JP2005170784A - Hydrogen generator, method of operating hydrogen generator and fuel cell power system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen generator with high hydrogen generation efficiency and high reliability, which is capable of reducing start time of the hydrogen generator depending on a temperature condition thereof at the start of a start operation and of increasing a temperature of a water evaporator while inhibiting an excessive temperature increase in a reforming catalyst layer, a method of operating the hydrogen generator and a fuel cell power system comprising the hydrogen generator. <P>SOLUTION: The hydrogen generator comprises a controller 20 configured to control the supply of the material from the material supply portion 3 and the supply of the water from the water supply portion 2, to observe the temperature of a water evaporator 4 and the temperature of a reforming catalyst layer 5 and to properly control the supply of water from the water supply portion 2 to the water evaporator 4 based on the observation result. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydrogen generator that generates a hydrogen-rich gas by a steam reforming reaction using a hydrocarbon-based material such as natural gas, LPG, gasoline, naphtha, kerosene, and methanol as a main raw material, and an operation method thereof, in particular, a fuel cell, etc. The present invention relates to a hydrogen generator for generating hydrogen gas to be supplied to a hydrogen-using device and an operation method at the time of startup.

  In the hydrogen generator, a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms is steam reformed in a reforming section provided with a reforming catalyst layer. By this reforming reaction, a hydrogen rich gas (hereinafter referred to as hydrogen gas) is generated as the reformed gas. When water is directly supplied to the reforming catalyst layer during the reforming reaction, there is a possibility that the gas flow path formed inside or downstream of the reforming catalyst layer may be blocked by water. Therefore, water is supplied to the reforming catalyst layer in a steam state.

For example, in a conventional hydrogen generator, the temperature of the reforming catalyst in the reforming unit is detected during the preheating operation at startup, and when the detected temperature reaches a predetermined value, water is supplied from the water supply unit to the reforming unit. Is started (see, for example, Patent Document 1). In addition, there is a structure in which a water supply channel communicating with the reforming catalyst layer of the reforming unit has a rising structure and a water evaporation unit is formed at the bottom of the channel formed by this structure. In such a configuration, the supplied water evaporates in the water evaporating unit and is supplied to the reforming catalyst layer, and water that has not evaporated in the water evaporating unit is stored in the bottom (see, for example, Patent Document 2).
JP 2001-302207 A JP 2002-252604 A

  In the hydrogen generator, if the amount of water vapor supplied to the reforming catalyst layer heated to a high temperature is not sufficient with respect to the supply amount of the raw material, only the raw material becomes hot and the inside of the catalyst layer of the reforming section and the gas flow Flowing on the road. For example, in the hydrogen generator in which the water evaporation section is formed at the bottom of the water supply flow path having the rising structure as described above, when the reforming catalyst layer is heated to a high temperature but the temperature of the water evaporation section is low, Despite the supply of water, the water does not evaporate, and the supplied water accumulates at a low position in the water evaporation section and the reforming section flow path. Therefore, sufficient steam is not supplied to the reforming catalyst layer, and only the raw material flows through the high-temperature reforming catalyst layer and the flow path. Here, since the raw material is mainly composed of an organic compound composed of carbon and hydrogen, under such circumstances, the raw material is thermally decomposed to be in a carbon state and deposited on the reforming catalyst and in the flow path. For this reason, the catalyst activity is lowered and the flow path is blocked, which may hinder the operation of the hydrogen generator.

  Further, when the reforming catalyst layer reaches a high temperature exceeding the reforming reaction temperature, the catalyst may aggregate and the catalytic activity may be reduced. Furthermore, if the high temperature reforming catalyst layer is in an air atmosphere, the reforming catalyst may be oxidized and the catalytic activity may be reduced.

  On the other hand, in the above method for controlling the start of water supply according to the temperature of the reforming catalyst, water and raw materials are supplied when the reforming catalyst reaches a predetermined temperature regardless of the temperature state of the hydrogen generator at the start of startup. Perform the reforming reaction. For this reason, for example, when the hydrogen generator is restarted in a state where not much time has passed since the operation was stopped, the water evaporation unit has a temperature at which water vapor can be generated immediately from the supplied water. Regardless, water cannot be supplied until the reforming catalyst reaches the predetermined high temperature. Therefore, regardless of whether or not the temperature of the water evaporation unit at the start of startup is a temperature at which water vapor can be generated, the time until the supply of water is started (hereinafter referred to as startup time) is substantially constant.

  The present invention solves these problems, and it is possible to shorten the start-up time according to the temperature state of the hydrogen generator at the start of start-up, and to suppress the temperature rise of the reforming catalyst layer. It is an object of the present invention to provide a hydrogen generation apparatus with high hydrogen generation efficiency and reliability, an operation method thereof, and a fuel cell power generation system including the same, which can raise the temperature of the water evaporation section.

  In order to solve the above problems, a hydrogen generator according to the present invention generates hydrogen by reforming a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms and steam using a reforming catalyst. A reforming unit, a raw material supply unit that supplies a raw material to the reforming unit, a water supply unit that supplies water to the reforming unit, a heating unit that heats the reforming unit, and a raw material supply unit A control unit that controls the raw material supply and the water supply from the water supply unit, wherein the reforming unit is a water evaporation unit that evaporates the supplied water, A reforming catalyst layer including a reforming catalyst; and a reforming temperature detection unit that detects a temperature of the reforming catalyst layer; and whether the control unit has a temperature at which the water evaporation unit can generate water vapor. Whether or not based on the temperature of the reforming catalyst layer detected by the reforming temperature detector And a supply control unit that controls at least the water supply from the water supply unit based on a determination result of the determination unit, wherein the determination unit starts the heating and generates the hydrogen The first determination that the temperature of the reforming catalyst layer detected at the start of starting the apparatus is compared with a first reference temperature is executed, and as a result of the first determination, the reforming catalyst layer When the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the temperature of the reforming catalyst layer detected in the process of heating the reforming unit after the first determination is set to the first reference temperature. A second determination of comparing with a higher second reference temperature, and as a result of the first determination, when the temperature of the reforming catalyst layer exceeds the first reference temperature, or As a result of the second determination, the temperature of the reforming catalyst layer is If it exceeds the reference temperature, the supply control means is a device for initiating the water supply to the reformer unit.

  Thereby, it is possible to shorten the start-up time according to the temperature state of the hydrogen generator at the start of start-up, and to increase the temperature of the water evaporation part while suppressing the temperature increase of the reforming catalyst layer. Therefore, a hydrogen generation apparatus with high hydrogen generation efficiency and high reliability can be obtained.

  The second reference temperature is preferably a temperature at which the catalytic activity of the reforming catalyst layer does not deteriorate in the absence of water vapor.

  The first reference temperature may be 50 ° C. or more and 150 ° C. or less, and the second reference temperature may be 300 ° C. or more and 500 ° C. or less.

  Further, the reforming unit of the hydrogen generator further includes a water evaporation unit temperature detection unit that detects a temperature of the water evaporation unit, and the control unit is capable of generating water vapor when the start-up is started. Determination means for determining whether or not the temperature is based on the temperature of the water evaporation section detected by the water evaporation section detection section, and at least the water from the water supply section based on the determination result of the determination means Supply control means for controlling supply, and as a result of determination by the determination means, if the temperature of the water evaporation section exceeds a water evaporation section reference temperature, which is a temperature capable of generating water vapor, the supply control section Starts the water supply, and when the temperature of the water evaporation part is equal to or lower than the water evaporation part reference temperature, the heating is performed, and when the water evaporation part reference temperature is exceeded, the supply control means Water supply may be started.

  Here, the hydrogen generator according to the present invention includes a reforming unit that generates hydrogen by reforming a raw material containing at least an organic compound composed of carbon atoms and hydrogen atoms and steam using a reforming catalyst. A raw material supply unit that supplies a raw material to the reforming unit, a water supply unit that supplies water to the reforming unit, a heating unit that heats the reforming unit, the raw material supply from the raw material supply unit, and A hydrogen generator comprising: a control unit that controls the water supply from the water supply unit, wherein the reforming unit includes a water evaporation unit that evaporates the supplied water, and the reforming catalyst. A reforming catalyst layer, and a reforming temperature detection unit that detects the temperature of the reforming catalyst layer, and the control unit determines whether the water evaporation unit is at a temperature at which steam can be generated. Determination means for determining based on the temperature of the reforming catalyst layer detected by the reforming temperature detector Supply control means for controlling at least the water supply supplied from the water supply unit based on the determination result of the determination means, and the determination means starts the heating and starts the hydrogen generator And performing a first determination of comparing the temperature of the reforming catalyst layer detected at the start of startup with a first reference temperature, and as a result of the first determination, the temperature of the reforming catalyst layer is When the temperature is equal to or lower than the first reference temperature, the temperature of the reforming catalyst layer detected in the process of heating the reforming portion after the first determination is higher than the first reference temperature. After the first determination, the second determination of comparing with the second reference temperature is performed, and the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature as a result of the first determination. Detected in the process of heating the reforming part A third determination is performed in which the temperature of the reforming catalyst layer is compared with a third reference temperature that is higher than the first reference temperature and lower than the second reference temperature, and as a result of the third determination, The heating is stopped when the temperature of the reforming catalyst layer exceeds the third reference temperature, and the temperature of the reforming catalyst layer after the heating is stopped is lower than the third reference temperature. A fourth determination of comparing with a fourth reference temperature higher than the first reference temperature is performed, and as a result of the fourth determination, the temperature of the reforming catalyst layer is lower than the fourth reference temperature. It is an apparatus in which the heating is resumed at the time.

  By repeatedly stopping and restarting the heating in the heating unit, it is possible to promote the heating of the water evaporation unit while suppressing the temperature increase of the reforming catalyst layer.

  The third reference temperature may be 200 ° C. or higher and 300 ° C. or lower.

  The heating and stopping of the reforming part is performed at a predetermined number of times one or more times at the start of starting, or the heating of the reforming part accompanied by the stopping and restarting is performed for a predetermined time, and then the third reference When the temperature exceeds the temperature, the heating is executed, and then, as a result of the second determination, when the temperature of the reforming catalyst layer exceeds the second reference temperature, the supply control means starts the water supply You may let them.

  The controller determines in advance the number of times of stopping and restarting the heating, or the time of heating with the stopping and restarting, according to the temperature of the reforming catalyst layer detected at the start of the start-up. Also good.

The reforming unit further includes a water evaporation unit temperature detection unit that detects a temperature of the water evaporation unit,
The control unit is configured to determine, based on the temperature of the water evaporation unit detected by the water evaporation unit detection unit, whether or not the water evaporation unit has a temperature capable of generating water vapor at the start of the activation. Supply control means for controlling at least the water supply from the water supply unit based on the determination result of the determination means, and as a result of determination by the determination means, the temperature of the water evaporation unit is capable of generating water vapor. When the temperature of the reforming unit is lower than the water evaporation unit reference temperature, the heating is stopped when the temperature of the reforming catalyst layer reaches the third reference temperature, and the heating is performed. While the heating is resumed when the temperature of the reforming catalyst layer after the stop reaches the fourth reference temperature, the temperature of the water evaporation section is changed based on the signal output from the water evaporation section temperature detection section. Exceeds the water evaporation unit reference temperature If the said supply control means may initiate the water supply.

  The water evaporation part reference temperature may be 50 ° C. or higher and 150 ° C. or lower.

  The water evaporation unit may be disposed on the outermost periphery of the reforming unit, and the reforming catalyst layer may be disposed on the inner side of the water evaporation unit.

  The heating unit includes a burner that burns combustion fuel and air, a fuel supply unit that supplies the combustion fuel to the burner, and an air supply unit that supplies the air to the burner. After the heat exchange between the combustion exhaust gas generated in the burner and the reforming catalyst layer is performed, the heat exchange between the combustion exhaust gas and the water evaporation unit may be performed.

