JP2018090461A - Hydrogen production apparatus, and operational method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent degradation of a catalyst caused by its excessive temperature rise regardless of a flow rate and composition of a gas discharged from a CO reducer in a hydrogen production apparatus using a raw material containing propane and butane as main components.SOLUTION: A hydrogen production apparatus 101 includes a raw material supply unit 3, a reformer 1, a CO reducer 2, a combustion chamber 4, a combustion air supply unit 5, an igniter 6, a flame detector 7, a heater 8, and a controller 20. When the raw material supply unit 3 stops and the combustion air supply unit 5 supplies air to the combustion chamber 4 at start-up of the hydrogen production apparatus 101, the controller 20 makes the heater 8 begin heating and the igniter 6 ignite. When the flame detector 7 detects flame before a first time after the heater 8 begins heating, the heater 8 stops heating. Therefore, the temperature rise of a catalyst is stopped and the discharge of a gas from the catalyst is stopped. Because combustion in the combustion chamber 4 is thus stopped, degradation of the catalyst caused by its excessive temperature rise is prevented.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen generation apparatus that reforms a raw material mainly composed of hydrocarbons to generate a hydrogen-containing gas, and an operation method thereof, and more specifically, combustion of a raw material discharged from the hydrogen generation apparatus at start-up The present invention relates to a hydrogen generation apparatus that heats each catalyst of the hydrogen generation apparatus and an operation method thereof.

  Since a hydrogen-containing gas used as fuel at the time of power generation of a fuel cell is not maintained as a general infrastructure gas, a fuel cell system usually includes a hydrogen generator. In this hydrogen generator, LP gas, city gas, or natural gas, which is a general infrastructure, is reformed by a reformer to generate a hydrogen-containing gas.

  As a reforming reaction performed in the hydrogen generator, for example, a steam reforming reaction is generally used. In this steam reforming reaction, LP gas, which is a raw material, and steam are reacted at a high temperature of about 600 ° C. to 700 ° C. by using a reforming catalyst such as a Ni-based, Ru-based, or Rh-based material, thereby generating hydrogen. Generates hydrogen-containing gas as the main component.

  Further, in order to bring the reforming catalyst of the reformer to a temperature necessary for the steam reforming reaction, the reformer is heated by the combustor. In addition, since carbon monoxide is produced as a side reaction in the reformer, when carbon monoxide poisons the anode catalyst of the fuel cell to lower the voltage (for example, in the case of a polymer electrolyte fuel cell), A CO reducer is provided downstream of the reformer.

  This CO reducer includes a CO conversion catalyst that reduces the concentration of carbon monoxide by reacting carbon monoxide and water vapor, and a selective oxidation catalyst that reacts carbon monoxide and oxygen to oxidize and remove carbon monoxide. There are many cases.

  By the way, when the power generation of the fuel cell system is stopped, the supply of the raw material and water vapor to the hydrogen generator is stopped. At this time, the gas flow path of the hydrogen generator is depressurized due to volume shrinkage due to a temperature drop of the hydrogen-containing gas remaining in the gas flow path of the hydrogen generator and condensation of water vapor in the hydrogen-containing gas accompanying the temperature drop. When the gas flow path of the hydrogen generator is depressurized, there is an adverse effect such that air leaks from the outside into the gas flow path and the catalyst comes into contact with the air and oxidizes.

  Therefore, when the hydrogen generator is stopped, the supply of the raw material and water vapor is first stopped, the flame of the combustor is extinguished, and the temperature of the hydrogen generator is lowered to a predetermined temperature. Purge any hydrogen-containing gas remaining in the path. And when the pressure of the gas flow path of the hydrogen generation device drops below a predetermined pressure, a fuel cell system that replenishes the hydrogen generation device with raw materials and maintains the positive pressure of the gas flow path of the hydrogen generation device has been proposed. (For example, refer to Patent Document 1).

  By the way, at the time of start-up operation of the hydrogen generator, it is necessary to raise the temperature of each catalyst of the hydrogen generator to a temperature suitable for a predetermined reaction in order to generate reformed gas from the raw material.

