JPH1192102A - Reforming device of fuel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make the inner temp. of a fuel cell device uniform in a specified temp. range. SOLUTION: A source fuel gas containing air is supplied from a second fuel supply passage 64 to a reforming device 34 equipped with a Cu-Zn catalyst, the reforming reaction with water vapor and the oxidation reaction proceed inside the device, and the produced hydrogen-rich fuel gas is discharged to a third fuel supply passage 65. The reforming device 34 consists of a reaction part 80 in the upstream side and a reaction part 81 in the downstream side. Both of the reaction parts 80, 81 consists of a honeycomb structure in such a manner that the sum of the cross section of the passage in each reaction part, namely, the sum of the cross-sectional area of cells which constitute the respective honeycomb structures is smaller in the reaction part 80 in the upstream side. Therefore, the flow rate of the gas passing through the reforming device 34 is higher in the upstream side than in the downstream side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fuel reformer, and more particularly, to a fuel reformer that generates a hydrogen-rich gas from hydrocarbons and steam.

[0002]

2. Description of the Related Art A fuel reforming apparatus for producing a hydrogen-rich gas from hydrocarbons and water vapor is known as an apparatus for supplying a fuel gas to a fuel cell. A fuel cell is a device that directly converts chemical energy of a fuel into electric energy without passing through mechanical energy or thermal energy, and can realize high energy efficiency. In such a fuel cell, a fuel gas containing hydrogen is supplied to a cathode side, and an oxidizing gas containing oxygen is supplied to an anode side, and an electromotive force is obtained by an electrochemical reaction occurring at both electrodes. The following shows an equation representing an electrochemical reaction occurring in a fuel cell.
Equation (1) represents the reaction on the cathode side, and equation (2) represents the reaction on the anode side, and the reaction shown in equation (3) proceeds in the entire fuel cell.

H ₂ → 2H ⁺ + 2e ⁻ (1) (1/2) O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O (2) H ₂ + (1/2) O ₂ → H ₂ O (3) )

Among various fuel cells, a polymer electrolyte fuel cell, a phosphoric acid fuel cell, a molten carbonate electrolyte fuel cell and the like use an oxidizing gas or a fuel gas containing carbon dioxide due to the properties of the electrolyte. It is possible to use. Therefore, these fuel cells usually use air as an oxidizing gas, and use a hydrogen-rich gas generated by steam reforming a hydrocarbon such as methanol or natural gas as a fuel gas. Therefore, a fuel cell system including such a fuel cell is provided with the above-described fuel reformer,
The fuel reformer performs a steam reforming reaction to generate a fuel gas. Hereinafter, the reforming reaction that proceeds inside the fuel reformer will be described. Here, a case where methanol is used as the hydrocarbon to be subjected to the reforming reaction will be described. The following shows an equation representing a reaction for steam reforming methanol.

CH ₃ OH + H ₂ O → CO ₂ + 3H ₂ −49.5 (kJ / mol) (4)

As shown in the above formula (4), since the steam reforming reaction is an endothermic reaction, it is necessary to supply thermal energy in order for the reforming reaction to proceed. As a method of supplying thermal energy required for the reforming reaction, a method of providing an external heating by providing a burner, a heater, or the like in the fuel reforming apparatus, or an exothermic reaction in addition to the steam reforming reaction inside the fuel reforming apparatus. There is known a method in which a certain oxidation reaction is performed, and a steam reforming reaction is advanced using heat generated in the oxidation reaction. Among these methods, a method of causing the oxidation reaction to proceed together with the steam reforming reaction inside the fuel reformer will be described.

CH ₃ OH + (１ ／) O ₂ → CO ₂ + 2H ₂ +189.5 (kJ / mol) (5)

The above equation (5) represents an example of the methanol oxidation reaction (partial oxidation reaction). If oxygen is supplied to the fuel reforming apparatus that performs the steam reforming reaction and the methanol oxidation reaction is performed together with the steam reforming reaction represented by the equation (4), the heat energy generated by the oxidation reaction is converted into steam reforming. Can be used in quality reactions. Here, if the amount of oxygen supplied to the fuel reformer is adjusted, the amount of heat required for the steam reforming reaction can be balanced with the amount of heat generated in the oxidation reaction. Can all be covered by the heat generated by the oxidation reaction. Such a method in which the amount of heat required for the steam reforming reaction is covered by the amount of heat generated in the oxidation reaction can reduce the amount of energy lost due to heat radiation and achieve higher energy efficiency, as compared with the above-described method of performing external heating. Can be realized. Further, the configuration of the fuel reformer can be simplified and the entire system can be reduced in size as compared with the method of performing external heating.

[0009]

However, the above-mentioned method of supplying oxygen together with methanol and steam to a fuel reformer and utilizing the heat energy generated by the oxidation reaction in the steam reforming reaction is described in US Pat. There is a problem that the temperature distribution state becomes non-uniform inside the apparatus. FIG. 38 is an explanatory diagram showing a state of a temperature distribution inside the fuel reforming apparatus when oxygen is supplied to the fuel reforming apparatus together with methanol and steam, and an oxidation reaction is performed together with the steam reforming reaction. When oxygen is introduced together with methanol and steam into the fuel reformer,
Since the oxidation reaction has a higher reaction rate than the steam reforming reaction, the amount of heat generated in the oxidation reaction exceeds the amount of heat required for the steam reaction, and as shown in FIG. 38, the upstream side (methanol, steam and On the side that introduces a gas containing oxygen), the internal temperature rises sharply to form a peak in the temperature distribution. Also, after oxygen is consumed in the oxidation reaction, only the steam reforming reaction will proceed,
After the peak of the temperature distribution described above, the internal temperature of the fuel reformer continues to decrease toward the downstream side (the side from which the hydrogen-rich gas is discharged).

If the temperature distribution forms a peak inside the fuel reformer and the temperature rises too high, problems such as deterioration of the catalyst and generation of by-products occur. First, the deterioration of the catalyst will be described. For example, when a Cu—Zn catalyst is used as a catalyst for promoting a steam reforming reaction and an oxidation reaction of methanol, this C
When a u-Zn catalyst is used, the durability of the catalyst may be reduced and sintering may occur. Here, the sintering refers to a phenomenon in which the catalyst supported on the surface of the carrier aggregates. The Cu-Zn catalyst usually has a shape in which copper fine particles are scattered on the surface of zinc particles. However, when sintering occurs, the copper fine particles aggregate and the particles become large. When such a phenomenon occurs, the active area of the catalyst decreases as the surface area of the copper particles decreases, so that the performance of the fuel reformer decreases.

The generation of by-products, which is another problem caused by an excessive rise in the catalyst temperature, refers to a reaction other than the normal reaction described above when the reforming reaction proceeds at a predetermined high temperature. Occurs and methane is generated, or nitrogen gas in the supplied pressurized air reacts to generate nitrogen oxides. These by-products are not decomposed in the range of the reforming reaction temperature in the fuel reformer, and are supplied to the fuel cell as fuel gas as they are. In particular, an increase in the amount of generated methane or the like is not preferable because it leads to a decrease in the hydrogen partial pressure in the fuel gas.

On the other hand, when the internal temperature decreases on the downstream side of the fuel reforming apparatus, there arises a problem that the activity of the steam reforming reaction decreases as the temperature decreases. If the activity of the steam reforming reaction is reduced, there is a possibility that a gas in which the reforming reaction has not been completed, that is, a gas having insufficient hydrogen concentration due to remaining methanol may be generated. Alternatively, it is necessary to provide a sufficiently large fuel reformer so that the reforming reaction is completed even if the internal temperature decreases on the downstream side.

[0013] The fuel reforming apparatus of the present invention has been made to solve the above-mentioned problems and has the object of making the internal temperature of the fuel reforming apparatus uniform within a predetermined temperature range, and has the following configuration.

[0014]

The first fuel reformer of the present invention is a reaction involving endotherm, and comprises a steam reforming reaction for producing hydrogen from hydrocarbon and steam, A fuel reforming apparatus that utilizes heat generated by the oxidation reaction when a reaction involving heat generation and an oxidation reaction to oxidize the hydrocarbon proceeds, and the steam reforming reaction proceeds. A catalyst unit having a catalyst that promotes a steam reforming reaction and the oxidation reaction, and a raw fuel gas supply unit that supplies a raw fuel gas containing the hydrocarbon, steam, and oxygen to the catalyst unit, A fuel gas discharging unit configured to discharge a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction that proceed in the catalyst unit from the catalyst unit; On the side of the Gas flow rate adjusting means for increasing the flow rate of the raw fuel gas in a portion on the side where the raw fuel gas is introduced so that the heat generated by the oxidation reaction is sufficiently transferred to the downstream side. Make a summary.

[0015] The first fuel reforming apparatus of the present invention having the above-described structure converts hydrocarbon, steam, and oxygen into a catalyst section having a catalyst for promoting a steam reforming reaction and an oxidation reaction. When the contained raw fuel gas is supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation, and the hydrocarbon is oxidized. Oxidation reaction.
At this time, the steam reforming reaction proceeds using heat generated by the oxidation reaction, and a hydrogen-rich fuel gas is generated and discharged from the catalyst unit. Here, in the catalyst section, the heat generated by the oxidation reaction occurring in the portion on the side where the raw fuel gas is supplied is transferred to the downstream side such that the heat generated by the oxidation reaction is sufficiently transferred to the downstream side. The flow rate of the raw fuel gas in the section is adjusted.

According to such a fuel reformer, the heat generated by the oxidation reaction occurring on the side where the raw fuel gas is introduced is sufficiently transferred to the downstream side. There is no possibility that the temperature will be too high in the part on the side where the heat is applied. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved. Furthermore, by sufficiently transferring the heat generated by the oxidation reaction to the downstream side, the activity of the steam reforming reaction can be sufficiently increased on the downstream side, and the fuel reformer can be downsized. Become.

Here, hydrocarbons constituting the raw fuel gas,
It is not necessary to supply the water vapor and oxygen after mixing them in advance, and at least one component or a part of the raw fuel gas may be supplied separately. Even if they are not mixed in advance, the above-mentioned effects can be obtained if these components constituting the raw fuel gas are supplied from the upstream side of the gas flow direction in the catalyst section. Further, the catalyst that promotes the steam reforming reaction and the catalyst that promotes the oxidation reaction may be the same or different. That is, both the steam reforming reaction and the oxidation reaction may be promoted by a single catalyst, or the respective reactions may be promoted by different catalysts. When using different catalysts, it is desirable that both are sufficiently mixed in the reformer.

In the first fuel reforming apparatus according to the present invention, the gas flow rate adjusting means is arranged such that a side of the catalyst section where the raw fuel gas is supplied is more than a side where the fuel gas is discharged. The total area of the cross section of the flow path through which the raw fuel gas flows may be reduced. With such a configuration, the flow rate of the raw fuel gas on the side where the raw fuel gas is supplied can be faster than that on the side where the fuel gas is discharged, and the above-described effects can be obtained. Can be.

The second fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for producing hydrogen from hydrocarbons and steam, and a reaction involving heat generation, wherein An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A catalyst unit having a catalyst to perform, a raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon, steam and oxygen to the catalyst unit, and the steam reforming reaction which proceeds in the catalyst unit. And a fuel gas discharging means for discharging a hydrogen-rich fuel gas generated as a result of the oxidation reaction from the catalyst section, wherein the catalyst in the catalyst section is formed of a material having relatively high thermal conductivity. The carrier The the gist.

In the second fuel reforming apparatus of the present invention having the above-described structure, the hydrocarbon, steam and oxygen are supplied to a catalyst section having a catalyst for promoting the steam reforming reaction and the oxidation reaction. When the contained raw fuel gas is supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation, and the hydrocarbon is oxidized. Oxidation reaction proceeds, and the generated hydrogen-rich fuel gas is discharged. Here, since the catalyst is supported on a catalyst carrier formed of a material having relatively high thermal conductivity, heat generated by the oxidation reaction is quickly transmitted to the peripheral portion by the catalyst carrier, and the steam reforming is performed. Used for quality reaction.

According to such a fuel reforming apparatus, the heat generated by the oxidation reaction is quickly diffused, so that the side on which the raw fuel gas is supplied and on which the oxidation reaction actively proceeds is provided. The temperature does not rise too much.
Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved. Further, the heat generated by the oxidation reaction is diffused and transmitted to the downstream side, so that the activity of the steam reforming reaction can be sufficiently increased on the downstream side, and the fuel reformer can be downsized. Becomes

The third fuel reforming apparatus of the present invention is a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbon and steam, and a reaction involving exothermic reaction. An oxidizing reaction that oxidizes, a fuel reforming apparatus that utilizes heat generated in the oxidation reaction when the steam reforming reaction proceeds, and a catalyst that promotes the steam reforming reaction and the oxidizing reaction. A catalyst unit having a catalyst that promotes a reaction, raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit, and oxygen to the catalyst unit. An oxidizing gas supply unit that supplies an oxidizing gas to be contained, and a fuel gas discharging unit that discharges, from the catalyst unit, a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction that proceed in the catalyst unit. , Wherein the side where the oxidation gas is introduced, is summarized in that and a suppressing oxidation suppression means the progress of the oxidation reaction that.

The third fuel reforming apparatus of the present invention having the above-described structure contains hydrocarbons and steam with respect to a catalyst section having a catalyst for promoting a steam reforming reaction and an oxidation reaction. When the raw fuel gas and the oxidizing gas containing oxygen are supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation. And an oxidation reaction for oxidizing the hydrocarbon proceeds. At this time, the steam reforming reaction proceeds using heat generated by the oxidation reaction, and a hydrogen-rich fuel gas is generated and discharged from the catalyst unit. Here, in the catalyst section, the progress of the oxidation reaction is suppressed on the side where the oxidizing gas is introduced.

According to such a fuel reformer, since the progress of the oxidation reaction is suppressed on the side where the oxidizing gas is introduced, the temperature is excessively increased on the side where the oxidizing gas is introduced. I won't. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved. Further, the progress of the oxidation reaction is suppressed on the side where the oxidizing gas is introduced, so that the region where the oxidation reaction proceeds is spread more downstream, thereby increasing the temperature on the downstream side, and increasing the temperature of the steam reforming reaction. The activity can be sufficiently increased. Therefore, the size of the fuel reformer can be reduced.

[0025] In the third fuel reforming apparatus of the present invention, the oxidation reaction suppressing means may be arranged such that a side of the catalyst section where the oxidizing gas is introduced is closer than a side where the fuel gas is discharged. Alternatively, the catalyst may be formed so that the amount of the catalyst that promotes the oxidation reaction is small.

In the third fuel reforming apparatus according to the present invention, the catalyst for promoting the steam reforming reaction and the catalyst for promoting the oxidation reaction are the same catalyst, and the oxidation reaction suppressing means includes The catalyst may be formed such that the amount of the catalyst is smaller on the side where the oxidizing gas is introduced than on the side where the fuel gas is discharged.

The fourth fuel reforming apparatus of the present invention is a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbon and steam, and a reaction involving exothermic reaction. A fuel reforming device that utilizes an heat generated by the oxidation reaction when the steam reforming reaction proceeds, wherein a catalyst that promotes the steam reforming reaction and the oxidation A catalyst unit having a catalyst that promotes a reaction, raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit, and oxygen to the catalyst unit. An oxidizing gas supply unit that supplies an oxidizing gas to be contained, and a fuel gas discharging unit that discharges, from the catalyst unit, a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction that proceed in the catalyst unit. In the catalyst section And a reaction state detection means for detecting a traveling state of the row to the reaction, the oxidizing gas supply means,
While maintaining a desired amount of oxygen per unit time to be supplied to the catalyst unit, the oxygen in the oxidizing gas supplied to the catalyst unit based on the progress of the reaction detected by the reaction state detection unit. The gist of the present invention is to further include oxygen concentration adjusting means for controlling the concentration.

The fourth fuel reforming apparatus of the present invention having the above-described structure contains hydrocarbons and steam with respect to a catalyst section having a catalyst for promoting a steam reforming reaction and an oxidation reaction. When the raw fuel gas and the oxidizing gas containing oxygen are supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation. And an oxidation reaction for oxidizing the hydrocarbon proceeds. At this time, the steam reforming reaction proceeds using heat generated by the oxidation reaction, and a hydrogen-rich fuel gas is generated and discharged from the catalyst unit. Here, the progress of the reaction that proceeds in the catalyst unit is detected, and while maintaining the desired amount of oxygen per unit time supplied to the catalyst unit, based on the detected progress of the reaction, The oxygen concentration in the oxidizing gas supplied to the catalyst unit is controlled.

According to such a fuel reformer, since the oxygen concentration in the oxidizing gas is controlled, it is possible to control the reaction rate of the oxidizing reaction which proceeds on the side where the oxidizing gas is introduced. It is possible to prevent the temperature from excessively increasing on the side where the oxidizing gas is introduced. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved.
Further, by controlling the reaction rate of the oxidation reaction by controlling the oxygen concentration in the oxidizing gas, the region where the oxidation reaction proceeds can be expanded further downstream, thereby increasing the temperature on the downstream side and increasing the temperature of the steam. The activity of the reforming reaction can be sufficiently increased. Therefore, the size of the fuel reformer can be reduced.

In the above-described fourth fuel reforming apparatus of the present invention, the catalyst section comprises a plurality of reaction sections provided with the catalyst, and the oxidizing gas supply means is provided for each of the plurality of reaction sections. The oxidizing gas may be supplied. With such a configuration, the effect of equalizing the temperature inside the catalyst unit can be further enhanced by providing a plurality of locations to which the oxidizing gas is supplied.

The fifth fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for producing hydrogen from hydrocarbons and steam, and a reaction involving heat generation, wherein An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A raw fuel gas supply unit for supplying a raw fuel gas containing the hydrocarbon, steam, and oxygen to the catalytic unit, and the steam reforming reaction that proceeds in the catalytic unit. And a hydrogen-rich fuel gas generated as a result of the oxidation reaction, a fuel gas discharge unit that discharges the catalyst unit, and a part of the catalyst unit where the raw fuel gas is introduced from the raw fuel gas supply unit. The fuel gas exhaust Interchanging the site for discharging the fuel gas by means, summarized as further comprising a gas supply direction changing means for reversing the flow of the gas in the catalytic section.

The fifth fuel reforming apparatus according to the present invention having the above-described structure converts a hydrocarbon, steam and oxygen into a catalyst having a catalyst for promoting a steam reforming reaction and an oxidation reaction. When the contained raw fuel gas is supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation, and the hydrocarbon is oxidized. Oxidation reaction.
At this time, the steam reforming reaction proceeds using heat generated by the oxidation reaction, and a hydrogen-rich fuel gas is generated and discharged from the catalyst unit. When such a reaction proceeds, a portion where the raw fuel gas is introduced and a portion where the fuel gas is discharged are exchanged in the catalyst section.

According to such a fuel reforming apparatus, since the part where the raw fuel gas is introduced and the part where the fuel gas is discharged are exchanged in the catalyst section, the raw fuel gas is introduced. The temperature does not rise too much in the specific region to be processed. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved. Further, the temperature of the specific downstream side does not decrease, and the activity of the steam reforming reaction can be sufficiently increased in the entire catalyst section. Therefore, the size of the fuel reformer can be reduced.

[0034] In the fifth fuel reforming apparatus of the present invention described above, the end portion temperature detection for detecting the temperature at a predetermined position on the side where the raw fuel gas is supplied from the raw fuel gas supply means in the catalyst section. Means for changing the gas supply direction, based on a detection result of the end temperature detection means, a portion to which the raw fuel gas is introduced from the raw fuel gas supply means, and a fuel gas discharge means. The part for discharging the fuel gas may be replaced. With such a configuration, it is possible to prevent the temperature from excessively increasing on the side where the raw fuel gas is supplied,
It can be reliably prevented.

The sixth fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbon and steam, and a reaction involving heat generation, An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A catalyst section in which particles including a catalyst to be filled are enclosed, a raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon, water vapor, and oxygen to the catalyst section; A fuel gas discharging means for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction progressing in the catalyst section from the catalyst section, and a catalyst for stirring particles including the catalyst in the catalyst section. With stirring means The gist of the door.