The supply control means further controls air supply from the air supply unit to the burner,
After the water supply by the water supply unit is started, the air corresponding to the first supply amount is supplied to the burner, and the temperature of the reforming catalyst layer is determined as a result of the first determination. When the temperature is equal to or lower than the first reference temperature, the air corresponding to the second supply amount is supplied from the air supply unit to the burner, and the air corresponding to the first supply amount is supplied. In the combustion, the supplied combustion fuel in the combustion in which the ratio of the first supply amount to the theoretical air amount in the complete combustion of the supplied combustion fuel corresponds to the second supply amount is supplied. It may be smaller than the ratio of the second supply amount to the theoretical air amount in the complete combustion.

  In the combustion in which the air corresponding to the second supply amount is supplied, the ratio of the second supply amount to the theoretical air amount in the complete combustion of the supplied combustion fuel may be 2.0 or more. .

  The supply control means may cause the air to be ejected from the air supply unit to the burner during a heating stop period in which combustion in the combustion unit is stopped according to the result of the third determination.

  The supply control means is configured to supply the raw material after a predetermined time has elapsed from the start of the water supply according to the first determination result or after a predetermined time has elapsed from the start of the water supply according to the second determination result. You may start the said raw material supply from a supply part.

  By intentionally shifting the timing of water supply and raw material supply to the reforming section, the steam generated in the water evaporation section is used to easily purge the hydrogen generator before the reforming reaction is performed. Is possible.

  The water may be stored in advance in the water evaporation unit before the water evaporation unit reaches a temperature at which hydrogen can be generated.

  The operation method of the hydrogen generator according to the present invention includes a reforming unit that generates hydrogen by reforming a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms and steam using a reforming catalyst. A raw material supply unit that supplies a raw material to the reforming unit, a water supply unit that supplies water to the reforming unit, a heating unit that heats the reforming unit, the raw material supply from the raw material supply unit, and A control unit that controls the water supply from the water supply unit, wherein the reforming unit includes a water evaporation unit that evaporates the supplied water, and the reforming unit. A reforming catalyst layer provided with a catalyst and a reforming temperature detector for detecting the temperature of the reforming catalyst layer, and starting the heating by starting the heating by the controller The temperature of the reforming catalyst layer sometimes detected is a first reference temperature. A first determination is performed, and if the result of the first determination is that the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the first determination after the first determination A second determination is performed in which the temperature of the reforming catalyst layer detected in the process of heating the reforming unit is compared with a second reference temperature higher than the first reference temperature, and the first determination is performed. As a result of the determination, when the temperature of the reforming catalyst layer exceeds the first reference temperature, or as a result of the second determination, the temperature of the reforming catalyst layer exceeds the second reference temperature. In this case, the water supply from the water supply unit to the reforming unit is started.

  Thereby, it is possible to shorten the start-up time according to the temperature state of the hydrogen generator at the start of start-up, and to increase the temperature of the water evaporation part while suppressing the temperature increase of the reforming catalyst layer. Therefore, it is possible to obtain a method of operating a hydrogen generation apparatus that is capable of generating hydrogen and having high reliability.

  The reforming unit further includes a water evaporation unit temperature detection unit that detects the temperature of the water evaporation unit, and the temperature of the water evaporation unit detected by the water evaporation unit temperature detection unit is a temperature at which water vapor can be generated. When the water evaporation unit reference temperature is exceeded, the water supply is started, while when the temperature of the water evaporation unit is equal to or lower than the water evaporation unit reference temperature, the reforming unit is heated, Thereafter, the water supply may be started when the temperature of the water evaporation unit exceeds the water evaporation unit reference temperature.

  Here, the operation method of the hydrogen generator according to the present invention is a modified method for generating hydrogen by reforming a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms and steam using a reforming catalyst. A raw material supply unit for supplying raw material to the reforming unit, a water supply unit for supplying water to the reforming unit, a heating unit for heating the reforming unit, and the raw material supply unit And a control unit that controls the water supply from the raw material supply and the water supply unit, wherein the reforming unit includes a water evaporation unit that evaporates the supplied water, A reforming catalyst layer including the reforming catalyst; and a reforming temperature detection unit that detects a temperature of the reforming catalyst layer, and starts the heating by the control unit to start the hydrogen generator The temperature of the reforming catalyst layer detected at the start of starting When the first determination of comparing with the temperature is executed and the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature as a result of the first determination, the first determination is performed. A second determination is performed in which the temperature of the reforming catalyst layer detected in the process of heating the reforming unit is compared with a second reference temperature higher than the first reference temperature, If the result of determination 1 is that the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the reforming catalyst layer detected in the process of heating the reforming unit after the first determination. Is compared with a third reference temperature that is higher than the first reference temperature and lower than the second reference temperature, and as a result of the third determination, the reforming catalyst layer If the heating is stopped when the temperature exceeds the third reference temperature, A fourth determination is performed in which the temperature of the reforming catalyst layer after stopping the heating is compared with a fourth reference temperature lower than the third reference temperature and higher than the first reference temperature; As a result of the fourth determination, the heating is resumed when the temperature of the reforming catalyst layer falls below the fourth reference temperature.

  By repeatedly stopping and restarting the heating in the heating unit, it is possible to promote the heating of the water evaporation unit while suppressing the temperature increase of the reforming catalyst layer.

  The controller controls the number of times heating is stopped and restarted for the reforming unit or the heating of the reforming unit with the stopping and restarting according to the temperature of the reforming catalyst layer detected at the start of startup. An execution time is determined in advance, and after stopping and restarting the heating for the determined number of executions or the execution time, the heating is executed exceeding the third reference temperature, and then the second As a result of the determination, the water supply from the water supply unit to the reforming unit may be started when the temperature of the reforming catalyst layer exceeds the second reference temperature.

  The reforming unit further includes a water evaporation unit temperature detection unit that detects the temperature of the water evaporation unit, and the temperature of the water evaporation unit detected by the water evaporation unit detection unit is a water evaporation unit reference capable of generating water vapor. When the temperature is equal to or lower than the temperature, heating of the reforming unit is performed, the heating is stopped when the temperature of the reforming catalyst layer exceeds the third reference temperature, and the reforming after the heating is stopped. The heating is resumed when the temperature of the catalyst layer falls below the fourth reference temperature, and the temperature of the water evaporation part is determined based on the signal output from the water evaporation part temperature detection part. When the temperature is exceeded, the water supply may be started.

  The heating unit includes a burner that burns combustion fuel and air, a fuel supply unit that supplies the combustion fuel to the burner, and an air supply unit that supplies the air to the burner, and the control unit includes In the heating after the air supply unit is controlled and the water supply by the water supply unit is started, the air corresponding to a first supply amount is supplied to the burner and at the start of the start-up. As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the air corresponding to the second supply amount is supplied from the air supply unit to the burner. In the combustion in which the air corresponding to the first supply amount is supplied, the ratio of the first supply amount to the theoretical air amount of complete combustion of the supplied combustion fuel is the second supply amount. Before the corresponding air is supplied In the combustion, it may be smaller than the ratio of the second supply amount to the theoretical air amount of complete combustion of the supplied fuel burned.

  The heating unit includes a burner that burns combustion fuel and air, a fuel supply unit that supplies the combustion fuel to the burner, and an air supply unit that supplies the air to the burner. The air may be ejected from the air supply unit to the burner during a heating stop period in which the combustion in the burner is stopped according to the result.

  After a predetermined time has elapsed from the start of the water supply after the first determination, or after a predetermined time has elapsed from the start of the water supply after the second determination, the control unit changes the revision from the raw material supply unit. You may start supply of the said raw material to a mass part.

  By intentionally shifting the timing of water supply and raw material supply to the reforming section, the steam generated in the water evaporation section is used to easily purge the hydrogen generator before the reforming reaction is performed. Is possible.

  A combustion battery power generation system according to the present invention generates power by reacting the hydrogen generator described above, an air supply device, hydrogen supplied from the hydrogen generator and air supplied from the air supply device. A fuel cell to perform.

  According to the hydrogen generator and the operation method thereof according to the present invention, since the timing of water supply start can be appropriately adjusted according to the temperature state at the start of startup of the hydrogen generator, the startup time of the hydrogen generator is shortened Can be planned. In addition, since the steam can be generated in the water evaporation section before the reforming catalyst layer is heated and supplied to the reforming catalyst layer, the catalyst performance of the reforming catalyst is deteriorated, carbon is deposited from the raw material, etc. Therefore, it is possible to prevent the blockage of the channel from being blocked and to achieve high reliability.

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

(Embodiment 1)
FIG. 1 is a schematic cross-sectional view showing the configuration of the hydrogen generator according to Embodiment 1 of the present invention. In particular, the reforming unit, which is the main component of the hydrogen generator, and the configuration around it are shown in detail. Show.

  As shown in FIG. 1, the hydrogen generator includes a reforming unit 3 composed of a cylindrical main body 50 whose upper and lower ends are closed, and a raw material composed of an organic compound containing carbon and hydrogen. 3, a water supply unit 2 for supplying water to the reforming unit 3, a combustion unit 12 (heating unit) for heating the reforming unit 3, and a combustion fuel to the combustion unit 12 A fuel supply unit 8, an air supply unit 7 that supplies air to the combustion unit 12, and a control unit 20 are provided.

  In the reforming unit 3, a plurality of cylindrical vertical walls 51 having different radii and axial lengths are concentrically arranged inside the cylindrical main body 50, whereby the inside of the main body 50 is radially aligned. It is divided into. A disc-like or hollow disc-like lateral wall 52 is appropriately disposed at a predetermined end of the vertical wall 51. Specifically, a plurality of vertical walls 51 are concentrically arranged upright inside the main body 50 to form a gap 53 between the vertical walls 51, and a desired gas flow path is formed using the gap 53. As shown, the predetermined end of the vertical wall 51 is appropriately closed by the horizontal wall 52. As a result, the reforming raw material flow path a, the combustion gas flow path b1, the reformed gas flow path c, the reforming catalyst layer 5, and the combustion gas flow path b2 are formed in the main body 50. Are arranged in this order from the outer peripheral side in the radial direction of the main body toward the center.

  The reforming raw material flow path a has an upstream end connected to the raw material supply unit 1 and the water supply unit 2 provided outside the main body 50, and a downstream end has a reforming catalyst layer. 5 is connected to the upper end surface. The reforming raw material flow path a has a double structure, and has a rising structure so that the moving direction of the substance moving in the flow path changes from the axially downward direction to the axially upward direction. And the water evaporation part 4 is formed in the bottom part of the reforming raw material flow path a. As will be described later, the water supplied from the water supply unit 2 is temporarily stored in the water evaporation unit 4 and evaporated here.

  The reforming catalyst layer 5 is formed by filling the gap 53 with the reforming catalyst, and is disposed along the upper end surface and the outer peripheral surface of the radiant cylinder 13 of the combustion section 12 described later. Here, a reforming catalyst containing Ru as a main component is used, but the reforming catalyst is not particularly limited as long as a reforming reaction is possible. For example, a reforming catalyst composed of a noble metal such as Pt or Rh, Ni or the like may be used. The upper end surface of the reforming catalyst layer 5 is connected to the reforming raw material channel a, and the lower end surface is connected to the upstream end of the reformed gas channel c. The downstream end portion of the reformed gas flow path c is configured so that the reformed gas can be taken out of the reforming unit 3. Inside the reformed gas channel c, reforming temperature detecting means 15 for detecting the temperature of the gas that passes through the reforming catalyst layer 5 and flows in the channel is disposed. A thermocouple is provided as the mass temperature detecting means 15. The installation location of the reforming temperature detection means 15 is not particularly limited as long as the temperature of the gas that has passed through the reforming catalyst layer 5 can be detected. Here, the reforming temperature detecting means 15 is provided so as to detect the temperature of the gas immediately after passing through the reforming catalyst layer 5, and the detected temperature of the gas is used as the temperature of the reforming catalyst layer 5. Further, the temperature in the reforming catalyst layer 5 may be directly detected, or the temperature of the vertical wall 51 and the horizontal wall 52 constituting the reforming catalyst layer 5 may be detected. The temperature information of the reforming catalyst layer 5 detected by the reforming temperature detecting means 15 is transmitted to the control unit 20. Although the configuration and function of the control unit 20 will be described later, the control unit 20 outputs a raw material and water supply start signal to the raw material supply unit 1 and the water supply unit 2 in accordance with this temperature information.

