gas is increased (step 9), and the vaporized methanol is introduced into the fuel gas passage 21 as a fuel gas together with the supporting gas. Fin 2 above
Since the temperature of the oxidation catalyst layer on the three surfaces has risen to a temperature at which catalytic combustion of methanol is possible, the fuel gas starts catalytic combustion promptly.

When it is confirmed that the catalytic combustion of methanol has been performed well and the catalyst temperature T detected by the temperature sensor S has increased (steps 10 and 11), the reforming methanol supply pump P1 and the water supply The reforming methanol and water are supplied by the pump P2 (step 12). The reforming methanol and water are supplied to the heated fluid introduction passage 22.
and heated to high-temperature methanol steam while flowing through the tubes 22a and 22b. Here, it is confirmed whether or not the heat generated by the catalytic combustion of methanol satisfies the amount of heat necessary for heating the aqueous methanol solution, for example, by detecting the outlet temperature of the fluid passage to be heated (step 13). If heat = the required amount of heat, the flow rate of each fluid is maintained (step 14). If the heat of combustion of the catalyst is larger than the required amount of heat, the flow rate of methanol for combustion is reduced (steps 15 and 16).

Thus, the methanol steam maintained at a predetermined high temperature is reformed into hydrogen in the reformer 4 and supplied to the fuel cell 5. About 2/3 of the reformed hydrogen is consumed in the fuel cell 5, and the remaining hydrogen is introduced into the fuel mixing section 25 from the off-gas introduction path 6 together with carbon dioxide and the like. Then, the fuel gas is mixed with the supporting gas supplied from the supporting gas supply passage 7 and supplied to the fuel gas passage 21. As the flow rate of the hydrogen-containing offgas increases, the combustion methanol supply pump P
The supply amount of methanol for combustion from 3 is reduced, and when the amount becomes sufficient to heat the fluid to be heated, the supply of methanol for combustion is stopped.

As described above, the temperature of the catalyst can be quickly and easily raised without using the electric heater to heat the supporting gas or using a burner that emits NOx. Therefore, even when used in an environment where the outside air temperature is extremely low, the catalytic combustion heating device can be started quickly and with low power, and the power generation by the fuel cell 5 can be performed satisfactorily.

Here, the reason for not starting with only hydrogen is as follows.
Since it is generally difficult to store a large amount of hydrogen, a large amount of hydrogen is required to heat the fluid to be heated necessary for starting the fuel cell system, which increases the size of the apparatus. It is. If hydrogen is used only for heating to about 20 ° C., which is the catalytic combustion start temperature of methanol, as in the present embodiment, the required amount of hydrogen is very small, and a small pressure vessel or the like is sufficient. it can.
Therefore, with a simple configuration, the device does not become large,
High practicality.

FIG. 3 shows a second embodiment of the present invention.
In this embodiment, the hydrogen storage container 8 used in the first embodiment is not provided, and instead, the off-gas introduction path 6
A large diameter portion is provided in the middle of the process to form a hydrogen storage portion 62. Opening / closing valves 63, 6 are located upstream and downstream of the hydrogen storage unit 62.
4 is provided to control the introduction of off-gas from the fuel cell 5 to the hydrogen storage unit 62 and from the hydrogen storage unit 62 into the heat exchanger 2 with catalyst. Further, a branch passage 71 having a valve 72 is provided in the middle of the supporting gas supply path 7 from the supporting gas supply pump P4 to the methanol vaporizer 3 to introduce off-gas between the valve 63 and the hydrogen storage unit 62. It is connected to road 6. The volume determined by the diameter and length of the hydrogen storage unit 62 is appropriately determined from the heat capacity of the heat exchanger with catalyst 2. In this case, by adjusting the supply amount of the supporting gas introduced from the branch passage 71 in accordance with the volume of the hydrogen storage unit 62, the hydrogen concentration can be reduced to less than 4% by volume. There is no risk of fire. Other configurations are the same as those of the first embodiment.