The sixth fuel reforming apparatus according to the present invention having the above-described structure is characterized in that a catalyst portion having a catalyst for accelerating a steam reforming reaction and an oxidation reaction is filled in a catalyst portion. And a raw fuel gas containing hydrocarbons, water vapor and oxygen. At that time, in the catalyst section, while stirring the particles provided with the catalyst, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation, And an oxidation reaction for oxidizing hydrocarbons. At this time, the steam reforming reaction proceeds using heat generated by the oxidation reaction, and a hydrogen-rich fuel gas is generated and discharged from the catalyst unit.

According to such a fuel reforming apparatus, the catalyst section agitates the particles provided with the catalyst.
The catalyst included in the particles is involved in the oxidation reaction sequentially,
The temperature does not rise too much in the specific area where the raw fuel gas is introduced. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved. Further, the temperature of the specific downstream side does not decrease, and the activity of the steam reforming reaction can be sufficiently increased in the entire catalyst section. Therefore, the size of the fuel reformer can be reduced.

[0038] In the above-described sixth fuel reforming apparatus of the present invention, the catalyst stirring means is provided in the raw fuel gas supply means and contains at least one of the hydrocarbon, steam and oxygen. A gas may be sprayed into the catalyst section, and particles including the catalyst may be stirred in the catalyst section. With such a configuration, the stirring operation can be performed simultaneously by spraying the gas constituting the raw fuel onto the catalyst section.

The seventh fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for producing hydrogen from hydrocarbons and steam, and a reaction involving heat generation, and An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A catalyst unit having a catalyst to be supplied, raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit, and an oxidizing gas containing oxygen for the catalyst unit An oxidizing gas supply unit for supplying hydrogen gas, a fuel gas discharging unit for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst unit from the catalyst unit, and the catalyst unit. In the oxidation The location where the oxidizing gas from the scan supply means is supplied, and summarized in that and a feed point changing means for temporally changing.

The seventh fuel reformer of the present invention having the above-described structure contains hydrocarbons and steam with respect to a catalyst section having a catalyst for promoting a steam reforming reaction and an oxidation reaction. When the raw fuel gas and the oxidizing gas containing oxygen are supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation. And an oxidation reaction for oxidizing the hydrocarbon proceeds. At this time, the location where the oxidizing gas is supplied in the catalyst section is changed with time. The steam reforming reaction proceeds by utilizing heat generated in the oxidation reaction that proceeds using the oxidizing gas supplied in this manner, and a hydrogen-rich fuel gas is generated and discharged from the catalyst unit. You.

According to such a fuel reforming apparatus, the location where the oxidizing gas is supplied changes with time in the catalyst section. Don't overdo it. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved.

The eighth fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for producing hydrogen from hydrocarbons and steam, and a reaction involving heat generation, wherein An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A catalyst unit having a catalyst to be supplied, raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit, and an oxidizing gas containing oxygen for the catalyst unit An oxidizing gas supply unit for supplying hydrogen gas, a fuel gas discharging unit for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst unit from the catalyst unit, and the catalyst unit. In the said fuel A supply side to which an oxidizing gas is supplied together with a gas; and a discharge side from which the fuel gas is discharged, adjacent to the supply side, and a heat equalizing means for performing heat exchange between the supply side and the discharge side. Is the gist.

[0043] The eighth fuel reforming apparatus of the present invention configured as described above contains hydrocarbons and steam with respect to a catalyst section having a catalyst for promoting a steam reforming reaction and an oxidation reaction. When the raw fuel gas and the oxidizing gas containing oxygen are supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation. And an oxidation reaction for oxidizing the hydrocarbon proceeds. Here, since the catalyst section is formed adjacent to a supply side on which the oxidizing gas is supplied together with the raw fuel gas and a discharge side on which the fuel gas is discharged, the supply side and the discharge side are formed. And heat exchange is performed between the catalyst and the steam reforming reaction using the heat generated by the oxidation reaction, and a hydrogen-rich fuel gas is generated and discharged from the catalyst section.

According to such a fuel reforming apparatus, in the catalyst section, heat exchange is performed between the supply side where the oxidizing gas is supplied together with the raw fuel gas and the discharge side where the fuel gas is discharged. The temperature is not excessively increased in a specific region where the oxidizing gas is introduced. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved.
Further, the temperature of the specific downstream side does not decrease, and the activity of the steam reforming reaction can be sufficiently increased in the entire catalyst section. Therefore, the size of the fuel reformer can be reduced.

In the above-described eighth fuel reforming apparatus of the present invention, each of the catalyst units includes the catalyst therein, and at least two of the catalyst units each having the supply side and the discharge side opposite to each other. The above reaction unit may be provided, and the two or more reaction units may be provided such that the supply side of one reaction unit and the discharge side of the other supply unit are adjacent to each other.

Further, in the eighth fuel reforming apparatus according to the present invention, the catalyst section has a turn-up portion in a flow path of the raw fuel gas formed therein, and has an inlet and an outlet of the flow path. May be provided adjacent to each other.

The ninth fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for producing hydrogen from hydrocarbons and steam, and a reaction involving heat generation, wherein An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A catalyst unit having a catalyst, a raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit, and an oxidizing gas containing oxygen for the catalyst unit An oxidizing gas supply means for supplying hydrogen gas; a fuel gas discharging means for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section from the catalyst section; System with quality equipment A predetermined fluid to transfer heat generated in the predetermined member constituting the arm, and subject matter to be provided with a heating means the oxidizing gas to heat the portion other than the side to be supplied.

The ninth fuel reforming apparatus of the present invention configured as described above contains hydrocarbons and steam with respect to a catalyst section having a catalyst for promoting a steam reforming reaction and an oxidation reaction. When the raw fuel gas and the oxidizing gas containing oxygen are supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation. And an oxidation reaction for oxidizing the hydrocarbon proceeds. Here, in the region where the oxidizing gas is supplied and the oxidizing reaction is performed in the catalyst section, the steam reforming reaction proceeds using heat generated by the oxidizing reaction. In a portion other than the side to which the oxidizing gas is supplied, heat generated in a predetermined member of the system including the fuel reformer is transmitted by a predetermined fluid, and the heat is used to convert the steam. Quality reaction proceeds. The generated hydrogen-rich fuel gas is discharged from the catalyst section.

According to such a fuel reforming apparatus, in a portion other than the side to which the oxidizing gas is supplied, the oxidizing gas is heated by using heat generated in a predetermined member constituting a system including the fuel reforming apparatus. Since the reaction proceeds, the amount of the oxidizing gas supplied to the catalyst unit can be reduced with respect to the amount of the raw fuel gas supplied to the catalyst unit. Does not rise too much. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved. Further, in a portion other than the side to which the oxidizing gas is supplied, heat generated in a predetermined member constituting the system including the fuel reformer is transmitted, so that the activity of the steam reforming reaction is reduced by lowering the temperature. It does not drop. Therefore, the activity of the steam reforming reaction can be sufficiently increased in the entire catalyst section, and the size of the fuel reformer can be reduced. Further, in order to utilize heat generated in a predetermined member constituting a system including the fuel reformer, by heating a portion other than the side to which the oxidizing gas is supplied, energy efficiency of the entire system is reduced. There is no end.

In the ninth fuel reforming apparatus according to the present invention, the oxidizing gas is heated by a high-temperature gas discharged from a predetermined member constituting a system including the fuel reforming apparatus. A portion other than the side to be supplied may be heated.

The tenth fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbon and steam, and a reaction involving exothermic reaction, wherein An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A catalyst unit having a catalyst, a raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit, and an oxidizing gas containing oxygen for the catalyst unit An oxidizing gas supply unit for supplying hydrogen, a fuel gas discharging unit for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction progressing in the catalyst unit from the catalyst unit, And out of the water The liquid consisting of one even without, the gist further comprising an end cooling means for spraying to the portion on the side where the raw fuel gas and the oxidizing gas is supplied.

[0052] The tenth fuel reformer of the present invention having the above-described structure contains hydrocarbons and steam with respect to a catalyst section having a catalyst for promoting the steam reforming reaction and the oxidation reaction. When the raw fuel gas and the oxidizing gas containing oxygen are supplied, in the catalyst section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and a reaction involving heat generation. And an oxidation reaction for oxidizing the hydrocarbon proceeds. Here, in the catalyst section, in a region where the oxidizing gas is supplied and the oxidizing reaction is performed, the steam reforming reaction proceeds using heat generated by the oxidizing reaction. For the part on the side where the raw fuel gas and the oxidizing gas are supplied,
A liquid composed of at least one of the hydrocarbon and water is sprayed, and a portion where the liquid is sprayed is cooled. The generated hydrogen-rich fuel gas is discharged from the catalyst section.

According to such a fuel reforming apparatus, a liquid composed of at least one of the hydrocarbon and water is sprayed at a portion where the raw fuel gas and the oxidizing gas are supplied. Part of the heat generated by the oxidation reaction is consumed as heat of vaporization, and the temperature does not excessively increase on the side where the oxidizing gas is supplied. Therefore, inconveniences such as deterioration of the catalyst and generation of by-products due to an excessive rise in temperature do not occur, and the durability of the reformer can be greatly improved.

The eleventh fuel reformer of the present invention is a reaction involving endotherm, a steam reforming reaction for producing hydrogen from hydrocarbons and steam, and a reaction involving heat generation, wherein An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A catalyst unit comprising a first reaction unit provided with a catalyst for performing the above, a second reaction unit provided with a catalyst for promoting the steam reforming reaction, and the hydrocarbon containing steam and steam with respect to the catalyst unit. A raw fuel gas supply unit for supplying a raw fuel gas; an oxidizing gas supply unit for supplying an oxidizing gas containing oxygen to the first reaction unit; and a steam reforming reaction that proceeds in the catalyst unit. The hydrogen lip formed as a result of the oxidation reaction A fuel gas, and a fuel gas discharge means for discharging from the catalytic section, the catalyst unit, is adjacent and between the first reaction portion and the second reaction unit, the first
The point is that heat exchange is performed between the reaction section of (1) and the second reaction section.

The eleventh fuel reforming apparatus according to the present invention having the above-described structure is characterized in that a first reaction section provided with a catalyst for promoting a steam reforming reaction and an oxidation reaction is provided with a hydrocarbon and steam. When a raw fuel gas containing oxygen and an oxidizing gas containing oxygen are supplied, in the first reaction section, a reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and And an oxidation reaction that is an exothermic reaction that oxidizes the hydrocarbon. In addition, for a second reaction section provided with a catalyst for promoting the steam reaction,
When the raw fuel gas is supplied, the steam reforming reaction proceeds in the second reaction section. Here, the first
In the reaction section, the steam reforming reaction proceeds using heat generated by the oxidation reaction, but the second reaction section also
By exchanging heat with the adjacent first reaction section,
The steam reforming reaction proceeds using heat generated by the oxidation reaction in the first reaction section. The generated hydrogen-rich fuel gas is discharged from the catalyst section.

According to such a fuel reforming apparatus, in the first reaction section, in the region where the oxidizing gas is supplied and the oxidizing reaction proceeds, the heat generated by the oxidizing reaction is equal to the first heat. In addition to being used for the steam reforming reaction that proceeds in the reaction section, it is also transmitted to an adjacent second reaction section and used for the steam reforming reaction that proceeds in the second reaction section. . Therefore, the temperature of the catalyst section is not excessively increased due to the heat generated by the oxidation reaction, so that inconveniences such as catalyst deterioration and generation of by-products do not occur.
The durability of the reformer can be greatly improved.

Here, in the first or second fuel reformer of the present invention or the fifth to tenth fuel reformers of the present invention, the hydrocarbon is methanol, and the steam reforming reaction is performed. And the catalyst that promotes the oxidation reaction,
It may be a single copper-based catalyst.

Further, in the third or fourth fuel reformer of the present invention, the hydrocarbon is methanol, and the catalyst for promoting the steam reforming reaction and the catalyst for promoting the oxidation reaction are the same copper. It may be a system catalyst.

[0059] In the eleventh fuel reformer of the present invention, the hydrocarbon may be methanol, and the catalyst provided in the first reaction section may be a single copper-based catalyst.

In the fuel reforming apparatus having such a configuration, the steam reforming reaction of methanol and the oxidation reaction of methanol are promoted by a single copper-based catalyst. When the oxidation reaction of methanol is promoted by a copper-based catalyst, unlike the case of promoting the oxidation reaction by using other known oxidation catalysts such as platinum, most of the proceeding oxidation reaction produces carbon monoxide. No reaction. Therefore, with such a configuration, a fuel gas having a lower concentration of carbon monoxide can be generated.

The twelfth fuel reformer of the present invention is a reaction involving heat absorption, a steam reforming reaction for producing hydrogen from hydrocarbons and steam, and a reaction involving heat generation, wherein An oxidation reaction that oxidizes and a fuel reformer that utilizes heat generated by the oxidation reaction when the steam reforming reaction proceeds, and promotes the steam reforming reaction and the oxidation reaction. A raw fuel gas supply unit for supplying a raw fuel gas containing the hydrocarbon, steam, and oxygen to the catalytic unit, and the steam reforming reaction that proceeds in the catalytic unit. And a fuel gas discharging means for discharging a hydrogen-rich fuel gas generated as a result of the oxidation reaction from the catalyst section, wherein the catalyst performs, as the oxidation reaction, a reaction that does not pass through a reaction path that generates carbon monoxide. Promote The gist of the door.

According to such a fuel reforming apparatus, since the catalyst can promote the oxidation reaction without passing through the reaction path for generating carbon monoxide, the catalyst produced by the reaction proceeding in the catalyst section can be promoted. It is possible to suppress the carbon amount and generate a fuel gas having a low carbon monoxide concentration.

In the twelfth fuel reformer of the present invention,
The hydrocarbon may be methanol, and the catalyst that promotes the steam reforming reaction and the oxidation reaction may be a single copper-based catalyst.

In the fuel reforming apparatus having such a configuration, the oxidation reaction of methanol is promoted by the copper-based catalyst. Most of the oxidation reactions that do not produce carbon monoxide. Therefore, with such a configuration, a fuel gas having a lower concentration of carbon monoxide can be generated. Further, since the steam reforming reaction of methanol and the oxidation reaction of methanol are promoted by a single copper-based catalyst, the configuration of the fuel reformer can be simplified.

[0065]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to further clarify the structure and operation of the present invention described above, embodiments of the present invention will be described below based on examples. FIG. 1 shows a preferred first embodiment of the present invention.
1 is a schematic configuration diagram illustrating the configuration of a fuel cell device 20 including a reformer according to an embodiment. The fuel cell device 20 includes a methanol tank 22 for storing methanol, a water tank 24 for storing water, a burner 26 for generating combustion gas, a compressor 28 for compressing air, and an evaporator provided with the burner 26 and the compressor 28. A reformer 32, a reformer 34 that generates a fuel gas by a reforming reaction, a CO reducing unit 36 that reduces the concentration of carbon monoxide (CO) in the fuel gas, a fuel cell 40 that obtains an electromotive force by an electrochemical reaction, and a computer The configured control unit 50 is a main component. First, the fuel cell 40 that is the main power generator in the fuel cell device 20 will be described.

The fuel cell 40 is a solid polymer electrolyte type fuel cell and has a stack structure in which a plurality of unit cells as constituent units are stacked. FIG. 2 is a cross-sectional view illustrating the configuration of a single cell 48 configuring the fuel cell 40. The single cell 48 includes an electrolyte membrane 41, a cathode 42 and an anode 43, and separators 44 and 45.

The cathode 42 and the anode 43 are gas diffusion electrodes having a sandwich structure sandwiching the electrolyte membrane 41 from both sides. The separators 44 and 45 form flow paths for fuel gas and oxidizing gas between the cathode 42 and the anode 43 while further sandwiching the sandwich structure from both sides. A fuel gas flow path 44P is formed between the cathode 42 and the separator 44, and the anode 4
An oxidizing gas flow path 45P is formed between 3 and the separator 45. Although the separators 44 and 45 each have a flow path formed on only one side in FIG. 2, ribs are actually formed on both sides thereof, and a fuel gas flow path 44 P is formed on one side with the cathode 42. The other surface forms an oxidizing gas channel 45P with the anode 43 provided in the adjacent single cell. As described above, the separators 44 and 45 have a function of forming a gas flow path between the gas diffusion electrodes and separating the flows of the fuel gas and the oxidizing gas between the adjacent single cells. Of course, when stacking the unit cells 48 to form a stack structure, the two cells located at both ends of the stack structure
The ribs may be formed only on one side of the separator in contact with the gas diffusion electrode.

Here, the electrolyte membrane 41 is a proton-conductive ion exchange membrane formed of a solid polymer material, for example, a fluorine-based resin, and has good electric conductivity in a wet state. In this embodiment, a Nafion membrane (manufactured by DuPont) is used.
It was used. On the surface of the electrolyte membrane 41, platinum as a catalyst or an alloy composed of platinum and another metal is supported.

The cathode 42 and the anode 43 are both formed of carbon cloth woven with carbon fiber yarns. The cathode 42 and the anode 43
Is preferably formed of carbon paper or carbon felt made of carbon fiber, in addition to being formed of carbon cloth.

The separators 44 and 45 are formed of a gas-impermeable conductive member, for example, dense carbon which is made by compressing carbon to be gas-impermeable. Separator 4
4 and 45 have a plurality of ribs arranged in parallel on both surfaces thereof. As described above, the fuel gas flow path 44P is formed with the surface of the cathode 42, and the anode 43 of the adjacent single cell is formed. And an oxidizing gas flow path 45P. Here, the ribs formed on the surface of each separator need not be formed in parallel on both surfaces, and may be at a predetermined angle such as perpendicular to each surface. The ribs do not need to be parallel grooves, but may be any as long as a fuel gas or an oxidizing gas can be supplied to the gas diffusion electrode.

The configuration of the single cell 48 which is the basic structure of the fuel cell 40 has been described above. When the fuel cell 40 is actually assembled, the separator 44 and the cathode 4
2. A plurality of single cells 48 composed of an electrolyte membrane 41, an anode 43, and a separator 45 are stacked in this order (100 sets in this embodiment), and a current collector plate formed of a dense carbon or copper plate at both ends thereof Are arranged to form a stack structure.

Hereinafter, components other than the fuel cell 40 constituting the fuel cell device 20 and their connection relationship will be sequentially described. The evaporator 32 is a device that receives supply of methanol and water from the methanol tank 22 and the water tank 24 and vaporizes the methanol and water. The evaporator 32 includes the burner 26 and the compressor 28 as described above, but the combustion exhaust gas of the burner 26 is guided through the compressor 28 as described later, and the combustion heat is
Is transmitted to a heat exchanger (not shown) provided in the evaporator 32.
Boil and vaporize the methanol and water supplied to the vessel.

A second pump 71 is provided in a methanol flow path 60 for feeding the raw fuel methanol from the methanol tank 22 to the evaporator 32, and the amount of methanol supplied to the evaporator 32 can be adjusted. The second pump 71 is connected to the control unit 50,
Is controlled by a signal output from the controller to adjust the flow rate of methanol supplied to the evaporator 32.

A third pump 72 is provided in a water supply path 62 for feeding water from the water tank 24 to the evaporator 32.
The amount of water supplied to the evaporator 32 can be adjusted.
The third pump 72 is connected to the control unit 50 similarly to the second pump 71, is driven by a signal output from the control unit 50, and adjusts the amount of water supplied to the evaporator 32. The methanol flow path 60 and the water supply path 62 merge to form a first fuel supply path 63, and the first fuel supply path 6
3 is connected to the evaporator 32. Since the flow rate of methanol and the amount of water are adjusted by the second pump 71 and the third pump 72, the methanol and water mixed by a predetermined amount are supplied to the evaporator 32 through the first fuel supply path 63. .

The compressor 28 attached to the evaporator 32 is a device for taking in air from the outside of the fuel cell device 20, compressing the air, and supplying the compressed air to the anode side of the fuel cell 40. The compressor 28 includes a turbine 28a and a compressor 28b, which are formed in an impeller shape. The turbine 28a and the compressor 28b are connected by a coaxial shaft 28c.
By driving the rotation of the compressor 8a, the compressor 28b can be driven to rotate. The evaporator 32 is further provided with a burner 26, and the high-temperature combustion gas from the burner 26 drives the turbine 28a. The compressor 28b also rotates with the rotation of the turbine 28a,
The compressor 28b compresses air as described above. Air can be taken into the compressor 28b from the outside via an air introduction passage 29, and the air compressed by the compressor 28 is supplied to the fuel cell 40 via the oxidizing gas supply passage 68, It is subjected to an electrochemical reaction at 40.