  The combustion section 12 is disposed on the air flow path 6 so as to surround the burner 9, the air flow path 6 formed on the outer periphery of the burner 9, and the portion of the burner 9 protruding upward from the air flow path 6. The radiation cylinder 13 is provided, and the radiation cylinder 13 is housed inside the main body 50 of the reforming unit 3 and is disposed concentrically. The burner 9 is connected to the fuel supply unit 8, and the air flow path 6 is connected to the air supply unit 7. Combustion fuel is supplied from the burner 9 to the inside of the radiant tube 13 and air is supplied, and combustion is performed to form a flame. Thus, the combustion space 14 is formed inside the radiation cylinder 13. The combustion space 14 communicates with the combustion gas flow path b <b> 2 of the reforming unit 3 through an opening 13 a formed at the upper end of the radiation cylinder 13. The combustion gas flow path b2 and the combustion gas flow path b1 communicate with each other at the bottom of the reforming section 3, and the downstream end of the combustion gas flow path b1 can extract the combustion gas to the outside of the reforming section 3. It is configured.

  FIG. 2 is a block diagram showing the configuration of the control unit 20 of the hydrogen generator, and FIG. 3 is a flowchart schematically showing the contents of the program stored in the control unit 20 of FIG. As illustrated in FIG. 2, the control unit 20 includes a computer such as a microcomputer, and includes a processing control unit 21, an operation input unit 22, a display unit 23, and a storage unit 24. The control unit 20 controls the raw material supply unit 1, the water supply unit 2, the fuel supply unit 8, and the air supply unit 7, and adjusts the supply amounts of the raw material, water, combustion fuel, and air. Although not shown, the raw material supply unit 1, the water supply unit 2, the air supply unit 7, and the fuel supply unit 8 are configured to be able to adjust the flow rate of the supply object. For example, the supply units 1, 2, 7, and 8 may include a driving unit such as a pump and a fan, and the driving unit may be controlled by the control unit 20 to adjust each supply flow rate. Further, a flow rate adjusting means such as a valve may be further provided in the downstream flow path of the driving means, and the flow rate adjusting means may be controlled by the control unit 20 to adjust each supply amount.

  Next, the operation of the hydrogen generator will be described. The operation of the hydrogen generator includes an operation of heating the reforming unit 3 until the water evaporation unit 4 reaches a temperature at which steam can be generated (hereinafter referred to as a start-up operation), and a water evaporation unit 4 heated to the temperature. An operation of heating the reforming unit 3 until the reforming catalyst layer 5 reaches the reforming reaction temperature while supplying water to the reforming reaction temperature (hereinafter referred to as a preheating operation), and hydrogen by the reforming reaction in the reforming catalyst layer 5 Can be divided into an operation (hereinafter referred to as a hydrogen generation operation).

 In the start-up operation, the supply of the raw material and water to the reforming unit 3 is stopped, and the supply of the raw material and water is started to the reforming unit 5 when the water evaporation unit 4 reaches a temperature capable of generating steam. Switch from starting operation to preheating operation. When the reforming catalyst layer 5 reaches the reforming reaction temperature (for example, 500 ° C. to 700 ° C.) by this preheating operation, hydrogen gas is generated from the raw material and steam by the reforming reaction using the reforming catalyst, thereby Then, the preheating operation is switched to the hydrogen generation operation. Here, the period from the start of startup of the hydrogen generator (specifically, the start of startup corresponds to the start of combustion in the combustion unit 12) until the water is supplied to the water evaporation unit 4. Is called the startup time as the time required for the startup operation of the hydrogen generator.

  Such start-up operation, preheating operation, and hydrogen generation operation are executed in accordance with a program stored in the control unit 20, as shown in FIG. Hereinafter, the operation of the hydrogen generator will be described in accordance with the program execution process shown in FIG.

  As shown in FIG. 3, an operation start signal is output from the process control unit 21 of the control unit 20 to start the starting operation. Specifically, combustion fuel is supplied from the fuel supply unit 8 to the combustion unit 12 at a predetermined flow rate, and air is supplied from the air supply unit 7 to the combustion unit 12 at a predetermined flow rate. Here, 1.5 times the theoretical air amount in the complete combustion of the combustion fuel supplied to the combustion unit 12 is supplied to the combustion unit 12. In order to realize stable combustion in the combustion section 12, the supply amounts of combustion fuel and air to the combustion section 12 during operation of the hydrogen generator are kept constant.

  In the combustion unit 12, a flame is formed in the combustion space 14 by a combustion reaction between the supplied combustion fuel and air. The reforming catalyst layer 5 is heated by the combustion heat generated by the combustion, and the reforming catalyst layer 5 is also introduced by the retained heat of the combustion gas introduced from the combustion space 14 into the combustion gas channel b2 and flowing in the channel. Is heated. Further, the combustion gas is introduced from the combustion gas flow path b2 to the combustion gas flow path b1 and flows in the flow path, but the combustion gas flow path b1 is in contact with the reforming raw material flow path a through the vertical wall 51. The heat of the combustion gas flowing through the combustion gas channel b1 is transferred to the reforming material channel a. Thereby, the water evaporation part 4 formed in the bottom part of the reforming raw material flow path a is heated. Thus, both the reforming catalyst layer 5 and the water evaporation unit 4 are heated by the combustion in the combustion unit 12, and the reforming catalyst layer 5 located on the upstream side of the heat transfer path becomes the water evaporation located on the downstream side. Heated prior to section 4.

  Here, in the heating of the reforming unit 3, the temperature of the reforming catalyst layer 5 is constantly detected by the reforming temperature detection unit 15, and the detected temperature is transmitted to the control unit 20. Then, as shown in FIG. 3, it functions as a determination unit that determines whether or not the water evaporation unit 4 has a temperature capable of generating water vapor based on the temperature of the reforming catalyst layer detected by the reforming temperature detection unit 15. The processing control unit 21 that compares the first reference temperature T1 preset in the processing control unit 21 and the detected temperature of the reforming catalyst layer 5 compares the temperature of the reforming catalyst layer 5 with the first reference temperature T1. It is judged whether it is higher than (step S1). Here, the first reference temperature T1 is 100 ° C. If the temperature of the reforming catalyst layer 5 is higher than the first reference temperature T1, the raw material supply unit 1 and the water supply unit from the processing control unit 21 that also functions as a supply control unit that controls the water supply to the water evaporation unit 4. A control signal is output to No. 2, whereby supply of the raw material and water to the reforming unit 3 is started, and the process proceeds to a preheating operation (step S4).

  On the other hand, if the temperature of the reforming catalyst layer 5 is equal to or lower than the first reference temperature T1, the heating is continued without supplying the raw material and water (step S2). In this heating process, the process controller 21 compares the second reference temperature T2 preset in the process controller 21 with the detected temperature of the reforming catalyst layer 5, and the temperature of the reforming catalyst layer 5 is It is determined whether or not the temperature is higher than the second reference temperature T2 (step S3). Here, the second reference temperature T2 is 400 ° C. If the temperature of the reforming catalyst layer 5 is equal to or lower than the second reference temperature T2, heating is continued in this state. On the other hand, if the temperature of the reforming catalyst layer 5 is higher than the second reference temperature T2, a control signal is output from the processing control unit 21 to the raw material supply unit 1 and the water supply unit 2, and supply of the raw material and water is started. Then, the operation proceeds to the preheating operation (step S4).

  In the preheating operation, the raw material supplied from the raw material supply unit 1 and the water vapor generated by evaporating the water supplied from the water supply unit 2 in the water evaporation unit 4 are reformed through the reforming raw material channel a. After being supplied to the layer 5 and flowing through the reforming catalyst layer 5, it is supplied to the reformed gas flow path c. Then, it is taken out of the reforming unit 3 through the reformed gas flow path c. Thus, in the reforming catalyst layer 5 heated in a state where the raw material and the steam are passed, when the reforming reaction temperature is reached, the reforming reaction is performed by the raw material and the steam to generate hydrogen (step S5). ). Here, the reforming reaction does not start suddenly with a certain temperature as a threshold value, but when the temperature of the reforming catalyst layer 5 reaches about 500 ° C., the supplied raw material and a part of the steam start to react. As the temperature rises, the proportion of the raw material and water vapor that react with each other increases, and when it reaches about 700 ° C., it reacts almost completely. Therefore, in the preheating operation in which the reforming unit 3 is heated in a state where the raw material and the steam are supplied as described above, the reforming reaction is appropriately started when the temperature condition of the reforming catalyst layer 5 is adjusted. Therefore, here, the temperature of the reforming catalyst layer 5 is, for example, about 700 ° C., and the raw material and water vapor supplied to the reforming unit 4 are almost completely reacted to generate hydrogen. This is called operation. Therefore, the operation of heating the reforming unit 3 until the reforming catalyst layer 5 reaches the reforming reaction temperature is defined as the preheating operation. Even during the preheating operation period, the reforming reaction is performed from the raw material and steam. As a result, hydrogen is partially generated.

  This hydrogen generation operation is the same as the operation of the existing hydrogen generator. That is, a reformed gas containing hydrogen as a main component is generated in the reforming catalyst layer 5 by the raw material, the water vapor, and the reforming catalyst supplied to the reforming catalyst layer 5 through the reforming material channel a. The generated reformed gas, that is, hydrogen gas, is taken out of the reforming unit 3 through the reformed gas flow path c.

  The first and second reference temperatures T1 and T2 that are the determination criteria for the starting timing of the raw material and water supply in Steps S1 and S3 of the start-up operation are the values when the reforming unit 3 is heated and when the hydrogen generator is stopped. The first and second reference temperatures are set in consideration of the temperature changes of the reforming catalyst layer 5 and the water evaporation unit 4 and the relationship between the temperature states of the reforming catalyst layer 5 and the water evaporation unit 4. The start-up time can be shortened by controlling the timing of starting the supply of the raw materials and water based on T1 and T2.

  Hereinafter, this effect will be described in detail with reference to FIG.

  FIG. 4A is a diagram illustrating an example of a stop operation of the hydrogen generator and a change over time of the temperatures of the reforming catalyst layer 5 and the water evaporation unit 4 after the hydrogen generator is stopped. The stop operation is an operation from when the process control unit 21 of the control unit 20 outputs an operation stop signal until the hydrogen generator is completely stopped.

  As shown in FIG. 4A, in the hydrogen generator during the hydrogen generation operation, the temperature of the reforming catalyst layer 5 is maintained at about 700 ° C., while the temperature of the water evaporation unit 4 is about 120 ° C. Is retained. When the operation stop signal is output from the processing control unit 21 and the stop operation is started, the raw material supply unit 1 and the water supply unit 2 are stopped and the fuel supply unit 8 is stopped. The quality reaction and the combustion in the combustion section 12 are stopped.

  At this time, the air blown from the air supply unit 7 quickly takes away the temperature of the reforming catalyst layer 5, while the water located downstream of the reforming catalyst layer 5 based on the heated air. It continues to be supplied to the burner 9 for the purpose of raising the temperature of the evaporator 4.

  When combustion in the combustion unit 12 stops and heating of the reforming unit 3 stops, the temperature of the reforming catalyst layer 5 that has been maintained at a high temperature during the hydrogen generation operation rapidly decreases. On the other hand, in the water evaporation section 4, since the temperature during the hydrogen generation operation is lower than the temperature of the reforming catalyst layer 5, the temperature does not drop suddenly due to the stop of heating like the reforming catalyst layer 5, but rather On the contrary, the water evaporation part 4 is continuously heated by the heat release from the reforming catalyst layer 5 and the heat exchange with the air, and the temperature rises, as the reforming reaction which is an endothermic reaction is not performed. As described above, in the combustion stop operation, the temperature is reduced in the reforming catalyst layer 5, while the temperature is increased in the water evaporation unit 4. Therefore, after a predetermined time has elapsed from the start of the combustion stop operation, the temperature is higher than that in the reforming catalyst layer 5. The temperature of the water evaporation part 4 becomes high. After the reversal of temperature occurs between the reforming catalyst layer 5 and the water evaporation unit 4, the temperature increase of the water evaporation unit 4 also stops. Then, when the temperature of the reforming catalyst layer 5 is about 150 ° C. and the temperature of the water evaporation unit 4 is about 180 ° C., the operation of the air supply unit 7 is also stopped, and thus the hydrogen generator is completely stopped. To do. After the hydrogen generator stops, the temperature of the hydrogen generator including the reforming catalyst layer 5 and the water evaporation unit 4 gradually decreases to room temperature.