FIG. 4 shows the operation of the present embodiment.
This will be described based on FIG. In this embodiment, as shown in FIG. 4, prior to the start command of the fuel cell system, at the time of the previous operation stop, that is, when the stop command of the fuel cell system is issued, the open / close valves 63 and 64 of the offgas introduction passage 6 are turned on. Close at almost the same time (step 0). Thereby, the hydrogen storage unit 6
2 stores the off-gas containing hydrogen. Thereafter, when the catalyst temperature T is lower than the combustion start temperature Ta of methanol when the fuel cell system is restarted by a start command of a new fuel cell system, the valves 64 and 72 are opened (steps 1 to 3),
The supply of the supporting gas from the supporting gas supply pump P4 is started (step 4). Then, a part of the supporting gas is turned into the branch passage 71.
The fuel gas is further introduced into the off-gas introduction path 6 and supplied from the off-gas introduction port 61 to the fuel gas flow path 21 while being mixed with hydrogen, and catalytically combusted. At this time, similarly to the first embodiment, the supply of the fluid to be heated is not performed, and the catalyst temperature can be quickly raised by effectively utilizing the heat generated by the catalytic combustion.

Thereafter, when the catalyst temperature T becomes higher than the combustion start temperature Ta (about 20 ° C.) of methanol (step 5,
6) Then, the electric heater 32 is energized (step 7), and the supply of methanol for combustion is started (step 8). At the same time, the valve 72 is closed to stop the supply of the supporting gas to the off-gas introduction path 6, and the valve 63 for introducing the off-gas from the fuel cell 5 is opened. Next, the flow rate of the supporting gas is increased (step 9), the catalytic combustion with methanol is started, and it is confirmed that the catalyst temperature T detected by the temperature sensor S is increasing (steps 10 and 11). The methanol for reforming and the water to be heated are supplied (step 12). Step 13 and subsequent steps are the same as in the first embodiment.

With the above configuration, the same effect as in the first embodiment can be obtained. In addition, since part of the hydrogen generated in the fuel cell 5 is used as fuel for starting, it is not necessary to provide a separate hydrogen storage container. Therefore, the device configuration can be simpler and smaller. In the first and second embodiments, the catalytic combustion heating device is set vertically, but may be set horizontally.

FIGS. 5 and 6 show a third embodiment of the present invention. This embodiment is different from the first embodiment in that the heat exchanger with catalyst 2 of the catalytic combustion heating device has a basic structure of a stacked type.
Is connected to the upper part of the heat exchanger with catalyst 2 (FIG. 5).
The basic configuration for supplying the fluid to be heated and the fuel gas to the heat exchanger with catalyst 2 is substantially the same as that of the first embodiment, and the following description will focus on the differences.

In FIGS. 5 and 6, the inside of the container 1 having a rectangular cross section is partitioned by a partition wall 13 and 14 into a heat exchange section and fluid reservoirs 11 and 12 above and below the heat exchange section. The heat exchange section has a large number of partition plates 17 arranged in parallel in the left-right direction in FIG. 6, and the fuel gas flow path 21 and the heated fluid flow path 22 alternate between two adjacent partition plates 17. Formed. As shown in FIG. 5, each fuel gas passage 21 has a partitioning spacer 1 therein.
By arranging 5 and 16, it is divided into three vertically. The methanol vaporizer 3 is connected to the left end of the uppermost stage, and the exhaust gas port 24 is connected to the right end of the lowermost stage.
The fuel gas flows in a zigzag manner from the upper side to the lower side in the figure by being connected by a and 21b.

Corrugated plate-like fins 23 each having a rectangular cross section are inserted through each stage of the fuel gas flow path 11.
As shown in FIG. 6, the fins 23 are sandwiched between two partition plates 17 serving as flow path walls to further partition the fuel gas flow path 21 into a larger number of flow paths. On the surface of the plate 17, an oxidation catalyst layer is formed which supports an oxidation catalyst such as platinum or palladium using a porous body such as alumina as a carrier.

On the other hand, as shown in FIG.
The upper and lower ends of 2 penetrate partition walls 13 and 14 and communicate with fluid reservoirs 11 and 12, respectively. As shown in FIG. 5, the lower fluid reservoir 12 is connected to a heated fluid introduction path 22d serving as a heated fluid supply means, and is connected from the lower side to the upper side in the figure.
That is, the fluid to be heated flows from the downstream side of the fuel gas flow path 21 to the upstream side. The introduction path 22d is connected to a methanol storage tank T1 and a water storage tank T2 as methanol storage means via a reforming methanol supply pump P1 and a water supply pump P2, respectively.

