JP4500092B2 - HYDROGEN GENERATOR, ITS OPERATION METHOD, AND FUEL CELL SYSTEM INCLUDING THE SAME - Google Patents

Description

The present invention relates to a hydrogen generation apparatus that generates hydrogen using an organic compound such as methane, city gas, propane, gasoline, and alcohol, an operating method thereof , and a fuel cell system that generates power using hydrogen as fuel.

  2. Description of the Related Art Conventionally, a fuel cell cogeneration system (hereinafter referred to as a fuel cell system) with high power generation efficiency and overall efficiency has attracted attention as a distributed power generation apparatus that generates power by effectively using energy.

  In this fuel cell system, various types of fuel cells are used. For example, as a fuel cell that is already in practical use, there is a phosphoric acid fuel cell. Further, as a fuel cell being developed for practical use, for example, there is a solid polymer fuel cell.

  By the way, many of the fuel cells used in these fuel cell systems generate electricity using hydrogen as fuel. However, this hydrogen supply means is not currently established as an infrastructure. Therefore, in order to operate the fuel cell system and obtain a predetermined power, for example, a hydrogen generation device is installed at the installation location of the fuel cell system, and the hydrogen to be supplied to the fuel cell by the installed hydrogen generation device is used. Must be generated. Therefore, most fuel cell systems have a hydrogen generator in the fuel cell system.

  In a hydrogen generator, hydrogen to be supplied to a fuel cell is usually generated using a steam reforming method, which is one of hydrogen generation methods. In this steam reforming method, a hydrocarbon-based raw material or an alcohol-based raw material (hereinafter referred to as raw material) is mixed with water, and then the mixed raw material and water are chemically reacted at a high temperature using a predetermined reaction catalyst. This is a method for generating hydrogen. The chemical reaction used in the steam reforming method for generating hydrogen is called a steam reforming reaction. The reaction catalyst used in this steam reforming reaction is called a reforming catalyst. Here, the reforming catalyst is disposed inside a reforming section of the hydrogen generator, and a steam reforming reaction is performed in the reforming section. A high-temperature gas containing the generated hydrogen (hereinafter referred to as reformed gas) is discharged from the reforming section where the steam reforming reaction has been performed. In addition, natural gas, liquefied propane gas (LPG), naphtha, gasoline, kerosene and the like are preferably used as the hydrocarbon-based raw material used in the steam reforming method. Moreover, as an alcohol-type raw material, methanol etc. are used suitably, for example.

  The reformed gas discharged from the reforming unit of the hydrogen generator usually contains carbon monoxide as a subcomponent. Specifically, the reformed gas contains hydrogen as a main component and contains about 10 to 15% of carbon monoxide as a subcomponent. Therefore, in general, the hydrogen generator is provided with a shift section having a predetermined reaction catalyst in addition to the reforming section described above, and in this shift section, carbon monoxide and water, which are subcomponents, are subjected to a predetermined temperature condition. In this way, hydrogen is generated by a chemical reaction in order to increase the hydrogen concentration of the reformed gas. The chemical reaction that generates hydrogen from carbon monoxide and water in this metamorphic part is called a water gas shift reaction. The reaction catalyst used in this water gas shift reaction is called a shift catalyst. The carbon monoxide concentration in the reformed gas is reduced to about 0.5% by the water gas shift reaction of carbon monoxide and water in this metamorphic part.

  However, even if the carbon monoxide contained in the reformed gas is reduced to about 0.5% in the reforming portion as described above, the electrode catalyst disposed inside the fuel cell remains in a small amount. Poisoned by carbon. This becomes a particularly significant problem when a polymer electrolyte fuel cell is used as the fuel cell. Therefore, when supplying the reformed gas to a fuel cell that is easily poisoned such as a polymer electrolyte fuel cell, the carbon monoxide concentration of the reformed gas supplied to the polymer electrolyte fuel cell or the like is 100 ppm or less, Preferably, it is necessary to reduce it to 10 ppm or less. Therefore, in general, the hydrogen generator is further provided with a purification unit having a predetermined reaction catalyst in addition to the above-described reforming unit and shift unit, and carbon monoxide remaining in the purification unit and oxygen in the air are removed. Carbon dioxide is generated by a chemical reaction, thereby reducing carbon monoxide remaining in the reformed gas. The chemical reaction that generates carbon dioxide from carbon monoxide and oxygen in this purification section is called a selective oxidation reaction. The reaction catalyst used in this selective oxidation reaction is called a purification catalyst. By the selective oxidation reaction of carbon monoxide and oxygen in the purification unit, the carbon monoxide concentration in the reformed gas is reduced to 100 ppm or less.

  A high quality reformed gas that can be supplied to a polymer electrolyte fuel cell or the like that is sufficiently reduced in carbon monoxide and rich in hydrogen is discharged from the purification unit of the hydrogen generator, and then the predetermined reformed gas piping Is supplied to the fuel cell. In a fuel cell, power is generated by using hydrogen contained in the reformed gas supplied from the hydrogen generator as a fuel.

  By the way, in the fuel cell system, the supply amount of the reformed gas from the hydrogen generator to the fuel cell is generally adjusted by adjusting the supply amount of the raw material to the reforming section of the hydrogen generator. Specifically, when the amount of raw material supplied to the reforming unit is large, the amount of reformed gas supplied from the hydrogen generator to the fuel cell is large. On the contrary, when the supply amount of the raw material to the reforming unit is small, the supply amount of the reformed gas from the hydrogen generator to the fuel cell is small. Therefore, for example, when the amount of power generated by the fuel cell is small, that is, when the amount of reformed gas supplied from the hydrogen generator to the fuel cell is small, the amount of raw material supplied to the reforming section of the hydrogen generator is low. It is said that. At this time, since the supply amount of the raw material to the reforming section is low, the supply amount of the reformed gas from the reforming section to the shift section is also low. When the amount of reformed gas supplied to the shift section is low, the amount of heating of the shift catalyst by the reformed gas is small, and the amount of heat generated by the water gas shift reaction in the shift catalyst is small. Since the rate of heat release from the hydrogen generator increases, the temperature of the shift catalyst decreases.

  When the temperature of the shift catalyst in the shift section is lowered, carbon monoxide contained in the reformed gas may not be sufficiently reduced in the shift section. This is because the temperature of the shift catalyst is lowered and the water gas shift reaction in the shift section may not proceed with good yield. In this case, since the carbon monoxide concentration in the reformed gas cannot be sufficiently reduced in the subsequent purification section, the quality of the reformed gas supplied to the fuel cell is deteriorated. Therefore, in order to stably supply a high-quality reformed gas having a sufficiently reduced carbon monoxide concentration from the hydrogen generator to the fuel cell, this is the first carbon monoxide reduction unit in the hydrogen generator. It is necessary to sufficiently reduce the carbon monoxide contained in the reformed gas at the metamorphic part. For this purpose, the temperature of the shift catalyst disposed in the shift section needs to be maintained at a predetermined temperature for allowing the above-described water gas shift reaction to proceed with high yield.

Therefore, carbon monoxide or hydrogen and air in the reformed gas generated by using a noble metal catalyst as the shift catalyst and providing an air supply section upstream of the shift section in the hydrogen generator and supplying air from the air supply section. A hydrogen generator that maintains the temperature of the shift catalyst at a predetermined temperature using heat of reaction with oxygen therein has been proposed (see, for example, Patent Document 1, hereinafter referred to as a first conventional example). There has also been proposed a hydrogen generating apparatus in which a predetermined temperature adjusting means is provided in a shift section in a hydrogen generator, and the temperature of the shift section is adjusted by the temperature adjusting means, thereby maintaining the temperature of the shift catalyst at a predetermined temperature. (For example, refer to Patent Document 2. Hereinafter, referred to as a second conventional example).
JP 2000-178007 A JP 2000-185901 A

  According to the first and second conventional examples described above, the temperature of the shift catalyst disposed in the shift section is always maintained at a predetermined temperature for causing the water gas shift reaction to proceed. Therefore, the carbon monoxide concentration in the reformed gas is sufficiently reduced in the shift section of the hydrogen generator even when the amount of raw material supplied to the reforming section is small.

  However, in the first conventional example in which air is supplied from the air supply unit to the shift unit to maintain the temperature of the shift catalyst at a predetermined temperature, the air supply unit is used to maintain the temperature of the shift catalyst at a predetermined temperature. Since air is constantly supplied from the gas to the transformation section, hydrogen contained in the reformed gas supplied from the reforming section reacts with oxygen contained in the air supplied from the air supply section, so that hydrogen is wasted. The hydrogen generation efficiency of the hydrogen generator decreases.

  Further, in the second conventional example in which the temperature adjusting means is provided in the shift portion and the temperature of the shift catalyst is maintained at a predetermined temperature by the temperature adjusting means, parts for configuring the temperature adjusting means are further required. For this reason, the manufacturing cost of the hydrogen generator increases. In this conventional example, the control for temperature adjustment is complicated.

  Furthermore, the optimum temperature of the shift catalyst for allowing the water gas shift reaction to proceed with good yield varies greatly depending on the amount of reformed gas introduced into the shift section, that is, the amount of raw material supplied to the reformer. To do. Specifically, when the change in the amount of reformed gas supplied to the shift section is small, the optimal temperature of the shift catalyst is substantially constant. However, when the supply amount of the reformed gas to the shift section is greatly changed, the optimum temperature of the shift catalyst changes greatly. Therefore, when the supply amount of the raw material to the reforming section is greatly increased as the amount of power generated by the fuel cell is increased, the first and second conventional examples in which the temperature of the shift catalyst is maintained at a predetermined temperature. Then, in some cases, carbon monoxide contained in the reformed gas cannot be sufficiently or hardly reduced in the metamorphic part.