  Here, when the operation is resumed in a short time after the hydrogen generator is stopped, the water evaporation unit 4 and the reforming catalyst unit 5 are maintained at a relatively high temperature. If it is 100 degreeC or more, it is possible to supply water immediately and to produce | generate water vapor | steam.

  Therefore, as understood from FIG. 4A, if the temperature of the reforming catalyst layer 5 is 100 ° C. or higher, the temperature of the water evaporation section 4 is always over 100 ° C. If the temperature of the reforming catalyst layer 5 detected by the reforming temperature detection unit 15 at the start of startup exceeds the first reference temperature, water supply is performed. Even if water is supplied from the unit 2 to the water evaporation unit 4, water vapor can be generated in the water evaporation unit 4.

  On the other hand, when a long time has passed since the hydrogen generator stopped, the temperature of the water evaporation unit 4 and the reforming catalyst unit 5 decreases to near the room temperature level, thereby restarting the operation from this state. Therefore, it is necessary to sufficiently heat the water evaporation part 4 to a temperature at which water vapor can be generated.

  FIG. 4B shows a modification when the hydrogen generator is restarted from a state where the temperature of the water evaporation unit 4 and the reforming catalyst unit 5 has decreased to room temperature after a long time has passed since the hydrogen generator stopped. It is a figure which shows an example of the time-dependent change of the temperature of the quality catalyst layer 5 and the water evaporation part 4. FIG.

  As shown in FIG. 4B, the reforming catalyst layer 5 near the combustion unit 12 starts to be preferentially heated by the heating of the combustion unit 12, and then the water is delayed after the temperature of the reforming catalyst layer 5 rises. The temperature of the evaporation unit 4 rises. Since heating of the reforming catalyst layer 5 is prioritized over heating of the reforming unit 3, it takes time to heat the water evaporating unit 4 to a temperature capable of generating steam. If the temperature of the layer 5 reaches 400 ° C., it can be determined that the temperature of the water evaporation unit 4 exceeds 100 ° C. Therefore, the second reference temperature of the reforming catalyst layer 5 is set to 400 ° C., the reforming temperature detector 15 detects the temperature of the reforming catalyst layer 5 and the reforming catalyst layer 5 sets the second reference temperature to the second reference temperature. If water is supplied from the water supply unit 2 to the water evaporation unit 4 at a time exceeding this, the temperature of the water evaporation unit 4 exceeds 100 ° C., and water vapor can be reliably generated.

  Thus, in the hydrogen generator, the timing at which water vapor can be generated varies depending on the temperature state of the hydrogen generator at the start of operation (in other words, at the start of startup), and the length of the startup time varies. Therefore, in the present embodiment, as described below, water is supplied to the reforming unit 3 in accordance with the temperature state of the hydrogen generator at the start of startup (specifically, the temperature state of the reforming catalyst layer 5). The start time is shortened by adjusting the start timing.

  Specifically, in this embodiment, in order to determine whether or not the water evaporation unit 4 at the start of startup is in a state where water can be supplied immediately (that is, a state where water vapor can be generated from the supplied water). In addition, the first reference temperature T1 is set, and the second reference temperature T2 is set in order to determine whether or not the water evaporation unit 4 has been heated to a state where water vapor can be generated by the start-up operation. ing. As described above, here, the first reference temperature T1 is set to 100 ° C., and the second reference temperature T2 is set to 400 ° C.

  For example, when the operation is resumed in a short time after the operation is stopped, the temperatures of the reforming catalyst layer 5 and the water evaporation unit 4 are kept high, and as shown in FIG. 4, the first reference temperature T1 is 100. If the temperature of the reforming catalyst layer 5 is higher than ° C., the water evaporation section 4 is 100 ° C. or higher. Therefore, if the temperature of the reforming catalyst layer 5 detected by the reforming temperature detecting unit 15 is higher than the first reference temperature T1, the supply of water to the reforming unit 3 can be started quickly and started. Time can be shortened. In this case, since the reforming catalyst layer 5 is heated in a state where water vapor is sufficiently supplied, deterioration of catalyst performance due to the high temperature of the reforming catalyst layer 5 and carbon deposition of raw materials due to insufficient steam are prevented. It becomes possible to do.

  In the above description, the case where the first reference temperature T1 is set to 100 ° C. has been described. However, if it can be determined that the water evaporation unit 4 is in a state capable of generating water vapor, the first reference temperature T1 is set. The value may be other than this, and is appropriately set according to, for example, the configuration of the reforming unit 3. 50-150 degreeC may be sufficient as the 1st reference temperature T1, and since it is the range, since the water evaporation part 4 retains the heat | fever in the last driving | operating, it is estimated that water vapor | steam production | generation is possible immediately. . The first reference temperature T1 may be as low as about 50 ° C., for example, when the operation of the hydrogen generator is stopped, the air is reformed through the air flow path 6 of the combustion unit 12. When a cooling operation such as supplying a large amount to 3 to cool the reforming section 3 is performed, the water evaporation section 4 is 100 ° C. or higher even if the temperature of the reforming catalyst layer 5 is so low. Because there are cases.

  On the other hand, when the operation is restarted after a long time has elapsed since the stop, the temperature of the reforming catalyst layer 5 and the water evaporation unit 4 has decreased to room temperature, and the temperature of the reforming catalyst layer 5 at the start of startup is the first It is lower than the standard temperature of 100 ° C. Therefore, in this case, even if water is supplied to the water evaporation unit 4, water vapor cannot be generated. Therefore, in this case, the supply of water is not started immediately, but the reforming unit 3 is heated by combustion in the combustion unit 12 for a predetermined time. And it is determined using the 2nd reference temperature T2 whether the heated water evaporation part 4 is a state which can produce | generate water vapor | steam. Since the reforming catalyst layer 5 is preferentially heated over the water evaporation unit 4 in the heating of the starting operation, the temperature of the water evaporation unit 4 is a temperature at which water vapor can be generated until the temperature of the reforming catalyst layer 5 rises to some extent. When the temperature of the reforming catalyst layer 5 becomes higher than 400 ° C. which is the second reference temperature T2, the water evaporation unit 4 is also sufficiently heated and the temperature is 100 ° C. or higher. Therefore, if the temperature of the reforming catalyst layer 5 detected by the reforming temperature detection unit 15 is higher than the second reference temperature T2, water supply to the water evaporation unit 4 can be started. As described above, by controlling the timing of supplying water by comparison with the second reference temperature T2, the reforming catalyst layer 5 is further heated in a state where water vapor is sufficiently supplied. Therefore, it becomes possible to prevent the catalyst performance from being deteriorated due to the high temperature of the reforming catalyst layer 5 and the carbon deposition of the raw material due to the lack of water vapor.

  In the above description, the case where the second reference temperature T2 is set to 400 ° C. has been described. However, the second reference temperature T2 is not limited to this, and the water evaporation unit 4 is in a state capable of generating water vapor. If the temperature is the temperature of the reforming catalyst layer 5 and does not cause deterioration of the reforming catalyst or carbon deposition of the feedstock in the absence of water vapor, the second reference temperature T2 may be other than this, and The second reference temperature T2 is appropriately set according to the configuration of the mass portion 3 and the like. For example, if the temperature of the reforming catalyst layer 5 exceeds 500 ° C., the reforming catalyst, the container filled with the reforming catalyst and the gas flow path also exceed 500 ° C., and water vapor is not present at this temperature state. If the raw material is supplied to the reforming unit 3, carbon deposition occurs in the flow path of the reforming unit 3 or on the reforming catalyst due to the thermal decomposition of the raw material. In any case, aggregation of the catalyst and oxidation occur, and as a result, there is a possibility that problems such as blockage of the flow path and decrease in the activity of the catalyst are induced. Therefore, the second reference temperature T2 is preferably set in the range of 300 to 500 ° C.

  As described above, in the hydrogen generator of the present embodiment, the timing of the water supply start can be adjusted according to the temperature state of the water evaporation unit 4 at the start of startup, so the temperature of the water evaporation unit 4 at the start of startup When the temperature is such that water vapor can be generated, the time required for the start-up operation can be shortened. Further, since the reforming catalyst layer 5 is heated in a state where water vapor is sufficiently supplied, carbon deposition or reforming catalyst aggregation in the flow path of the reforming unit 3 or on the reforming catalyst due to thermal decomposition of the raw material. And oxidation can be prevented. Further, since water is supplied to the water evaporation unit 4 in a state where water vapor can be generated, it is possible to reliably generate water vapor, and thus it is possible to prevent blockage of the flow path due to liquid water. . From the above, high reliability can be realized in the hydrogen generator of this embodiment.

  Further, in the configuration of the hydrogen generator described above, the water evaporation unit 4 is disposed on the outermost periphery of the reforming unit 3, so that heat radiated from the high-temperature reforming catalyst layer 5 to the outer peripheral side is water evaporation. It is used as the latent heat of vaporization of water in the section 4. Therefore, the temperature increase in the water evaporation unit 4 is suppressed. Thus, if the temperature of the water evaporation part 4 located in the outermost periphery of the modification | reformation part 3 is restrained low, since the surface temperature of the main body 50 of the modification | reformation part 3 will fall, it will suppress the heat radiation from the main body surface. Therefore, the thermal energy efficiency of the hydrogen generator is improved.

  The configuration of the reforming unit 3 is not limited to the above-described configuration, and the shape and internal structure of the main body 50, the arrangement of each flow path in the reforming unit 3 and the like may be other than those described above. Here, in the configuration in which the water evaporation part 4 is arranged on the outermost periphery of the reforming part 3 so as to suppress the heat radiation from the surface as described above, the heat generated by the combustion in the combustion part 12 is transferred to the water evaporation part 4. In the conventional heating method in the start-up operation, the temperature of the reforming unit 3 rises remarkably, whereas the temperature of the water evaporation unit 4 hardly rises, and deterioration of the catalyst, carbon deposition of raw materials, etc. Problems are likely to occur. Therefore, with this configuration, the effect of the present invention is more effectively achieved.

  Further, the temperature detector that detects the temperature of the reforming catalyst layer 4 in the configuration of the hydrogen generator is provided at a location that detects the temperature of the gas flowing in the reformed gas flow path that has passed through the reforming catalyst layer 5. Although the timing of water supply is changed based on the detected temperature, the temperature obtained from the temperature detecting unit installed at the appropriate position on the surface of the structure of the reforming unit 3 including the reforming catalyst layer 5 is improved. The temperature obtained from the temperature detection unit installed at a proper position of the flow path a through which the water vapor and the raw material and the reformed gas flow in the mass part 3, the temperature obtained from the temperature detection unit installed at a proper position of the combustion space 14, Alternatively, even if the temperature is obtained from a temperature detector installed at appropriate positions in the combustion gas flow paths b1 and b2, the temperature has a high correlation with the temperature of the reforming catalyst layer 5 at or near the reforming catalyst layer 4 Can be detected, and the water evaporation section 4 can generate steam. If whether a possible determination range is a temperature capable, it may be installed in any location.

  In this case, however, the second reference temperature T2 is set as a temperature at which deterioration of the reforming catalyst and carbon deposition due to the feedstock do not occur in the absence of steam due to the correlation with the maximum temperature of the reforming catalyst layer 5. There must be.

  As will be described later, a water evaporation unit temperature detection unit 16 for detecting the temperature of the water evaporation unit 4 shown in FIG. 8 is provided at an appropriate position on the outer surface of the water evaporation unit 4 or inside the water evaporation unit 4. If the temperature involved in the evaporation of the water evaporation unit 4 is directly measured, the state of the water evaporation unit 4 can be grasped more accurately, and the water vapor can be reliably supplied.