Here, since the turbine 28a is driven by the high-temperature combustion gas from the burner 26, it is formed of a super heat-resistant alloy, ceramics or the like in order to realize heat resistance and durability. In this embodiment, a nickel-based alloy (Inconel 700, Inc.) was used. The compressor 28b is formed of a lightweight aluminum alloy.

The burner 26 for driving the turbine 28a is
Fuel for combustion is supplied from the cathode side of the fuel cell 40 and the methanol tank 22. The fuel cell 40 performs an electrochemical reaction using hydrogen-rich gas generated by reforming methanol in the reformer 34 as a fuel.
Not all of the hydrogen supplied to the fuel cell is consumed in the electrochemical reaction, and the fuel exhaust gas containing unreacted hydrogen is discharged to the fuel discharge passage 67. Burner 26
Is connected to the fuel discharge passage 67 to receive the supply of the fuel exhaust gas, and to completely combust the remaining hydrogen that has not been consumed, thereby improving the fuel utilization rate. Normally, such exhaust fuel alone is insufficient as fuel for the combustion reaction in the burner 26, so that the fuel corresponding to the shortage and the supply of the exhaust fuel from the fuel cell 40 as in the start-up of the fuel cell device 20. When the fuel cannot be received, the fuel for the combustion reaction in the burner 26 is supplied from the methanol tank 22 to the burner 26. A methanol branch 61 is provided for supplying methanol to the burner 26.
The methanol branch path 61 is used to supply methanol from the methanol tank 22 to the evaporator 32.
Branches from 0.

Here, the first temperature sensor 7 is connected to the burner 26.
3 is provided, the temperature of the combustion heat in the burner 26 is measured, and the measurement result is input to the control unit 50. The control unit 50 outputs a drive signal to the first pump 70 based on the input result from the first temperature sensor 73,
The combustion temperature in the burner 26 is maintained in a predetermined range (about 800 ° C. to 1000 ° C.) by adjusting the amount of methanol supplied to 6. The combustion gas in the burner 26 is guided to the evaporator 32 after rotating the turbine 28a. Since the heat exchange efficiency in the turbine 28a is not so high (about 1
(Within 0%), the temperature of the combustion exhaust gas guided to the evaporator 32 reaches about 600 to 700 ° C., which is sufficient as a heat source of the evaporator 32. Here, the mixed solution of methanol and water supplied via the first fuel supply passage 63 described above is used for the evaporator 3.
The gas is vaporized by the high-temperature combustion exhaust gas of the burner 26 guided to 2. The raw fuel gas composed of methanol and water vaporized in the evaporator 32 is guided to the second fuel supply path 64 and transmitted to the reformer 34.

The reformer 34 reforms the supplied raw fuel gas composed of methanol and water to generate a hydrogen-rich fuel gas. The configuration of the reformer 34 and the reforming reaction performed in the reformer 34 correspond to the main parts of the present invention, and will be described later in detail. A second temperature sensor 74 is provided in a second fuel supply path 64 for supplying a raw fuel gas composed of methanol and water to the reformer 34.
The temperature of the raw fuel gas composed of methanol and water supplied to the fuel cell is measured. The measurement result regarding the temperature of the raw fuel gas is input to the control unit 50. The control unit 50 performs the first operation based on the input result from the first temperature sensor 73 described above.
When a drive signal is output to the pump 70, the drive amount of the first pump 70 is corrected based on the signal from the second temperature sensor 74, and the amount of methanol supplied to the burner 26 is adjusted. By controlling the temperature of the combustion gas in the burner 26 in this manner, the temperature of the raw fuel gas vaporized in the evaporator 32 is adjusted. The temperature of the raw fuel gas supplied from the evaporator 32 is usually raised to about 250 ° C.

As will be described later, oxygen is involved in the reforming reaction in the reformer 34. In order to supply oxygen necessary for the reforming reaction, the reformer 34 is provided with a blower 38. I have. The blower 38 takes in air from the outside, compresses the air, and supplies the taken-in air to the reformer 34 via the air supply path 39. In this embodiment, the air supply path 39 is connected to the second fuel supply path 64 and the blower 38
Is supplied to the reformer 34 together with the raw fuel gas supplied from the evaporator 32. The blower 38 is connected to the control unit 50, and the driving state of the blower 38 is controlled by the control unit 50.

The CO reduction unit 36 is a device for reducing the concentration of carbon monoxide in the fuel gas supplied from the reformer 34 via the third fuel supply path 65. Although the general reforming reaction of methanol has already been shown in equation (4), when the reforming reaction is actually performed, the reaction does not proceed ideally as shown in these equations, and the reformer does not proceed. The fuel gas generated at 34 contains a predetermined amount of carbon monoxide. Therefore, by providing the CO reduction unit 36, the concentration of carbon monoxide in the fuel gas supplied to the fuel cell 40 is reduced.

The fuel cell 40 of the present embodiment is a polymer electrolyte fuel cell, which is provided with a catalyst composed of platinum or platinum and another metal which promotes a cell reaction. Was applied to the surface of the electrolyte membrane 41), and when carbon monoxide was contained in the fuel gas, this carbon monoxide was adsorbed on the platinum catalyst to reduce its function as a catalyst,
The reaction at the anode shown in the equation (1) is hindered and the performance of the fuel cell is reduced. Therefore, the fuel cell 4
In order to perform power generation using a polymer electrolyte fuel cell such as 0, it is essential to reduce the carbon monoxide concentration in the supplied fuel gas to a predetermined amount or less to prevent a decrease in cell performance. . In such a polymer electrolyte fuel cell, the allowable concentration of carbon monoxide in the supplied fuel gas is usually about several ppm or less.

The fuel gas supplied to the CO reduction unit 36 is
As described above, the gas is a hydrogen-rich gas containing a predetermined amount of carbon monoxide, and the CO reduction unit 36 oxidizes carbon monoxide in preference to hydrogen in the fuel gas. CO
The reduction unit 36 is filled with a carrier that carries a platinum catalyst, a ruthenium catalyst, a palladium catalyst, a gold catalyst, or an alloy catalyst using these as the first element, which are selective oxidation catalysts for carbon monoxide. The concentration of carbon monoxide in the fuel gas treated by the CO reduction unit 36 is determined by the operating temperature of the CO reduction unit 36, the concentration of carbon monoxide in the supplied fuel gas, and the volume of catalyst per unit catalyst to the CO reduction unit 36. It is determined by the supply flow rate of the fuel gas and the like. The CO reducing unit 36 is provided with a carbon monoxide concentration sensor (not shown), and based on the measurement result, adjusts the operating temperature of the CO reducing unit 36 and the flow rate of the supplied fuel gas, and adjusts the amount of fuel gas in the processed fuel gas. Carbon oxide concentration is several p
pm or less.

The fuel gas whose carbon monoxide concentration has been reduced as described above in the CO reduction unit 36 is guided to the fuel cell 40 by the fourth fuel supply path 66 and is subjected to a cell reaction on the cathode side. The fuel exhaust gas used for the cell reaction in the fuel cell 40 is discharged to the fuel discharge path 67 and guided to the burner 26 as described above, and the hydrogen remaining in the fuel exhaust gas is used as fuel for combustion. Consumed as On the other hand, the oxidizing gas related to the cell reaction on the anode side of the fuel cell 40 is supplied from the compressor 28 to the oxidizing gas supply path 6 as described above.
8 is supplied as compressed air. The remaining oxidized exhaust gas used for the battery reaction is discharged to the outside via the oxidized exhaust gas passage 69.

The control unit 50 is configured as a logic circuit mainly composed of a microcomputer. More specifically, the control unit 50 executes a predetermined operation or the like according to a preset control program. A ROM 56 in which necessary control programs, control data, and the like are stored in advance, and an R for temporarily reading and writing various data necessary for performing various arithmetic processing by the CPU 54.
An AM 58 and an input / output port 52 for inputting detection signals from the above-described various temperature sensors and outputting drive signals to the above-described various pumps, blowers 38, and the like in accordance with the calculation results of the CPU 54 are provided.

Next, the reformer 34 corresponding to the main part of the present invention
Will be described. FIG. 3 is an explanatory diagram schematically illustrating the outline of the configuration of the reformer 34. The reformer 34 of this embodiment receives supply of raw fuel gas and air from the end connected to the second fuel supply path 64, and the raw fuel gas and air pass through the inside of the reformer 34. While being subjected to a steam reforming reaction and an oxidation reaction (partial oxidation reaction). In the reformer 34, the hydrogen-rich fuel gas generated by the steam reforming reaction shown in the equation (4) and the oxidation reaction shown in the equation (5) is supplied to the third fuel supply path 65 from the other end. Is discharged. The reformer 34 includes a first reaction section 80 and a second reaction section 81 therein. The first reaction section 80 and the second reaction section 81 have Cu
A first reaction unit 80 formed on the upstream side (closer to the connection with the second fuel supply path 64), and configured as a metal honeycomb supporting the Zn catalyst. It is formed such that the number of cells described later is smaller than that of the second reaction section 81 formed on the side (closer to the connection portion with the first reaction section 65).

FIG. 4 is a schematic diagram showing a part of the cross section of the metal honeycomb forming the first reaction section 80 and the second reaction section 81. The metal honeycomb is a stainless steel plate 82,
83 are laminated. That is, a flat stainless steel plate 82 and a stainless steel plate 83
Are alternately arranged to form a metal honeycomb. Since the stainless steel plate 83 is bent in a wave shape at 1 mm intervals, the stainless steel plate 83 and the flat stainless steel plate 82 are alternately laminated to form a substantially square cross section having a side length of 1 mm. Can be formed.

Here, the first reaction section 80 and the second reaction section 81
The thicknesses of the stainless steel plates 82 and 83 used for forming the metal honeycomb are different from each other, whereby the first reaction unit 80 and the second reaction unit 81 are formed with different numbers of cells. Is done. First reaction unit 80
Is made of a honeycomb formed by stainless steel plates 82 and 83 having a thickness of 0.1 mm, and the second reaction section 81 is formed of a honeycomb formed by stainless steel plates 82 and 83 having a thickness of 0.03 mm. Therefore, the first reaction unit 8
0 has about 75 cells per 1 cm ^{2 of} the cross-sectional area, and the second reaction section 81 has about 91 cells per 1 cm ² . Since the cross-sectional area of the entire reformer 34 is constant, the first plate is formed by forming the honeycomb with stainless steel plates having different thicknesses as described above.
The total area of the cross section of the gas flow path in the reaction section 80 (the sum of the cross-sectional areas of the cells constituting the first reaction section 80) is the total area of the cross section of the gas flow path in the second reaction section 81 (the second reaction section). 8
1) (the sum of the cross-sectional areas of the cells constituting the first cell 1).

The first reaction section 80 and the second reaction section 81
Since the catalyst is carried on the surface of the honeycomb constituting each, when the raw fuel gas is supplied from the upstream side, the raw fuel gas is subjected to a steam reforming reaction and an oxidation reaction while passing through the honeycomb surface, and hydrogen is supplied. It becomes rich fuel gas.
In this example, the catalyst to be supported on the honeycomb surface was manufactured by a coprecipitation method using copper and zinc oxide. The Cu—Zn catalyst obtained by the coprecipitation method can be supported on the honeycomb by a method of pulverizing the Cu—Zn catalyst, further adding a binder such as alumina sol, and applying the binder on the honeycomb.

When the raw fuel gas is supplied to the reformer 34 configured as described above, the raw fuel gas is first supplied to the first reaction section 80 having a small number of cells, that is, a small total area of the gas flow path cross section. Then, it passes through the second reaction section 81 having a large number of cells, that is, a large total area of the gas flow path cross section. As described above, after the predetermined amount of the raw fuel gas passes through the honeycomb having the small total area of the gas flow path cross section, it passes through the honeycomb having the large total area of the gas flow path cross section. The flow rate of the raw fuel gas passing through the first reactor 80
The speed when passing through the inside is faster than the time when passing through the inside of the second reaction section 81.

Therefore, according to the reformer 34 of the first embodiment, by increasing the flow rate of the raw fuel gas on the upstream side, a sharp rise in temperature on the upstream side is suppressed, and the temperature of the entire reformer 34 is reduced. This has the effect of making the distribution state uniform within a temperature range of 250 to 300 ° C., which is a temperature range suitable for the reforming reaction. FIG. 5 is an explanatory diagram showing the internal temperature distribution state in the gas flow direction of the conventionally known reformer having a constant honeycomb sectional area and the reformer 34 of the present embodiment. As described above, since the oxidation reaction has a higher reaction rate than the steam reforming reaction, in the conventional reformer, the oxidation reaction actively proceeds near the inlet of the raw fuel gas, and the temperature near the inlet becomes higher. Rises to about 400 ° C. On the other hand, in the reformer 34 of this embodiment, since the flow rate of the raw fuel gas on the upstream side is high, the heat generated by the oxidation reaction that has proceeded on the upstream side is quickly transferred to the downstream side by the fast gas flow. Carried. In addition, since the flow rate of the raw fuel gas on the upstream side is high, the oxidation reaction does not end in a narrow region on the upstream side, and the region where the oxidation reaction actively proceeds spreads further downstream. Therefore, the temperature does not rise rapidly near the entrance. Furthermore, since the first reaction section 80 provided on the upstream side has a honeycomb formed using a thick stainless steel plate, the first reaction section 80 has a large heat capacity, and heat generated by the oxidation reaction is applied to this honeycomb. Before being transmitted and raising the temperature of the honeycomb, it is easier to transmit the downstream to the gas flow.

As described above, since the temperature of the reformer 34 does not rise sharply near the entrance thereof, the above-described inconveniences such as deterioration of the catalyst and generation of by-products due to the rise in temperature are eliminated. Can be prevented. By suppressing the deterioration of the catalyst, the durability of the reformer can be greatly improved. Vessel 3
No. 4 can be used for 5000 hours or more.

Further, as described above, the region in which the oxidation reaction proceeds proceeds to the downstream side, and the heat generated by the oxidation reaction proceeding upstream is quickly transferred to the downstream side. In the reformer 34, the temperature does not excessively decrease on the downstream side unlike the conventional reformer. Therefore, the activity of the steam reforming reaction is maintained at a high level even on the downstream side of the reformer, the catalyst provided on the downstream side can be sufficiently used, and the speed of the steam reforming reaction can be improved. . As described above, the activity of the steam reforming reaction on the downstream side is enhanced, so that the reformer can be made more compact.

In the first embodiment described above, the honeycomb provided in the reformer 34 is a metal honeycomb, but a ceramic honeycomb may be used. A configuration using a metal honeycomb is shown below as a modification of the first embodiment. The reformer in this modified example also includes a first reaction section 80 and a second reaction section 81, like the reformer 34 of the first embodiment.
FIG. 6 shows a schematic view of a cross section of the first reaction section 80 and the second reaction section 81 formed by the ceramic honeycomb. FIG.
(A) shows a first reaction section 8 composed of a ceramic honeycomb.
0B, FIG. 6B is another example of the first reaction unit 80, and FIG.
This shows a reaction section 81.

In FIG. 6A, the cross-sectional area of each cell constituting the honeycomb is formed small, and in FIG.
By reducing the total number of cells constituting the honeycomb, the total area of the gas flow path cross section is reduced as compared with the honeycomb of FIG. Therefore, FIG. 6 (A) and FIG.
In any of the first reaction sections 80 shown in FIG. 6B, the reformer 34 is configured in combination with the second reaction section 81 shown in FIG. The same effect as described above can be obtained.

In the above embodiment, the inside of the reformer 34 is divided into two parts, a first reaction part 80 and a second reaction part 81,
Although the flow rate of the raw fuel gas passing through the inside is different between the first half and the second half, the inside of the reformer may be divided into three or more. Also in this case, the same effect as in the above-described embodiment can be obtained by adopting a configuration in which the gas flow rate on the upstream side is higher than that on the downstream side.

In the above-described embodiment, the number of cells per unit cross-sectional area is reduced or the cross-sectional area of each cell is reduced in the honeycomb disposed on the upstream side of the reformer. The total area of the gas flow path cross section on the side is made smaller than that on the downstream side. Examples of the configuration of the reformer in which the gas flow speed on the upstream side is faster than that on the downstream side include, in addition to the configuration described above, a configuration in which the cross-sectional area of the entire reformer is formed to be smaller on the upstream side. be able to. FIG. 7 shows the configuration of such a reformer 34A. The reformer 34A is
It is composed of three honeycombs with different total cross-sectional areas,
The upstream side is formed by a honeycomb having a smaller total sectional area. With such a configuration, the gas flow rate on the upstream side becomes faster than that on the downstream side, so that the same effect as in the above-described embodiment can be obtained. FIG. 5 shows an internal temperature distribution state in the reformer 34A. If the total cross-sectional area of the entire reformer is gradually increased like the reformer 34A, the number of cells per unit cross-sectional area and the cross-sectional area of each single cell may be the same. Further, when the reformer is constituted by a plurality of portions having different total cross-sectional areas, the reformer may be constituted by a plurality of portions other than three, and the configuration is such that the total area of the flow path cross section becomes smaller toward the upstream side. Then, the effect described above can be obtained.

Next, as another configuration for positively transmitting the heat generated by the oxidation reaction that proceeds in the upstream portion of the reformer to the downstream side, a catalyst that promotes the steam reforming reaction and the oxidation reaction is replaced with a heat transfer catalyst. A configuration in which a carrier made of a material having relatively high performance is used to hold the carrier will be described below as a second embodiment. FIG.
FIG. 4 is an explanatory diagram schematically showing a configuration of a reformer 90 according to a second embodiment. The reformer 90 of the second embodiment is provided in a fuel cell device having the same configuration as the fuel cell device 20 of FIG. As shown in FIG. 8, the reformer 90 includes a single reaction section 92 formed of a honeycomb. This reaction part 9
9 (A) is a schematic cross-sectional view showing a part of the cross section of the honeycomb constituting the honeycomb structure No. 2 and part of the surface of the honeycomb shown in FIG. 9 (A) (in FIG. FIG. 9 is a diagram schematically showing a state in which (circled area) is further enlarged.
It is shown in (B).

[0099] The reformer 90 of this embodiment is made of a metal honeycomb, like the reformer 34 of the first embodiment. In this example, the honeycomb was formed using a stainless plate 94 having a thickness of 0.05 mm. On the surface of the stainless steel plate 94, a catalyst layer 96 containing a catalyst for promoting the steam reforming reaction and the oxidation reaction and having a thickness of about 0.05 mm is formed. In the catalyst layer 96, Cu-Zn
Copper molecules and zinc oxide molecules constituting the catalyst are supported in a state of being dispersed in a binder having high thermal conductivity.

Here, a method for preparing the catalyst layer 96 will be described. First, as a catalyst raw material, C
A uO.ZnO powder is prepared, and a 5% alumina sol as a binder and a substance having higher thermal conductivity than aluminum oxide are added to the powder. The material having high thermal conductivity used here is aluminum nitride (A
1N), titanium nitride (TiN), or carbides such as silicon carbide (SiC), boron carbide (B ₄ C), and graphite. The addition amount is preferably 5 to 30%. For example, among the above substances having high thermal conductivity, AlN is 0.07 cal / cm /
It shows a thermal conductivity of s / ° C, and SiC is 0.1 cal / cm
/ S / ° C, graphite is 0.30.1 cal / cm /
It shows a thermal conductivity of s / ° C., all of which are conventionally used aluminum oxide (0.02 cal / cm / s / ° C.)
It shows higher thermal conductivity than that of.

These are diluted with water, pulverized and mixed by a ball mill, applied on a stainless steel plate 94, and further subjected to heat treatment and reduction treatment. By such treatment, the catalyst raw material becomes Cu-Z composed of copper molecules and zinc oxide molecules.
These Cu-Zn catalysts form a catalyst layer 96 while being dispersed and supported in a binder containing a substance having high thermal conductivity.

When the reformer 90 configured as described above is applied to the fuel cell device 20 and the raw fuel gas is supplied to the reformer 90, as described above, on the upstream side where oxygen is supplied, The oxidation reaction takes place actively, generating a lot of heat. The heat generated by the oxidation reaction as described above is not only used in the steam reforming reaction that proceeds on the upstream side, but is also quickly transmitted through the binder containing the above-described substance having high thermal conductivity. As described above, a predetermined amount of the heat transmitted through the binder is further transmitted to the honeycomb substrate formed of stainless steel having high thermal conductivity. The heat transmitted to the honeycomb substrate made of stainless steel is transmitted to the downstream side through the honeycomb substrate. Further, the remaining heat that cannot be transmitted to the honeycomb substrate is transmitted to the downstream side in the binder as it is. The heat transferred to the downstream side of the reformer 90 is used in the steam reforming reaction that proceeds on the downstream side.