The present invention has been made to solve the above-described problems, and is a high-quality reformed gas that is sufficiently reduced in carbon monoxide and rich in hydrogen in response to the increase or decrease in the amount of power generated by the fuel cell. It aims efficiently and inexpensively hydrogen generating apparatus and method operating capable of generating, as well as to provide a fuel cell system including the same a.

In order to solve the above-described problem, a hydrogen generator according to the present invention includes a reforming unit that generates a reformed gas containing hydrogen by supplying a raw material containing an organic compound composed of at least carbon and hydrogen and water. A heating unit that heats the reforming unit to a temperature necessary for generating the reformed gas, and a carbon monoxide reduction catalyst that reduces carbon monoxide contained in the reformed gas generated in the reforming unit. A hydrogen generator comprising: a carbon monoxide reduction unit; a temperature detection unit that detects at least one of the temperature of the reformed gas in the carbon monoxide reduction catalyst or the carbon monoxide reduction unit; and a control unit, The control unit compares an increase in the supply amount of the raw material supplied to the reforming unit with a detected temperature detected by the temperature detection unit and a reference temperature set according to the supply amount of the raw material. controlled, the results of the comparison on the basis of Wherein when the detected temperature is lower than the reference temperature, the without increasing the supply amount of the raw material supplied to the reforming unit, the detected temperature is Ru is increased if more than the reference temperature (claim 1 ). With such a configuration, it is possible to obtain a high quality reformed gas with a sufficiently reduced carbon monoxide concentration.

In this case, when the detected temperature is lower than the reference temperature, the control unit controls the detected temperature to be equal to or higher than the reference temperature, and when the detected temperature reaches the reference temperature or higher, the supply amount of the raw material (Claim 2 ). With such a configuration, control is performed so that the detected temperature becomes equal to or higher than the reference temperature as necessary, so that the supply of the reformed gas to the fuel cell is further stabilized.

In this case, when the detected temperature is lower than the reference temperature, the control unit increases the amount of heating in the heating unit and controls the detected temperature to be equal to or higher than the reference temperature (Claim 3 ). With this configuration, the detected temperature can be easily controlled by controlling the amount of fuel such as methane gas supplied to the heating unit when the amount of power generated by the fuel cell is increased.

In this case, the water supply unit further supplies water to the reforming unit, and the control unit supplies the reforming unit from the water supply unit when the detected temperature is lower than the reference temperature. was reduced to the water to be, the detected temperature is controlled to be more than the reference temperature (claim 4). With this configuration, the detected temperature can be easily controlled by controlling the amount of water supplied to the reforming unit when the amount of power generated by the fuel cell is increased.

In this case, the carbon monoxide reduction unit further includes an oxidant gas supply unit that supplies an oxidant gas to the inside of the carbon monoxide reduction unit, and the control unit, when the detected temperature is lower than the reference temperature, to supply the oxidant gas from the oxidant gas supply unit to the carbon reduction portion, the detected temperature is controlled to be more than the reference temperature (claim 5). With such a configuration, the detected temperature can be easily controlled by controlling the supply amount of an oxidant gas such as air supplied to the carbon monoxide reduction unit when the power generation amount of the fuel cell is increased.

In the above case, the carbon monoxide reduction catalyst is a shift catalyst that promotes a water gas shift reaction in which hydrogen and carbon dioxide are generated from carbon monoxide and water, and the carbon monoxide reduction section is configured to convert the shift catalyst. a shift converter comprising (claim 6). With this configuration, the carbon monoxide concentration in the reformed gas can be reduced without changing the conventional configuration of the hydrogen generator.

In this case, the catalyst bodies in said shift catalyst is at least a noble metal, cerium, and a metal oxide of at least one element of zirconium or aluminum (claim 7). With this configuration, the carbon monoxide concentration in the reformed gas can be efficiently reduced.

In the above case, the carbon monoxide reduction catalyst is a carbon monoxide selective oxidation catalyst for causing a selective oxidation reaction of carbon monoxide, and the carbon monoxide reduction unit includes the carbon monoxide selective oxidation catalyst. (Claim 8 ). Even with this configuration, the carbon monoxide concentration in the reformed gas can be reduced without changing the conventional configuration of the hydrogen generator.

A fuel cell system according to the present invention includes the hydrogen generator according to any one of claims 1 to 8 , and a fuel cell that generates power using hydrogen generated by the hydrogen generator and oxidant gas. And when the detected temperature detected by the temperature detection unit reaches the reference temperature or higher, the control unit increases the supply amount of the raw material to the reforming unit and the power generation amount thereof. (Claim 9 ). With such a configuration, a decrease in the output voltage of the fuel cell can be effectively prevented, and a fuel cell system with good power generation efficiency can be constructed.
In addition, the operation method of the hydrogen generator according to the present invention includes a reforming unit that supplies a raw material and water to generate a reformed gas containing hydrogen, and the reformed gas generated in the reforming unit. A carbon monoxide reduction unit having a carbon monoxide reduction catalyst for reducing carbon monoxide; and a temperature detection unit for detecting at least one of the temperature of the reformed gas in the carbon monoxide reduction catalyst or the carbon monoxide reduction unit; The increase in the supply amount of the raw material supplied to the reforming unit is set according to the detected temperature detected by the temperature detection unit and the supply amount of the raw material Is controlled based on the comparison with the reference temperature, and as a result of the comparison, when the detected temperature is lower than the reference temperature, without increasing the supply amount of the raw material supplied to the reforming unit, Increased when the detected temperature is above the reference temperature. It is (claim 10). With such a configuration, it is possible to obtain a high quality reformed gas with a sufficiently reduced carbon monoxide concentration.

The present invention is implemented by the means described above, and can efficiently generate a high quality reformed gas that is sufficiently reduced in carbon monoxide and rich in hydrogen in response to the increase or decrease in the power generation amount of the fuel cell. It is possible to provide an inexpensive hydrogen generator that can be operated, a method for operating the same , and a fuel cell system including the same.

  The best mode for carrying out the present invention will be described below with reference to the drawings.

(Embodiment 1)
FIG. 1 is a schematic diagram showing the configuration of the hydrogen generator according to Embodiment 1 of the present invention. In FIG. 1, only the configuration of the hydrogen generator in the fuel cell system to be described later is extracted and shown.

  As shown in FIG. 1, a hydrogen generator 100a according to the present embodiment includes a hydrocarbon-based raw material such as natural gas, liquefied propane gas (LPG), naphtha, gasoline, kerosene, or an alcohol-based raw material such as methanol. And a reforming unit 1 for generating hydrogen from a raw material composed of at least carbon and hydrogen and water by a steam reforming reaction, and carbon monoxide discharged together with hydrogen from the reforming unit 1 with water. A conversion section 7 for converting to hydrogen by a water gas shift reaction of the gas, a purification section 11 for converting carbon monoxide further discharged together with hydrogen from the conversion section 7 to carbon dioxide by a selective oxidation reaction with oxygen in the air, and And a control device 101 that controls the operation of the reforming unit 1, the transformation unit 7, and the purification unit 11.

  The reforming unit 1 includes a raw material supply unit 3 that supplies raw materials to the reforming unit 1. This raw material supply unit 3 is for sending a raw material containing an organic compound composed of at least carbon and hydrogen exemplified by methane, city gas, natural gas, alcohol and the like to the reforming unit 1 from the raw material supply unit 3 The raw material supply pipe 3 a is connected to a predetermined position of the reforming unit 1. For example, a booster or the like is used as the raw material supply unit 3. The reforming unit 1 includes a water supply unit 4 that supplies water necessary for the steam reforming reaction to the reforming unit 1. The water supply unit 4 is connected to a predetermined position of the reforming unit 1 through a water supply pipe 4 a for sending water from the water supply unit 4 to the reforming unit 1. On the other hand, the reforming unit 1 includes a reforming catalyst 2 for advancing a steam reforming reaction that generates hydrogen using the raw material supplied from the raw material supply unit 3 and the water supplied from the water supply unit 4. Have. The reforming catalyst 2 has a heating section 5 for heating and keeping the temperature at a temperature necessary for the steam reforming reaction to proceed. The reforming catalyst 2 and the heating unit 5 are respectively disposed at a position suitable as a reaction field for the steam reforming reaction in the reforming unit 1 and a position suitable for heating and keeping the reforming catalyst 2. ing. Furthermore, the reforming unit 1 has a temperature detection unit 6 that detects the temperature of the reformed gas containing hydrogen discharged through the reforming catalyst 2. The temperature detector 6 is disposed at a suitable position for detecting the temperature of the reformed gas discharged through the reforming catalyst 2. Here, in the present embodiment, the temperature detector 6 is disposed at a predetermined position downstream of the reforming catalyst 2. The installation location of the temperature detection unit 6 is not limited to the downstream position of the reforming catalyst 2 but is a position where the temperature of the reformed gas in the reforming unit 1 or the reforming catalyst 2 can be detected. If it exists, it may be provided at any location. From this reforming section 1, a reformed gas pipe 1 a for introducing the reformed gas discharged from the reforming section 1 into the shift section 7 extends to the shift section 7.