  In the method of supplying the fuel from the fuel source directly to the combustor at the time of start-up and burning each catalyst of the hydrogen generator with the combustion heat, a route for supplying the fuel from the fuel source directly to the combustor is provided. Since the cost of providing is increased, the raw material is supplied to the hydrogen generator at the time of start-up, and the raw material that has come out without being reformed from the hydrogen generator is combusted in the combustor, and the hydrogen heat is generated by the combustion heat. There has been proposed a method of heating each of the catalysts (for example, see Patent Document 2).

Japanese Patent No. 4130603 JP 2008-218355 A

  However, in the conventional hydrogen generator, after the temperature of the hydrogen generator that has stopped operating is lowered to a predetermined temperature, the hydrogen-containing gas remaining in the gas flow path is purged and the pressure of the gas flow path is predetermined. In order to increase the temperature of each catalyst to a temperature suitable for hydrogen generation during start-up operation, the raw material is supplied with a reformer and a CO reducer. In order to be supplied to the combustor and burnt, there are the following problems.

  That is, as the temperature of each catalyst is reduced while the hydrogen generator is stopped, at least a part of the raw material is adsorbed on each catalyst, and is adsorbed on each catalyst as the temperature of each catalyst rises during start-up operation. Since the components of the raw material are desorbed and combusted in the combustor together with the raw material supplied to the hydrogen generator, there is a problem that when the combustion in the combustor becomes excessive, the catalyst is excessively heated and deteriorates.

  In particular, when LP gas mainly composed of propane or butane is used as a raw material for the hydrogen generator, the above-described adsorption and desorption phenomena are more prominent than when city gas mainly composed of methane is used. In LP gas, when butane (normal butane, 0.05 MPa at 10 ° C.) is used, the above phenomenon of adsorption and desorption occurs more than when propane (0.53 MPa at 10 ° C.) is used. It is remarkable.

  Therefore, particularly when the butane concentration of the raw material is high, there has been a problem that combustion in the combustor becomes excessive, and the catalyst tends to deteriorate due to excessive temperature rise.

  Therefore, the present invention can prevent excessive heating of the catalyst due to combustion of the desorbed gas regardless of the flow rate and composition of the desorbed gas that flows from the catalyst heated at the start and flows to the combustor. An object of the present invention is to provide a hydrogen generator that can be used as a heat source at the time of startup of the hydrogen generator and has high energy efficiency and durability.

  In order to solve the above-described conventional problems, a hydrogen generator of the present invention includes a raw material supplier that supplies a raw material mainly composed of hydrocarbons, and a reformer that generates a hydrogen-containing gas from the raw material using a reforming catalyst. A CO reducer that reduces the carbon monoxide concentration of the hydrogen-containing gas produced in the reformer with a carbon monoxide reduction catalyst, and a gas discharged from the CO reducer is burned to form a reformer and a CO reducer. Among them, a combustor that heats at least the reformer, a combustion air supply that supplies combustion air to the combustor, an igniter that performs an ignition operation in the combustor, and a flame detection that detects the presence or absence of a flame in the combustor A heater, a heater for heating the CO reducer, and a controller.

  Then, when starting the hydrogen generator, the controller first starts the heating operation of the heater while the raw material supplier is stopped and the combustion air supplier is supplying air to the combustor. In addition, when the flame detector detects a flame before the first time after the ignition operation of the igniter is started and the heating operation of the heater is started, control is performed so as to end the heating operation of the heater. It is.

As a result, the rate of increase in the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst by the heating operation of the heater at the start-up of the hydrogen generator is slow, and the gas concentration in the combustor is reduced. In the case of a raw material component that takes the longest time to enter the combustible range and ignite, if the ignition time from the start of the heating operation of the heater to the detection of the flame is set as the first time, after the hydrogen generator stops operating Even when the raw material is purged, if a flame is detected before the first time from the start of the heating operation, the operation of the heater is terminated, so that the desorption of gas from the catalyst is stopped by stopping the temperature rise of the catalyst. In addition, since combustion in the combustor is stopped, it is possible to prevent deterioration of the catalyst due to excessive temperature rise.

  According to the present invention, excessive heating of the catalyst due to combustion of the desorbed gas can be prevented regardless of the flow rate or composition of the desorbed gas flowing from the catalyst heated at the start and flowing to the combustor. It can be used as a heat source when starting up the hydrogen generator, and a hydrogen generator having high energy efficiency and durability can be realized.