Therefore, according to the reformer 90 of the present embodiment, since the catalyst is supported in the binder having high thermal conductivity, the heat generated by the oxidation reaction on the upstream side is quickly transferred to the downstream side. In this way, it is possible to suppress a rapid temperature rise on the upstream side. FIG. 10 shows the internal temperature distribution state in the gas flow direction for the conventionally known reformer using the binder containing no substance having a high thermal conductivity and the reformer 90 of the present embodiment. FIG. In the reformer 90 of this embodiment, unlike the conventional reformer, the heat generated by the oxidation reaction that proceeds on the upstream side is quickly transmitted to the downstream side, so that the temperature on the upstream side does not rise rapidly. The internal temperature of the reformer can be made uniform within a temperature range of 250 to 300C. As described above, since the temperature of the reformer 90 does not suddenly increase near the entrance thereof, it is possible to prevent the above-described inconveniences such as catalyst deterioration and generation of by-products due to the temperature increase. Can be. By suppressing the deterioration of the catalyst, the durability of the reformer can be greatly improved. Vessel 90
Can be used for 5000 hours or more.

Further, as described above, since the heat generated by the oxidation reaction proceeding on the upstream side is quickly transmitted to the downstream side, the reformer 90 of the present embodiment uses the conventional reformer in the downstream region. The temperature does not drop too much unlike the case described above. Therefore, the activity of the steam reforming reaction is maintained at a high level even on the downstream side of the reformer, the catalyst provided on the downstream side can be sufficiently used, and the speed of the steam reforming reaction can be improved. . Therefore, the reformer can be made more compact.

In the second embodiment, the catalyst layer 96 using a binder containing a substance having high thermal conductivity was formed on a honeycomb formed of a stainless steel plate having excellent thermal conductivity. The heat conduction was carried out both by the catalyst layer 96 itself and through the stainless steel plate 94, so that heat transfer could be performed with high efficiency, and particularly excellent effects could be obtained. Here, the catalyst layer 96 may be formed on a ceramic honeycomb, or the catalyst may be formed into a pellet shape together with a binder having a high thermal conductivity and charged into the reformer. A predetermined effect due to the improvement in conductivity can be obtained.

Next, as a third embodiment, a configuration in which the amount of catalyst carried on the upstream side in the reformer is made smaller than that on the downstream side to suppress the activity of the oxidation reaction on the upstream side will be described below. FIG. 11 is an explanatory diagram schematically showing the configuration of the reformer 100 of the third embodiment. This reformer 100
Is provided in a fuel cell device having the same configuration as the fuel cell device 20 in FIG. As shown in FIG.
0 has a first reaction unit 101 and a second reaction unit 102. The first reaction unit 101 and the second reaction unit 102
Is constituted by a honeycomb having a similar shape, and the same Cu—Zn as in the above-described embodiment is
Although the catalyst is supported, the amount of the catalyst supported on the honeycomb is larger in the second reaction section 102 than in the first reaction section 101. That is, the first reaction unit 101
While the Cu-Zn catalyst is supported at a rate of 0 g / l (the amount of catalyst per unit volume of the honeycomb), the second reaction unit 102 supports the Cu-Zn catalyst at a rate of 180 g / l. I have.

According to the reformer 100 configured as described above, since the amount of catalyst carried by the first reaction section 101 on the upstream side is small, the progress of the oxidation reaction on the side where the raw fuel gas and air are introduced is suppressed. Can be Therefore, the oxidation reaction does not proceed abruptly on the upstream side of the reformer, and the region where the oxidation reaction is performed spreads further downstream. Therefore, a rapid temperature rise on the upstream side can be suppressed.

FIG. 12 shows a conventional reformer equipped with a honeycomb supporting the same amount of catalyst on the upstream side and the downstream side, and the reformer 100 of the present embodiment, which shows the internal structure of the gas flow direction. It is explanatory drawing showing the temperature distribution state. Unlike the conventional reformer, the reformer 100 of the present embodiment suppresses the progress of the oxidation reaction on the upstream side, so that the internal temperature of the reformer is maintained at 250 ° C. without rapidly increasing the temperature on the upstream side. ~ 30
It can be homogenized in a temperature range of 0 ° C. As described above, since the temperature of the reformer 100 does not suddenly increase near the entrance thereof, it is possible to prevent the above-described inconvenience such as catalyst deterioration and generation of by-products due to the temperature increase. Can be. By suppressing the deterioration of the catalyst, the durability of the reformer can be greatly improved. Container 100 is 5000
It can be used for more than hours.

Further, as described above, since the region where the oxidation reaction accompanied by heat generation progresses further downstream, in the reformer 100 of the present embodiment, the downstream region has the same temperature as the conventional reformer. Does not decrease too much. Therefore, the activity of the steam reforming reaction is maintained at a high level even on the downstream side of the reformer, the catalyst provided on the downstream side can be sufficiently used, and the speed of the steam reforming reaction can be improved. . Therefore, the reformer can be made more compact.

In the third embodiment, the reformer 100
In the above, the amount of catalyst to be supported is changed in two stages, but may be changed in three or more stages, and the above-described predetermined effect can be obtained by reducing the amount of catalyst supported on the upstream side. Here, the configuration is such that the amount of supported catalyst is reduced toward the upstream side, and by adjusting the number of steps for changing the amount of supported catalyst, the temperature inside the reformer can be made more uniform, as described above. The effect can be enhanced.

In the third embodiment, the steam reforming reaction and the oxidation reaction are promoted by the same Cu-Zn catalyst. However, the steam reforming reaction and the oxidation reaction are promoted by different catalysts. It may be that. In such a case, instead of changing the total supported amount of the catalyst on the upstream side and the downstream side of the reformer, only the supported amount of the catalyst that promotes the oxidation reaction may be reduced on the upstream side.

Next, as a fourth embodiment, the activity of the oxidation reaction on the upstream side is suppressed by lowering the oxygen concentration in the gas supplied to the reformer, and the flow rate of the supplied gas is increased to increase the upstream side. 2 shows a configuration for transmitting heat generated by the oxidation reaction in the downstream to the downstream side. FIG. 13 shows the reformer 110 of the fourth embodiment.
FIG. 3 is an explanatory diagram schematically showing the configuration of FIG. This reformer 11
Numeral 0 is provided in a fuel cell device having substantially the same configuration as the fuel cell device 20 in FIG. 1, and common members will be assigned the same member numbers and will be described below.

Here, in the embodiment described above, the blower 38 is used.
The air supply path 39 for supplying air from the
Although the raw fuel gas is mixed with air and supplied to the reformer after being mixed with the fuel supply passage 64, the fuel cell device including the reformer 110 of the fourth embodiment has The supply path 39 is directly connected to the reformer 110. Also,
In the fuel cell device including the reformer 110 of the present embodiment, the oxidizing exhaust gas discharged from the fuel cell 40 to the oxidizing exhaust gas passage 69 can be supplied to the reformer 110 together with the air taken in from the blower 38. I have. Normal air contains about 20% oxygen, but the oxidizing exhaust gas discharged from the fuel cell consumes a predetermined amount of oxygen in the electrochemical reaction in the fuel cell. Less than air. The oxygen concentration in the oxidizing exhaust gas varies depending on the excess air ratio (the ratio of the amount of oxygen in the actually supplied air to the amount of oxygen theoretically required) in the oxidizing gas supplied to the fuel cell. In the example fuel cell device, the oxygen concentration in the oxidizing exhaust gas is about 10%. Therefore, by allowing the air and the oxidizing exhaust gas to be mixed and supplied to the reformer 110, the oxygen concentration in the air supplied to the reformer 110 is set within a range of about 10% to about 20%. It can be adjusted with.

The structure of the reformer 110 will be described in detail with reference to FIG. The reformer 110 includes a single reaction unit 111 formed of a honeycomb having a Cu-Zn catalyst supported on the surface. The air supply path 39 and the oxidizing exhaust gas path 69 join to form a second air supply path 115. The second air supply path 115 connects the raw fuel gas from the second fuel supply path 64 in the reformer 110. Is supplied to a gaseous mixture of air and oxidizing exhaust gas (hereinafter referred to as
(Referred to as mixed air). In the air supply path 39, a mass flow controller 112 is provided near a junction with the second air supply path 115.
The amount of air supplied to the side can be adjusted. In addition, a mass flow controller 113 is provided in the oxidizing exhaust gas passage 69 in the vicinity of a junction with the second air supply passage 115 so that the amount of oxidizing exhaust gas supplied to the second air supply passage 115 can be adjusted. Has become. These mass flow controllers 112 and 113 are connected to the control unit 50 described above, and the control unit 50 mixes the air supplied from the air supply path 39 and the oxidized exhaust gas supplied from the oxidized exhaust gas path 69. The mixing amount at the time of performing is controlled. Further, an oxygen concentration sensor 114 is provided in the second air supply path 115. This oxygen concentration sensor 114 is also
And information on the oxygen concentration in the mixed air can be input to the control unit 50. Further, a temperature sensor 117 is provided inside the reaction section 111 at a predetermined position from the upstream end. This temperature sensor 117 is also connected to the control unit 50,
The information on the temperature in 1 can be input to the control unit 50.

When the reformer 110 of this embodiment supplies mixed air containing a predetermined amount of oxygen to the reformer 110, the reformer 110 reduces the oxygen concentration in the mixed air,
11 to increase the flow velocity of the entire gas passing through the reformer 1
Suppress a rapid rise in temperature upstream of 10. That is, by lowering the oxygen concentration in the mixed air supplied to the reformer 110, the oxygen concentration in the gas passing through the reaction section 111 is also reduced, thereby suppressing the activity of the oxidation reaction on the upstream side. , Can prevent a rapid rise in temperature. Further, by reducing the oxygen concentration in the mixed air containing a predetermined amount of oxygen,
And the flow rate of the gas passing through the reaction section 111 is increased. This allows oxygen to be transported further downstream before oxygen is exhausted in the oxidation reaction that proceeds on the upstream side, and the region in which the oxidation reaction proceeds to be further expanded on the downstream side. Furthermore, by increasing the flow rate of the gas passing through the inside of the reaction unit 111, heat generated by the oxidation reaction that proceeds on the upstream side is quickly transmitted to the downstream side,
It is possible to prevent the temperature on the upstream side of the reaction section from rising too much.

FIG. 14 is a flow chart showing an air mixing amount control processing routine executed in the fuel cell device including the reformer 110 of this embodiment. In this routine, in the fuel cell device including the reformer 110, after the start of the fuel cell device is instructed by operating a predetermined start switch (not shown), the temperature inside the reformer 110 is sufficiently increased. When it is determined that the steady state has been reached, the process is executed at predetermined time intervals.

When this routine is executed, the CPU 54
First, the amount of methanol in the raw fuel gas supplied to the reformer 110 is read based on the driving amount of the second pump 71 provided in the methanol flow channel 60 (step S).
200). Next, based on the amount of methanol, the amount of oxygen to be supplied to the reformer 110 is determined, and the mass flow controllers 112 and 11 are supplied so that a required amount of oxygen can be supplied.
3 is driven (step S210). That is, if the amount of methanol supplied to the reformer is determined, the amount of oxygen required to balance the amount of heat required in the steam reforming reaction and the amount of heat generated in the oxidation reaction can be determined,
The mass flow controllers 112 and 113 supply the air containing the determined amount of oxygen to the reformer 110.
Drive. Here, when the amount of oxygen to be supplied is determined, the driving amount for driving each mass flow controller to supply the amount of oxygen to be supplied is set as a reference driving amount, and is set in advance with respect to each supplied oxygen amount. Determined control unit 50
Is stored within.

By driving the mass flow controllers 112 and 113, the mixed air containing a necessary amount of oxygen is supplied to the reformer 11
When the supply to 0 is started, the internal temperature T1 on the upstream side of the reaction section 111 is read from the temperature sensor 117 (step S220). Next, the internal temperature T1
Is compared with a predetermined reference temperature Ta (step S23).
0). Here, the predetermined reference temperature Ta is a value which is set in advance as an upper limit of the internal temperature T1 on the upstream side and stored in the control unit 50, and is set to 300 ° C. in this embodiment.

In step S230, if the upstream internal temperature T1 is lower than the predetermined reference temperature Ta, it is determined that the upstream internal temperature T1 of the reaction section 111 is sufficiently low, and This routine ends. The upstream internal temperature T1 is equal to the predetermined reference temperature Ta.
In the case described above, the drive amount of the mass flow controller 112 is reduced and the drive amount of the mass flow controller 113 is increased. That is, in the mixed air supplied to the reformer 110, the ratio of the oxidizing exhaust gas is increased without changing the amount of oxygen supplied per unit time (step S240). In this embodiment, the amount of change in the ratio of the oxidizing exhaust gas in step S240, that is, the amount of change in the oxygen concentration in the mixed air supplied to the reformer 110, is determined in advance in the minimum unit. The oxygen concentration was reduced for each unit. Alternatively, the temperature may be adjusted according to the amount by which the internal temperature T1 exceeds the reference temperature Ta. By increasing the proportion of the oxidizing exhaust gas, the oxygen concentration in the entire gas supplied to the reformer 110 decreases, so that the oxidation reaction that proceeds on the upstream side is suppressed. Also, by increasing the ratio of the oxidizing exhaust gas without changing the amount of oxygen supplied per unit time, the amount of mixed air supplied to the reformer 110 increases, and the flow rate of the gas passing through the reformer 110 increases. And heat generated by the oxidation reaction progressing on the upstream side is more quickly transferred to the downstream side.
Therefore, by executing step S240, the internal temperature T1 on the upstream side of the reaction section 111 can be reduced.

When the ratio of the oxidizing exhaust gas is changed in step S240, the process returns to step S220 again, and
The operation of reading the internal temperature T1 and comparing the internal temperature T1 with a predetermined reference temperature Ta is repeated. Step S
When the internal temperature T1 becomes lower than the predetermined reference temperature Ta in 230, the ratio of the oxidizing exhaust gas in the mixed air supplied to the reformer 110 becomes appropriate, and the internal temperature T1 on the upstream side of the reaction section 111 becomes sufficiently low. This routine is determined to have been completed, and this routine ends.

Note that the fuel cell device including the reformer 110 of this embodiment includes the oxygen concentration sensor 114 in the second air supply path 115 as described above, and performs reforming based on the detection result. The oxygen concentration in the mixed air supplied to the heater 110 is corrected. That is, step S210 or step S240 in the air mixing amount control processing routine.
When the mass flow controller is driven,
The oxygen concentration in the mixed air supplied to the reformer 110 is detected by the oxygen concentration sensor 114, and the driving amount of the mass flow controller is corrected based on the result.

According to the fuel cell system including the reformer 110 of the fourth embodiment configured as described above, the reformer 110
Since the oxygen concentration in the mixed air supplied to the fuel cell can be controlled, the oxygen concentration in the mixed air is reduced to suppress the progress of the oxidation reaction on the introduction side of the raw fuel gas and the mixed air. Can be. Therefore, a rapid temperature rise on the upstream side can be suppressed. Further, a predetermined amount of oxygen per unit time is supplied to the reformer 11.
By lowering the oxygen concentration in the mixed air while supplying the gas to zero, the flow rate of the mixed air increases, and the flow rate of the gas passing through the inside of the reaction section 111 increases. Therefore, the heat generated by the oxidation reaction that proceeds on the upstream side is quickly transmitted to the downstream side, so that the temperature on the upstream side can be prevented from rising too much.

Further, since the oxidation reaction is suppressed on the upstream side as described above, the region in which the oxidation reaction proceeds is further expanded on the downstream side.
Thus, unlike the conventional reformer, the temperature does not excessively decrease in the downstream region. Furthermore, since the heat generated on the upstream side is easily transmitted to the downstream side by increasing the flow rate of the gas passing through the inside of the reaction section 111, the temperature drop in the downstream region is further suppressed. Therefore, in the reformer 110, the activity of the steam reforming reaction is kept high even on the downstream side, the catalyst provided on the downstream side can be sufficiently used, and the speed of the steam reforming reaction can be improved. Can be. Therefore, the reformer can be made more compact.

In the fourth embodiment, the methanol flow path 60
Based on the driving amount of the second pump 71 provided in the reformer 1
The amount of methanol in the raw fuel gas supplied to 10 is read, and based on the detection result of the temperature sensor 117, it is determined whether or not the oxidation reaction has progressed excessively on the upstream side. Such a determination as to the amount of methanol supplied to the reformer 110 and the progress of the oxidation reaction and the steam reforming reaction in the reformer 110 is based on a measured amount other than the above or a measured amount other than the above. It may be further utilized. For example, in order to determine the progress of the steam reforming reaction and the oxidation reaction in the reformer 110, the third fuel supply path 65 is connected to the third fuel supply path 65.
Equipment that can analyze the components in the gas passing through 5,
Methanol in the fuel gas discharged from the reformer 110,
The amounts of hydrogen, carbon dioxide, oxygen, and the like may be measured, and the measurement results may be further used to determine the progress of the steam reforming reaction and the oxidation reaction in the reformer 110.

In the fourth embodiment, the mixed air is supplied only from the upstream side of the reformer 110, but the mixed air is preferably supplied from a plurality of locations. Such a configuration is shown below as a modification of the fourth embodiment. FIG.
FIG. 9 is an explanatory diagram schematically showing a configuration of a reformer 110A which is a modification of the fourth embodiment. The reformer 110A includes two reaction units 111A and 111B, and mixed oxygen is supplied to each of the reaction units. Here, the raw fuel gas supplied to the reformer 110A is supplied to the reaction unit 111A,
Pass in the order of 111B. The air supply path 39 and the oxidizing exhaust gas path 69 for supplying air and oxidizing exhaust gas to the reformer 110A are air branch paths 39A and 39A, respectively.
39B, branch into oxidizing exhaust gas branch paths 69A, 69B.
The air branch path 39A and the oxidizing exhaust gas branch path 69A join to form a second air supply path 115A, which supplies mixed air to the reaction section 111A disposed on the upstream side. The air branch path 39B and the oxidizing exhaust gas branch path 69B merge to form a second air supply path 115B, and the reaction unit 1 disposed on the downstream side.
The mixed air is supplied to 11B. As in the fourth embodiment, the oxygen amount and oxygen concentration in the mixed air supplied to each reaction section are based on the methanol amount supplied to the reformer 110A, the upstream temperature of each reaction section, and the like. And the mass flow controllers 112A, 112B, 113A, 1
It is controlled by adjusting the driving amount of 13B.

According to the reformer 110A configured as described above, since the mixed air is divided and supplied, the amount of oxygen in the mixed gas supplied at one time can be reduced, and the temperature can be locally reduced. The effect of preventing the excessive rise of the height can be further enhanced. Furthermore, by dividing the inside of the reformer into a plurality of reaction sections and supplying mixed air to each reaction section, it is possible to control the temperature distribution inside the reformer with higher accuracy, and to easily modify the temperature distribution. The entire interior of the porcelain can be kept in a desired temperature range.

FIG. 16 shows a conventional reformer for supplying only ordinary air to the reformer as an oxygen source required for the oxidation reaction, and the reformer 110A described above. FIG. 3 is an explanatory diagram showing an internal temperature distribution state of the internal combustion engine. Unlike the conventional reformer, the reformer 110A suppresses the progress of the oxidation reaction on the upstream side,
The internal temperature of the reformer can be made uniform within a temperature range of 250 to 300 ° C. without the temperature of the upstream side being rapidly increased. As described above, the reformers 110 and 110A according to the present embodiment do not have a sharp rise in temperature near the entrance thereof, and therefore have the above-described catalyst deterioration and by-products caused by the temperature rise. Can be prevented. Therefore, it is possible to greatly improve the durability of the reformer as in the above-described embodiment.

Although the reformers 110 and 110A of the above-described embodiments have a reaction section constituted by a honeycomb, the reformer has a structure in which pellets supporting a catalyst are filled inside the reformer. Is also good. Also in this case, the same effect can be obtained by controlling the oxygen concentration in the mixed air supplied to the reformer as the oxygen source required for the oxidation reaction.