  The metamorphic unit 7 includes a water supply unit 9 that supplies water necessary for the water gas shift reaction to the metamorphic unit 7. The water supply unit 9 is connected to a predetermined position of the shift unit 7 through a water supply pipe 9 a for sending water from the water supply unit 9 to the shift unit 7. In addition, the shift unit 7 includes an air supply unit 15 that supplies air (oxygen in the air) necessary for controlling the temperature of the shift catalyst 8 described later to the shift unit 7. The air supply unit 15 is connected to a predetermined position of the transformation unit 7 via an air supply pipe 15 a for sending air from the air supply unit 15 to the transformation unit 7. On the other hand, the shift unit 7 uses hydrogen monoxide contained in the reformed gas introduced from the reforming unit 1 through the reformed gas pipe 1 a and water supplied from the water supply unit 9. And a shift catalyst 8 for advancing a water gas shift reaction that reduces carbon monoxide in the reformed gas. In this embodiment, the shift catalyst 8 is a cordierite honeycomb coated with Ce oxide supporting Pt. The shift catalyst 8 is disposed at a position suitable as a reaction field for the water gas shift reaction in the shift section 7. Further, the shift unit 7 includes a temperature detection unit 10 that detects the temperature of the reformed gas with improved hydrogen content discharged through the shift catalyst 8. The temperature detection means 10 is disposed at a suitable position for detecting the temperature of the reformed gas discharged through the shift catalyst 8. Here, in the present embodiment, the temperature detector 10 is disposed at a predetermined position downstream of the shift catalyst 8. The installation location of the temperature detection unit 10 is not limited to the downstream position of the shift catalyst 8, and can be any position where the temperature of the reformed gas in the shift unit 7 or the shift catalyst 8 can be detected. You may provide in any location. Then, from a predetermined position of the shifter 7, a reformed gas pipe 7 a for introducing the reformed gas having an improved hydrogen content discharged from the shifter 7 into the purifier 11 is supplied to the purifier 11. It extends.

  On the other hand, the purification unit 11 includes an air supply unit 13 that supplies air (oxygen in the air) necessary for the selective oxidation reaction to the purification unit 11. The air supply unit 13 is connected to a predetermined position of the purification unit 11 via an air supply pipe 13 a for sending air from the air supply unit 13 to the purification unit 11. In addition, the purifying unit 11 includes carbon monoxide contained in the reformed gas in order to further reduce carbon monoxide contained in the reformed gas introduced through the reformed gas pipe 7a. And a purifying catalyst 12 for advancing a selective oxidation reaction for generating carbon dioxide from oxygen supplied from the air supply unit 13. In the present embodiment, as the purification catalyst 12, a cordierite honeycomb coated with alumina supporting Pt and Ru is used. The purification catalyst 12 is disposed at a position suitable as a reaction field for the selective oxidation reaction in the purification unit 11. Further, the purification unit 11 has a temperature detection unit 14 that detects the temperature of the reformed gas whose hydrogen content discharged through the purification catalyst 12 is further improved. The temperature detector 14 is disposed at a suitable position for detecting the temperature of the reformed gas discharged through the purification catalyst 12. Here, in the present embodiment, the temperature detector 14 is disposed at a predetermined position downstream of the purification catalyst 12. In addition, the installation location of this temperature detection part 14 is not limited to the downstream position of the purification catalyst 12, but if it is the position which can detect the temperature of the reformed gas in the purification part 11, or the purification catalyst 12, You may provide in any location. From a predetermined position of the purifying unit 11, a reformed gas pipe 11a for discharging the reformed gas whose hydrogen content is further improved by the selective oxidation reaction discharged from the purifying unit 11 extends. . The reformed gas pipe 11a is connected to a fuel cell not shown in FIG. The reformed gas is supplied to the fuel cell through the reformed gas pipe 11a, and is used for power generation in the fuel cell. In addition, when it is not necessary to reduce the carbon monoxide concentration in the reformed gas to, for example, 100 ppm or less, it is not necessary to provide the purification unit 11.

  Extending from the control device 101 to the reforming unit 1, the shift unit 7 and the purification unit 11 constituting the hydrogen generator 100 a described above, and thus to the respective components constituting the reforming unit 1, the shift unit 7 and the purification unit 11. The outgoing control wiring is connected.

  Next, a basic operation for generating hydrogen in the hydrogen generator according to the present embodiment will be described. Here, the case where methane gas is used as the hydrocarbon-based raw material will be described.

  When hydrogen is generated by operating the hydrogen generator 100a, methane gas as a raw material is supplied from the raw material supply unit 3 to the reforming unit 1, and water is supplied from the water supply unit 4. At this time, by operating the heating unit 5, the temperature of the reforming catalyst 2 is heated to a predetermined temperature which is necessary and sufficient to cause the steam reforming reaction to proceed. In the present embodiment, by operating the heating unit 5, the temperature of the reforming catalyst 2 is controlled so that the temperature detected by the temperature detection unit 6 is 650 ° C. Then, in the reforming unit 1, a steam reforming reaction between methane gas and water proceeds, and hydrogen is generated by the steam reforming reaction. However, in the steam reforming reaction between methane gas and water, about 10 to 15% of carbon monoxide and a small amount of carbon dioxide are generated in addition to mainly generating hydrogen. That is, in the reforming unit 1, a reformed gas containing hydrogen as a main product and containing carbon monoxide and carbon dioxide as byproducts is generated. Here, since carbon monoxide poisons the electrode catalyst disposed inside the fuel cell, it must be reduced to a predetermined amount or less. Therefore, the reformed gas discharged from the reforming unit 1 is introduced into the shift unit 7 through the reformed gas pipe 1a, and the carbon monoxide concentration in the reformed gas is reduced in the shift unit 7.

  When the reformed gas flows through the reformed gas pipe 1a and is introduced into the shift section 7, the shift section 7 reacts with carbon monoxide and water to generate hydrogen and carbon dioxide, thereby generating a water gas shift reaction. The carbon monoxide concentration in the reformed gas is reduced. At this time, water necessary for the water gas shift reaction is supplied from the water supply unit 9. In order to advance the water gas shift reaction, it is necessary to maintain the shift catalyst 8 at a predetermined temperature. This is because the shift catalyst 8 is heated by the high-temperature reformed gas introduced from the reforming section 1. It is appropriately controlled by heating the shift catalyst 8 by reaction heat generated by the water gas shift reaction or by cooling the shift catalyst 8 by water supplied from the water supply unit 9. The carbon monoxide concentration in the reformed gas is reduced to about 0.3 to 1% by the water gas shift reaction of carbon monoxide and water in the shift section 7.

  The reformed gas whose carbon monoxide concentration is reduced to about 0.3 to 1% in the shift unit 7 is introduced into the purification unit 11 through the reformed gas pipe 7a. When the carbon monoxide concentration is further reduced in the purification unit 11, a predetermined amount of air is supplied from the air supply unit 13 to the purification unit 11. Then, in the purification unit 11, a selective oxidation reaction between the carbon monoxide in the introduced reformed gas and the oxygen in the supplied air proceeds, and carbon dioxide is generated by this selective oxidation reaction. That is, since carbon monoxide contained in the reformed gas is consumed by the selective oxidation reaction, the concentration of carbon monoxide in the reformed gas is further reduced. By the selective oxidation reaction of carbon monoxide and oxygen in the purification unit 11, the carbon monoxide concentration in the reformed gas is reduced to about 100 ppm or less. Depending on the type of fuel cell provided in the fuel cell system, the carbon monoxide concentration is reduced to 10 ppm or less. The high-quality reformed gas whose carbon monoxide concentration is further reduced in the purification section 11 is supplied to a fuel cell (not shown in FIG. 1) through the reformed gas pipe 11a. In the fuel cell, the reformed gas supplied through the reformed gas pipe 11a is used to generate power.

  The operation of the reforming unit 1, the shift unit 7 and the purifying unit 11 constituting the hydrogen generator 100a described above, and the operation of each component constituting the reforming unit 1, the shift unit 7 and the purifying unit 11 are as follows. 101 is appropriately controlled.

  By the way, the optimum temperature of the shift catalyst 8 for allowing the water gas shift reaction to proceed at a high yield in the shift section 7 is supplied to the reformed section 1, that is, the reformed gas introduced into the shift section 7. It varies greatly depending on the amount of raw material supplied. For example, when the amount of reformed gas introduced into the shift section 7 is small, the optimum temperature for efficiently proceeding the water gas shift reaction of the shift catalyst 8 is a relatively low temperature. However, when the amount of reformed gas introduced into the shift section 7 is large, the optimum temperature for efficiently proceeding the water gas shift reaction of the shift catalyst 8 must be high. Accordingly, the power consumption of a load such as an electric appliance connected to a fuel cell system (not shown in FIG. 1) increases, and accordingly, the supply amount of the raw material to the reforming unit 1 is increased and supplied to the transformation unit 7. In the hydrogen generation method in which the temperature of the shift catalyst 8 is maintained at a predetermined temperature when the supply amount of reformed gas to be increased is increased, carbon monoxide contained in the reformed gas may not be sufficiently reduced in the shift section 7 There is sex. In particular, the power consumption of the load is significantly increased, and accordingly, the supply amount of the raw material to the reforming unit 1 is greatly increased and the supply amount of the reformed gas supplied to the shift unit 7 is greatly increased. In such a case, there is a high possibility that carbon monoxide contained in the reformed gas cannot be almost reduced. In this case, since the concentration of carbon monoxide contained in the reformed gas cannot be sufficiently or hardly reduced in the shift unit 7, it is impossible to supply a high-quality reformed gas to the fuel cell. Hereinafter, the characteristics of the water gas shift reaction that generates hydrogen from carbon monoxide and water will be described in detail with reference to the drawings.

  FIG. 2 is a graph showing the relationship between the shift catalyst temperature for each raw material flow rate and the carbon monoxide concentration in the reformed gas after passing through the shift section. Here, the vertical axis in FIG. 2 indicates the concentration (%) of carbon monoxide contained in the reformed gas after passing through the shift section, and the horizontal axis indicates the temperature (° C.) of the shift catalyst in the shift section. . Curve a is a raw material flow rate of 1.0 (NL / min), curve b is a raw material flow rate of 2.0 (NL / min), and curve c is a raw material flow rate of 3.0 (NL / min). Min), the curve d shows the case where the raw material flow rate is 4.0 (NL / min).