The block diagram which shows the structure of the hydrogen generator in Embodiment 1 and 2 of this invention The characteristic view which shows the time change of the flow volume of the gas which desorbs from the CO reducer of the hydrogen generator in Embodiment 1 and 2 of this invention, and the combustible gas concentration of the mixed gas formed with a combustor. The flowchart which shows the starting method of the hydrogen generator in Embodiment 1 of this invention The flowchart which shows the starting method of the hydrogen generator in Embodiment 2 of this invention The block diagram which shows the structure of the hydrogen generator in Embodiment 3 and 4 of this invention The flowchart which shows the starting method of the hydrogen generator in Embodiment 3 of this invention The flowchart which shows the starting method of the hydrogen generator in Embodiment 4 of this invention

  According to a first aspect of the present invention, there is provided a raw material supplier for supplying a raw material mainly composed of hydrocarbons, a reformer for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and a hydrogen-containing gas generated by the reformer. A CO reducer that reduces the carbon monoxide concentration with a carbon monoxide reducing catalyst, a combustor that burns the gas discharged from the CO reducer and heats at least the reformer of the reformer and the CO reducer; A combustion air supply for supplying combustion air to the combustor, an igniter for performing an ignition operation in the combustor, a flame detector for detecting the presence or absence of a flame in the combustor, and a heater for heating the CO reducer; A controller, and when the controller starts the hydrogen generator, first, heating is performed in a state where the raw material supplier is in a stopped state and the combustion air supplier is supplying air to the combustor. Start the heating operation of the heater and make the igniter ignite so that the heater From the start of the operation if the flame detector detects a flame before the first hour, a hydrogen generator to terminate the heating operation of the heater.

  As a result, the rate of increase in the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst by the heating operation of the heater at the start-up of the hydrogen generator is slow, and the gas concentration in the combustor is reduced. In the case of a raw material component that takes the longest time to enter the combustible range and ignite, if the ignition time from the start of the heating operation of the heater to the detection of the flame is set as the first time, after the hydrogen generator stops operating Even when the raw material is purged, if a flame is detected before the first time from the start of the heating operation, the operation of the heater is terminated, so that the desorption of gas from the catalyst is stopped by stopping the temperature rise of the catalyst. In addition, since combustion in the combustor is stopped, it is possible to prevent deterioration of the catalyst due to excessive temperature rise.

In a second aspect of the invention, in particular, in the first aspect of the invention, the raw material contains at least one of propane and butane as a main component, and the hydrogen generator is purged with the raw material after the operation is stopped. When the desorption gas desorbed from the carbon monoxide reduction catalyst by the heating operation is propane, this is the time until combustion in the combustor starts.

  As a result, when the desorbed gas contains butane in addition to propane, the heating time by the heater is stopped early, so that the desorption of the gas from the catalyst is stopped by stopping the temperature rise of the catalyst, and the combustor Therefore, it is possible to more reliably prevent deterioration due to excessive temperature rise of the catalyst.

  In a third aspect of the invention, particularly in the first or second aspect of the invention, the hydrogen generator includes a switch on a product gas flow path that guides the gas discharged from the CO reducer to the combustor, and the controller generates hydrogen. When starting the apparatus, the heating operation of the heater is started with the switch open, and if the flame detector detects a flame within the first time after the heating operation of the heater is started, The heating operation is finished and the switch is closed.

  Thereby, since the flow of desorbed gas into the combustor is blocked by the switch, combustion in the combustor is stopped, so that a hydrogen generator that can more reliably prevent deterioration due to excessive temperature rise of the catalyst can be configured.

  In the fourth aspect of the invention, particularly in the third aspect of the invention, the controller opens the switch again when the flame detector stops detecting the flame after closing the switch.

  Thereby, after the combustion in the combustor is stopped, even if the temperature of the hydrogen generator changes, by opening the switch, the pressure inside the hydrogen generator is substantially the same as the atmospheric pressure. It is not necessary to make the structure of the hydrogen generating device resistant to excessive pressure, and the hydrogen generating device can be configured at low cost.

  According to a fifth aspect of the invention, particularly in the fourth aspect of the invention, when the controller detects the flame within the first time after starting the heating operation of the heater, the mixing is formed in the combustor. The flow rate of the combustion air supplied from the combustion air supply device to the combustor is increased so that the combustible gas concentration of the gas is outside the combustible range.