In the third and fourth embodiments, the activity of the oxidation reaction progressing on the upstream side of the reformer is suppressed so that a rapid temperature rise does not occur on the upstream side. By making it possible to change the region where the oxidation reaction proceeds actively and the region where the oxidation reaction progresses inactively, it is possible to change the region where heat is generated and prevent the temperature from excessively increasing locally. It is possible. less than,
As such a configuration, a description will be given as a fifth embodiment of a reformer capable of switching between an inlet for introducing raw fuel gas and oxygen and an outlet for discharging hydrogen-rich fuel gas.

FIG. 17 is an explanatory diagram schematically showing the structure of the reformer 120 of the fifth embodiment. This reformer 120
Is provided in a fuel cell device having the same configuration as the fuel cell device 20 in FIG. As shown in FIG.
No. 0 has a single reaction section 121 constituted by a honeycomb supporting a Cu—Zn catalyst on the surface. The reaction section 121 includes a temperature sensor 122 and a temperature sensor 123 for measuring the internal temperatures at both ends. These temperature sensors are connected to the control unit 50 described above,
Information about the internal temperatures at both ends of the reaction section 121 is input to the control section 50.

In this embodiment, the second fuel supply path 64
Is branched into a first supply branch 124 and a second supply branch 125, each branch being connected to a respective end of the reformer 120. Here, one end of the reformer 120 is connected to the first supply branch 124,
It is also connected to the discharge branch 126. In addition, the reformer 12
The other end of 0 is connected to the second supply branch 125 and to the second discharge branch 127. The first discharge branch 126 and the second discharge branch 127 merge to form the third fuel supply path 65, which is connected to the CO reduction unit 36. Further, the first supply branch 124, the second supply branch 125, the first discharge branch 126, and the second discharge branch 1
27 have solenoid valves 128, 129, 128, respectively.
A, 129A. These solenoid valves 12
8, 129, 128A and 129A are connected to the control unit 50, and the open / close state of the control unit 50 is controlled by the control unit 50.

In such a reformer 120, normally, the open / close state of the solenoid valve is the first state in which the solenoid valves 128 and 128A are in the open state and the solenoid valves 129 and 129A are in the close state, and the solenoid valve is in the open / close state. 129 and 129A are in the open state, and the solenoid valves 128 and 128A are in the second state in the closed state.
When the open / close state of the solenoid valve is the first state, the raw fuel gas supplied from the second fuel supply passage 64 passes from the left side to the right side in FIG. When the open / close state of the solenoid valve is the second state, the raw fuel gas passes from the right side to the left side in FIG.

FIG. 18 is a flowchart showing a gas inlet switching process routine executed by the fuel cell device 20 when the above-described gas inlet is switched in the reformer 120. This routine is
In the fuel cell device 20, when a start of the fuel cell device 20 is instructed by operating a predetermined start switch (not shown), the operation is executed at predetermined time intervals.

When this routine is executed, first, the CPU
54 determines whether the open / closed state of the solenoid valve is the first state based on the open / closed state of each solenoid valve described above (step S300). If it is determined to be in the first state,
Internal temperature T1 at the upstream end where gas is supplied
Is read from the temperature sensor 122 (step S31).
0). Next, the internal temperature T1 is compared with a predetermined reference temperature T0 (step S320). Here, the predetermined reference temperature T0 is a value previously stored in the control unit 50 as a reference temperature indicating that the internal temperature of the reaction unit 121 is rising to an undesired state. In this example, the temperature was set to 300 ° C. Step S3
If the internal temperature T1 has not reached the reference temperature T0 in step 20, the process returns to step S310, and the above-described operation of reading and comparing the internal temperature is repeated until the internal temperature T1 reaches the reference temperature T0.

If it is determined in step S320 that the internal temperature T1 is equal to or higher than the reference temperature T0, then all the solenoid valves are closed and a predetermined timer (not shown) provided in the control unit 50 is used. The measurement of the time t is started (Step S330). By closing all the valves in step S330, the reformer 12
Inlet and exit of the gas at 0 are stopped, and the steam reforming reaction and the oxidation reaction using the remaining raw fuel gas continue in the reaction section 121. Next, the elapsed time t is
A comparison is made with a predetermined reference time t0 (step S340). Here, the predetermined reference time t0 is defined as the time when all the valves are closed as described above.
0 is a value previously stored in the control unit 50 as a time required for completing the steam reforming reaction and the oxidation reaction using the raw fuel gas remaining in the inside.
ec. In step S340, the elapsed time t
Does not reach the reference time t0, the reference time t0
The operation of step S340 is repeated until elapses. In step S340, when the elapsed time t reaches the reference time t0, a drive signal is output to a predetermined solenoid valve to change the open / close state of the solenoid valve to the second state (step S35).
0), end this routine.

If it is determined in step S300 that the current state is not the first state, the reformer 120
The internal temperature T2 at the upstream end to which gas is supplied is read from the temperature sensor 123 (step S360). After that, step S37
0 to step S390, step S320 already described
The same processing as in steps S340 to S340 is performed. That is, when the internal temperature T2 reaches a predetermined reference value T0 (300 ° C. in this embodiment) with the progress of the oxidation reaction, all valves are closed for a predetermined time (1 second in this embodiment), and then the solenoid valves are closed. Set the open / closed state to the first state (step S
400), this routine ends.

As described above, the gas inlet switching processing routine is executed every predetermined time when the start of the fuel cell device 20 is instructed by operating a predetermined start switch (not shown). However, as an initial state in which the start of the fuel cell device 20 is instructed, the open / close state of each solenoid valve may be set to the first state or the second state described above. For example,
In the same state as when the fuel cell device 20 was stopped last time,
The fuel cell device 20 may be started next time, or the opening / closing state of each solenoid valve may be set to the first state or the second state when the fuel cell device 20 starts. .

According to the fuel cell system including the reformer 120 of the fifth embodiment configured as described above, the reformer 120
The supply point in the mixed air supplied to the reaction unit 121 is switched between the upstream side and the downstream side, and the direction of the gas flow in the reaction unit 121 can be reversed.
Only one end of the reformer does not overheat. Therefore, a rapid temperature rise on the upstream side can be suppressed. Here, the switching of the gas flow direction is performed based on the temperature at the end of the reaction section 121, so that it is possible to more reliably prevent the temperature at the end of the reaction section 121 from excessively rising. Become.

By switching the gas flow direction as described above, both ends of the reaction section 121 can be on the upstream side, so that the temperature is too low on a specific downstream side as in a conventional reformer. There is no. Therefore, the reformer 1
In 20, the activity of the steam reforming reaction is kept high on both sides, and the catalyst provided in the entire reaction section 121 can be sufficiently used, and the speed of the steam reforming reaction can be improved. Therefore, the reformer can be made more compact.

FIG. 19 shows the state of the internal temperature distribution from one end to the other end of a conventionally known reformer in which the flow direction of the internal gas is constant and the above-mentioned reformer 120. FIG. The reformer 120 is different from the conventional reformer in that the oxidation reaction is prevented from excessively progressing at a specific end portion, and since both end portions can be upstream, the internal temperature of the reformer is reduced. It can be made uniform within a temperature range of 250 to 300 ° C. As described above, since the temperature of the reformer 120 of the present embodiment does not rise sharply near the entrance, the catalyst deterioration and the generation of by-products described above due to the temperature rise are caused. Such inconveniences can be prevented. Therefore, it is possible to greatly improve the durability of the reformer as in the above-described embodiment.

Although the reformer 120 of this embodiment is provided with a reaction section constituted by a honeycomb, a configuration in which pellets supporting a catalyst are filled inside the reformer may be employed. Also in this case, the same effect can be obtained by switching the direction of the flow of the gas passing through the inside of the reforming section.

Although the reformer 120 of this embodiment switches the direction of the gas flow based on the temperature at the end of the reaction section 121, the switching timing may be based on other factors. It is good. When the temperature is based on the temperature at the end of the reaction section 121, the amount of the raw fuel gas supplied to the reformer 120 fluctuates, and the amounts of the steam reforming reaction and the oxidation reaction proceeding inside the reformer 120 are reduced. Even if it fluctuates, there is an advantage that a high effect can be obtained in keeping the internal temperature within a predetermined range. For example, when the fluctuation of the amount of raw fuel gas supplied to the reformer is small, The direction of the gas flow may be switched every time.

Next, as a sixth embodiment, there will be described a configuration in which the catalyst particles sealed in the reformer are stirred to prevent the temperature of only a specific upstream side in the reformer from being excessively increased. . FIG. 20 is an explanatory diagram schematically showing the configuration of the reformer 130 of the sixth embodiment and the members connected to the reformer 130. Since the reformer 130 of the present embodiment is provided in a fuel cell device having the same configuration as the fuel cell device 20 of FIG. 1, in the following description, common members are denoted by the same member numbers and detailed. Description is omitted.

The reformer 130 has the above-described particles made of the Cu—Zn catalyst sealed therein. This catalyst was prepared by adding a Cu—Zn catalyst prepared by a well-known
It was granulated to a particle size of μm. Alternatively, the Cu-Zn catalyst may be dispersed in a predetermined solvent, supplied to a spray dryer, and sprayed to produce fine particles having the above-described particle diameter. Further, the particle size of the catalyst particles may be a size that can be sufficiently stirred by the gas when the gas is injected into the reformer that encloses the catalyst particles as described above.
The particle size is preferably from 100 μm to several mm. Also, the shape of the catalyst particles may be any,
Considering the efficiency of stirring described later, it is preferable that the shape is close to spherical.

The reformer 130 is supplied with raw fuel gas composed of methanol and water vapor from the evaporator 32 and air from the blower 38, as in the above-described embodiment. These raw fuel gas and air are supplied into the reformer 130 via the pressure regulating valve 132 and the injection nozzle 134. In the evaporator 32, since methanol and water are vaporized and heated, the raw fuel gas is discharged from the evaporator 32 at a predetermined temperature and pressure. The raw fuel gas is mixed with air supplied from the air supply path 39 and then injected into the reformer 130 via the pressure regulating valve 132 and the injection nozzle 134. Reformer 1
Since the catalyst particles are sealed in the fuel cell 30 as described above, the catalyst particles are injected into the reformer 130 as shown by arrows in FIG.
Fluid within and stirred. Here, the reformer 1 of the present embodiment
In 30, the injection of the raw fuel containing air is performed from seven locations, but the number of injection locations may be different if the catalyst particles can be sufficiently stirred in the reformer. Further, the volume inside the reformer 130 is such that a predetermined amount of catalyst particles
Any size may be used as long as it can be sufficiently stirred by a gas (a raw fuel gas containing oxygen) supplied at a predetermined flow rate and a predetermined pressure.

In the reformer 130, a filter 136 made of foamed nickel is provided at an end opposite to the end to which the injection nozzle is connected. Since the filter 136 is formed in a sufficiently fine mesh shape, the catalyst particles sealed in the reformer 130 are prevented from leaking to the outside, but the fuel gas generated in the reformer 130 is prevented. Is not prevented from being supplied to the CO reduction unit 36 side.
The fuel gas that has passed through the filter 136 is
Is supplied to the fuel cell 40 to reduce the concentration of carbon monoxide.

According to the fuel cell device having the reformer 130 configured as described above, the catalyst particles sealed in the reformer 130 are constantly stirred by the raw fuel gas containing air. The catalyst particles present at the position where the raw fuel gas containing high concentration of oxygen is supplied are constantly replaced, so that the heat generated by the oxidation reaction does not cause the temperature of only a specific region of the catalyst to rise too much. Here, the gas injected into the reformer to stir the catalyst particles is a gas (raw fuel gas containing air) for use in the steam reforming reaction and the oxidation reaction that proceed in the reformer. Therefore, the operation of supplying the raw fuel to the reformer 130 and the operation of stirring the catalyst particles can be performed simultaneously. Further, by injecting the gas into the reformer, the reaction in the reformer and the electrochemical reaction in the fuel cell are not affected.

Further, the heat generated by the oxidation reaction is dispersed in the reformer 130 due to the stirring of the catalyst particles in the reformer 130, so that the temperature is reduced at a specific downstream side as in a conventional reformer. It does not drop too much. Therefore, the reformer 1
In the case of 30, the activity of the steam reforming reaction is kept high in the entire catalyst particles, and the speed of the steam reforming reaction can be improved.

FIG. 21 shows the state of internal temperature distribution from one end to the other end of a conventionally known reformer in which the flow direction of the internal gas is constant and the above-described reformer 130. FIG. Here, the gas supplied to the reformer 130 is a mixture of a raw fuel gas having a temperature of 250 ° C. and a flow rate of 670 l / min and air having a flow rate of 140 l / min.
It was injected into the reformer 130 from the injection nozzle 134 at atmospheric pressure. In the reformer 130, unlike the conventional reformer, the oxidation reaction does not proceed excessively on the specific end side, and the catalyst particles inside are involved in the reaction in a uniform state,
The internal temperature of the reformer can be made uniform within a temperature range of 250 to 300 ° C. As described above, since the temperature of the reformer 130 of the present embodiment does not rise sharply near the entrance thereof, the above-described catalyst deterioration and the generation of by-products due to the temperature rise Such inconveniences can be prevented. Therefore, similar to the embodiment described above,
The durability of the reformer can be greatly improved.

In the sixth embodiment, the raw fuel gas containing air is used as the gas to be injected into the reformer 130 for stirring. However, at least one of methanol gas, water vapor, and air is used. A single gas may be used. In this case, the remaining components not used for injection into the reformer for stirring the catalyst are removed from a predetermined position of the reformer (preferably upstream from the above injection position). In this case, the catalyst particles may be supplied to the reformer while maintaining the sealed state.

In the sixth embodiment, the reformer 130
By injecting high pressure gas into the reformer 130
Although the catalyst particles encapsulated therein are agitated, the catalyst particles may be agitated by means other than gas injection. For example, a mechanical means capable of stirring the internal catalyst particles may be provided in the reformer.

Next, as a seventh embodiment, there will be described a configuration in which a portion of the catalyst section to which the air for the oxidation reaction is supplied is changed with time. FIG. 22 is an explanatory diagram schematically showing the configuration of the reformer 140 of the seventh embodiment. The reformer 140 is provided in a fuel cell device having the same configuration as the fuel cell device 20 in FIG. As shown in FIG. 22, the reformer 140 includes a single reaction section 141 formed on the surface by a honeycomb supporting a Cu—Zn catalyst, and is formed in a substantially cylindrical shape. Further, the reformer 140 is rotatable by a predetermined motor (not shown). Here, the reformer 140 supplies the raw fuel gas from the second fuel supply path 64 and discharges the generated fuel gas to the third fuel supply path 65, as in the above-described embodiment. The second fuel supply path 64 and the third fuel supply path 65 are connected to a substantially central portion of a substantially circular cross section of the reformer 140. By driving the motor described above, the reformer 1
Reference numeral 40 rotates at a speed of one rotation per second around the center of the cross section.

Further, the raw fuel gas is supplied to the reformer 140 from the second fuel supply passage 64 and the reformer 140 is supplied with the air supply passage 3.
In the present embodiment, the end of the air supply path 39 on the connection side with the reformer 140 is formed in the second fuel supply path 64. The end of the air supply passage 39 formed in the second fuel supply passage 64 is connected to the reformer 1
At 40, it is curved in the space provided on the upstream side of the reaction section 141, and thereafter is opened as the outlet 142. The outlet 142 is open facing the upstream end of the reaction section 141, and the opening position is, in the present embodiment, the center point of the cross section of the end of the reaction section 141, and the end of the same. It was near the middle of the circumference of the cross section. Air supply path 3
9 is blown out from the outlet 142 so that about half of the cells of the honeycomb constituting the reaction section 141 are centered on the cells on the entire surface of the outlet 142. Can be supplied.

Therefore, when the reformer 140 of the present embodiment is used, in the cell receiving the supply of air from the outlet 142, both the steam reforming reaction and the oxidation reaction proceed, and the supply of air is not received. In the cell, only the steam reforming reaction proceeds. At this time, the reformer 140 rotates as described above, and the position of the outlet 142 is
The cell receiving air supply changes over time because it does not change regardless of the state of rotation of 40.

According to the reformer 140 of the seventh embodiment configured as described above, the cells which undergo the oxidation reaction by receiving the supply of air change with time, so that the upstream part of the specific cell The temperature does not rise too much. The oxidation reaction proceeds with the supply of air, and in the cell where the temperature on the upstream side is about to rise, the supply of air is immediately stopped and the oxidation reaction stops, and the generated heat is consumed by the steam reforming reaction. Therefore, the temperature does not rise any more. Also,
In a cell in which heat is consumed by a steam reaction without being supplied with air, air is immediately supplied and heat is generated by an oxidation reaction, so that the temperature does not drop too much.

In the reformer 140, the ratio of the supplied amount of methanol to the amount of air is determined by the amount of heat required for the steam reforming reaction progressing in the reformer and the amount of oxidation, as in the above-described embodiment. It is constant because it is determined from the amount of heat generated in the reaction. Here, in the reformer 140 of this embodiment, the number of cells supplied with air is always about half of the entire cells constituting the honeycomb. Therefore, when each cell receives the supply of air, an excess amount of oxygen is supplied to the cell relative to the amount of methanol, which is more than the heat required for steam reforming the supplied methanol. An oxidation reaction that produces heat occurs. However, as described above, since the supply of air to these cells is immediately stopped, the temperature does not excessively increase on the upstream side to which the air is supplied. In addition, since air and raw fuel gas are supplied in a state of excess oxygen,
The region where the oxidation reaction occurs is further extended to the downstream side than when supplying oxygen at a normal concentration. Therefore, unlike the conventional reformer, the temperature does not decrease too much on the downstream side. As described above, in the reformer 140, the entire reaction section can be kept in a predetermined temperature range, the activity of the steam reforming reaction can be kept high, and the speed of the steam reforming reaction can be improved.

FIG. 23 shows a conventional reformer that always supplies a predetermined ratio of oxygen to the entire cell constituting the honeycomb, and the above-described reformer 140, and shows the internal structure from the upstream side to the downstream side. It is explanatory drawing showing the temperature distribution state. The measurement of the temperature distribution state is based on the fact that in the gas supplied to the reformer 140, LHSV (volume of methanol to be processed in one hour / catalyst volume) = 3, and the ratio of oxygen / methanol of 11% to air / water / methanol. The test was carried out under conditions including water having a ratio of 2. The reformer 140 is different from the conventional reformer in that the temperature does not rise excessively on the upstream side,
The internal temperature of the reformer can be made uniform within a temperature range of 250 to 300 ° C. Therefore, the reformer 1 of the present embodiment
40 can prevent inconveniences such as the deterioration of the catalyst and the generation of by-products due to the temperature rise, and can greatly improve the durability of the reformer as in the above-described embodiment. Becomes When fuel gas is generated using the reformer 140 under the above conditions, H ₂ = 50%,
CO ₂ = 23%, H ₂ O = 17.5%, N ₂ = 9%, C
A fuel gas with O = 0.5% was obtained, and it was confirmed that the fuel cell operated well.

The reformer 140 of the seventh embodiment described above.
Although the outlet 142 to which air is supplied is fixed and the reformer 140 rotates, the outlet may rotate and the reformer may be fixed. A reformer having such a configuration will be described below as a modification of the seventh embodiment. FIG. 24 shows a reformer 1 which is a modification of the seventh embodiment.
It is explanatory drawing which represents the structure of 40A typically. Reformer 1
40A has substantially the same configuration as that of the reformer 140, and the corresponding members are denoted by the same reference numerals and denoted by the reference character A. In this reformer 140A, the reformer 140A
Does not rotate. In addition, a predetermined rotation mechanism 144 is provided in the above-described curved portion provided on the end side of the air supply path 39 that reaches the outlet 142A. By the rotation mechanism 144, the outlet 142
A of the air supply channel 39 provided with the
On the upstream end surface of 1A, a region to which air is supplied from the outlet 142A changes with time.

When the reformer 140A configured as described above is used, the same effect as the reformer 140 of the seventh embodiment can be obtained. The rotation mechanism 144 provided near the end of the air supply path 39 is provided with a blowout port 142A.
And the base of the air supply passage 39 is rotatably supported. The end member 143 is
The rotation may be performed by a reaction force from which air is blown out from the outlet 142A, or a rotation force may be generated using a predetermined power supplied from the outside.