  As shown in FIG. 2, the concentration of carbon monoxide contained in the reformed gas that has undergone the water gas shift reaction in the shift unit 7 is determined by the temperature of the shift catalyst 8 and the supply amount of the raw material. For example, when the supply amount of the raw material to the reforming unit 1 is as small as 1.0 (NL / min) as shown by the curve a, even if the shift catalyst 8 is in a low temperature state (for example, 150 ° C.) Carbon monoxide is effectively reduced. On the other hand, when the supply amount of the raw material to the reforming unit 1 is as large as 4.0 (NL / min) as shown by the curve d, the oxidation catalyst 8 is in a low temperature state (for example, 170 ° C. or less), and is oxidized. Carbon is hardly reduced.

  That is, the supply amount of the raw material to the reforming unit 1 is reduced according to the decrease in the power generation amount of the fuel cell, and the reformed gas from the reforming unit 1 to the shift unit 7 is caused by the decrease in the supply amount of the raw material. Even when the temperature of the shift catalyst 8 is decreased due to a decrease in the supply amount of the catalyst, the supply amount of the raw material to the reforming unit 1 is, for example, 1.0 (NL / min) indicated by the curve a, and at that time If the temperature of the shift catalyst 8 is 150 ° C., it is possible to sufficiently reduce the carbon monoxide concentration in the reformed gas. More specifically, when the carbon monoxide concentration of the reformed gas that has undergone the water gas shift reaction in the shift unit 7 is, for example, 0.5% or less as shown by the broken line in FIG. If the supply amount is 1.0 (NL / min) shown as curve a, the requirement can be achieved when the temperature of the shift catalyst 8 is in the range of about 150 ° C. to about 180 ° C. Further, when the supply amount of the raw material to the reforming unit 1 is 2.0 (NL / min) shown as the curve b, the temperature of the shift catalyst 8 may be in the range of about 160 ° C. to about 180 ° C. . Moreover, when the supply amount of the raw material to the reforming unit 1 is 3.0 (NL / min) shown as the curve c, the temperature of the shift catalyst 8 may be in the range of about 170 ° C. to about 180 ° C. . Further, when the supply amount of the raw material to the reforming unit 1 is 4.0 (NL / min) shown as the curve d, the temperature of the shift catalyst 8 may be within the temperature range shown as the range A. However, as the amount of power generated by the fuel cell decreases, the amount of raw material supplied to the reforming unit 1 becomes, for example, 3.0 (NL / min) shown by the curve c, and accordingly, the temperature of the shift catalyst 8 becomes 180, for example. When the temperature is lower than ° C., the amount of raw material supplied to the reforming unit 1 is increased to 4.0 (NL / min) shown by the curve d in order to cope with the increase in the power generation amount of the fuel cell. Unless the temperature of the catalyst 8 quickly rises to the temperature range indicated as the range A, the concentration of carbon monoxide in the reformed gas exceeds the target value of 0.5%. Therefore, when increasing the supply amount of the raw material supplied to the reforming unit 1 of the hydrogen generator 100a in order to cope with the increase in the power generation amount of the fuel cell, the temperature of the shift catalyst 8 determines the supply amount of the raw material. It is necessary to adjust in advance within the optimum temperature range after the increase.

  Therefore, in the present embodiment, when dealing with an increase in the power generation amount of the fuel cell, the supply amount of the raw material is increased before the supply amount of the raw material supplied to the reforming unit 1 of the hydrogen generator 100a is increased. After that, the conversion catalyst 8 is heated by supplying air from the air supply unit 15 to the conversion unit 7 until reaching an optimum temperature (hereinafter referred to as a reference temperature) at which the water gas shift reaction proceeds with the highest yield. Then, after the temperature of the shift catalyst 8 reaches the reference temperature, the supply amount of the raw material to the reforming unit 1 is increased. In addition, after the temperature of the shift catalyst 8 reaches the reference temperature, the supply of air from the air supply unit 15 to the shift unit 7 is stopped. Hereinafter, an example of the operation of the hydrogen generator 100a when dealing with an increase in the power generation amount of the fuel cell will be described with reference to the drawings.

  FIG. 4 is a flowchart illustrating an example of the operation of the hydrogen generator when dealing with an increase in the amount of power generated by the fuel cell.

  Referring to FIGS. 1, 2, and 4, for example, when the load on the fuel cell is low for a long time, and therefore the power generation amount of the fuel cell is low for a long time, the hydrogen generator Since the supply amount of the raw material to the reforming section 1 of 100a is low, the temperature of the shift catalyst 8 of the shift section 7 to which the reformed gas is supplied from the reforming section 1 is lowered. At this time, the temperature of the reformed gas passing through the shift catalyst 8 is detected by the temperature detector 10 provided in the shift unit 7, and the detected temperature (hereinafter referred to as the detected temperature) is It is stored in the storage unit (step S1). For example, when the temperature detection unit 10 disposed downstream of the shift catalyst 8 in the shift unit 7 detects that the temperature of the reformed gas that has passed through the shift catalyst 8 is 170 ° C., the detection is performed. The detected temperature is stored in the storage unit of the control device 101. Since the temperature of the reformed gas detected by the temperature detector 10 approximates the temperature of the shift catalyst 8, in the present embodiment, the temperature of the shift catalyst 8 is detected by detecting the temperature of the reformed gas. It was decided to detect the temperature.

  On the other hand, when the load on the fuel cell fluctuates from a low load to a high load, the raw material to be supplied to the reforming unit 1 of the hydrogen generator 100a before increasing the power generation amount of the fuel cell to cope with the fluctuation of the load. Is supplied by the control device 101 (step S2). For example, the supply amount of the raw material to the reforming unit 1 that has been 3.0 (NL / min) is increased to 4.0 (NL / min) in order to correspond to the increase in the power generation amount of the fuel cell. It is predicted by the control device 101 that it is necessary to do this. Here, the supply amount of the raw material is predicted based on a reaction formula of power generation.

  Next, when an appropriate supply amount of the raw material to the reforming unit 1 corresponding to the increase in the power generation amount of the fuel cell is predicted by the control device 101, a reference temperature corresponding to the predicted appropriate supply amount Is set by the control device 101 (step S3). Here, for example, the storage unit of the control device 101 stores data corresponding to the graph shown in FIG. The reference temperature set by the controller 101 is the reforming temperature shown in FIG. 2 when the carbon monoxide concentration in the reformed gas after passing through the shift section 7 is, for example, 0.5% or less. The curve d in which the amount of raw material supplied to the section 1 is 4.0 (NL / min) is within the temperature range of the range A. In view of the fact that the water gas shift reaction proceeding in the shift unit 7 is an exothermic reaction, it is desirable that the reference temperature is set as the temperature of the low temperature part within the temperature range of the range A. The temperature of the low temperature part within the temperature range of the range A shown in FIG. 2 is an optimum temperature for effectively reducing the carbon monoxide concentration in the reformed gas, as is apparent from FIG. For example, as is apparent from FIG. 2, when the flow rate of the raw material to be supplied to the reforming unit 1 is predicted to be 4.0 (NL / min) shown in the curve d, carbon monoxide in the reformed gas The optimum reference temperature for reducing the temperature is 180 ° C.

  When the current detected temperature is stored in step S1 and the reference temperature is set in step S3 to correspond to the increase in the amount of power generated by the fuel cell, the detected temperature and the reference temperature are compared in the control device 101. (Step S4). Here, when it is found that the detected temperature is equal to or higher than the reference temperature (YES in step S4), the control device 101 controls the raw material supply unit 3 to increase the supply amount of the raw material to the reforming unit 1. A signal is output, whereby the supply amount of the raw material to the reforming unit 1 is increased (step S8). On the other hand, when it is found that the detected temperature is lower than the reference temperature (NO in step S4), a temperature difference between the detected temperature and the reference temperature is calculated in the control device 101 based on the comparison, and thereby the shift catalyst is converted. A temperature rise amount of 8 is calculated (step S5). For example, when the detected temperature is 170 ° C. and the reference temperature is 180 ° C., it is calculated that the temperature of the shift catalyst 8 needs to be increased by + 10 ° C.

  When the temperature increase amount of the shift catalyst 8 for the increase in the power generation amount of the fuel cell is calculated, air supply is performed until the temperature detected by the temperature detection unit 10 rises to a temperature corresponding to the temperature increase amount. Air is supplied from the part 15 to the inside of the transformation part 7 (step S6). In the present embodiment, the amount of air supplied from the air supply unit 15 to the inside of the transformation unit 7 is set to 0.5 (NL / min). As a result, in the shift catalyst 8, hydrogen and carbon monoxide in the reformed gas react with oxygen in the supplied air, and the temperature of the shift catalyst 8 rises quickly. That is, the detected temperature detected by the temperature detector 10 rises to the reference temperature.

  By supplying air from the air supply unit 15 to the inside of the shift unit 7, the temperature of the shift catalyst 8 rises, and thus the detected temperature detected by the temperature detection unit 10 reaches a reference temperature, for example, 180 ° C. Stops the supply of air from the air supply unit 15 to the shift unit 7 in order to prevent wasteful consumption of hydrogen due to the reaction with oxygen in the shift unit 7 (step S7). At this time, the temperature of the shift catalyst 8 is constantly monitored by the temperature detection unit 10, and when the temperature of the shift catalyst 8 falls below the reference temperature, air is appropriately supplied from the air supply unit 15 to the shift unit 7. Thereby, the temperature of the shift catalyst 8 is always kept at the reference temperature.