  As a result, the combustible gas concentration of the mixed gas formed in the combustor becomes lower than the lower limit of the combustible range, so that the gas released out of the system of the hydrogen generator is assumed to have an ignition source. A highly safe hydrogen generator can be constructed without burning.

  According to a sixth aspect of the invention, particularly in the first or second aspect of the invention, the controller detects the flame when the flame detector detects a flame before the first time after starting the heating operation of the heater. While finishing the heating operation, the flow rate of the combustion air supplied from the combustion air supply device to the combustor is increased until the flame detector no longer detects the flame.

  As a result, the combustible gas concentration of the mixed gas formed in the combustor becomes lower than the lower limit of the combustible range, and combustion in the combustor stops, so that deterioration due to excessive temperature rise of the catalyst can be prevented more reliably. .

  According to a seventh invention, in any one of the first to sixth inventions, a reformer temperature detector for detecting the internal temperature of the reformer and a CO reducer temperature for detecting the internal temperature of the CO reducer. And the controller, after finishing the heating operation of the heater, the internal temperature of the CO reducer is lower than the first temperature, and the internal temperature of the reformer is lower than the second temperature, and After the predetermined non-combustion time has elapsed, the igniter is ignited and the heating operation of the heater is restarted.

  Accordingly, the process of burning the desorbed gas in the combustor and the process of supplying air and cooling the combustor without burning the desorbed gas in the combustor after stopping the combustion are repeated. It is possible to configure a hydrogen generator that can increase the temperature to a temperature suitable for generating a hydrogen-containing gas while preventing deterioration due to excessive temperature increase.

  In an eighth aspect of the invention, in particular, in any one of the first to sixth aspects of the invention, the controller includes a CO reducer temperature detector that detects the internal temperature of the CO reducer, and the controller detects the flame by the flame detector. When the internal temperature of the CO reducer is lower than the first temperature after running out, the combustible gas concentration of the mixed gas formed in the combustor is supplied from the combustion air supply device to the combustor so that it is outside the combustible range. The heating operation of the heater is resumed after increasing the flow rate of the combustion air.

  As a result, the combustible gas concentration of the mixed gas formed in the combustor becomes lower than the lower limit of the combustible range, so that the gas released out of the system of the hydrogen generator is assumed to have an ignition source. A highly safe hydrogen generator can be constructed without burning.

  In a ninth aspect of the invention, in particular, in any one of the first to eighth aspects, a CO reducer temperature detector that detects the internal temperature of the CO reducer is provided, and the controller starts a heating operation of the heater. If the flame detector does not detect the flame after the first time has elapsed, the heating operation of the heater is continued until the internal temperature of the CO reducer becomes equal to or higher than the first temperature, When the internal temperature of the CO reducer becomes equal to or higher than the first temperature, the heating operation of the heater is terminated.

  As a result, when the flame detector does not detect the flame before the first time, the heater is continuously operated, so that the steam contained in the hydrogen-containing gas generated by the reformer is shortened to a temperature at which it does not condense. A hydrogen generator capable of raising the temperature over time can be configured.

  The tenth invention is the reformer temperature detector for detecting the internal temperature of the reformer and the CO reducer temperature for detecting the internal temperature of the CO reducer, particularly in any one of the first to ninth inventions. A combustion air supply device so that the combustible gas concentration of the mixed gas formed in the combustor falls within the combustible range when the internal temperature of the CO reducer exceeds the first temperature. The combustion air is supplied to the combustor and the igniter is ignited to operate the raw material supplier so that the internal temperature of the reformer exceeds the third temperature.

  As a result, the raw material is combusted in the combustor, and the temperature inside the hydrogen generator is heated so that the internal temperature of the reformer exceeds the third temperature. Even when the temperature inside the hydrogen generator cannot be heated to a temperature suitable for the generation of the containing gas, a hydrogen generator capable of heating the temperature inside the hydrogen generator to a temperature suitable for the generation of the hydrogen-containing gas can be configured.

  An eleventh aspect of the present invention is a raw material supplier for supplying a raw material mainly composed of hydrocarbons, a reformer for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and a hydrogen-containing gas generated by the reformer. A CO reducer that reduces the carbon monoxide concentration with a carbon monoxide reducing catalyst, a combustor that burns the gas discharged from the CO reducer and heats at least the reformer of the reformer and the CO reducer; A combustion air supply for supplying combustion air to the combustor, an igniter for performing an ignition operation in the combustor, a flame detector for detecting the presence or absence of a flame in the combustor, and a heater for heating the CO reducer; When the hydrogen generator is started, first, the raw material supply device is in a stopped state, and the combustion air supply device is supplying air to the combustor. Start the heating operation of the heater and ignite the igniter. A first step, and when the flame detector detects a flame before the first time after starting the heating operation of the heater in the first step, a second step of ending the heating operation of the heater; It is what has.