In the above embodiment, one of the air outlet and the reformer is rotated. However, a plurality of air supply ports are provided upstream of the reformer, and the air is actually supplied. The air supply port to which the air is supplied may be switched over time, as long as the air supply portion in the reaction section can be changed over time. Further, although the reformer 140 and the reformer 140A have the reaction units formed of the honeycomb, each of the reaction units may be configured by filling pellets supporting the catalyst. Also in this case, by changing the portion to which air is supplied in the reaction section over time,
The same effect as that of the embodiment can be obtained.

Further, in addition to the above-described effects, the reformers of the sixth and seventh embodiments described above allow more oxidation reactions to proceed internally at the time of start-up, thereby making the reformer faster. This also has the effect that the temperature can be raised to a steady state. At the time of start-up, the temperature of the reformer has dropped to around room temperature, so it is necessary to quickly raise the temperature to a steady state. Here, a method in which a large amount of methanol and oxygen are supplied to actively cause an oxidation reaction and the reformer is heated from the inside can be considered, but in a conventional reformer, a large amount of air is supplied to oxidize the reformer. When the reaction is caused, even in the case where the temperature of the entire reformer is low, there is a possibility that only the specific region on the upstream side is excessively heated. According to the reformers of the sixth and seventh embodiments, since the region where the oxidation reaction actively proceeds (the catalyst portion where oxygen is supplied at a high concentration) changes with time, a large amount of oxygen is supplied. Even if the oxidation reaction is positively performed, the temperature of the reformer can be raised quickly without increasing the temperature of only the specific portion.

Next, as an eighth embodiment, a plurality of reactors are provided in the reformer, and a part of these reactors is adjacent to the other reactors by reversing the gas flow. 1 shows a configuration in which heat is exchanged between an upstream side where raw fuel gas and air are supplied and a downstream side where fuel gas is discharged between the reaction sections. FIG. 25 shows a reformer 150 according to the eighth embodiment.
FIG. 2 is a schematic cross-sectional view illustrating the configuration of FIG. The reformer 150 is provided in a fuel cell device similar to the fuel cell device 20 in FIG. The reformer 150 is formed in a substantially columnar shape, has a reaction portion 152 in an annular shape along the inner wall thereof, has a reaction portion 151 inside the reaction portion 152, and has a double tubular structure. doing. The reaction section 151 receives the supply of the raw fuel gas and the air from one end thereof (the left side in FIG. 25), and discharges the fuel gas at the other end thereof (the right side in FIG. 25). The reaction section 152 also receives the supply of the raw fuel gas and the air from one end and discharges the fuel gas at the other end, but the respective positions are opposite to those of the reaction section 151. Therefore, the reaction unit 151 and the reaction unit 152
Then, the direction of the gas flow inside is reversed. Here, each of the reaction sections 151 and 152 may be formed of a honeycomb supporting a Cu-Zn catalyst on the surface, or may be formed by filling pellets made of a Cu-Zn catalyst.

According to the reformer 150 of the eighth embodiment configured as described above, the upstream side of the reaction section 151 provided inside and the downstream side of the reaction section 152 provided outside, and the reaction section 151 And the upstream side of the reaction section 152 are adjacent to each other, so that heat exchange can be performed between the upstream side and the downstream side, respectively. Therefore, the heat generated due to the oxidation reaction on the upstream side of one of the reaction sections is transmitted to the downstream side of the other adjacent reaction section (see the dotted arrow in FIG. 25), and the air is supplied together with the raw fuel gas. The temperature does not rise too high on the upstream side.

Further, as described above, since heat is supplied from the upstream side of the adjacent reaction section to the downstream side of each reaction section constituting the reformer 150, the downstream side is provided as in the conventional reformer. Temperature does not drop too much. Therefore, in the reformer 150, the activity of the steam reforming reaction is kept high in the entire reaction section, and the speed of the steam reforming reaction can be improved.

FIG. 26 shows, from one end side to the other end side, of a conventionally known reformer in which the direction of the gas flow in the reaction section provided in the reformer is constant and the above-described reformer 150. FIG. 3 is an explanatory diagram showing a temperature distribution state inside each of the reaction sections. Unlike the conventional reformer, the reformer 150 does not excessively raise the temperature due to the heat generated by the oxidation reaction on the specific upstream side, and the internal temperature decreases on the specific downstream side too much. Therefore, the internal temperature of the reformer can be made uniform within a temperature range of 250 to 300 ° C. As described above, the reformer 1 of the present embodiment
Since the temperature does not rise sharply near the entrance of the 50, it is possible to prevent inconveniences such as the above-described catalyst deterioration and the generation of by-products due to the temperature rise. Therefore, it is possible to greatly improve the durability of the reformer as in the above-described embodiment.

The reformer 150 of the eighth embodiment described above.
Is a double-pipe type having a reaction section 151 formed inside and a reaction section 152 formed outside, and the gas flow direction is reversed in each reaction section. Is constituted by a plurality of reaction sections, and the flow direction of the gas in some of the reaction sections is opposite to that in the other reaction sections. Heat can be exchanged with the downstream side having a large amount, and the same effect as that of the eighth embodiment can be obtained. For example, instead of using a double-tube type reformer, a stacked type in which a plurality of thin reaction sections are stacked,
The gas flow direction may be alternately reversed in each of the stacked reaction sections. In such a case as well, heat exchange is performed between the upstream side and the downstream side between the adjacent reaction sections, so that the internal temperature can be equalized.

Next, as a ninth embodiment, a folded portion is formed in the middle of the flow path formed by the predetermined reaction portion, and heat exchange is performed by adjoining the upstream side and the downstream side in the predetermined reaction portion. The following shows the configuration to be performed. FIG. 27 is a schematic sectional view showing the configuration of the reformer 160 according to the ninth embodiment. The reformer 160 is provided in a fuel cell device similar to the fuel cell device 20 in FIG. This reformer 160 is formed in a substantially columnar shape similarly to the reformer 150 of the eighth embodiment, and the inside thereof has a double pipe structure divided into an inner portion 161 and an outer portion 162. The inner part 161 and the outer part 162 are formed as a continuous structure, and both constitute a single reaction part 163.

The second fuel supply path 64 is connected to one end of the inner part 161, and the raw fuel gas and air supplied from the second fuel supply path 64 flow from one end to the other end in the inner part 161. Move. At the other end of the inner portion 161, the inner portion 161 is connected to the outer portion 162, and the gas passing through the inner portion 161 is introduced into the outer portion 162 at the other end (see a solid arrow in FIG. 27). ). The gas introduced into the outer portion 162 is directly
At the end corresponding to the one end on the inner side 161, and connected to the third fuel supply passage 65, and the fuel gas generated when the gas passes through the reaction section 163 is supplied to the third fuel supply passage 65. It is discharged to the supply path 65. The reaction unit 163
The inner part 161 and the outer part 162 constituting
It may be constituted by a honeycomb supporting a Zn catalyst, or may be formed by filling pellets made of a Cu-Zn catalyst.

According to the reformer 160 of the ninth embodiment configured as described above, the inner portion 161 provided on the inner side and the outer portion 162 provided on the outer side are adjacent to each other. Heat can be exchanged between the outer portion 161 and the outer portion 162. The inner portion 161 corresponds to the upstream side in the reaction portion 163, and the oxidation reaction is actively performed to generate much heat. Further, the outer portion 162 corresponds to the downstream side in the reaction portion 163, and only the steam reforming reaction is mainly performed and heat is required. In the reformer 160, heat is transmitted from the inner portion 161 that generates a large amount of heat to the outer portion 162 that requires heat (see the dotted arrow in FIG. 27). Does not rise too much.

In the reformer 160, heat is supplied from the adjacent inner portion 161 to the outer portion 162 corresponding to the downstream side, as described above. The temperature does not drop too much. Therefore, in the reformer 160, the activity of the steam reforming reaction is kept high in the entire reaction section, and the speed of the steam reforming reaction can be improved.

FIG. 28 shows a conventional fuel reformer in which the direction of the gas flow in the reaction section provided in the reformer is constant and the above-described reformer 160, the second fuel supply passage 64 FIG. 4 is an explanatory diagram showing an internal temperature distribution state from the connection side to the other end side. Unlike the conventional reformer, the reformer 160 does not excessively raise the temperature due to the heat generated by the oxidation reaction on the upstream side, and the internal temperature does not excessively decrease on the downstream side. The internal temperature of the reformer can be made uniform within a temperature range of 250 to 300 ° C. As described above, the reformer 160 of the present embodiment
Since the temperature does not rise sharply near the entrance, it is possible to prevent the above-mentioned inconveniences such as catalyst deterioration and generation of by-products due to the temperature rise. Therefore, it is possible to greatly improve the durability of the reformer as in the above-described embodiment.

The reformer 160 according to the ninth embodiment described above.
Is a double pipe type having an inner portion 161 formed on the inside and an outer portion 162 formed on the outside.
Although the gas flow direction is reversed between 1 and the outer portion 162, the reformer may be configured other than the double pipe. If a folded portion is provided in the flow path through which the raw fuel gas and the air pass, and the upstream side and the downstream side are adjacent to each other so that heat can be exchanged therebetween, the same as in the ninth embodiment described above. A predetermined effect can be obtained. For example, instead of using a double pipe type reformer, a configuration may be adopted in which a predetermined flow path is folded into two, and the direction of gas flow is opposite between the upstream side and the downstream side. FIG. 29 shows a reformer 160A having such a configuration. Even in such a case, heat is transferred from the adjacent upstream side to the downstream side (see FIG. 29).
The inner temperature can be soaked.

Next, as a tenth embodiment, a configuration in which the downstream side of the reformer is heated by using high-temperature combustion exhaust gas discharged from the evaporator 32 will be described. FIG. 30 is a schematic sectional view showing the configuration of the reformer 170 of the tenth embodiment. Reformer 1
70 is provided in a fuel cell device similar to the fuel cell device 20 of FIG. This reformer 170 has Cu-
It has two reaction units 171 and 172 constituted by honeycombs carrying a Zn catalyst. By dividing the inside of the reformer 170 into two reaction sections in this way, the gas separated by each cell of the honeycomb in the upstream reaction section 171 can be remixed on the way, and The state of the gas passing through can be made more uniform. The reformer 170 is connected to the second fuel supply path 64 to which air is supplied from the air supply path 39, and receives supply of raw fuel gas containing air. The raw fuel gas containing air and supplied from the second fuel supply passage 64 is supplied to the reaction unit 171,
The fuel gas passes in the order of 172 and becomes a hydrogen-rich fuel gas and is discharged to the third fuel supply path 65.

The reaction units 171 and 172 are provided with temperature sensors 173 and 174, respectively. These temperature sensors 173 and 174 are connected to the control unit 50, and information on the internal temperature of the reaction units 171 and 172 is
The information is transmitted to the control unit 50. As will be described later, the detection result of the temperature sensor 173 is used to prevent the internal temperature of the reaction unit 171 from excessively increasing, and the detection result of the temperature sensor 174 determines that the internal temperature of the reaction unit 172 excessively decreases. Used to prevent. Therefore, the temperature sensor 173
The temperature sensor 174 is located upstream of the reaction section 171.
Is desirably provided downstream of the reaction section 172.

In the reformer 170, the reaction section 17
An exhaust gas introduction portion 175 into which the combustion exhaust gas discharged from the evaporator 32 described above is introduced is provided at an outer peripheral portion corresponding to the position where 2 is provided. In the evaporator 32,
As described above, the combustion exhaust gas is supplied from the burner 26 via the compressor 28, and methanol and water are heated and vaporized using the calorie of the combustion exhaust gas. As described above, the combustion exhaust gas discharged from the compressor 28 after the temperature and vaporization of methanol and water has a predetermined calorific value even after the calorific value is consumed by the evaporator 32. In the reformer 170, the combustion exhaust gas is introduced into the exhaust gas introduction section 175 to heat the reaction section 172 provided on the downstream side.

The fuel cell device including the reformer 170 of this embodiment is provided with a flue gas passage 176 for supplying the flue gas discharged from the evaporator 32 to the flue gas introduction section 175. The 176 is provided with a mass flow controller 177 for adjusting the amount of the combustion exhaust gas supplied to the exhaust gas introduction unit 175. The mass flow controller 177 is connected to the control unit 50,
With 0, the amount of combustion exhaust gas supplied to the exhaust gas introduction unit 175 can be controlled. Here, the temperature of the combustion exhaust gas supplied from the evaporator 32 to the exhaust gas introduction unit 175 is:
The temperature is about 300 ° C., and the internal temperature of the reaction section 172 can be controlled by controlling the driving state of the mass flow controller 177 and adjusting the amount of combustion exhaust gas supplied to the exhaust gas introduction section 175. The combustion exhaust gas introduced into the exhaust gas introduction section 175 as described above is supplied to the reaction section 172.
Is heated and then discharged outside the fuel cell device.

In the upstream reactor 171 of the reformer 170 of this embodiment, the amount of heat required for the steam reforming reaction proceeding in the reactor 171 is covered by the amount of heat generated by the oxidation reaction. On the other hand, in the downstream reaction section 172, the amount of heat required for the steam reforming reaction proceeding in the reaction section 172 is supplied to the exhaust gas introduction section 175 in addition to the amount of heat generated in the oxidation reaction proceeding upstream. The heat of the combustion exhaust gas is used. Here, in the fuel cell device including the reformer 170 of the present embodiment, the control unit 50
Is a blower 38 that takes in air supplied to the reformer 170.
Is controlled based on the detection result of the temperature sensor 173, and the amount of air supplied to the reformer 170 is adjusted so that the internal temperature of the reaction section 171 does not exceed 300 ° C. In the fuel cell device of the present embodiment,
The control unit 50 controls the driving amount of the mass flow controller 177 based on the detection result of the temperature sensor 174 and supplies the driving amount to the exhaust gas introduction unit 175 such that the internal temperature of the reaction unit 172 becomes 250 ° C. or higher. The amount of flue gas to be emitted is adjusted.

According to the reformer 170 of the tenth embodiment configured as described above, the downstream reaction section 172 is heated by the above-mentioned combustion exhaust gas, and thus proceeds in the reformer 170. It is not necessary to cover all of the heat required in the steam reforming reaction with the heat generated in the oxidation reaction, and reduce the amount of air supplied to the reformer 170 in order to provide the oxidation reaction.
The amount of oxidation reaction that proceeds on the upstream side can be reduced.
Here, the amount of air supplied to the reformer 170 depends on the reaction unit 17.
Since the temperature is adjusted based on the internal temperature of the reaction unit 1, the temperature does not excessively increase in the reaction unit 171 where the oxidation reaction is actively performed.

In the reformer 170, the downstream reaction section 172 has the exhaust gas introduction section 175 as described above.
Since the heat is supplied from the combustion exhaust gas introduced into the reactor, the temperature does not excessively decrease on the downstream side unlike the conventional reformer. Therefore, in the reformer 170, the activity of the steam reforming reaction is kept high in the entire reaction section, and the speed of the steam reforming reaction can be improved. Further, since the heat of the fuel exhaust gas which has been conventionally discarded is used to heat the reaction section 172, the energy efficiency does not decrease by heating the reaction section 172.

FIG. 31 shows that the conventional fuel reformer, in which substantially all of the heat required in the steam reforming reaction is covered by the heat generated in the oxidation reaction, and the reformer 170 described above, the raw fuel gas containing air is It is explanatory drawing showing the internal temperature distribution state from the upstream to the downstream supplied. Reformer 170
Unlike the conventional reformer, the temperature of the reformer is not excessively increased by the heat generated by the oxidation reaction on the upstream side, and the internal temperature is not excessively decreased on the downstream side. The internal temperature can be made uniform within a temperature range of 250 to 300 ° C. As described above, since the temperature of the reformer 170 of this embodiment does not rise sharply near the entrance, the above-described catalyst deterioration and the generation of by-products due to the temperature rise Such inconveniences can be prevented. Therefore, it is possible to greatly improve the durability of the reformer as in the above-described embodiment.

The reformer 170 of the tenth embodiment described above.
Are two reaction units 171 and 171 constituted by honeycombs.
172 is provided, but instead of using a honeycomb, a configuration in which pellets supporting a catalyst are filled inside may be used. In this case, the inside of the reformer may be uniformly filled with the pellets without dividing the inside of the reformer into two parts.

In order to heat the downstream side, the evaporator 3
High-temperature gas other than the combustion exhaust gas discharged from 2 may be used. For example, in the fuel cell device including the reformer 170 of the present embodiment, a heat source for supplying heat required by the evaporator 32 and a driving source for the compressor 28 for supplying compressed air to the cathode side of the fuel cell 40 are used. If different, exhaust gas discharged from any of the heat source and the driving source may be used. Further, a gas discharged from another high-temperature portion constituting the fuel cell device may be used, and has energy usable to maintain the internal temperature of the reformer in a temperature range of 250 to 300 ° C. Just do it. Alternatively, instead of using the high-temperature exhaust gas discharged from the high-temperature member, a predetermined fluid is circulated between the high-temperature member and the reformer, and the fluid supplies the thermal energy of the high-temperature member to the reformer. You may do it.

Next, as the eleventh embodiment, there will be described a configuration in which a part of the raw fuel is supplied in a liquid state upstream of the reformer. FIG. 32 is an explanatory diagram showing an outline of the configuration of the reformer 180 of the eleventh embodiment. The reformer 180 is provided in a fuel cell device similar to the fuel cell device 20 in FIG. The reformer 180 includes a single reaction section 181 formed of a honeycomb supporting a Cu—Zn catalyst on the surface. Here, the reformer 180 is connected to the second fuel supply path 64 to receive the supply of the raw fuel gas, and also supplies a mixed liquid of methanol and water (hereinafter, referred to as a liquid raw fuel). receive. Liquid raw fuel, as described above,
The fuel is supplied to the evaporator 32 through the first fuel supply passage 63, and the first fuel supply passage 63 branches on the way to become a raw fuel branch passage 182, and the liquid raw fuel is also supplied to the reformer 180. It can be supplied. Further, in this embodiment, the air supply path 39 does not merge with the second fuel supply path 64, but merges with the raw fuel branch path 182 to become the raw fuel path 183. The raw fuel passage 183 is connected to the upstream end of the reformer 180, so that liquid raw fuel mixed with air can be supplied to the reformer 180.

A mass flow controller 184 is provided in the air supply path 39, and a mass flow controller 185 is provided in the raw fuel branch path 182. The mass flow controller 184 controls the amount of air supplied to the reformer 180 and the amount of liquid raw fuel. It can be controlled. These mass flow controllers 184 and 185 are connected to the control unit 50, and the control unit 50 controls the driving amount. Further, inside the reformer 180,
Near the upstream end of the reaction section 181, a raw fuel passage 183 is provided.
The injection nozzle 187 is provided as an end structure of the nozzle.
The liquid fuel mixed with air as described above is supplied from the injection nozzle 187 to the reaction unit 18 by utilizing the pressure of air.
1 and is supplied in a wide range with respect to the cross section of the end of the reaction section 181. The injection nozzle 18
7 only needs to be a shape capable of ejecting a liquid over a wide range,
A shape other than the nozzle shape may be used. Further, in the reformer 180, near the upstream end of the reaction section 181,
A temperature sensor 186 is provided. This temperature sensor 1
86 is connected to the control unit 50, and information on the temperature on the upstream side of the reaction unit 181 is input to the control unit 50.

As described above, when air is supplied to the reformer together with the raw fuel gas, the oxidation reaction actively proceeds on the upstream side where the oxygen concentration is high, and the temperature rises. In this example, the temperature of the upstream side is controlled by injecting the liquid raw fuel upstream of the reaction section 181. That is, when the liquid raw fuel is injected into the reaction section 181 having a predetermined high temperature, the liquid raw fuel vaporizes and raises the temperature by removing heat from the injected reaction section 181. Therefore, by adjusting the supply amount of the liquid raw fuel, the temperature on the upstream side of the reaction section 181 can be controlled to a predetermined temperature or lower.

When hydrogen-rich fuel gas is generated using the reformer 180 having such a configuration, the reformer 180 is controlled based on the temperature inside the reaction section 181 detected by the temperature sensor 186. Whether to supply liquid raw fuel
Alternatively, the supply amount is controlled. The total amount of methanol supplied to the reformer 180 is determined based on the magnitude of the load connected to the fuel cell 40, that is, the amount of fuel gas to be supplied to the fuel cell 40. Based on the result, the amount of methanol supplied to the reformer 180 as liquid from the first fuel supply channel 63 is adjusted. More specifically, when the temperature of the reaction unit 181 exceeds a predetermined temperature (300 ° C. in the present embodiment), the injection of the raw fuel liquid from the injection nozzle 187 is performed.
The amount of the raw liquid fuel supplied from the injection nozzle 187 is adjusted so that the temperature of the liquid fuel becomes equal to or lower than the predetermined temperature. In addition,
When the temperature of the reaction unit 181 is equal to or lower than the predetermined temperature,
From the injection nozzle 187, only air is injected.