  After the detected temperature detected by the temperature detection unit 10 reaches the reference temperature, a control signal for increasing the amount of raw material supplied to the raw material supply unit 3 is output from the controller 101 to the reforming unit 1. The supply amount of the raw material is increased to the supply amount to be supplied to the reforming unit 1 in order to cope with the increase in the power generation amount of the fuel cell (step S8). For example, the supply amount of the raw material to the reforming unit 1 is increased from 3.0 (NL / min) to 4.0 (NL / min). Thereby, in the shift part 7, even when the supply amount of the raw material to the reforming part 1 is increased, carbon monoxide in the reformed gas is effectively reduced. Then, the fuel cell is supplied with a sufficient amount of reformed gas of good quality that can cope with the increase in the amount of power generation, and power generation according to the load on the fuel cell is efficiently performed. .

  The operation of the above-described hydrogen generator 100a and components thereof is appropriately controlled by the control device 101.

  Thus, by supplying air from the air supply unit 15 to the shift unit 7 as necessary so that the temperature of the shift catalyst 8 becomes the reference temperature, the shift catalyst 8 in the shift unit 7 Hydrogen and carbon monoxide in the reformed gas react with oxygen in the supplied air, and the temperature of the shift catalyst 8 quickly rises to the reference temperature due to the reaction heat generated by this reaction. Then, after it is confirmed that the detected temperature detected by the temperature detecting unit 10 is equal to the optimum reference temperature in order to cause the water gas shift reaction to proceed with good yield, the supply amount of the raw material to the reforming unit 1 is increased. Therefore, carbon monoxide in the reformed gas is effectively reduced in the shift section 7. In addition, since the supply of air from the air supply unit 15 to the shift unit 7 is performed only when the supply amount of the raw material is increased, the shift unit 7 is prevented from consuming more hydrogen than necessary. That is, the hydrogen generator 100a can efficiently generate hydrogen.

  In this embodiment, air is supplied to the shift section 7 at a rate of 0.5 (NL / min). However, this is not limited to this supply amount, and is appropriate depending on the configuration of the hydrogen generator, the catalyst type, and the like. May be set. Further, air may be supplied while the supply amount is sequentially changed according to the temperature change of the shift catalyst 8.

  In the present embodiment, 180 ° C. is set as the reference temperature as an example, but the temperature is not limited to this temperature, and the reference temperature depends on the amount of raw material supplied to the reforming unit 1 after the amount is increased. Is set as appropriate. Here, the reference temperature is preferably a temperature at which the carbon monoxide concentration in each of the curves a to d shown in FIG. 2 can be reduced most. For example, when the supply amount of the raw material is 2.0 (NL / min) shown by the curve b in FIG. 2, the reference temperature is preferably about 160 ° C., and the flow rate of the raw material is 3.0 ( NL / min), the reference temperature is preferably 170 ° C. By setting such a temperature, the carbon monoxide concentration in the reformed gas can be reduced most efficiently.

  In the present embodiment, oxygen in the air is used as the oxidizing gas used to raise the temperature of the shift catalyst 8. However, the present invention is not limited to this, and hydrogen and carbon monoxide in the reformed gas are oxidized. Any chemical species that generates oxidation heat may be used.

  In this embodiment, platinum (Pt) is used as the catalyst body in the shift catalyst 8. However, the present invention is not limited to this, and other noble metals such as palladium (Pd), nickel (Ni), rhodium (Rh), transition Metal or the like may be used.

  In this embodiment, Ce oxide is used as a support for the noble metal catalyst in the shift catalyst 8. However, the present invention is not limited to this, and Ce-Zr composite oxide or Al oxide may be mixed.

  In this embodiment, in order to detect the temperature of the shift catalyst 8, the temperature detection unit 10 is provided at the downstream position of the shift catalyst 8. However, the present invention is not limited to this, and the temperature detection unit 10 is connected to the shift catalyst 8. You may arrange | position in an upstream position. Further, the temperature detection unit 10 may be provided in the shift catalyst 8 so that the temperature of the shift catalyst 8 is directly detected. When the position of the temperature detection unit 10 is changed in this way, the same effect can be obtained by setting an optimum reference temperature at the changed position.

  Further, the characteristic curve shown in FIG. 2 may change depending on the configuration of the hydrogen generator 100a and the parameters such as the type of catalyst body of the shift catalyst 8 and the amount of catalyst. Therefore, it is desirable to set the reference temperature so as to correspond to each parameter. Thereby, the same effect as this embodiment can be obtained.

  The supply of air from the air supply unit 15 to the shift unit 7 is not only performed when the amount of raw material supplied to the reforming unit 1 is increased in accordance with the increase in the amount of power generated by the fuel cell, but also the temperature of the shift catalyst 8. May be performed in order to maintain the temperature at a predetermined temperature. Although this operation increases the amount of hydrogen consumed in the shift section 7, it is possible to increase the rate of temperature increase of the shift catalyst 8 when increasing the supply amount of the raw material.

  In the present embodiment, the supply amount of the raw material to the reforming unit 1 is 1.0 (NL / min), 2.0 (NL / min), 3.0 (NL / min), 4.0 ( The reference temperature for the flow rate increase in units of 1.0 (NL / min) is exemplified as NL / min), but even if the reference temperature is set for the flow rate increase in units of 0.1 (NL / min) Good.

(Embodiment 2)
The hydrogen generation apparatus according to the second embodiment is different from the hydrogen generation apparatus according to the first embodiment in that the control program for increasing the amount of power generation stored in the control apparatus 101 is different from that in the first embodiment. This is the same as the hardware configuration of the hydrogen generator shown in the first embodiment. The basic operation of the hydrogen generator for generating hydrogen is the same as the basic operation of the hydrogen generator shown in the first embodiment. Therefore, the description on the hardware configuration of the hydrogen generator according to the present embodiment and the basic operation of generating the hydrogen is omitted here.

  In the present embodiment, when increasing the hydrogen generation amount in the hydrogen generation device 100a in order to cope with the increase in the power generation amount of the fuel cell, the temperature detection unit 10 is controlled by the control device 101 as in the case of the first embodiment. A determination is made as to whether or not the detected temperature detected by has reached the reference temperature. When it is determined that the detected temperature detected by the temperature detection unit 10 has reached the reference temperature, the amount of raw material supplied to the reforming unit 1 is increased. However, when it is determined that the detected temperature does not reach the reference temperature, unlike the case of the first embodiment, the operation for causing the detected temperature to reach the reference temperature is not performed, and the reforming unit 1 is performed. The raw material supply is not increased.

  The operation of the hydrogen generator 100a according to the present embodiment will be described with reference to the drawings. The operation of the hydrogen generator 100a according to the present embodiment is from step S1 to step S4 in the flowchart shown in FIG. It is the same operation. Then, when the detected temperature detected by the temperature detection unit 10 in step S4 is equal to or higher than the reference temperature (YES in step S4), the operation is performed in the same manner as in the first embodiment to the reforming unit 1. The supply of raw materials is increased. However, when the detected temperature is lower than the reference temperature (NO in step S4), the operations in steps S5 to S8 shown in FIG. 4 are not performed, and the amount of raw material supplied to the reforming unit 1 is not increased.

  As described above, according to the present embodiment, the supply amount of the raw material to the reforming unit 1 is equal to or higher than the reference temperature corresponding to the supply amount of the raw material to be supplied after the detected temperature detected by the temperature detection unit 10. Since the amount is increased when it has reached, the amount is not increased when it has not reached, so it is possible to prevent a sudden increase in the concentration of carbon monoxide in the reformed gas.

(Embodiment 3)
The hydrogen generation apparatus according to the third embodiment is different from the hydrogen generation apparatus according to the first embodiment in that the control program for increasing the amount of power generation stored in the control apparatus 101 is different from that in the first embodiment. This is the same as the hardware configuration of the hydrogen generator shown in the first embodiment. The basic operation of the hydrogen generator for generating hydrogen is the same as the basic operation of the hydrogen generator shown in the first embodiment. Therefore, also here, the description on the hardware configuration of the hydrogen generator according to the present embodiment and the basic operation for generating the hydrogen is omitted.

  Also in the present embodiment, when increasing the hydrogen generation amount in the hydrogen generation device 100a in order to cope with the increase in the power generation amount of the fuel cell, the temperature detection unit 10 is controlled by the control device 101 as in the case of the first embodiment. A determination is made as to whether or not the detected temperature detected by has reached the reference temperature. When it is determined that the detected temperature detected by the temperature detection unit 10 has reached the reference temperature, the amount of raw material supplied to the reforming unit 1 is increased. Similarly to the case of the first embodiment, when it is determined that the detected temperature does not reach the reference temperature, an operation for causing the detected temperature to reach the reference temperature is performed. Thereafter, the amount of raw material supplied to the reforming unit 1 is increased. Here, in the present embodiment, when it is determined by the control device 101 that the detected temperature detected by the temperature detection unit 10 has not reached the reference temperature, the temperature of the heating unit 5 is increased to increase the temperature. The temperature of the mass part 1 is raised, and thereby the temperature of the reformed gas discharged from the reforming part 1 is raised. Then, by supplying the reformed gas whose temperature has been raised to the shift section 7, the temperature of the shift catalyst 8 disposed inside the shift section 7 is raised. When the temperature of the shift catalyst 8 rises, the temperature of the reformed gas that has passed through the shift catalyst 8 rises, so that the detected temperature detected by the temperature detector 10 also rises. That is, by this, the detected temperature detected by the temperature detection unit 10 is controlled to reach the reference temperature.