(Embodiment 2)
The configuration of the water generator according to Embodiment 2 of the present invention is the same as the configuration of the hydrogen generator of Embodiment 1, and therefore the description thereof is omitted here. In the start-up operation of the hydrogen generator of the present embodiment, the first and second reference temperatures T1 and T2 are set and the temperature state of the water evaporation unit 4 is determined as in the first embodiment. Here, the third and fourth reference temperatures T3 and T4 are further set, and the heating state of the reforming catalyst layer 5 is controlled based on the third and fourth reference temperatures T3 and T4. More specifically, in the present embodiment, the reforming unit 3 is more actively heated than in the first embodiment, so that water evaporates over a long time after the hydrogen generator stops. Even when the hydrogen generator is restarted from the state in which the temperatures of the unit 4 and the reforming catalyst unit 5 are lowered to room temperature, the time for heating the water evaporation unit 4 to a steam generating temperature is shortened. It is expected. However, if the temperature of the reforming section 3 (reforming catalyst layer 5) is excessively raised, the reforming catalyst deteriorates and is not desirable. To eliminate such deterioration of the reforming catalyst, the temperature of the reforming section 3 is increased. By stopping, it is not desirable that the reforming unit 3 is too cold. Therefore, the temperature of the reforming unit 3 is controlled by the control unit 20 as described below.

  Hereinafter, the start-up operation of the present embodiment will be described with reference to FIGS.

  FIG. 5 is a flowchart schematically showing the contents of the program stored in the control unit 20 (FIG. 1) of the hydrogen generator of the present embodiment. As shown in FIG. 5, in the present embodiment, as in the case of the first embodiment, an operation start signal is output from the processing control unit 21 of the control unit 20 to start the operation of the hydrogen generator, and the fuel supply unit Combustion fuel and air are supplied from the air supply unit 8 and the air supply unit 7 to the combustion unit 12 for combustion. Thereby, the starting operation is started. The temperature of the reforming catalyst layer 5 at the start of activation is detected by the reforming temperature detection unit 15, and the detected temperature information is transmitted to the processing control unit 21. The process control unit 21 compares the detected temperature of the reforming catalyst layer 5 with the first reference temperature T1 (100 ° C.) (step S1). If the temperature of the reforming catalyst layer 5 is higher than the first reference temperature T1, the process proceeds to step S4 as described in the first embodiment. On the other hand, if the temperature of the reforming catalyst layer 5 is equal to or lower than the first reference temperature T1, the process proceeds to step S2 as described in the first embodiment. Then, the reforming catalyst layer 5 and the water evaporation unit 4 are heated to proceed to the process of step S3.

  Here, in the start-up operation of the present embodiment, the processes of steps S6 to S10 are further performed during the period from the step S2 to the process of step S3 as in the first embodiment. Thereby, until the temperature of the reforming catalyst layer 5 rises to the second reference temperature T2, the combustion in the combustion unit 12 is stopped and restarted according to the temperature state of the reforming catalyst layer 5 as shown in FIG. Thus, the heating amount of the reforming catalyst layer 5 is adjusted.

  FIG. 6 is a diagram showing a heating state of the reforming catalyst layer 5 and the water evaporation unit 4 in the start-up operation of the hydrogen generator of the present embodiment. As shown in FIG. 5, in the present embodiment, a third reference temperature T3 and a fourth reference temperature T4 are set between the first and second reference temperatures T1 and T2 of the first embodiment. Has been. The third reference temperature T3 is higher than the fourth reference temperature T4 (T3> T4). Here, the third reference temperature T3 is set to 250 ° C., and the fourth reference temperature T4 is set to 200 ° C. Is set.

  For example, in this case, the temperature at the start of the operation of the hydrogen generator is lower than the first reference temperature (100 ° C.), so that the supply of water is not started immediately as shown in step S2 of FIG. Subsequently, the reforming catalyst layer 5 and the water evaporation unit 4 are heated. Then, during this heating, it is determined whether or not the detected temperature of the reforming catalyst layer 5 is equal to or higher than the third reference temperature T3 (step S6). If it is determined that the temperature is lower than the third reference temperature T3, heating is continued. On the other hand, if the detected temperature of the reforming catalyst layer 5 is equal to or higher than the third reference temperature T3, the combustion in the combustion unit 12 is stopped (step S7). As the combustion is stopped, the temperature of the reforming catalyst layer 5 is decreased, while the temperature of the water evaporation unit 4 is increased by heat radiation from the reforming catalyst layer 5. Subsequently, when the temperature of the reforming catalyst layer 5 decreases to the fourth reference temperature T4 (step S8), combustion is started again (step S9). As the combustion resumes, the temperature of the reforming catalyst layer 5 rises again, and the temperature of the water evaporation unit 4 continues to rise. When the temperature of the reforming catalyst layer 5 becomes equal to or higher than the third reference temperature T3 by restarting combustion, the combustion is stopped again. Here, the process control unit 21 of the control unit 20 controls the stop and restart of combustion by controlling the supply of fuel from the fuel supply unit 8 to the combustion unit 12 (step S10).

  The combustion stop and restart as described above are performed a preset number of times. The set number of times is one or more, and is preferably set according to the positional relationship between the reforming catalyst layer 5 and the water evaporation unit 4 and the heat transfer state according to the configuration of the combustion gas flow paths b1 and b2. . After the combustion is stopped and restarted for the set number of times, the heating is further performed after exceeding the third reference temperature T3 (step 11), and the comparison with the second reference temperature T2 is performed as described above (step 11). S3).

  In this way, by controlling the combustion unit 12 based on the third and fourth reference temperatures T3 and T4 and adjusting the heating amount of the reforming catalyst layer 5, the temperature rise of the reforming catalyst layer 5 is reduced to 500 ° C. or less. The temperature rise of the water evaporation part 4 can be accelerated | stimulated, suppressing.

  In the above, the third reference temperature T3 is set to 250 ° C. and the fourth reference temperature T4 is set to 200 ° C., but the third and fourth reference temperatures T3 and T4 are limited to this. Instead, it is between the first reference temperature T1 and the second reference temperature T2, and the temperature of the reforming catalyst layer 5 is not increased to 500 ° C. or more, and the temperature increase of the water evaporation section 4 is promoted. Other than this, if possible.

  Here, in the temperature change of the reforming catalyst layer 5 when the combustion in the combustion unit 12 is stopped, even if the combustion is stopped at the time point P1 when the temperature of the reforming catalyst layer 5 reaches the third reference temperature T3, Since the reforming catalyst layer 5 is heated by the overshoot, the temperature of the reforming catalyst layer 5 continues to rise for a predetermined period after the combustion is stopped. At time P2, the temperature of the reforming catalyst layer 5 reaches a peak and becomes higher than the third reference temperature T3. For this reason, in setting the third reference temperature T3, it is necessary to consider the temperature increase due to such overshoot so that the temperature at the peak time P2 does not exceed the second reference temperature T2. For example, the third reference temperature T3 is set in the range of 200 to 300 ° C. On the other hand, the fourth reference temperature T4 may be set between the third reference temperature T3 and the first reference temperature T1 if the third reference temperature T3 is determined.

  As described above, according to the present embodiment, it is possible to control the amount of heating of the reforming catalyst layer 5 by controlling the combustion in the combustion section 12, so that the effects described in the first embodiment are more effective. It is effectively played, and thus higher reliability is realized.

  In the above description, the number of times of stopping and resuming the combustion in the combustion unit 12 is set in advance, and the case where the determination based on the second reference temperature T2 is performed after the number of times has been performed has been described. As a modification, instead of setting the number of times of stopping and restarting combustion, the time for performing the heating operation with stopping and restarting combustion may be set in advance. For example, the heating time that accompanies the stop and restart of combustion is set to 10 minutes in advance, and during this period, stop and restart of combustion are performed based on the third and fourth reference temperatures T3 and T4, and after 10 minutes have elapsed. The configuration may be such that heating exceeding the third reference temperature T3 is performed. Further, if a misfire occurs in the combustion section 12 after 10 minutes and the temperature of the reforming catalyst layer 5 is lowered, the combustion section 12 is reached when the temperature of the reforming catalyst layer 5 reaches the fourth reference temperature T4. It may be configured such that combustion at is resumed.

  Further, the example in which the water evaporation unit 4 is efficiently heated while adjusting the heating amount of the reforming catalyst layer 5 by repeatedly executing the stop and restart of the combustion in the combustion unit 12 has been described so far. However, as a modified example of the combustion operation of stopping and resuming the combustion unit 12, by switching the combustion unit 12 between a high heat amount heating state and a low heat amount heating state a predetermined number of times without stopping the combustion unit 12, Similar effects can be obtained (the third and fourth reference temperatures T3 and T4 need to be reset appropriately). For example, the amount of combustion fuel to the combustion unit 12 may be adjusted so that the ratio of the heat quantity of the high heat quantity to the low heat quantity is about 1.5 times.

  Alternatively, the heating of the low calorific value by the combustion unit 12 can be realized, for example, by increasing the amount of air relative to the amount of combustion fuel and lowering the temperature of the combustion flame as compared with normal combustion, as will be described in detail later.

(Embodiment 3)
The hydrogen generator according to the present embodiment has the same configuration as that of the hydrogen generator according to the first embodiment, and thus detailed description thereof is omitted here. Further, in the hydrogen generator of the present embodiment, the combustion in the combustion section 12 is controlled and the heating amount of the reforming catalyst layer 5 is adjusted as in the case of the second embodiment. It is different from Form 2.

  That is, in the second embodiment, the stop and restart of combustion in the combustion unit 12 are controlled based on the third and fourth reference temperatures T3 and T4. In the present embodiment, the start of the hydrogen generator is started. Depending on the temperature of the reforming catalyst layer 5 at the time, the number and timing of the stop and restart of the combustion are automatically set in advance, and the stop and restart of the combustion are performed according to this setting. The number and timing of stopping and resuming the combustion are the same as in the second embodiment, and the temperature of the reforming catalyst layer 5 is suppressed from becoming a high temperature of 500 ° C. or higher, and the temperature increase of the water evaporation unit 4 is promoted. Set to do. For example, data indicating the correlation between the number and timing of the stop and restart of combustion and the temperature changes of the reforming catalyst layer 5 and the water evaporation unit 4 are stored in the storage unit 24 of the control unit 20 in advance, and start-up is started. In accordance with the temperature information of the reforming catalyst layer 5 that is sometimes detected and transmitted to the processing control unit 21, the optimal number and timing are selected and set from the data in the storage unit 24. In this case, if the detected temperature of the reforming catalyst layer 5 is low, it is estimated that the temperature of the water evaporation unit 4 is also low. Therefore, in this case, the number of preheating is increased. On the other hand, if the detected temperature of the reforming catalyst layer 5 is high, it is estimated that the temperature of the water evaporation unit 4 is also high. Therefore, in this case, the number of times of preheating is reduced. As a specific example, when the first reference temperature T1 is 100 ° C. and the detected temperature of the reforming catalyst layer 5 at the start of startup is 80 to 99 ° C., a series of operations of stopping and restarting combustion are performed. The number of times is set to 1, if it is 60-79 ° C., it is 2 times, if it is 40-59 ° C., it is 3 times, and if it is lower, it is set to 4 times.

    As described above, according to the start-up operation of the present embodiment, the combustion in the combustion unit 12 is stopped according to the state of the hydrogen generator at the start of start-up, specifically, the temperature of the reforming catalyst layer 5. In addition, it is possible to optimize the number of restarts. Therefore, the same effect as in the second embodiment can be obtained, and in this case, heating can be performed more efficiently.

  In the above description, the case where the number of times of stopping and resuming the combustion is set in advance has been described. However, as in the case of the modification of the second embodiment, not the number of times but the heating involving the stopping and resuming of combustion is performed. The time may be set in advance.

(Embodiment 4)
FIG. 8 is a schematic cross-sectional view showing the configuration of the hydrogen generator according to Embodiment 4 of the present invention.