According to the reformer 180 of the eleventh embodiment configured as described above, the upstream portion of the reaction section 181 can be cooled by injecting and vaporizing the liquid in the reformer 180. Therefore, it is possible to prevent the temperature of the upstream part of the reaction part 181 from excessively rising due to heat generated by the oxidation reaction. Here, the liquid injected in the reformer 180 to cool the upstream portion of the reaction section 181 is supplied to the reformer 1
Since it is composed of the raw fuel used in the steam reforming reaction and the oxidation reaction that proceed in 80, the reaction that proceeds in the reformer 180 is not affected by performing such a liquid injection operation. .

FIG. 33 shows a conventional reformer supplied with an entire amount of methanol required to generate a desired amount of fuel gas via an evaporator 32 and the above-described reformer 1
FIG. 8 is an explanatory diagram showing the internal temperature distribution state from 80 on the upstream side to the downstream side on which the raw fuel gas containing air is supplied. The reformer 180 is different from the conventional reformer,
Since the temperature is not excessively increased by the heat generated by the oxidation reaction on the upstream side, the internal temperature of the reformer is set to 250 to 300
It can be homogenized in a temperature range of ° C. in this way,
Since the temperature of the reformer 180 of the present embodiment does not rise sharply near the entrance, it is possible to prevent the above-described inconveniences such as catalyst deterioration and generation of by-products due to the temperature rise. Can be. Therefore, it is possible to greatly improve the durability of the reformer as in the above-described embodiment.

When the temperature on the upstream side of the reformer 180 rises too much to increase the amount of liquid raw fuel injected from the injection nozzle 187, if the required power in the load connected to the fuel cell 40 decreases, In some cases, the amount of methanol supplied to the reformer 180 becomes excessive, and fuel gas exceeding the required amount is generated. In the fuel cell device including the reformer 180 according to the present embodiment, the fuel exhaust gas discharged from the fuel cell 40 is used as fuel for combustion in the burner 26 as described above. However, the energy efficiency of the entire system does not decrease.

In the reformer 180 of this embodiment, the mixture injected from the injection nozzle 187 to cool the upstream portion of the reaction section 181 is a mixture of methanol and water.
A configuration in which only methanol or water is injected may be employed. In this case, a branch path is provided in the methanol flow path 60 or the water supply path 62 instead of the first fuel supply path 63, and methanol or water is supplied to the same nozzle as the injection nozzle 187 by this branch path. What should be done. Even with such a configuration, the reaction unit 181
In the upstream part, the heat is taken off when the injected liquid is vaporized, so that the same effect as the reformer 180 of the eleventh embodiment can be obtained.

Next, as a twelfth embodiment, a reaction section in which both the steam reforming reaction and the oxidation reaction proceed and a reaction section in which only the steam reforming reaction proceeds are provided adjacent to each other. A configuration is shown in which heat exchange is performed to prevent an excessive rise in temperature due to heat generated by the oxidation reaction. FIG. 34 is an explanatory diagram showing an outline of the configuration of the reformer 190 of the twelfth embodiment. The reformer 190 is provided in a fuel cell device similar to the fuel cell device 20 in FIG.
This reformer 190 is formed in a substantially columnar shape, and has three reaction units 191, 192, and
193. A reaction section 193 is formed annularly along the inner wall of the reformer 190.
The reaction parts 191 and 192 are formed inside. Here, the reaction section 191 is provided on the upstream side and the reaction section 192 is provided on the downstream side, and a predetermined space 200 is formed between the two.

In the reformer 190, the reaction section 19
1, 192 and 193 are all Cu-Zn as described above.
The catalyst is supported on the surface. Here, the reaction unit 193
Although connected to the second fuel supply path 64 and supplied with the raw fuel gas but not supplied with air, the reaction section 193 performs a steam reforming reaction and does not perform an oxidation reaction. The second fuel supply path 64 is connected to the reaction section 191 in addition to the reaction section 193, and the raw fuel gas supplied to the reaction section 191 passes through the inside of the reaction section 191 and the reaction section 192 in this order. I do. Further, the air supply path 39 branches into air branch paths 194 and 195 on the way, and these air branch paths are connected to the upstream of the reaction section 191 and the reaction section 192, respectively. These air branches 194, 195
Air is supplied to each reaction section. Therefore, in the reaction section 191 and the reaction section 192, the oxidation reaction proceeds together with the steam reforming reaction. Reaction units 191, 192
The hydrogen-rich gas generated by the steam reforming reaction and the oxidation reaction in, and the hydrogen-rich gas generated by the steam reforming reaction in the reaction section 193 are discharged to the third fuel supply path 65 and supplied to the CO reduction section 36.

Further, mass flow controllers 196 and 197 are provided in the air branch passages 194 and 195 branched from the air supply passage 39, respectively.
The amount of air supplied to 92 can be adjusted. These mass flow controllers 196 and 197 are connected to the control unit 50, and the control unit 50 controls the amount of air supplied to each reaction unit. Also, the reaction units 191, 19
Temperature sensors 198 and 199 for detecting the internal temperature of each reaction section are provided on the upstream side of each of the two. These temperature sensors 198 and 199 are connected to the control unit 50, and the result of detecting the internal temperature of each reaction unit is transmitted to the control unit 50.
Is input to The control unit 50 controls the amount of air supplied to each reaction unit based on the detection result input from each temperature sensor.

The reaction section 1 in the reformer 190 of this embodiment
In 91 and 192, the amount of heat required for the steam reforming reaction that proceeds inside is covered by the amount of heat generated by the oxidation reaction that also proceeds inside. On the other hand, in the reaction section 193 provided on the outer peripheral portion, the heat required for the steam reforming reaction progressing in the reaction section 193 is not generated by the reaction sections 191 and 1 adjacent on the inside.
The heat generated by the oxidation reaction at 92 is utilized (FIG. 3).
4 (see dotted arrow). Here, the reformer 19 of the present embodiment
0, the control unit 50 controls the amount of driving of the mass flow controllers 196 and 197 for adjusting the amount of air supplied to the reaction units 191 and 192 by using the temperature sensor 1
The control is performed based on the detection results of 98 and 199, and the amount of supplied air is adjusted so that the internal temperature of the reaction sections 191 and 192 does not exceed 300 ° C.

According to the reformer 190 of the twelfth embodiment configured as described above, the heat generated by the oxidation reaction proceeding in the reaction units 191 and 192 is only the endothermic reaction in the adjacent reaction unit. It is also consumed in the proceeding reaction section 193.
Therefore, the reaction portion 191, in which the oxidation reaction actively proceeds,
In the upstream part of 192, it is possible to prevent the temperature from rising excessively. Here, since the amount of air supplied to the reaction units 191 and 192 is adjusted based on the internal temperature of each reaction unit, it is possible to control the internal temperature of each reaction unit to be kept at a predetermined temperature or lower.

In the reformer 190 of this embodiment, since air is supplied to each of the reaction sections 191 and 192, the reaction section 192 located downstream of the reaction section 191 is provided.
In this case, the oxidation reaction which is an exothermic reaction can be performed, and the temperature does not excessively decrease on the downstream side unlike the conventional reformer. Therefore, in the reformer 190, the activity of the steam reforming reaction is kept high in the entire reaction section, and the speed of the steam reforming reaction can be improved.

FIG. 35 shows a case where the raw fuel gas is supplied to a conventionally known reformer constituted only by a reaction section which proceeds both the steam reforming reaction and the oxidation reaction, and the above-described reformer 190. FIG. 4 is an explanatory diagram showing an internal temperature distribution state from an upstream side to a downstream side. Unlike the conventional reformer, the reformer 190 does not excessively raise the temperature due to the heat generated by the oxidation reaction on the upstream side, and the internal temperature does not decrease too much on the downstream side. The internal temperature of the reformer can be made uniform within a temperature range of 250 to 300 ° C. As described above, since the temperature of the reformer 190 of the present embodiment does not rise sharply near the entrance, the above-described catalyst deterioration and the generation of by-products due to the temperature rise are caused. Such inconveniences can be prevented. Therefore, it is possible to greatly improve the durability of the reformer as in the above-described embodiment.

In the reformer 190 of the twelfth embodiment, air is supplied to each of the reaction units 191 and 192 which are provided inside and advance both the steam reforming reaction and the oxidation reaction. With the configuration, the effect of suppressing the temperature drop on the downstream side could be increased.However, even when the air supply was performed only from the upstream side,
A predetermined effect of suppressing an excessive rise in temperature on the upstream side can be obtained.

In the reformer 190 of the twelfth embodiment, the reaction section for performing both the steam reforming reaction and the oxidation reaction and the reaction section for performing only the steam reforming reaction are divided into an inner portion and an outer peripheral portion. And formed into a double tube type.
As a modified example of the embodiment, a laminated type configuration in which the above two types of reaction sections are alternately laminated is shown. FIG. 36 is an explanatory diagram schematically showing the outline of the configuration of a reformer 190A which is a modification of the twelfth embodiment. The reformer 190A is provided in a fuel cell device similar to the fuel cell device 20 in FIG. 1 similarly to the reformer 190, and members common to the reformer 190 are denoted by reference numerals A in the member numbers. The following description will be made.

[0200] The reformer 190A has a structure in which a plurality of reaction portions 191A and 193A formed in a flat plate shape are alternately stacked. These reaction parts 191A
And 193A are constituted by a honeycomb having a Cu—Zn catalyst supported on the surface.
Raw fuel gas is supplied from the second fuel supply path 64. In addition, the air supply path 39 is branched to each of the reaction sections 19.
It connects to the upstream part of 1A and supplies air to each reaction part 191A. The amount of air to be supplied to the plurality of reaction units 191A is controlled by a mass flow controller 196A provided in the air supply path 39.
As in the case of the second embodiment, the detection is performed based on the detection result of a temperature sensor (not shown) provided upstream of each reaction section 191A.

According to the reformer 190A which is a modification of the twelfth embodiment configured as described above, similarly to the reformer 190 of the twelfth embodiment, the heat generated by the oxidation reaction is adjacent to the adjacent reaction. Since it is consumed in the steam reforming reaction that proceeds in the section, the temperature in the upstream section where the oxidation reaction actively proceeds does not excessively increase. Therefore, similar to the reformer 190,
The effect of preventing inconveniences such as catalyst deterioration and generation of by-products can be obtained, and the durability of the reformer can be greatly improved.

Next, as a second modification of the twelfth embodiment, a multi-tube insertion type reformer 190B will be described. FIG. 37 is a schematic sectional view schematically showing the configuration of a reformer 190B which is a second modification of the twelfth embodiment. FIG. 37A is a longitudinal sectional view of the reformer 190B, and FIG.
It is a cross-sectional view in the BB line of (A). Reformer 19
0B is the fuel cell device 20 of FIG.
Is provided in the same fuel cell device as
The following description will be made by assigning the reference number B to the member numbers common to the above.

[0203] The reformer 190B is formed in a substantially columnar shape, and has a reaction section 191B and a reaction section 193B therein. The reaction section 191B is formed in a substantially columnar shape with a short bottom surface, and seven reaction sections are formed in the reformer 190B. In the reformer 190B, the reaction unit 191
The space where B is not formed constitutes the reaction section 193B. Each of the reaction sections 191B and 193B is formed of a honeycomb having a Cu—Zn catalyst supported on its surface, and a raw fuel gas is supplied from the second fuel supply path 64 to each reaction section. The air supply path 39 is
Branch and connect to the upstream part of each reaction part 191B,
Air is supplied to each reaction section 191B. The amount of air supplied to the plurality of reaction units 191B is determined by the air supply path 39.
The control is performed by a mass flow controller 196B provided in the reaction unit 191B. As in the twelfth embodiment, the control is performed by a temperature sensor (not shown) provided upstream of each reaction unit 191B.
This is performed based on the detection result by

According to the reformer 190B, which is a modification of the twelfth embodiment configured as described above, the heat generated by the oxidation reaction is reduced by the adjacent reaction as in the reformer 190 of the twelfth embodiment. Since it is consumed in the steam reforming reaction that proceeds in the section, the temperature in the upstream section where the oxidation reaction actively proceeds does not excessively increase. Therefore, similar to the reformer 190,
The effect of preventing inconveniences such as catalyst deterioration and generation of by-products can be obtained, and the durability of the reformer can be greatly improved.

The above-mentioned reformers 190, 190A, 190
In B, the oxidation reaction is performed in a limited reaction section. When the heat required for the steam reforming reaction that proceeds in the reformer is constant, if the region where the oxidation reaction proceeds is reduced, the amount of catalyst becomes insufficient compared to the amount of oxygen supplied, and oxygen is supplied. The rate of the oxidation reaction in the region can be suppressed. Therefore, the region where the oxidation reaction proceeds can be expanded further downstream, and the effect of suppressing the temperature from being too low downstream of the reformer can be further increased.

In the reformers 190A and 190B, which are modifications of the twelfth embodiment, similarly to the reformer 190, air is supplied not only to the upstream side of the reformer but also in the middle thereof. It may be. With such a configuration, it is possible to prevent the temperature from dropping too much downstream of the reformer. In addition, although each reaction section constituting each of the reformers 190, 190A, and 190B is formed of a honeycomb, a configuration in which pellets carrying a catalyst may be filled. In this case, too, by adjoining the reaction section that proceeds with the oxidation reaction together with the steam reforming reaction and the reaction section that proceeds only with the steam reforming reaction, the temperature is excessively increased on the upstream side of the reaction section. Can be prevented.

In the first to twelfth embodiments described above, since the Cu—Zn catalyst is used as a catalyst provided in each reformer, a single catalyst can be used to perform the steam reforming shown in the equation (4). And the oxidation reaction shown in the equation (5) can be promoted. Needless to say, a catalyst (for example, a Pd-Zn catalyst or the like) other than the Cu-Zn catalyst that can promote both the steam reforming reaction and the oxidation reaction may be used. Even when such a catalyst is used, by providing the catalyst in the reformer of the above-described embodiment, it is possible to prevent the internal temperature from being excessively increased in a part of the inside of the reformer. The effects described above can be obtained.

Further, in each of the above embodiments, instead of promoting the steam reforming reaction and the oxidation reaction by a single catalyst, each of the reactions may be promoted by using a different catalyst. Alternatively, another catalyst that promotes the oxidation reaction may be further added to the Cu—Zn catalyst and used. Thus, even when a plurality of types of catalysts are used, the mixed state of these catalysts in the reformer is sufficient, and in a region where oxygen is supplied,
If both the oxidation reaction shown in equation (5) and the steam reforming reaction shown in equation (4) can proceed with sufficient efficiency,
In the configuration of each embodiment, the above-described effect of suppressing the internal temperature from excessively increasing in a part of the area inside the reformer can be obtained. Here, as another catalyst capable of promoting the oxidation reaction, for example, palladium, platinum, nickel, rhodium, chromium, tungsten, rhenium,
Examples thereof include metals such as gold, silver, and iron, and alloys of these metals with other metals.

In the above-described embodiments, methanol is used as a raw fuel. However, another kind of hydrocarbon may be used as a raw fuel, and this raw fuel may be subjected to a steam reforming reaction and an oxidation reaction. good. As described above, even when a raw fuel other than methanol is used, a catalyst corresponding to the raw fuel to be used is provided in the reformer having the configuration of the above-described embodiment, so that a partial area inside the reformer is provided. Thus, the above-described effect of suppressing the internal temperature from excessively rising can be obtained.

The Cu-Zn catalyst provided in the reformers of the first to twelfth embodiments is a well-known catalyst that promotes the steam reforming reaction of methanol. As described above, the Cu-Zn catalyst has a temperature of 300 ° C.
If the raw fuel is a hydrocarbon having a high reaction temperature at which the steam reforming reaction proceeds, it cannot be used as a catalyst for accelerating the steam reforming reaction. When methanol, which has a lower reaction temperature in the steam reforming reaction than hydrocarbons, is used as a raw fuel, it works well as a catalyst for promoting this reaction.
However, a method of using this Cu—Zn catalyst as an oxidation catalyst has not been known. That is, C
The u-Zn catalyst has the property of being easily oxidized (copper is oxidized and deteriorated), and is rapidly oxidized in the presence of oxygen to deteriorate its catalytic activity. Can not. In contrast, this Cu-
When a Zn catalyst is used in the presence of methanol, methanol is more easily oxidized than copper due to a difference in oxidation free energy, so that the catalyst itself does not oxidize and works effectively as a catalyst that promotes the above two reactions. be able to.

As described above, by using the Cu—Zn catalyst, both the steam reforming reaction and the oxidation reaction of methanol can be promoted by a single catalyst, and the structure of the reformer can be simplified. Is obtained, but Cu-Z
By promoting the oxidation reaction of methanol using the n catalyst, it is possible to further obtain an effect that the concentration of carbon monoxide in the hydrogen-rich fuel gas generated in the reformer can be further reduced. Here, carbon monoxide generated in the reformer will be described. The Cu-Zn catalyst has an activity of slightly progressing the reaction of the following formula (6) in the presence of carbon dioxide and hydrogen.

CO ₂ + H ₂ → CO + H ₂ O (6)

When the steam reforming reaction of methanol or simultaneously with the oxidation reaction of methanol is promoted by the Cu—Zn catalyst, hydrogen and carbon dioxide are produced as described above. As the amount increases, the reaction of the above formula (6) proceeds slightly, and carbon monoxide is generated. As a result, the fuel gas generated in the reformer contains a predetermined amount of carbon monoxide.

As described above, the use of the Cu—Zn catalyst for reforming methanol involves the generation of a predetermined amount of carbon monoxide. When a Cu—Zn catalyst is used as a catalyst that promotes the oxidation reaction of methanol that proceeds at the same time, carbon monoxide is not generated when the oxidation reaction proceeds, so that the concentration of carbon monoxide in the fuel gas increases. Can be suppressed.
The methanol oxidation reaction promoted by the Cu—Zn catalyst is represented by the above-mentioned equation (5), and this reaction mainly comprises the reactions represented by the following equations (7) and (8). The reaction of the formula (5) proceeds as a whole.

CH ₃ OH + (１ ／) O ₂ → HCHO + H ₂ O (7) HCHO + H ₂ O → CO ₂ + 2H ₂ (8)

As shown in equations (7) and (8), C
The oxidation reaction of methanol promoted by the u-Zn catalyst mainly passes through a reaction route that does not generate carbon monoxide. On the other hand, the oxidation reaction promoted by the above-mentioned conventionally known oxidation catalyst, for example, a platinum catalyst is mainly
The reaction consists of the following equations (9) and (10). Since the reaction of equation (5) proceeds as a whole, carbon monoxide is generated during the reaction. Therefore, when the oxidation reaction of methanol is promoted using a conventionally known oxidation catalyst such as a platinum catalyst, a part of the carbon monoxide thus generated is converted into a fuel gas generated in the reformer. It remains in the fuel gas and further raises the concentration of carbon monoxide in the fuel gas.

CH ₃ OH → CO + 2H ₂ (9) CO + (１ ／) O ₂ → CO ₂ (10)

When both the steam reforming reaction and the oxidation reaction of methanol are promoted by using a Cu—Zn catalyst as in the above-described embodiment, the oxidation reaction is carried out by a reaction path that does not generate carbon monoxide. To promote the oxidation reaction of methanol using a conventionally known oxidation catalyst such as platinum,
As compared with the case where the steam reforming reaction is promoted by using the Cu-Zn catalyst, the concentration of carbon monoxide in the generated fuel gas can be made much lower. When a conventionally known oxidation catalyst such as platinum is provided in a reformer, and a steam reforming reaction of methanol is advanced by a Cu-Zn catalyst and an oxidation reaction of methanol is advanced by the oxidation catalyst, usually, 1. 5 to 2% or more of carbon monoxide remains in the fuel gas. On the other hand, when the steam reforming reaction and the oxidation reaction of methanol are advanced using only the Cu—Zn catalyst, the concentration of carbon monoxide remaining in the fuel gas is reduced to 0.1.
It can be suppressed to about 5%.