  More specifically, the supply amount of the raw material to the reforming unit 1 is increased from, for example, 1.0 (NL / min) to 2.0 (NL / min) in order to cope with an increase in the power generation amount of the fuel cell. When the temperature is detected by the temperature detector 10 is less than 160 ° C., it is possible to effectively reduce the carbon monoxide concentration in the reformed gas in the shifter 7 as is apparent from FIG. Have difficulty. Therefore, in the present embodiment, when the detected temperature detected by the temperature detecting unit 6 for detecting the temperature of the reformed gas that has passed through the reforming catalyst 2 is, for example, 650 ° C., the temperature detecting unit 6 The temperature of the reforming unit 1 is increased by the heating unit 5 so that the detected temperature detected by the above is 660 ° C., for example. This is performed by increasing the amount of fuel supplied to the heating unit 5 from a fuel supply unit (not shown in FIG. 1). As a result, since the temperature of the reformed gas discharged from the reforming unit 1 and supplied to the shift unit 7 has risen, the temperature of the shift catalyst 8 rises and is detected by the temperature detection unit 10 in the shift unit 7. The detected temperature also increases. In this way, the temperature of the shift catalyst 8 in the shift section 7 rises from less than 160 ° C. to 160 ° C., so that the amount of raw material supplied to the reforming section 1 is reduced from 1.0 (NL / min) to 2 The amount can be increased to 0.0 (NL / min). Similarly, the supply amount of the raw material to the reforming unit 1 is, for example, from 2.0 (NL / min) to 3.0 (NL / min), or from 3.0 (NL / min) to 4. Even in the case where the amount is increased to 0 (NL / min), the amount of fuel supplied to the heating unit 5 is increased to increase the temperature of the reforming unit 1, thereby increasing the temperature of the reformed gas and If the supply amount is increased, the concentration of carbon monoxide in the reformed gas discharged from the hydrogen generator will not increase rapidly. That is, the amount of hydrogen generated in the hydrogen generator can be increased according to the increase in the amount of power generated by the fuel cell.

  The operation of the hydrogen generator 100a according to the present embodiment will be described with reference to the drawings. The operation of the hydrogen generator 100a according to the present embodiment also includes steps S1 to S4 in the flowchart shown in FIG. It is the same operation. Then, when the detected temperature detected by the temperature detection unit 10 in step S4 is equal to or higher than the reference temperature (YES in step S4), the operation is performed in the same manner as in the first embodiment to the reforming unit 1. The supply of raw materials is increased. On the other hand, when the detected temperature is lower than the reference temperature (NO in step S4), after step S5 is executed in the same manner as in the first embodiment, a predetermined control signal is sent from the control device 101 as step S6. As a result, the amount of fuel supplied to the heating unit 5 is increased. Since the amount of fuel supplied to the heating unit 5 is increased by this step S6, the temperature of the reforming unit 1 rises. Next, when the temperature of the reformed gas rises in step S6 and the detected temperature detected by the temperature detection unit 10 in the shift unit 7 is raised to the reference temperature, wasteful consumption of fuel supplied to the heating unit 5 is prevented. Therefore, the increase in the amount of fuel supplied to the heating unit 5 is stopped as step S7. At this time, the temperature of the reformed gas discharged from the reformer 1 and supplied to the shifter 7 is constantly monitored by the temperature detector 6, and when the temperature of the reformed gas falls below a predetermined temperature, Fuel is appropriately supplied from the fuel supply unit to the heating unit 5. As a result, the temperature of the shift catalyst 8 in the shift section 7 is maintained at the reference temperature. Thereafter, in the same manner as in the first embodiment, the control device 101 outputs a control signal for increasing the supply amount of the raw material to the raw material supply unit 3, and the reforming unit 1 is output by this output control signal. The supply amount of the raw material is increased to the supply amount that should be supplied to the reforming unit 1 to cope with the increase in the power generation amount of the fuel cell (step S8).

  As described above, according to this embodiment, the temperature of the reforming unit 1 is controlled by the heating unit 5, so that the temperature of the reformed gas discharged from the reforming unit 1 and supplied to the shift unit 7 is increased. Be controlled. Thereby, the temperature of the shift catalyst 8 is controlled to an appropriate reference temperature. And the supply amount of the raw material to the reforming unit 1 is increased when the detected temperature detected by the temperature detection unit 10 reaches the reference temperature corresponding to the supply amount of the raw material to be supplied thereafter, If not reached, the amount is increased after being controlled to reach the reference temperature, so that a sudden increase in the carbon monoxide concentration in the reformed gas can be prevented.

  Depending on the configuration of the reforming unit 1 in which the temperature detecting unit 6 is installed or a parameter such as a target conversion rate in the reforming reaction, the control temperature of the detected temperature detected by the temperature detecting unit 6 may be different. In this case, by setting the control temperature of the detected temperature detected by the temperature detection unit 6 to an optimum temperature corresponding to each configuration or control parameter in the reforming unit 1, the same effect as in the first embodiment is obtained. Is obtained.

(Embodiment 4)
The hydrogen generation apparatus according to the fourth embodiment is different from the hydrogen generation apparatus according to the first embodiment in that the control program for increasing the amount of power generation stored in the control apparatus 101 is different from the first embodiment. This is the same as the hardware configuration of the hydrogen generator shown in the first embodiment. The basic operation of the hydrogen generator for generating hydrogen is the same as the basic operation of the hydrogen generator shown in the first embodiment. Therefore, also here, the description on the hardware configuration of the hydrogen generator according to the present embodiment and the basic operation for generating the hydrogen is omitted.

  Also in the present embodiment, when increasing the hydrogen generation amount in the hydrogen generation device 100a in order to cope with the increase in the power generation amount of the fuel cell, the temperature detection unit 10 is controlled by the control device 101 as in the case of the first embodiment. A determination is made as to whether or not the detected temperature detected by has reached the reference temperature. When it is determined that the detected temperature detected by the temperature detection unit 10 has reached the reference temperature, the amount of raw material supplied to the reforming unit 1 is increased. Similarly to the case of the first embodiment, when it is determined that the detected temperature does not reach the reference temperature, an operation for causing the detected temperature to reach the reference temperature is performed. Thereafter, the amount of raw material supplied to the reforming unit 1 is increased. Here, in the present embodiment, when it is determined by the control device 101 that the detected temperature detected by the temperature detection unit 10 has not reached the reference temperature, the water supply unit 4 supplies the reforming unit 1 with the detected temperature. By reducing the amount of water supplied, the temperature of the reforming unit 1 is increased, and thereby the temperature of the reformed gas discharged from the reforming unit 1 is increased. Then, by supplying the reformed gas whose temperature has been raised to the shift section 7, the temperature of the shift catalyst 8 disposed inside the shift section 7 is raised. When the temperature of the shift catalyst 8 rises, the temperature of the reformed gas that has passed through the shift catalyst 8 rises, so that the detected temperature detected by the temperature detector 10 also rises. That is, by this, the detected temperature detected by the temperature detection unit 10 is controlled to reach the reference temperature.

  More specifically, the supply amount of the raw material to the reforming unit 1 is increased from, for example, 1.0 (NL / min) to 2.0 (NL / min) in order to cope with an increase in the power generation amount of the fuel cell. When the temperature is detected by the temperature detector 10 is less than 160 ° C., it is possible to effectively reduce the carbon monoxide concentration in the reformed gas in the shifter 7 as is apparent from FIG. Have difficulty. Therefore, in the present embodiment, when the detected temperature detected by the temperature detecting unit 6 for detecting the temperature of the reformed gas that has passed through the reforming catalyst 2 is, for example, 650 ° C., the temperature detecting unit 6 The temperature of the reforming unit 1 is increased by reducing the amount of water supplied from the water supply unit 4 to the reforming unit 1 so that the detected temperature detected by the above is 660 ° C., for example. As a result, since the temperature of the reformed gas discharged from the reforming unit 1 and supplied to the shift unit 7 has risen, the temperature of the shift catalyst 8 rises and is detected by the temperature detection unit 10 in the shift unit 7. The detected temperature also increases. In this way, the temperature of the shift catalyst 8 in the shift section 7 is increased from less than 160 ° C. to 160 ° C., so that the amount of raw material supplied to the reforming section 1 is reduced from 1.0 (NL / min). The amount can be increased to 2.0 (NL / min). The supply amount of the raw material to the reforming unit 1 is, for example, from 2.0 (NL / min) to 3.0 (NL / min), or from 3.0 (NL / min) to 4.0 (NL / min) The same applies when the amount is increased to (min).

  The operation of the hydrogen generator 100a according to the present embodiment will be described with reference to the drawings. The operation of the hydrogen generator 100a according to the present embodiment also includes steps S1 to S4 in the flowchart shown in FIG. It is the same operation. Then, when the detected temperature detected by the temperature detection unit 10 in step S4 is equal to or higher than the reference temperature (YES in step S4), the operation is performed in the same manner as in the first embodiment to the reforming unit 1. The supply of raw materials is increased. On the other hand, when the detected temperature is lower than the reference temperature (NO in step S4), after step S5 is executed in the same manner as in the first embodiment, a predetermined control signal is sent from the control device 101 as step S6. The amount of water supplied from the water supply unit 4 to the reforming unit 1 is reduced. Since the amount of water supplied to the reforming unit 1 is reduced by this step S6, the temperature of the reforming unit 1 rises. Next, when the temperature of the reformed gas rises in step S6 and the detected temperature detected by the temperature detection unit 10 in the shift unit 7 rises to the reference temperature, a step is performed to prevent an excessive temperature rise of the reformed gas. In S7, the reduced amount of water supplied from the water supply unit 4 to the reforming unit 1 is released. At this time, the temperature of the reformed gas discharged from the reformer 1 and supplied to the shifter 7 is constantly monitored by the temperature detector 6, and when the temperature of the reformed gas falls below a predetermined temperature, The amount of water supplied from the water supply unit 4 to the reforming unit 1 is appropriately reduced. As a result, the temperature of the shift catalyst 8 in the shift section 7 is maintained at the reference temperature. The subsequent operation of the hydrogen generator 100a is the same as in the first and third embodiments.