  In the hydrogen generator according to the present embodiment, a water evaporation unit temperature detection unit 16 that detects the temperature of the water evaporation unit 4 is additionally provided in the reforming unit of the hydrogen generation device described in the first embodiment (see FIG. 1). Accordingly, a signal (temperature information) output from the water evaporation temperature detection unit 16 is transmitted to the control unit 20.

  FIG. 9 is a flowchart schematically showing the contents of a program stored in the control unit of the hydrogen generator according to this embodiment.

  In the flowchart shown in FIG. 9, the “first reference temperature” in step S1 and the “second reference temperature” in step S3 of the flowchart shown in FIG.

  In this embodiment, the clogging is shown in FIG. 9 by measuring the temperature of the water evaporation unit 4 by the water evaporation unit temperature detection unit 16 instead of indirectly predicting the temperature of the water evaporation unit 4 from the reforming temperature detection unit 15. The state of the water evaporation part 4 in step S1 and step S3 is detected more directly and accurately, and it is determined whether water can be generated by supplying water. Therefore, when the combustion is stopped and restarted, the execution of the process between steps S6 to S10 shown in FIG. 9 is determined according to the number of processes and the processing time as in the third embodiment. Instead, it can be determined directly by the temperature state of the water evaporation section 4.

  Further, the determination of the timing of stopping and resuming combustion is performed by the control unit 20 based on the temperature information output from the reforming catalyst temperature detection unit 15 as in the third embodiment, whereby the reforming catalyst layer 5 The catalyst is prevented from deteriorating due to the high temperature of the catalyst.

  In addition, the water evaporation part temperature detection part 16 is a position which can grasp | ascertain accurately whether water vapor | steam is generable in the water evaporation part 4, such as the outer surface of the structure of the water evaporation part 4, and the evaporation space where the water inside a structure evaporates. Install it. Here, the water evaporation unit reference temperature at which the water evaporation unit 4 can generate water vapor varies depending on the configuration of the water evaporation unit 4, the installation position of the water evaporation unit temperature detection unit 16, and the like. If it is degreeC, it will become 100 degreeC in the location where water evaporation is mainly performed of the water evaporation part 4, and evaporation of water is accelerated | stimulated appropriately.

  The configuration of the hydrogen generator according to the present embodiment described above is the same as the configuration of the hydrogen generator described in the first embodiment except that the water evaporation unit temperature detector 16 is added. The description of the common configuration is omitted.

  Further, the operations according to the present embodiment other than the processing operations in step S1 and step S3 shown in FIG. 9 are the same as the processing operations described in the second embodiment (FIG. 6), and an explanation of operations common to both of them. Is also omitted.

(Embodiment 5)
The hydrogen generator according to Embodiment 5 of the present invention has the same configuration as that of hydrogen generator 100 of Embodiment 1, and therefore detailed description thereof is omitted here. In the present embodiment, the startup operation similar to that of the first embodiment is performed, but the amount of air supplied to the combustion unit 12 in the combustion of the startup operation is the normal combustion performed in the preheating operation or the hydrogen generation operation. This is different from the first embodiment in that it is larger than the air supply amount. Hereinafter, this difference will be described.

  In normal combustion, the ratio of the theoretical air amount in the complete combustion of the combustion fuel supplied from the fuel supply unit 8 to the combustion unit 12 and the air amount actually supplied from the air supply unit 7 to the combustion unit 12 (hereinafter, (Referred to as air ratio) is set to about 1.5. This depends on the fact that the air ratio in combustion with the best fuel characteristics is around 1.5 in normal combustion, although it depends on the configuration of the combustion section 12 and the combustion method. Therefore, in the present embodiment, the air ratio in the preheating operation and the hydrogen generation operation is set to the air ratio in normal combustion, that is, 1.5. On the other hand, in the starting operation of the present embodiment, the air ratio in combustion is set to be larger than the air ratio in normal combustion (that is, 1.5). Specifically, the air ratio in the combustion at the start-up operation is set to 2.0 or more and the combustion characteristics are not deteriorated, for example, in the range of 2.0 to 5.0. Here, it is 2.0. The reason for this setting is as follows.

  When the amount of combustion fuel supplied to the combustion unit 12 is constant, the amount of heat generated in the combustion unit 12 is constant. For this reason, in this state, the temperature of the flame formed in the radiant cylinder of the combustion unit 12 changes as the air supply amount from the air supply unit 7 to the combustion unit 12 changes. For example, if the air ratio is made larger than the air ratio (1.5) in normal combustion and the air supply amount is made larger than that in normal combustion, the amount of combustion exhaust gas generated by the combustion increases. As a result, the temperature of the flame decreases. Here, the flame temperature of the flame is the flame temperature. From this, when the control unit 20 controls the air supply unit 7 to adjust the air supply amount so that the air ratio at the start-up operation becomes 2.0, more air than the normal combustion is supplied to the combustion unit 12. Since the fuel is supplied and combusted, the temperature of the flame formed during the start-up operation becomes lower than the temperature of the flame in normal combustion formed during the preheating operation and the hydrogen generation operation. Due to such a decrease in the flame temperature, the temperature of the combustion exhaust gas introduced from the combustion section 12 into the combustion gas flow path b2 becomes lower than that in normal combustion during the start-up operation. Therefore, during the start-up operation, the temperature difference between the reforming catalyst layer 5 that is the heating target and the combustion exhaust gas that is the heat source is reduced, and therefore, the reforming is performed from the combustion exhaust gas compared to the preheating operation and the hydrogen generation operation. The amount of heat transferred to the catalyst layer 5 is reduced. On the other hand, since the amount of heat transfer to the reforming catalyst layer 5 is reduced in this way, the combustion exhaust gas moving in the combustion gas flow path b1 through heat exchange with the reforming catalyst layer 5 holds the amount of heat held. Will increase.

  Here, the combustion exhaust gas that has undergone heat exchange with the reforming catalyst layer 5 moves in the combustion gas flow path b1 and is taken out of the reforming unit 3. During this movement, the combustion exhaust gas and the combustion exhaust gas Heat exchange is performed with the water evaporation unit 4, and heat is transferred to the water evaporation unit 4. Here, as described above, in the start-up operation in which the air ratio is 2.0, the combustion exhaust gas that performs heat exchange with the water evaporation unit 4 is retained as compared with the case where the air ratio is 1.5. Since the amount of heat to be increased increases, the temperature difference between the water evaporation unit 4 and the combustion exhaust gas becomes large. Therefore, the amount of heat transferred to the water evaporation unit 4 is larger than that when the air ratio is 1.5. And increase. From the above, the water evaporation part 4 can be heated while suppressing the temperature rise of the reforming catalyst layer 5 by setting the combustion air ratio in the start-up operation to 2.0 to be larger than the normal combustion air ratio. It becomes possible to promote. As a result, it is possible to realize a highly reliable hydrogen generator in which the startup operation time is shortened.

  It should be noted that if the amount of combustion fuel supplied to the combustion unit 12 is reduced compared to normal combustion and the air ratio is increased, the water evaporation unit 4 can be more effectively suppressed while suppressing the temperature rise of the reforming catalyst layer 5. Heating can be promoted.

  In the above description, the case where the start-up operation of the present embodiment is the same as the start-up operation of Embodiment 1 except that the air ratio is made larger than that of normal combustion has been described. And the structure based on the starting operation | movement of Embodiment 3 may be sufficient.

  Further, in the starting operation based on the configuration of the second and third embodiments, as already described, when the combustion in the combustion unit 12 is stopped, the reforming from the air supply unit 7 to the combustion unit 12 is performed. Air is supplied for cooling the catalyst layer 5. By supplying air for cooling in this way, the heat of the reforming unit 3 is transferred to the water evaporation unit 4 located downstream of the reforming catalyst layer 5 through the supplied air. However, since the amount of supplied air is larger than usual, the amount of heat transferred to the water evaporation unit 4 is particularly large. Therefore, the above-described effect can be achieved more effectively.

(Embodiment 6)
The hydrogen generator according to Embodiment 6 of the present invention has the same configuration as the hydrogen generator of Embodiment 1, and therefore detailed description thereof is omitted here. In the present embodiment, the transition process from the startup operation to the preheating operation is different from that of the first embodiment. Hereinafter, this difference will be described, and the rest is the same as in the first embodiment.

  In the first embodiment, as described above, water and raw materials are supplied together and supplied to the reforming unit 3 at the start of the preheating operation, but in this embodiment, the supply of water is started first, and thereafter The supply of raw materials is started. That is, in the present embodiment, in the start-up operation, the temperature of the reforming catalyst layer 5 is equal to or higher than the first reference temperature T1 (step S1 in FIG. 3), or equal to or higher than the second reference temperature T2 ( In step S3) of FIG. 3, water is supplied from the water supply unit 2 to the reforming raw material flow path a of the reforming unit 3, and the start operation is shifted to the preheating operation. At this time, the raw material supply from the raw material supply unit 1 to the reforming unit 3 is not yet performed. The supplied water evaporates in the water evaporation unit 4 to become water vapor, and this water vapor is supplied to the reforming catalyst layer 5 and the reformed gas flow path c and flows through them. Here, in the raw material supply flow path a, the reforming catalyst layer 5, and the reformed gas flow path c, there are some gases such as the generated gas in the previous operation and the air that flows in after the operation is stopped. For example, when the reforming catalyst layer 5 is heated to a high temperature by a preheating operation in the presence of these gases, the reforming catalyst is oxidized and the catalytic activity is lowered, and the raw material may be oxidized. is there. Therefore, in order to improve the reliability of the hydrogen generator, it is preferable that the inside of the main body 50 of the reforming unit 3 be in a state where no unspecified substances are present.

Therefore, in the present embodiment, when the temperature of the reforming catalyst layer 5 reaches the first reference temperature T1 and the second reference temperature T2 in step S1 and step S3, before the raw material is supplied to the reforming unit 3. First, as described above, water is first supplied to the reforming unit 3 to generate water vapor, and this water vapor is passed through the reforming raw material channel a, the reforming catalyst layer 5 and the reformed gas channel c. Thus, the inside is purged with water vapor. In this way, at the start of the preheating operation, after performing a steam purge for a predetermined time, the raw material supply from the raw material supply unit 1 to the reforming unit 3 is started. Thus, the time required for the steam purge is within the hydrogen generator including the flow path formed in the reforming unit 3, that is, the reforming raw material flow path a, the reforming catalyst layer 5, and the reformed gas flow path c. This is the time required for purging the entire formed channel with water vapor. For example, when the total volume of the flow paths formed in the hydrogen generator is 1 L, when water is supplied to the reforming unit 3 of the hydrogen generator at a supply rate of 18 g / min, the water vapor generated in the water evaporation unit 4 is reduced. Since the amount is 22.4 L / min, the time required for purging (ie,
The time during which only water is supplied in the preheating operation) is 1 / 22.4 minutes. Actually, in consideration of the safety factor, the time of 2 to 3 times is set as the purge time.

  As described above, according to this embodiment, since the purge is performed with the steam before the raw material is supplied to the reforming unit 3, a more reliable hydrogen generator can be realized. Further, in the conventional purge, it is necessary to supply an inert gas such as nitrogen from a separately provided supply means to perform the purge with the gas. In the present embodiment, the water vapor generated in the water evaporation unit 4 is used. Therefore, it is not necessary to separately provide a purge gas supply means. Therefore, the purge can be easily performed only by adjusting the supply timing of the water and the raw material at the start of the preheating operation.

  In the above description, the case has been described in which the present embodiment is the same as the first embodiment except that the water vapor generated in the water evaporation unit 4 is used for purging. The configuration based on the operation of the third embodiment, the fourth embodiment, and the fifth embodiment may be used.

(Embodiment 7)
The configuration of the hydrogen generator according to Embodiment 7 of the present invention is the same as the configuration of the hydrogen generator of Embodiment 1, and thus detailed description thereof is omitted here.