When a fuel gas containing residual carbon monoxide is supplied to the fuel cell, the carbon monoxide is adsorbed on the platinum-containing catalyst layer provided on the electrolyte membrane, and inhibits the progress of the electrochemical reaction. I will. In the fuel cell device of the above-described embodiment, the CO reduction unit is provided downstream of the reformer to reduce the concentration of carbon monoxide in the fuel gas supplied to the fuel cell.
A process required for a CO reduction unit by promoting a methanol oxidation reaction and a steam reforming reaction by using a u-Zn catalyst and reducing a concentration of carbon monoxide in a fuel gas generated in a reformer. The amount (the amount of carbon monoxide to be oxidized in the CO reduction unit) is reduced. Therefore, even if the CO reduction unit is reduced in size, a fuel gas having a sufficiently low carbon monoxide concentration can be supplied to the fuel cell. Incidentally, if the concentration of carbon monoxide in the fuel gas generated in the reformer is sufficiently low,
It is good also as not providing a CO reduction part. in this way,
By promoting both the steam reforming reaction of methanol and the oxidation reaction of methanol by using a Cu-Zn catalyst, the concentration of carbon monoxide in the fuel gas generated in the reformer can be lowered, and this reforming can be performed. The entire fuel cell device including the porcelain can be made compact.

In the Cu-Zn catalyst of the above-described embodiment, copper oxide (CuO) and zinc oxide (ZnO) were used as materials for producing this catalyst, but when these were coprecipitated, other substances were used. May be further added. For example, when producing a Cu-Zn catalyst by coprecipitating copper oxide and zinc oxide, alumina may be added in an amount of about 2 to 5%. With such a configuration, the heat resistance of the Cu-Zn catalyst is reduced. It is possible to improve the dispersion state between copper and zinc oxide forming the catalyst.

In the above description, Cu-Zn made of copper oxide and zinc oxide is used as a catalyst for promoting both the steam reforming reaction of methanol and the oxidation reaction of methanol.
Although an n catalyst was used, even when a copper-based catalyst other than Cu-Zn was used, the steam reforming reaction and the oxidation reaction of methanol were promoted, and the effect that a fuel gas having a low carbon monoxide concentration could be generated was obtained. Obtainable. For example, even if copper oxide and chromium oxide (Cr ₂ O ₃ ) are used as materials, copper oxide and silicon oxide (SiO ₂ ) are used as materials, or copper oxide and another metal oxide are used as materials, A catalyst capable of promoting both of the above-described reactions can be obtained. At this time, as a method for producing these copper-based catalysts, in addition to the coprecipitation method described above, a production method depending on the material to be used, such as an impregnation method, a kneading method, or an ion exchange method, may be used.

Although the embodiments of the present invention have been described above,
The present invention is not limited to such embodiments at all, and it goes without saying that the present invention can be implemented in various modes without departing from the gist of the present invention.

[Brief description of the drawings]

FIG. 1 shows a fuel cell device 2 according to a preferred embodiment of the present invention.
FIG. 2 is a block diagram schematically illustrating a configuration of a zero.

FIG. 2 is a schematic cross-sectional view illustrating a configuration of a single cell 48 included in the fuel cell 40.

FIG. 3 is an explanatory diagram schematically showing a configuration of a reformer 34.

FIG. 4 is an explanatory view schematically showing a cross section of a honeycomb constituting the reformer.

FIG. 5 is an explanatory diagram showing internal temperature distribution states in a reformer 34 and a conventionally known reformer.

FIG. 6 is an explanatory diagram showing a state of a honeycomb cross section in a modification of the first embodiment.

FIG. 7 is an explanatory diagram schematically showing a configuration of a reformer which is another modification of the first embodiment.

FIG. 8 is an explanatory diagram schematically showing a configuration of a reformer 90 of a second embodiment.

9A is a schematic cross-sectional view showing a part of a cross section of a honeycomb constituting a reaction section 92, and FIG. 9B is a schematic view showing a state where a part of the surface of the honeycomb is further enlarged.

FIG. 10 is an explanatory diagram showing internal temperature distribution states in a reformer 90 and a conventionally known reformer.

FIG. 11 is an explanatory diagram schematically showing a configuration of a reformer 100 according to a third embodiment.

FIG. 12 is an explanatory diagram showing internal temperature distribution states in a reformer 100 and a conventionally known reformer.

FIG. 13 is an explanatory diagram schematically showing a configuration of a reformer 110 according to a fourth embodiment.

FIG. 14 is a flowchart illustrating an air mixing amount control processing routine executed in the fuel cell device including the reformer 110.

FIG. 15 is an explanatory diagram schematically showing a configuration of a reformer 110A which is a modification of the fourth embodiment.

FIG. 16 is an explanatory diagram showing internal temperature distribution states in a reformer 110A and a conventionally known reformer.

FIG. 17 is an explanatory diagram schematically showing a configuration of a reformer 120 according to a fifth embodiment.

FIG. 18 is a flowchart illustrating a gas inlet switching process routine executed in the fuel cell 20.

FIG. 19 is an explanatory diagram showing internal temperature distribution states in a reformer 120 and a conventionally known reformer.

FIG. 20 is an explanatory diagram schematically showing a configuration of a reformer 130 of a sixth embodiment and members connected to the reformer 130.

FIG. 21 is an explanatory diagram showing internal temperature distribution states in a reformer 130 and a conventionally known reformer.

FIG. 22 is an explanatory diagram schematically showing a configuration of a reformer 140 according to a seventh embodiment.

FIG. 23 is an explanatory diagram showing internal temperature distribution states in a reformer 140 and a conventionally known reformer.

FIG. 24 is an explanatory diagram schematically showing a configuration of a reformer 140A which is a modification of the seventh embodiment.

FIG. 25 is a schematic sectional view illustrating a configuration of a reformer 150 according to an eighth embodiment.

FIG. 26 is an explanatory diagram showing internal temperature distribution states in a reformer 150 and a conventionally known reformer.

FIG. 27 is a schematic sectional view illustrating a configuration of a reformer 160 according to a ninth embodiment.

FIG. 28 is an explanatory diagram showing internal temperature distribution states in a reformer 160 and a conventionally known reformer.

FIG. 29 is an explanatory diagram schematically showing a configuration of a reformer 160A as a modification of the ninth embodiment.

FIG. 30 is a schematic sectional view illustrating a configuration of a reformer 170 according to a tenth embodiment.

FIG. 31 is an explanatory diagram showing internal temperature distribution states in a reformer 170 and a conventionally known reformer.

FIG. 32 is an explanatory diagram schematically showing a configuration of a reformer 180 according to an eleventh embodiment.

FIG. 33 is an explanatory diagram showing internal temperature distribution states in the reformer 180 and a conventionally known reformer.

FIG. 34 is an explanatory diagram schematically showing a configuration of a reformer 190 according to a twelfth embodiment.

FIG. 35 is an explanatory diagram showing internal temperature distribution states in a reformer 190 and a conventionally known reformer.

FIG. 36 is a reformer 190A as a modification of the twelfth embodiment.
FIG. 3 is an explanatory diagram schematically showing the configuration of FIG.

FIG. 37 is a reformer 190B as a modification of the twelfth embodiment.
FIG. 3 is an explanatory diagram schematically showing the configuration of FIG.

FIG. 38 is an explanatory diagram showing a state of a temperature distribution inside a conventional fuel reformer.

[Explanation of symbols]

 Reference Signs List 20 fuel cell device 22 methanol tank 24 water tank 26 burner 28 compressor 28a turbine 28b compressor 28c shaft 29 air introduction path 32 evaporator 34, 34A reformer 36 CO reduction unit 38 Blower 39 Air supply path 39A, 39B Air branch path 40 Fuel cell 41 Electrolyte membrane 42 Cathode 43 Anode 44, 45 Separator 44P Fuel gas flow path 45P Oxidation gas flow path 48 Single cell 50 control unit 52 input / output port 54 CPU 56 ROM 58 RAM 60 methanol flow path 61 methanol branch path 62 water supply path 63 first fuel supply path 64 second fuel supply path 65 second 3 fuel supply path 66 ... fourth fuel supply path 67 ... fuel discharge path 68 ... oxidizing gas supply path 69 ... oxidizing exhaust gas path 69A 69B: oxidizing exhaust gas branch 70: first pump 71: second pump 72: third pump 73: first temperature sensor 74: second temperature sensor 80: first reaction section 81: second reaction section 82, 83 ... stainless steel Plate 90 Reformer 92 Reactor 94 Stainless steel plate 96 Catalyst layer 100 Reformer 101 First reactor 102 Second reactor 110 Reformer 110A Reformers 111, 111A, 111B ... Reaction parts 112, 112A, 112B ... Mass flow controllers 113, 113A, 113B ... Mass flow controllers 114 ... Oxygen concentration sensors 115, 115A, 115B ... Second air supply path 117 ... Temperature sensors 120 ... Reformers 121 ... Reaction parts 122 temperature sensor 123 temperature sensor 124 first supply branch 125 second supply branch 126 first discharge branch 27 second discharge branch passage 128, 129, 128A, 129A solenoid valve 130 reformer 132 pressure regulator 134 injection nozzle 136 filter 140, 140A reformer 141, 141A reaction unit 142, 142A Outlet 143 End member 144 Rotating mechanism 150 Reformer 151 Reactor 152 Reactor 160, 160 A Reformer 161 Inner part 162 Outer part 163 Reactor 170 Reformer 171, 172: reaction section 171, 172: reaction section 173, 174: temperature sensor 175: exhaust gas introduction section 176 ... combustion exhaust gas path 177 ... mass flow controller 180 ... reformer 181, reaction section 182 ... raw fuel branch path 183 ... raw fuel Roads 184, 185: Mass flow controller 186: Temperature sensor 187: Injection nozzle 190, 190A 190B ... reformer 191, 192, 193 ... reaction part 191A, 193A ... reaction part 191B, 193B ... reaction part 194, 195 ... air branch path 196, 197 ... mass flow controller 196A, 196B ... mass flow controller 198, 199 ... Temperature sensor

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masayoshi Taki 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Co., Ltd. (72) Inventor Katsuhiko 1 Toyota Motor Town Toyota City, Aichi Prefecture Toyota Motor Corporation ( 72) Inventor Yoshimasa Negishi 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation

Claims (26)

[Claims] 1. A reaction involving an endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat and oxidizing the hydrocarbons, A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon, water vapor and oxygen to the section; and a hydrogen-rich gas produced as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section. A fuel gas discharge means for discharging a fuel gas from the catalyst section; and, in the catalyst section, heat generated by the oxidation reaction occurring in a portion on the side where the raw fuel gas is supplied is sufficiently transferred to the downstream side. As before Raw fuel reformer and a gas flow rate adjusting means fuel gas to increase the flow rate of the raw fuel gas in the portion of the side to be introduced. 2. The gas flow rate adjusting means has a total cross-section of a flow path through which the raw fuel gas flows, on the side of the catalyst section where the raw fuel gas is supplied, than on the side where the fuel gas is discharged. 2. The fuel reformer according to claim 1, wherein the area is reduced. 3. A reaction involving an endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat and oxidizing the hydrocarbon, A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon, water vapor and oxygen to the section; and a hydrogen-rich gas produced as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section. A fuel gas discharging means for discharging a fuel gas from the catalyst section, wherein the catalyst in the catalyst section is held on a catalyst carrier made of a material having relatively high thermal conductivity. 4. The fuel reformer according to claim 1, wherein the hydrocarbon is methanol, and the catalyst that promotes the steam reforming reaction and the oxidation reaction is a single copper. A fuel reformer that is a system catalyst. 5. A reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat, the reaction involving heat generation, and A fuel reforming apparatus that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and a catalyst that promotes the oxidation reaction. A raw fuel gas supply unit for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit; and an oxidizing gas supply for supplying an oxidizing gas containing oxygen to the catalyst unit Means, a fuel gas discharging means for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section from the catalyst section, and introducing the oxidizing gas in the catalyst section. Is On the side, a fuel reformer and a suppressing oxidation suppression means the progress of the oxidation reaction. 6. The fuel reformer according to claim 5, wherein the oxidation reaction suppressing means is configured such that, in the catalyst section, a side on which the oxidizing gas is introduced is a side on which the fuel gas is discharged. A fuel reformer formed so that the amount of the catalyst that promotes the oxidation reaction is smaller than that of the catalyst. 7. The fuel reformer according to claim 6, wherein the catalyst that promotes the steam reforming reaction and the catalyst that promotes the oxidation reaction are the same catalyst, and the oxidation reaction suppressing means includes: A fuel reformer formed so that the amount of the catalyst is smaller on the side where the oxidizing gas is introduced than on the side where the fuel gas is discharged. 8. A reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat, which is an oxidation reaction for oxidizing the hydrocarbon, A fuel reforming apparatus that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and a catalyst that promotes the oxidation reaction. A raw fuel gas supply unit for supplying a raw fuel gas containing the hydrocarbon and water vapor to the catalyst unit; and an oxidizing gas supply for supplying an oxidizing gas containing oxygen to the catalyst unit Means, fuel gas discharge means for discharging the hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section from the catalyst section, and progress of the reaction proceeding in the catalyst section. Check the condition The oxidizing gas supply means, while maintaining a desired amount of oxygen per unit time supplied to the catalyst unit, the progress state of the reaction detected by the reaction state detection means A fuel reforming apparatus further comprising an oxygen concentration adjusting means for controlling an oxygen concentration in the oxidizing gas supplied to the catalyst section based on the above. 9. The fuel reforming apparatus according to claim 8, wherein the catalyst unit includes a plurality of reaction units including the catalyst, and the oxidizing gas supply unit controls each of the plurality of reaction units. A fuel reformer for supplying the oxidizing gas. 10. The fuel reformer according to claim 5, wherein the hydrocarbon is methanol, and the catalyst that promotes the steam reforming reaction and the catalyst that promotes the oxidation reaction are the same. A fuel reformer that is a copper-based catalyst. 11. A reaction involving an endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat and oxidizing the hydrocarbon, A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon, water vapor and oxygen to the section; and a hydrogen-rich gas produced as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section. A fuel gas discharge unit for discharging a fuel gas from the catalyst unit; a part of the catalyst unit where the raw fuel gas is introduced from the raw fuel gas supply unit; Interchanging the site for discharging the fuel reformer and a gas supply direction changing means for reversing the flow of the gas in the catalytic section. 12. The fuel reformer according to claim 11, wherein the temperature of the catalyst section is detected at a predetermined position on the side to which the raw fuel gas is supplied from the raw fuel gas supply means. A gas supply direction changing unit, based on a detection result of the end temperature detection unit, wherein the raw fuel gas is introduced from the raw fuel gas supply unit, and a fuel gas discharge unit. A fuel reformer for exchanging a part for discharging the fuel gas. 13. A reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat, which is an reaction involving heat generation, A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, wherein particles including a catalyst that promotes the steam reforming reaction and the oxidation reaction are enclosed therein. A raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon, water vapor, and oxygen to the catalyst unit; and a steam reforming reaction that proceeds in the catalyst unit. A fuel reformer comprising: a fuel gas discharging unit configured to discharge a hydrogen-rich fuel gas generated as a result of the oxidation reaction from the catalyst unit; and a catalyst stirring unit configured to stir particles including the catalyst in the catalyst unit. 14. The fuel reforming apparatus according to claim 13, wherein the catalyst stirring means is provided in the raw fuel gas supply means, and contains at least one of the hydrocarbon, steam and oxygen. A fuel reformer that sprays a gas to be injected into the catalyst unit and agitates particles including the catalyst in the catalyst unit. 15. A reaction involving an endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat and oxidizing the hydrocarbon, A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply unit that supplies a raw fuel gas containing the hydrocarbon and water vapor to the unit; an oxidizing gas supply unit that supplies an oxidizing gas containing oxygen to the catalyst unit; A fuel gas discharging means for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section from the catalyst section; and The portion where the scan is supplied, the fuel reformer and a feed point changing means for temporally changing. 16. A reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat, oxidizing the hydrocarbon. A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply unit that supplies a raw fuel gas containing the hydrocarbon and water vapor to the unit; an oxidizing gas supply unit that supplies an oxidizing gas containing oxygen to the catalyst unit; A fuel gas discharging means for discharging a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section from the catalyst section; Offering A supply side that is, the fuel gas adjacent the discharge side to be discharged, the fuel reformer and a soaking means to perform heat exchange between the discharge side and the supply side. 17. The fuel reforming apparatus according to claim 16, wherein each of the catalyst units includes the catalyst therein, and the supply side and the discharge side of each of the catalyst units are opposite to each other. A fuel reformer comprising: at least one reaction unit, wherein the two or more reaction units are provided adjacent to the supply side of one reaction unit and the discharge side of the other supply unit. 18. The fuel cell according to claim 16, wherein the catalyst portion has a turn-back portion in the flow path of the raw fuel gas formed therein, and has an inlet and an outlet of the flow passage adjacent to each other.
The fuel reformer according to any one of the preceding claims. 19. A reaction involving an endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat by oxidizing the hydrocarbon, A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply unit that supplies a raw fuel gas containing the hydrocarbon and water vapor to the unit; an oxidizing gas supply unit that supplies an oxidizing gas containing oxygen to the catalyst unit; A fuel gas discharging unit configured to discharge a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction progressing in the catalyst unit from the catalyst unit; Element A predetermined fluid conveying Oite resulting heat, the fuel reformer and a heating means for the oxidizing gas to heat the portion other than the side to be supplied. 20. The heating means for heating a portion other than the side to which the oxidizing gas is supplied by a high-temperature gas discharged from a predetermined member constituting a system including the fuel reformer. Fuel reformer. 21. A reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat by oxidizing the hydrocarbon. A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply unit that supplies a raw fuel gas containing the hydrocarbon and water vapor to the unit; an oxidizing gas supply unit that supplies an oxidizing gas containing oxygen to the catalyst unit; Fuel gas discharging means for discharging, from the catalyst unit, a hydrogen-rich fuel gas generated as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst unit; and a liquid comprising at least one of the hydrocarbon and water. A fuel reforming apparatus comprising an end cooling unit that the raw fuel gas and the oxidizing gas is sprayed to the portion of the side to be supplied. 22. The fuel reformer according to claim 11, wherein the hydrocarbon is methanol, and the catalyst that promotes the steam reforming reaction and the oxidation reaction is a single copper. A fuel reformer that is a system catalyst. 23. A reaction involving endotherm, a steam reforming reaction for generating hydrogen from hydrocarbons and steam, and an oxidation reaction for generating heat, the reaction involving heat generation, and A fuel reforming apparatus that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, a first reaction unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; And a second reaction unit having a catalyst for promoting the steam reforming reaction; and a raw fuel gas supply for supplying a raw fuel gas containing the hydrocarbon and steam to the catalyst unit. Means, an oxidizing gas supply means for supplying an oxidizing gas containing oxygen to the first reaction section, and a hydrogen-rich gas produced as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section. Fuel gas is supplied to the catalyst unit. And a fuel gas discharging means for discharging the fuel gas from the first reaction portion and the second reaction portion, wherein the catalyst portion has the first reaction portion and the second reaction portion adjacent to each other, and is provided between the first reaction portion and the second reaction portion. A fuel reformer that performs heat exchange at 24. The fuel reformer according to claim 23, wherein the hydrocarbon is methanol, and the catalyst provided in the first reaction section is a single copper-based catalyst. 25. A reaction that involves an endotherm, a steam reforming reaction that generates hydrogen from hydrocarbons and steam, and an oxidation reaction that is an exothermic reaction that oxidizes the hydrocarbons, A fuel reformer that utilizes heat generated by the oxidation reaction when a steam reforming reaction proceeds, and a catalyst unit including a catalyst that promotes the steam reforming reaction and the oxidation reaction; A raw fuel gas supply means for supplying a raw fuel gas containing the hydrocarbon, water vapor and oxygen to the section; and a hydrogen-rich gas produced as a result of the steam reforming reaction and the oxidation reaction proceeding in the catalyst section. Fuel gas discharging means for discharging a fuel gas from the catalyst section, wherein the catalyst promotes a reaction that does not pass through a reaction path for generating carbon monoxide as the oxidation reaction. Masquerade . 26. The fuel reformer according to claim 25, wherein the hydrocarbon is methanol, and the catalyst that promotes the steam reforming reaction and the oxidation reaction is a single copper-based catalyst. Fuel reformer.