  Thus, according to the present embodiment, the amount of water supplied from the water supply unit 4 to the reforming unit 1 is controlled, and the temperature of the reforming unit 1 is thereby controlled. Then, by controlling the temperature of the reformed gas discharged from the reforming unit 1 and supplied to the shift unit 7, the temperature of the shift catalyst 8 is controlled to an appropriate reference temperature. Others are the same as in the first and third embodiments.

(Embodiment 5)
The hydrogen generation apparatus according to the fifth embodiment is different from the hydrogen generation apparatus according to the first embodiment in that the control program for increasing the amount of power generation stored in the control apparatus 101 is different from that in the first embodiment. This is the same as the hardware configuration of the hydrogen generator shown in the first embodiment. The basic operation of the hydrogen generator for generating hydrogen is the same as the basic operation of the hydrogen generator shown in the first embodiment. Therefore, also here, the description on the hardware configuration of the hydrogen generator according to the present embodiment and the basic operation for generating the hydrogen is omitted.

  In the present embodiment, when increasing the amount of hydrogen generated in the hydrogen generator 100a in order to cope with an increase in the amount of power generated by the fuel cell, the temperature detector 14 disposed in the purification unit 11 by the controller 101. It is determined whether or not the detected temperature detected by has reached a predetermined reference temperature. When it is determined that the detected temperature detected by the temperature detection unit 14 has reached a predetermined reference temperature, the amount of raw material supplied to the reforming unit 1 is increased. However, when it is determined that the detected temperature detected by the temperature detecting unit 14 in the purifying unit 11 has not reached the predetermined reference temperature, the detected temperature is set to the predetermined reference temperature as in the second embodiment. No operation is performed to reach the temperature, and the amount of raw material supplied to the reforming unit 1 is not increased.

  Here, the characteristics of the selective oxidation reaction in the purification unit 11 will be described in detail with reference to the drawings.

  FIG. 3 is a graph showing the relationship between the purification catalyst temperature for each raw material flow rate and the carbon monoxide concentration in the reformed gas after passing through the purification unit. Here, the vertical axis in FIG. 3 indicates the concentration (ppm) of carbon monoxide contained in the reformed gas after passing through the purification unit, and the horizontal axis indicates the temperature (° C.) of the purification catalyst in the purification unit. . Curve a is a raw material flow rate of 1.0 (NL / min), curve b is a raw material flow rate of 2.0 (NL / min), and curve c is a raw material flow rate of 3.0 (NL / min). Min), the curve d shows the case where the raw material flow rate is 4.0 (NL / min).

  As shown in FIG. 3, the concentration of carbon monoxide contained in the reformed gas that has undergone the selective oxidation reaction in the purification unit 11 is determined by the temperature of the purification catalyst 12 and the supply amount of the raw material. For example, when the supply amount of the raw material to the reforming unit 1 is as small as 1.0 (NL / min) as shown by the curve a, even if the purification catalyst 12 is in a low temperature state (for example, 110 ° C.) Carbon monoxide is effectively reduced. On the other hand, when the supply amount of the raw material to the reforming unit 1 is as large as 4.0 (NL / min) as shown by the curve d, when the purification catalyst 12 is in a low temperature state (for example, 130 ° C. or less), monoxide Carbon is hardly reduced.

  That is, the supply amount of the raw material to the reforming unit 1 is reduced according to the decrease in the power generation amount of the fuel cell, and the reformed gas from the shift unit 7 to the purification unit 11 is reduced due to the decrease in the supply amount of the raw material. Even when the flow rate is reduced and the temperature of the purification catalyst 12 is lowered, the supply amount of the raw material to the reforming unit 1 is, for example, 1.0 (NL / min) indicated by the curve a, and purification at that time If the temperature of the catalyst 12 is 110 ° C., it is possible to sufficiently reduce the carbon monoxide concentration in the reformed gas. More specifically, when the carbon monoxide concentration of the reformed gas that has undergone the selective oxidation reaction in the purification unit 11 is, for example, 10 ppm or less as shown by the broken line in FIG. 3, the supply amount of the raw material to the reforming unit 1 is If it is 1.0 (NL / min) shown as the curve a, the requirement can be achieved when the temperature of the purification catalyst 12 is in the range of about 110 ° C. to about 140 ° C. Further, when the supply amount of the raw material to the reforming unit 1 is 2.0 (NL / min) shown as the curve b, the temperature of the purification catalyst 12 may be in the range of about 120 ° C. to about 140 ° C. . Moreover, when the supply amount of the raw material to the reforming unit 1 is 3.0 (NL / min) shown as the curve c, the temperature of the purification catalyst 12 may be in the range of about 130 ° C. to about 140 ° C. . Further, when the supply amount of the raw material to the reforming unit 1 is 4.0 (NL / min) indicated by the curve d, the temperature of the purification catalyst 12 may be within the temperature range indicated by the range B. However, as the amount of power generated by the fuel cell decreases, the amount of raw material supplied to the reforming unit 1 becomes, for example, 3.0 (NL / min) as shown by the curve c, and the temperature of the purification catalyst 12 becomes 140, for example. When the temperature is lower than ° C., the amount of raw material supplied to the reforming unit 1 is increased to, for example, 4.0 (NL / min) indicated by the curve d in order to cope with the increase in the power generation amount of the fuel cell. Unless the temperature of the catalyst 12 quickly rises to the temperature range indicated as the range B, the carbon monoxide concentration in the reformed gas exceeds the target value of 10 ppm. Therefore, when the amount of raw material supplied to the reforming unit 1 of the hydrogen generator 100a is increased in order to cope with the increase in power generation amount of the fuel cell, the temperature of the purification catalyst 12 determines the amount of raw material supplied. It is necessary to determine whether or not the temperature is within the optimum temperature range after the increase.

  Therefore, in the present embodiment, when dealing with an increase in the power generation amount of the fuel cell, the supply amount of the raw material is increased before the supply amount of the raw material supplied to the reforming unit 1 of the hydrogen generator 100a is increased. The detection temperature detected by the temperature detection unit 14 disposed in the purification unit 11 has reached the optimum temperature (hereinafter referred to as the second reference temperature) at which the selective oxidation reaction thereafter proceeds with the highest yield. And when it is determined that the detected temperature detected by the temperature detection unit 14 has reached the second reference temperature, the supply amount of the raw material to the reforming unit 1 is increased. did. On the other hand, when it is determined that the detected temperature detected by the temperature detecting unit 14 in the purifying unit 11 has not reached the second reference temperature, the detected temperature is set to the second temperature as in the second embodiment. The operation for reaching the reference temperature is not performed, and the supply amount of the raw material to the reforming unit 1 is not increased.

  The operation of the hydrogen generator 100a according to the present embodiment will be described with reference to the drawings. The operation of the hydrogen generator 100a according to the present embodiment is basically from step S1 to step S4 in the flowchart shown in FIG. This is the same operation. However, in step S <b> 1, the detected temperature detected by the temperature detection unit 14 disposed inside the purification unit 11 is stored. In step S3, a second reference temperature is set in accordance with the raw material supply amount predicted in step S2. Here, for example, data corresponding to the graph of FIG. 3 is stored in the storage unit of the control device 101. The second reference temperature set by the control device 101 is the reforming shown in FIG. 3 when the carbon monoxide concentration in the reformed gas after passing through the purification unit 11 is, for example, 10 ppm or less. The curve d in which the amount of raw material supplied to the section 1 is 4.0 (NL / min) is within the temperature range of the range B. Then, considering that the selective oxidation reaction proceeding in the purification unit 11 is an exothermic reaction, the second reference temperature is desirably set as the temperature of the low temperature part within the temperature range of the range B. The temperature of the low temperature portion within the temperature range of the range B shown in FIG. 3 is an optimum temperature for effectively reducing the carbon monoxide concentration in the reformed gas, as is apparent from FIG. For example, as is apparent from FIG. 3, when the flow rate of the raw material to be supplied to the reforming unit 1 is predicted to be 4.0 (NL / min) shown in the curve d, carbon monoxide in the reformed gas The optimum second reference temperature for reducing the temperature is 140 ° C. In step S4 shown in FIG. 4, the detected temperature detected by the temperature detection unit 14 is compared with the second reference temperature set in step S3. When it is confirmed by the comparison in step 4 that the detected temperature detected by the temperature detection unit 14 has reached the second reference temperature set in step S3 (YES in step S4), By operating in the same manner as in the first mode, the supply amount of the raw material to the reforming unit 1 is increased. However, when it is confirmed that the detected temperature detected by the temperature detector 14 has not reached the second reference temperature (NO in step S4), this corresponds to steps S5 to S8 shown in FIG. The operation is not performed, and the supply amount of the raw material to the reforming unit 1 is not increased.

  As described above, according to the present embodiment, the supply amount of the raw material to the reforming unit 1 is the second according to the supply amount of the raw material to be supplied by the detected temperature detected by the temperature detection unit 14 thereafter. Since the amount is increased when the temperature is higher than the reference temperature and is not increased when the temperature is not reached, a rapid increase in the carbon monoxide concentration in the reformed gas can be prevented.

  Also in this embodiment, the supply amount of the raw material to the reforming unit 1 is 1.0 (NL / min), 2.0 (NL / min), 3.0 (NL / min), 4.0 ( The second reference temperature for the flow rate increase of 1.0 (NL / min) unit is illustrated as NL / min), but the second reference temperature for the flow rate increase of 0.1 (NL / min) unit is illustrated. The temperature may be set.

  In the present embodiment, a mixture of Pt and Ru is used as the catalyst body in the purification catalyst 12, but the present invention is not limited to this, and Pt or Ru may be used alone or other noble metals such as Pd may be used. Good.

  In the present embodiment, alumina is used as the carrier constituting the purification catalyst 12, but the present invention is not limited to this, and silica or a mixture of alumina and silica may be used.