  In the present embodiment having such a configuration, as in the case of the sixth embodiment, only the water is supplied before the raw material is supplied to the reforming unit 3, and the water vapor generated from the water is used for the reforming unit 3. Although purging is performed, water supply is not started after the water evaporation unit 4 reaches the temperature at which water vapor can be generated as in the sixth embodiment. A state in which water is supplied is realized, and a water vapor purge is performed using the saturated water vapor of the water. Details will be described below.

  By the way, in the first to sixth embodiments, the supply of water to the reforming unit 3 is started at the time of transition from the start-up operation to the preheating operation. In this embodiment, the water to the reforming unit 3 is started. Instead of setting the supply start time as the transition time, the water evaporation start time in the water evaporation unit 4 is set as the transition time. That is, here, an operation in which the water evaporation unit 4 in a state where water is supplied in advance is heated to a temperature capable of generating steam is called a start-up operation, and the reforming reaction is performed after the generation of water vapor in the water evaporation unit 4 is started. This operation is called preheating operation.

  In the present embodiment, a predetermined amount of water is supplied from the water supply unit 2 to the reforming unit 3 regardless of the temperature of the reforming catalyst layer 5 and the water evaporation unit 4 at the start of startup of the hydrogen generator. It is stored in the water evaporation unit 4. When the temperature of the reforming catalyst layer 5 at the start of startup of the hydrogen generator is lower than the first reference temperature T1, the water stored in the water evaporation unit 4 does not evaporate immediately after the start of startup, but the combustion unit 12 When the temperature of the water evaporation unit 4 starts to gradually increase due to heating by combustion, saturated water vapor corresponding to the temperature is generated in the water evaporation unit 4. In the present embodiment, the reforming unit 3 is purged using this saturated steam. On the other hand, when the temperature of the reforming catalyst layer 5 at the start of startup is higher than the first reference temperature T1 (step S1 in FIG. 3), the reforming catalyst layer 5 is heated and purged with saturated steam as described above. When the temperature of the catalyst catalyst layer 5 becomes higher than the second reference temperature T2 (step S3 in FIG. 3), the water evaporation unit 4 is in a state capable of generating water vapor, and is thus stored in the water evaporation unit 4. Water is supplied to the reforming catalyst layer 5 as water vapor, and the start operation is switched to the preheating operation. When the preheating operation is started, water is supplied from the water supply unit 1 to the reforming unit 3, and the raw material is supplied from the raw material supply unit 2 to the reforming unit 3 after a predetermined time has elapsed from the start of water supply. Thereby, as in the case of the sixth embodiment, the reforming unit 3 is purged with water vapor.

  As described above, according to the present embodiment, as in the case of the sixth embodiment, it is possible to purge the reforming unit 3 using water vapor, and thus the same effects as those described in the sixth embodiment. The effect is obtained. Furthermore, here, when the temperature of the reforming catalyst layer 5 at the start of the start-up of the hydrogen generator is lower than the first reference temperature T1, the inside of the reforming catalyst layer 5, the water evaporation unit 4 and the reforming unit 3 Even in a state in which the temperature of each flow path does not rise, the reforming unit 3 can be purged at any time using the saturated steam of the water stored in the water evaporation unit 4. Therefore, the substance removal capability by purging is improved, and the time required for purging performed at the start of the preheating operation can be shortened.

  The configuration and operation method of the hydrogen generator according to the present invention are not limited to the configurations and operation methods shown in the above first to sixth embodiments. For example, in the first to sixth embodiments, the reforming unit 3 is heated by the combustion in the combustion unit 12. However, the reforming unit 3 is heated by an electric heater or a heating means using a high-temperature inert gas. May be performed. In the first to sixth embodiments described above, the configuration of the reforming unit 3 of the hydrogen generator has been particularly described. However, the hydrogen generator appropriately includes a processing unit other than the reforming unit depending on the application. May be. For example, as will be described later in Embodiment 8, the hydrogen generator used in the fuel cell power generation system is provided with a CO conversion unit and a CO selective oxidation unit that process the reformed gas generated in the reforming unit 3. Yes.

(Embodiment 8)
FIG. 7 is a block diagram schematically showing the configuration of the combustion battery power generation system according to Embodiment 8 of the present invention. This fuel cell power generation system includes a hydrogen generator 100, a fuel cell 101, a heat recovery device 102, and a blower 103 as main components. The fuel cell 101 is, for example, a solid polymer fuel cell.

  The hydrogen generator 100 is the hydrogen generator according to any one of the first to seventh embodiments. Here, in addition to the reforming unit 3 and the combustion unit 12 described above, a CO conversion unit 20 and a CO selective oxidation unit are further provided. 21. Specifically, the reformed gas flow path c of the reforming section 3 in FIG. 1 is connected to the CO shift section 20, and the CO shift section 20 and the CO selective oxidation section 21 are connected by the post-shift gas path d. Has been. In the hydrogen generator 100 having such a configuration, the reformed gas generated in the reforming catalyst layer 5 is supplied to the CO shifter 20 via the reformed gas flow path c, and the CO concentration is reduced here. The post-transform gas obtained in the CO shift section 20 is supplied to the CO selective oxidation section 21 via the post-shift gas flow path d, where the CO concentration is further reduced. As described above, by performing the CO reduction process by the CO conversion unit 20 and the CO selective oxidation unit 21, the hydrogen generation apparatus 100 can obtain a hydrogen rich gas (hydrogen gas) having a low CO concentration.

  In the fuel cell power generation system, the hydrogen generator 100 is connected to the fuel cell 101 via a power generation fuel pipe 104 and a fuel offgas pipe 105. The fuel cell 101 is connected to the blower 103 via the air pipe 106. Further, the heat recovery device 102 is configured to be able to recover heat generated when the combustion battery 101 generates power. Here, the heat recovery device 102 is configured by a hot water generating device provided with a storage tank, and recovers heat during power generation of the fuel cell 101 with water in the storage tank to generate hot water. In addition, although illustration is abbreviate | omitted here, while the fuel cell power generation system is comprised so that the electric power obtained by electric power generation can be supplied to an electric power load terminal, the heat collect | recovered with the heat recovery apparatus 102 is made into a heat load terminal. It can be supplied.

  In the cogeneration operation of the fuel cell power generation system, first, the start-up operation, the preheating operation, and the hydrogen generation operation are performed in the hydrogen generator 100 as described above. These operations are the same as those described in the first to seventh embodiments, and a description thereof is omitted here. In the hydrogen generator 100, as described above in the first to seventh embodiments, it is possible to reduce the time required for the starting operation and to realize a highly reliable operation.

  Hydrogen gas produced by the hydrogen generator 100 is supplied to the fuel electrode side of the fuel cell 101 through the power generation fuel pipe 104 as power generation fuel. On the other hand, air is supplied from the blower 103 to the air electrode side of the fuel cell 101 via the air pipe 106. In the fuel cell 101, the supplied hydrogen gas and air react (hereinafter referred to as a power generation reaction) to generate power, and heat is generated along with this power generation reaction. The electric power obtained by the power generation reaction is supplied to an electric power load terminal (not shown) and used. Further, the heat generated with the power generation reaction is recovered by the heat recovery means 102, and then supplied to a heat load terminal (not shown) for use in various applications. In addition, unused hydrogen gas (so-called fuel offgas) that has not been used for the power generation reaction is recovered from the fuel cell 101 and supplied to the combustion unit 12 of the hydrogen generator 100 via the fuel offgas pipe 105 as combustion fuel. .

  In the fuel cell power generation system of the present embodiment, as described above, it is possible to produce hydrogen gas with high reliability in the hydrogen generator 100, so that hydrogen gas can be stably supplied to the fuel cell 101. Is possible. Therefore, in the fuel cell 101, it is possible to efficiently and stably generate electric power energy and thermal energy, and it is possible to realize a cogeneration system that is excellent in energy saving and economical efficiency.

  In the eighth embodiment, the case where the hydrogen generator according to the present invention is used in a fuel cell power generation system has been described. However, the hydrogen generator of the present invention can be applied to other than the fuel cell power generation system. .

  The hydrogen generator according to the present invention is useful as a hydrogen generator capable of shortening the time required for the start-up operation and performing a highly reliable operation.

  In particular, in a fuel cell system equipped with this hydrogen generator, it is possible to stably perform cogeneration operation that is excellent in economy and energy saving.

It is typical sectional drawing which shows the structure of the reforming part of the hydrogen generator which concerns on Embodiment 1 of this invention. It is a schematic diagram which shows the structure of the control part of the hydrogen generator of FIG. It is a flowchart which shows roughly the content of the program stored in the control part of FIG. It is a figure which shows the temperature change of the reforming catalyst layer and the water evaporation part in the driving | operation operation | movement of the hydrogen generator of FIG. It is a flowchart which shows roughly the content of the program stored in the control part of the hydrogen generator which concerns on Embodiment 2 of this invention. It is a figure which shows the temperature change of the reforming catalyst layer and water evaporation part which were heated according to the program of FIG. It is a block diagram which shows the structure of the fuel cell power generation system which concerns on Embodiment 8 of this invention. It is typical sectional drawing which shows the structure of the reforming part of the hydrogen generator which concerns on Embodiment 4 of this invention. It is a flowchart which shows roughly the content of the program stored in the control part of the hydrogen generator by Embodiment 4 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Raw material supply part 2 Water supply part 3 Reforming part 4 Water evaporation part 5 Reforming catalyst layer 6 Air flow path 7 Air supply part 8 Fuel supply part 9 Burner 12 Combustion part 15 Reforming temperature detection part 20 Control part 100 Hydrogen generation Device 101 Fuel cell 102 Heat recovery device 103 Blower

Claims (26)