In each of the heated fluid flow paths 22, corrugated fins (not shown) are inserted and arranged so as to be further divided into a number of flow paths, whereby a heat transfer area to the heated fluid is increased. Is increasing. At this time, the fins provided in the heated fluid flow path 22 are arranged so that the flow directions thereof are orthogonal to the fins 23 provided in the fuel gas flow path 11, and have a flat partition shape. The fins are alternately stacked with the plate 17 interposed therebetween, thereby constituting the heat exchange section.

The methanol vaporizer 3 is provided with a combustion methanol supply pump P from the methanol storage tank T1.
3 and methanol are supplied via a methanol supply path 31. In addition, methanol vaporizer 3
Is connected to a supporting gas supply passage 7 communicating with a supporting gas supply pump P4, and an electric heater 33 for vaporizing methanol is installed across the flow path at an opening on the right end. The electric heater 33 is formed with a large number of through-holes serving as an introduction path to the fuel gas flow path 21, and the vaporized methanol is mixed with a supporting gas (usually air), and as the fuel gas, The gas is supplied to the gas channel 21. The methanol vaporizer 3 and the methanol supply path 3
The first and first fuel gas supply passages 7 constitute a first fuel gas supply means for starting.

A hydrogen supply path 8 for supplying hydrogen as auxiliary fuel at the start of the system is connected to a lower wall of the methanol vaporizer 3. The hydrogen supply passage 8 communicates with a hydrogen storage container 81 serving as hydrogen storage means, and by opening and closing a valve 82 provided in the hydrogen supply passage 8, hydrogen can be supplied to the support gas supply passage 7. The hydrogen supply passage 8 and the combustion support gas supply passage 7 constitute second fuel gas supply means. The configurations of the reformer 4 and the fuel cell 5 communicating with the fluid reservoir 11 are the same as those of the first embodiment, and the off-gas from the fuel cell 5
By the off-gas introduction path 6 serving as a fuel gas supply means,
It is introduced into the methanol vaporizer 3.

A temperature sensor S for detecting the temperature of the oxidation catalyst layer on the surface of the fin 23 is provided at the uppermost stream of the fuel gas flow path 21. The detection result of the temperature sensor S is
In the present invention, based on the results, the reforming methanol supply pump P1, the water supply pump P2, the combustion methanol supply pump P3, and the combustion supporting gas supply pump P4 are used. By operating the valve 82 of the hydrogen supply path 8, the supply of methanol, water, combustion gas and hydrogen is controlled. The control method is the same as that of the first embodiment, and the same effect of starting the device early and with low power can be obtained.

In addition, the above-mentioned laminated heat exchanger with catalyst 2 comprises:
Since the specific surface area per volume can be increased, miniaturization is easy. Furthermore, since the laminated heat exchanger with a catalyst can be easily manufactured by laminating the press-formed components and brazing them integrally, the cost can be reduced.

FIG. 7 shows a fourth embodiment of the present invention.
The basic configuration of this embodiment is the same as that of the third embodiment, and a hydrogen storage unit 62 similar to that of the second embodiment is provided as a hydrogen storage unit instead of the hydrogen storage container 8. It is. As shown in FIG. 7, the hydrogen storage unit 62 is formed of a large diameter portion provided in the middle of the offgas introduction path 6, and open / close valves 63 and 64 are provided at upstream and downstream positions thereof.
From the fuel cell 5 to the hydrogen storage 62 and to the hydrogen storage 6
2 to control the introduction of off-gas into the heat exchanger with catalyst 2. Further, a branch passage 71 having a valve 72 is provided in the middle of the supporting gas supply path 7 from the supporting gas supply pump P4 to the methanol vaporizer 3 to introduce off-gas between the valve 63 and the hydrogen storage unit 62. It is connected to road 6. As described above, in the configuration of the stacked heat exchanger with catalyst 2, the hydrogen storage unit 62 can be provided as the hydrogen storage means. The control method of the control device 9 (not shown) is the same as in the second embodiment, and the same effects can be obtained.

In each of the above embodiments, an example in which the catalytic combustion heating device of the present invention is applied to a fuel cell system has been described. However, the present invention is not limited to this, and may be applied to uses other than the fuel cell system. Can also.