  Further, the characteristic curve shown in FIG. 3 may change depending on the configuration of the hydrogen generator 100a and the parameters such as the type of catalyst body of the purification catalyst 12 and the amount of catalyst. Therefore, it is desirable to set the reference temperature so as to correspond to each parameter. Thereby, the same effect as this embodiment can be obtained.

  In the present embodiment, the temperature detection unit 14 is provided at the downstream position of the purification catalyst 12 in order to detect the temperature of the purification catalyst 12. You may arrange | position in an upstream position. Further, the temperature detection unit 14 may be provided in the purification catalyst 12 so that the temperature of the purification catalyst 12 can be directly detected. When the position of the temperature detection unit 14 is changed in this way, the same effect can be obtained by setting the optimum second reference temperature at the changed position.

  Further, as shown in the third embodiment, the present embodiment may be configured to increase the amount of hydrogen generation by increasing the temperature of the purification catalyst 12 by increasing the temperature of the reformed gas. Or as shown in Embodiment 4, it is good also as a form corresponding to the increase in the amount of hydrogen production by raising the temperature of the purification catalyst 12 by reducing the supply_amount | feed_rate of the water to the reforming part 1. FIG.

  Moreover, it is good also as a form which combined this Embodiment and the form which sets a reference temperature to the shift catalyst 8 shown in Embodiment 1,3,4. According to such an embodiment, it is possible to more reliably suppress the generation of carbon monoxide when increasing the hydrogen generation amount according to the increase in the power generation amount of the fuel cell.

(Embodiment 6)
FIG. 5 is a schematic diagram showing a configuration of a fuel cell system including the hydrogen generator according to Embodiments 1 to 5 of the present invention. In FIG. 5, the description of the reference numerals given to the respective components constituting the hydrogen generator is omitted.

  As shown in FIG. 5, the fuel cell system 100 according to the sixth embodiment includes a hydrogen generator 100a configured by the hydrogen generator according to any one of the first to fifth embodiments, and the hydrogen generator 100a. A fuel cell 100b that generates electric power using supplied reformed gas and air, and a control device 101 that controls operations of the hydrogen generator 100a and the fuel cell 100b are provided. Although not shown in FIG. 5, the fuel cell system 100 includes an air supply device that supplies air for use in power generation to the fuel cell 100b.

  As shown in FIG. 5, the hydrogen generator 100a and the fuel cell 100b are connected to each other by a reformed gas pipe 11a. The air supply device and the fuel cell 100b are connected to each other by a predetermined pipe (not shown in FIG. 5). Further, the reforming unit 1, the shift unit 7 and the purifying unit 11 constituting the hydrogen generator 100a, and the constituent elements constituting the reforming unit 1, the shift unit 7 and the purifying unit 11, and the fuel cell 100b are included in the fuel cell 100b. A control wiring extending from the control device 101 is connected.

  When the fuel cell system 100 shown in FIG. 5 is operated to generate power, the hydrogen generator 100a supplies a reformed gas containing abundant hydrogen to the fuel cell 100b and also supplies air from the air supply device. . Then, in the fuel cell 100b, power generation is performed using hydrogen contained in the reformed gas supplied from the hydrogen generator 100a and oxygen contained in the air supplied from the air supply device. The operation of the fuel cell system 100 according to the present embodiment is appropriately controlled by the control device 101.

  In the present embodiment, when dealing with the fluctuation of the load on the fuel cell system 100 from a low load to a high load, that is, when increasing the power generation amount of the fuel cell 100b in order to deal with the fluctuation of the load. Increases the amount of reformed gas supplied to the fuel cell 100b by controlling the operation of the hydrogen generator 100a as shown in the first to fifth embodiments of the present invention. Thereby, the power generation amount of the fuel cell 100b is increased.

  Thus, according to the present embodiment, the supply amount of the raw material to the reforming unit 1 shown in FIG. 1 in order to increase the hydrogen generation amount in the hydrogen generator 100a in order to increase the power generation amount of the fuel cell 100b. Even when the amount is increased, a high quality reformed gas having a sufficiently reduced carbon monoxide concentration is supplied to the fuel cell 100b. Therefore, a decrease in the output voltage of the fuel cell 100b caused by the poisoning of the electrode catalyst disposed inside the fuel cell 100b with carbon monoxide is effectively prevented. In addition, the fuel cell 100b can reliably continue power generation.

A hydrogen generator according to the present invention, a method for operating the same , and a fuel cell system including the hydrogen generator are high-quality reforming in which carbon monoxide is sufficiently reduced and hydrogen is abundant in response to an increase or decrease in power generation amount of the fuel cell. It is useful as a hydrogen generator capable of efficiently generating gas, an operation method thereof, and a fuel cell system including the same.

It is a schematic diagram which shows the structure of the hydrogen generator which concerns on Embodiment 1 of this invention. It is a graph which shows the relationship between the shift catalyst temperature for every raw material flow rate, and the carbon monoxide density | concentration in the reformed gas after a shift part passage. It is a graph which shows the relationship between the purification catalyst temperature for every raw material flow volume, and the carbon monoxide density | concentration in the reformed gas after a purification | cleaning part passage. It is a flowchart which shows an example of operation | movement of the hydrogen generator at the time of respond | corresponding to the increase in the electric power generation amount of a fuel cell. It is a schematic diagram which shows the structure of the fuel cell system provided with the hydrogen generator concerning Embodiment 1-5 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reforming part 1a Reformed gas pipe 2 Reforming catalyst 3 Raw material supply part 3a Raw material supply pipe 4 Water supply part 4a Water supply pipe 5 Heating part 6 Temperature detection part 7 Transformation part 7a Reformed gas pipe 8 Transformation Catalyst 9 Water supply section 9a Water supply pipe 10 Temperature detection section 11 Purification section 11a Reformed gas pipe 12 Purification catalyst 13 Air supply section 13a Air supply pipe 14 Temperature detection section 15 Air supply section 15a Air supply pipe 100 Fuel Battery system 100a Hydrogen generator 100b Fuel cell 101 Control device

Claims (10)

A reforming unit that generates a reformed gas containing hydrogen by being supplied with raw materials and water, a heating unit that heats the reforming unit to a temperature necessary for the generation of the reformed gas, and generated by the reforming unit A carbon monoxide reduction part having a carbon monoxide reduction catalyst for reducing carbon monoxide contained in the reformed gas, and at least a temperature of the carbon monoxide reduction catalyst or the reformed gas in the carbon monoxide reduction part A hydrogen generation device including a temperature detection unit for detecting one and a control unit,
The control unit compares an increase in the supply amount of the raw material supplied to the reforming unit with a detected temperature detected by the temperature detection unit and a reference temperature set according to the supply amount of the raw material. and control on the basis of,
As a result of the comparison, when the detected temperature is lower than the reference temperature, the supply amount of the raw material supplied to the reforming unit is not increased, and is increased when the detected temperature is equal to or higher than the reference temperature. A hydrogen generator. The control unit controls the detected temperature to be equal to or higher than the reference temperature when the detected temperature is lower than the reference temperature, and increases the supply amount of the raw material when reaching the reference temperature or higher. The hydrogen generator according to claim 1 . The hydrogen generation apparatus according to claim 2 , wherein when the detected temperature is lower than the reference temperature, the control unit increases the amount of heating in the heating unit and controls the detected temperature to be equal to or higher than the reference temperature. . A water supply unit for supplying water to the reforming unit;
When the detected temperature is lower than the reference temperature, the control unit reduces the amount of water supplied from the water supply unit to the reforming unit, and controls the detected temperature to be equal to or higher than the reference temperature. The hydrogen generator according to claim 2 . An oxidant gas supply unit for supplying an oxidant gas into the carbon monoxide reduction unit;
When the detected temperature is lower than the reference temperature, the control unit causes the carbon monoxide reducing unit to supply an oxidant gas from the oxidant gas supply unit so that the detected temperature becomes equal to or higher than the reference temperature. The hydrogen generator according to claim 2 to be controlled.   The carbon monoxide reduction catalyst is a shift catalyst that promotes a water gas shift reaction in which hydrogen and carbon dioxide are generated from carbon monoxide and water, and the carbon monoxide reduction portion is a shift portion that includes the shift catalyst. The hydrogen generator according to claim 1. The hydrogen generator according to claim 6 , wherein the catalyst body in the shift catalyst is composed of at least a noble metal and a metal oxide of at least one element of cerium, zirconium, or aluminum.   The carbon monoxide reduction catalyst is a carbon monoxide selective oxidation catalyst for causing a selective oxidation reaction of carbon monoxide, and the carbon monoxide reduction unit is a selective oxidation unit including the carbon monoxide selective oxidation catalyst. 2. The hydrogen generator according to 1. A hydrogen generator according to any one of claims 1 to 8 , and a fuel cell that generates electricity using hydrogen generated by the hydrogen generator and oxidant gas,
When the detected temperature detected by the temperature detection unit reaches the reference temperature or more, the fuel cell increases the amount of power generation by increasing the amount of the raw material supplied to the reforming unit by the control unit. A fuel cell system. One having a reforming section for supplying a raw material and water to generate a reformed gas containing hydrogen, and a carbon monoxide reduction catalyst for reducing carbon monoxide contained in the reformed gas generated in the reforming section. A method for operating a hydrogen generator comprising: a carbon oxide reduction unit; and a temperature detection unit that detects at least one of the temperature of the reformed gas in the carbon monoxide reduction catalyst or the carbon monoxide reduction unit,
An increase in the supply amount of the raw material supplied to the reforming unit is controlled based on a comparison between a detection temperature detected by the temperature detection unit and a reference temperature set according to the supply amount of the raw material. ,
As a result of the comparison, when the detected temperature is lower than the reference temperature, the supply amount of the raw material supplied to the reforming unit is not increased, and is increased when the detected temperature is equal to or higher than the reference temperature. The operation method of the hydrogen generator.

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