A reforming unit that generates a hydrogen by reforming a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms and steam using a reforming catalyst, and a raw material supply that supplies the raw material to the reforming unit A water supply unit that supplies water to the reforming unit, a heating unit that heats the reforming unit, the raw material supply from the raw material supply unit, and the water supply from the water supply unit A hydrogen generator comprising a control unit,
The reforming unit includes a water evaporation unit that evaporates the supplied water, a reforming catalyst layer that includes the reforming catalyst, and a reforming temperature detection unit that detects the temperature of the reforming catalyst layer. Prepared,
The control unit determines whether or not the water evaporation unit has a temperature capable of generating steam based on the temperature of the reforming catalyst layer detected by the reforming temperature detection unit, and the determination unit Supply control means for controlling at least the water supply from the water supply unit based on the determination result of
The determination means performs a first determination of comparing the temperature of the reforming catalyst layer detected at the start of startup for starting the heating and starting the hydrogen generator with a first reference temperature. As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the temperature is detected in the process of heating the reforming unit after the first determination. Performing a second determination of comparing the temperature of the reforming catalyst layer with a second reference temperature higher than the first reference temperature;
As a result of the first determination, when the temperature of the reforming catalyst layer exceeds the first reference temperature, or as a result of the second determination, the temperature of the reforming catalyst layer is equal to the second reference temperature. A hydrogen generator in which the supply control means starts the water supply to the reforming unit when a reference temperature is exceeded.   2. The hydrogen generation apparatus according to claim 1, wherein the second reference temperature is a temperature at which the catalytic activity of the reforming catalyst layer is not deteriorated in the absence of water vapor.   The hydrogen generator according to claim 1, wherein the first reference temperature is 50 ° C or higher and 150 ° C or lower, and the second reference temperature is 300 ° C or higher and 500 ° C or lower. The reforming unit further includes a water evaporation unit temperature detection unit that detects the temperature of the water evaporation unit,
The control unit is configured to determine, based on the temperature of the water evaporation unit detected by the water evaporation unit detection unit, whether or not the water evaporation unit has a temperature capable of generating water vapor at the start of the activation. Supply control means for controlling at least the water supply from the water supply unit based on the determination result of the determination means,
As a result of determination by the determination unit, when the temperature of the water evaporation unit exceeds a water evaporation unit reference temperature that is a temperature capable of generating water vapor, the supply control unit starts the water supply, and the water evaporation unit 2. The hydrogen generation according to claim 1, wherein the heating is performed when the temperature of the water evaporation section is equal to or lower than a water evaporation section reference temperature, and the supply control means starts the water supply when the water evaporation section reference temperature is exceeded. apparatus. A reforming unit that generates a hydrogen by reforming a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms and steam using a reforming catalyst, and a raw material supply that supplies the raw material to the reforming unit A water supply unit that supplies water to the reforming unit, a heating unit that heats the reforming unit, the raw material supply from the raw material supply unit, and the water supply from the water supply unit A hydrogen generator comprising a control unit,
The reforming unit includes a water evaporation unit that evaporates the supplied water, a reforming catalyst layer that includes the reforming catalyst, and a reforming temperature detection unit that detects the temperature of the reforming catalyst layer. Prepared,
The control unit determines whether or not the water evaporation unit has a temperature capable of generating steam based on the temperature of the reforming catalyst layer detected by the reforming temperature detection unit, and the determination unit Supply control means for controlling the water supply supplied from at least the water supply unit based on the determination result of
The determination means performs a first determination of comparing the temperature of the reforming catalyst layer detected at the start of startup for starting the heating and starting the hydrogen generator with a first reference temperature. As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the temperature is detected in the process of heating the reforming unit after the first determination. Performing a second determination of comparing the temperature of the reforming catalyst layer with a second reference temperature higher than the first reference temperature;
As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the reforming detected in the process of heating the reforming unit after the first determination. A third determination is performed in which the temperature of the catalyst layer is compared with a third reference temperature that is higher than the first reference temperature and lower than the second reference temperature, and as a result of the third determination, the reforming is performed. The heating is stopped when the temperature of the catalyst layer exceeds the third reference temperature, and the temperature of the reforming catalyst layer after the heating is stopped is lower than the third reference temperature. A fourth determination of comparing with a fourth reference temperature that is higher than the reference temperature of the first reference temperature, and when the temperature of the reforming catalyst layer falls below the fourth reference temperature as a result of the fourth determination. A hydrogen generator in which the heating is resumed.   The hydrogen generator according to claim 5, wherein the third reference temperature is 200 ° C or higher and 300 ° C or lower.   The heating and stopping of the reforming unit is performed at a predetermined number of times at least once at the start of starting, or after the heating of the reforming unit with the stopping and restarting is performed for a predetermined time, the third reference When the temperature exceeds the temperature, the heating is executed, and then, as a result of the second determination, when the temperature of the reforming catalyst layer exceeds the second reference temperature, the supply control means starts the water supply The hydrogen generator according to claim 6.   The controller determines in advance the number of times of stopping and restarting the heating, or the time of heating with the stopping and restarting, according to the temperature of the reforming catalyst layer detected at the start of the start-up. Item 8. The hydrogen generator according to Item 7. The reforming unit further includes a water evaporation unit temperature detection unit that detects the temperature of the water evaporation unit,
The control unit is configured to determine, based on the temperature of the water evaporation unit detected by the water evaporation unit detection unit, whether or not the water evaporation unit has a temperature capable of generating water vapor at the start of the activation. Supply control means for controlling at least the water supply from the water supply unit based on the determination result of the determination means,
As a result of the determination by the determination means, when the temperature of the water evaporation section is equal to or lower than the water evaporation section reference temperature at which water vapor can be generated, the heating of the reforming section is performed, and the temperature of the reforming catalyst layer is The heating is stopped when the third reference temperature is reached, and the heating is resumed when the temperature of the reforming catalyst layer after the heating stops reaches the fourth reference temperature, 9. The hydrogen generator according to claim 8, wherein the supply control means starts the water supply when the temperature of the water evaporation unit exceeds the water evaporation unit reference temperature based on a signal output from the evaporation unit temperature detection unit. .   The hydrogen generator according to claim 9, wherein the water evaporation part reference temperature is 50 ° C. or higher and 150 ° C. or lower.   The hydrogen according to any one of claims 1, 4, 5, and 9, wherein the water evaporation section is disposed on an outermost periphery of the reforming section, and the reforming catalyst layer is disposed on the inner side of the water evaporation section. Generator. The heating unit includes a burner that burns combustion fuel and air, a fuel supply unit that supplies the combustion fuel to the burner, and an air supply unit that supplies the air to the burner,
In the reforming section, heat exchange between the combustion exhaust gas generated in the burner and the reforming catalyst layer is performed, and then heat exchange between the combustion exhaust gas and the water evaporation section is performed. The hydrogen generator according to any one of claims 1, 4, 5 and 9. The supply control means further controls air supply from the air supply unit to the burner,
After the water supply by the water supply unit is started, the air corresponding to the first supply amount is supplied to the burner,
As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the air corresponding to the second supply amount is supplied from the air supply unit to the burner. ,
In the combustion in which the air corresponding to the first supply amount is supplied, the ratio of the first supply amount to the theoretical air amount in the complete combustion of the supplied combustion fuel corresponds to the second supply amount. The combustion according to any one of claims 1, 4, 5 and 9, wherein the ratio of the second supply amount to the theoretical air amount in the complete combustion of the supplied combustion fuel in the combustion supplied with the air is smaller. Hydrogen generator.   The ratio of the second supply amount to the theoretical air amount in the complete combustion of the supplied combustion fuel in the combustion in which the air corresponding to the second supply amount is supplied is 2.0 or more. The hydrogen generator described.   The hydrogen generation device according to claim 5 or 9, wherein the supply control means causes the air to be ejected from the air supply unit to the burner during a heating stop period in which combustion in the burner is stopped according to the result of the third determination. .   The supply control means is configured to supply the raw material after a predetermined time has elapsed from the start of the water supply according to the first determination result or after a predetermined time has elapsed from the start of the water supply according to the second determination result. The hydrogen generator according to claim 1, wherein the raw material supply from a supply unit is started.   The hydrogen generator according to any one of claims 1, 4, 5, and 9, wherein the water is stored in the water evaporation unit in advance before the water evaporation unit reaches a temperature at which water vapor can be generated. A reforming unit that generates a hydrogen by reforming a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms and steam using a reforming catalyst, and a raw material supply that supplies the raw material to the reforming unit A water supply unit that supplies water to the reforming unit, a heating unit that heats the reforming unit, the raw material supply from the raw material supply unit, and the water supply from the water supply unit A control unit, and a method for operating a hydrogen generator,
The reforming unit includes a water evaporation unit that evaporates the supplied water, a reforming catalyst layer that includes the reforming catalyst, and a reforming temperature detection unit that detects the temperature of the reforming catalyst layer. Prepared,
A first determination is performed in which the temperature of the reforming catalyst layer detected at the start of startup for starting the heating and starting the hydrogen generator is compared with a first reference temperature by the control unit. As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the temperature detected in the process of heating the reforming unit after the first determination. A second determination of comparing the temperature of the reforming catalyst layer with a second reference temperature higher than the first reference temperature is performed;
As a result of the first determination, when the temperature of the reforming catalyst layer exceeds the first reference temperature, or as a result of the second determination, the temperature of the reforming catalyst layer is equal to the second reference temperature. The operation method of the hydrogen generator in which the water supply from the water supply unit to the reforming unit is started when the temperature exceeds the reference temperature. The reforming unit further includes a water evaporation unit temperature detection unit that detects the temperature of the water evaporation unit,
When the temperature of the water evaporation unit detected by the water evaporation unit temperature detection unit exceeds the water evaporation unit reference temperature, which is a temperature capable of generating water vapor, the water supply is started,
When the temperature of the water evaporation part is equal to or lower than the water evaporation part reference temperature, heating of the reforming part is performed, and then the temperature of the water evaporation part exceeds the water evaporation part reference temperature. The operation method of the hydrogen generator according to claim 18, wherein water supply is started. A reforming unit that generates a hydrogen by reforming a raw material containing an organic compound composed of at least carbon atoms and hydrogen atoms and steam using a reforming catalyst, and a raw material supply that supplies the raw material to the reforming unit A water supply unit that supplies water to the reforming unit, a heating unit that heats the reforming unit, the raw material supply from the raw material supply unit, and the water supply from the water supply unit A control unit, and a method for operating a hydrogen generator,
The reforming unit includes a water evaporation unit that evaporates the supplied water, a reforming catalyst layer that includes the reforming catalyst, and a reforming temperature detection unit that detects the temperature of the reforming catalyst layer. Prepared,
A first determination is performed in which the temperature of the reforming catalyst layer detected at the start of startup for starting the heating and starting the hydrogen generator is compared with a first reference temperature by the control unit. As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the temperature detected in the process of heating the reforming unit after the first determination. A second determination of comparing the temperature of the reforming catalyst layer with a second reference temperature higher than the first reference temperature is performed;
As a result of the first determination, when the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the reforming detected in the process of heating the reforming section after the first determination. A third determination is performed in which the temperature of the catalyst layer is compared with a third reference temperature that is higher than the first reference temperature and lower than the second reference temperature. As a result of the third determination, the reforming is performed. The heating is stopped when the temperature of the catalyst layer exceeds the third reference temperature, and the temperature of the reforming catalyst layer after the heating is stopped is lower than the third reference temperature. A fourth determination is performed to compare with a fourth reference temperature that is higher than the reference temperature, and as a result of the fourth determination, the temperature of the reforming catalyst layer falls below the fourth reference temperature. A method for operating the hydrogen generator in which the heating is resumed.   The control unit performs the number of times heating is stopped and restarted for the reforming unit or the heating of the reforming unit with the stopping and restarting according to the temperature of the reforming catalyst layer detected at the start of startup. An execution time is determined in advance, and after stopping and restarting the heating for the determined number of executions or the execution time, the heating is executed exceeding the third reference temperature, and then the second 21. The hydrogen generation according to claim 20, wherein, as a result of the determination, the water supply from the water supply unit to the reforming unit is started when the temperature of the reforming catalyst layer exceeds the second reference temperature. How to operate the device. The reforming unit further includes a water evaporation unit temperature detection unit that detects the temperature of the water evaporation unit,
When the temperature of the water evaporation part detected by the water evaporation part detection part is equal to or lower than the water evaporation part reference temperature at which water vapor can be generated, heating of the reforming part is performed, and the temperature of the reforming catalyst layer The heating is stopped when the temperature exceeds the third reference temperature, and the heating is restarted when the temperature of the reforming catalyst layer after the heating is lower than the fourth reference temperature. The operation method of the hydrogen generator according to claim 21, wherein the water supply is started when the temperature of the water evaporation unit exceeds the water evaporation unit reference temperature based on a signal output from the water evaporation unit temperature detection unit. . The heating unit includes a burner that burns combustion fuel and air, a fuel supply unit that supplies the combustion fuel to the burner, and an air supply unit that supplies the air to the burner.
The control unit controls the air supply unit;
In the heating after the water supply by the water supply unit is started, the air corresponding to the first supply amount is supplied to the burner, and the result of the first determination at the start of the start-up When the temperature of the reforming catalyst layer is equal to or lower than the first reference temperature, the air corresponding to the second supply amount is supplied from the air supply unit to the burner,
In the combustion in which the air corresponding to the first supply amount is supplied, the ratio of the first supply amount to the theoretical air amount of complete combustion of the supplied combustion fuel corresponds to the second supply amount. The hydrogen generation according to any one of claims 18, 19, 20 and 22, wherein in the combustion supplied with the air, a ratio of the second supply amount to a theoretical air amount of complete combustion of the supplied combustion fuel is smaller. How to operate the device. The heating unit includes a burner that burns combustion fuel and air, a fuel supply unit that supplies the combustion fuel to the burner, and an air supply unit that supplies the air to the burner,
The operation method of the hydrogen generator according to claim 20 or 22, wherein the air is jetted from the air supply unit to the burner during a heating stop period in which combustion in the burner is stopped according to the result of the third determination.   After a predetermined time has elapsed from the start of the water supply after the first determination, or after a predetermined time has elapsed from the start of the water supply after the second determination, the control unit changes from the raw material supply unit to the revision. The operation method of the hydrogen generator according to any one of claims 18, 19, 20 and 22, wherein the supply of the raw material to the mass part is started.   18. A fuel cell for generating electricity by reacting the hydrogen generator according to any one of claims 1 to 17, an air supply device, hydrogen supplied from the hydrogen generator and air supplied from the air supply device. And a fuel cell power generation system.

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