[Brief description of the drawings]

FIG. 1 is a view showing a first embodiment of the present invention and showing an entire configuration of a fuel cell system including a catalytic combustion heating device.

FIG. 2 is a diagram illustrating a control flowchart of each fluid in the first embodiment.

FIG. 3 is a view showing a second embodiment of the present invention and showing an entire configuration of a fuel cell system including a catalytic combustion heating device.

FIG. 4 is a diagram illustrating a control flowchart of each fluid in a second embodiment.

FIG. 5 shows a third embodiment of the present invention, and is a view showing an overall configuration of a fuel cell system including a catalytic combustion heating device,
FIG. 7 is a sectional view taken along line AA of FIG. 6.

FIG. 6 is a sectional view of a heat exchanger with a catalyst according to a third embodiment.

FIG. 7 shows a fourth embodiment of the present invention, and is a diagram illustrating an overall configuration of a fuel cell system including a catalytic combustion heating device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Container 2 Heat exchanger with a catalyst 21 Fuel gas flow path 22a Tube 22b U-turn tube 22c Heated fluid introduction path (heated fluid supply means) 23 Fin 24 Exhaust gas port 25 Fuel mixing section 3 Methanol vaporizer (first) Fuel gas supply means) 31 methanol supply path (first fuel gas supply means) 32 electric heater 4 reformer 5 fuel cell 6 off gas introduction path 61 off gas introduction port 7 supporting gas supply path (first and second fuels) 8 hydrogen supply path (second fuel gas supply means) 81 hydrogen storage container (hydrogen storage means) 82 valve 9 control device (control means) S temperature sensor T1 methanol storage tank (methanol storage means) T2 water storage Tank P1 Methanol supply pump for reforming P2 Water supply pump P3 Methanol supply pump for combustion P4 Fuel gas Feed pump

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shoji Hirose 14 Iwatani, Shimowakaku-cho, Nishio-shi, Aichi Pref. Japan Automobile Parts Research Institute Co., Ltd. (72) Inventor Atsushi Ogino 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Yoshimasa Negishi 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation

Claims (5)

[Claims] A fuel gas flow path through which a fuel gas flows and a heated fluid flow path through which a heated fluid flows are provided in a vessel, and the fuel gas flow path is contacted with the fuel gas in the fuel gas flow path to cause an oxidation reaction. A catalytic combustion heating device comprising a heat exchanger with a catalyst provided with an oxidation catalyst layer that generates an oxidation catalyst, and heating the fluid to be heated with the heat of oxidation reaction of the fuel gas, comprising methanol storage means, and methanol from the methanol storage means. A heated fluid supply means for supplying the heated fluid together with water into the heated fluid flow path; and a first fuel gas which vaporizes methanol from the methanol storage means and supplies the fuel to the fuel gas flow path together with the supporting gas. A catalytic combustion heating device comprising: a supply unit; a hydrogen storage unit; and a second fuel gas supply unit configured to supply a small amount of hydrogen from the hydrogen storage unit to the fuel gas flow path together with a supporting gas. Place. And a control means for controlling the operation of the first and second fuel gas supply means. When the temperature of the oxidation catalyst layer is lower than a predetermined temperature at the start of the apparatus,
A small amount of hydrogen is supplied to the fuel gas flow path together with the supporting gas by the second fuel gas supply means, and when the temperature of the oxidation catalyst layer reaches a predetermined temperature, the second fuel gas supply means is stopped. 2. The catalytic combustion heating device according to claim 1, wherein said first fuel gas supply means is operated. 3. The catalytic combustion heating device according to claim 1, wherein a small pressure vessel, a cold storage vessel, or a hydrogen storage alloy is used as the hydrogen storage means. 4. A fuel gas supply means for supplying a gas containing hydrogen discharged from the fuel cell to the fuel gas flow path, wherein the control means causes the fuel cell to start generating power. 4. The fuel gas supply means according to claim 2, wherein the first fuel gas supply means is stopped and the third fuel gas supply means is operated.
A catalytic combustion heating device as described in the above. 5. A storage section for storing the hydrogen-containing gas, the storage section storing the hydrogen-containing gas being provided in a flow path for supplying the hydrogen-containing gas discharged from the fuel cell to the fuel gas flow path. 5. The catalytic combustion heating device according to claim 4, wherein said device is a means.