  As a result, in the case of a raw material component in which the increase rate of the desorbed gas flow rate is slow and the gas concentration in the combustor enters the combustible range and the ignition time is the longest, the heating operation starts from the start of the heater to the flame detection. If the ignition time is set to the first time, even if the hydrogen generator is purged with the raw material after the operation is stopped, if the flame is detected before the first time from the start of the heating operation, the operation of the heater is changed. Thus, the desorption of the gas from the catalyst is stopped by stopping the temperature rise of the catalyst, and the combustion in the combustor is stopped. Therefore, it is possible to prevent the catalyst from being deteriorated due to excessive temperature rise.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(Embodiment 1)
FIG. 1 is a block diagram showing the configuration of the hydrogen generator in Embodiment 1 of the present invention.

  As shown in FIG. 1, the hydrogen generator 101 of the present embodiment includes a reformer 1, a CO reducer 2, a raw material supplier 3, a combustor 4, a combustion air supplier 5, and an igniter. 6, a flame detector 7, a heater 8, a switch 9, a reformer temperature detector 10, a CO reducer temperature detector 11, and a controller 20.

  The reformer 1 has a reforming catalyst (not shown) mounted (filled) therein, and generates a hydrogen-containing gas by a steam reforming reaction using raw materials and steam. In this embodiment, LP gas, which is a mixed gas of propane and butane, is used as a raw material.

  The CO reducer 2 is provided for removing carbon monoxide generated as a side reaction in the reformer 1, and CO that reduces carbon monoxide by reacting carbon monoxide with water vapor in a 2 L volume container. A shift catalyst (not shown) is filled with 1.8 L.

  The raw material supplier 3 is a pump that supplies the raw material to the reformer 1.

  The combustor 4 heats the reformer 1. As a fuel for the combustor 4, at least one of a raw material, a desorbed gas, and a hydrogen-containing gas discharged from the CO reducer 2 is used. The combustor 4 is connected to the reformer 1 so that when the flow rate of propane desorbed is maximum when the heating operation of the CO reducer 2 is started, the reformer 1 does not overheat. Thermally coupled.

  The combustion air supply device 5 is a fan that supplies combustion air to the combustor 4.

  The igniter 6 ignites the mixed gas of fuel and air supplied to the combustor 4 by spark discharge.

  The flame detector 7 is a frame rod. The flame rod inserts a metal rod electrically connected to a flame current detection circuit comprising a power source and a current sensor into the flame, and determines the flame state based on the magnitude of the current.

  The heater 8 is a heater that heats the CO reducer 2. In the present embodiment, the heater output is 500 W.

  The switch 9 is an electromagnetic valve on the generated gas flow path that guides the gas discharged from the CO reducer 2 to the combustor 4.

  The reformer temperature detector 10 is a thermocouple that measures the internal temperature of the reformer 1.

  The CO reducer temperature detector 11 is a thermocouple that measures the internal temperature of the CO reducer 2.

  The controller 20 controls the operation of the hydrogen generator 101. The controller 20 includes a signal input / output unit (not shown), an arithmetic processing unit (not shown), and a storage unit (not shown) that stores a control program.

  The operation and action of the hydrogen generator 101 of the present embodiment configured as described above will be described below. The following operation is performed by the controller 20 controlling the raw material supplier 3, the combustion air supplier 5, the igniter 6, the heater 8, and the switch 9 of the hydrogen generator 101.

  First, the first time will be specifically described with reference to FIG. The first time is a time until combustion in the combustor 4 starts when the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the heater 8 is propane. .

  FIG. 2 is a characteristic diagram showing the change over time in the flow rate of the gas desorbed from the CO reducer 2 of the hydrogen generator 101 and the combustible gas concentration of the mixed gas formed in the combustor 4 in the first embodiment.

  The plot shown in FIG. 2 is experimentally acquired in advance when the internal temperature of the CO reducer 2 at the start of operation of the heater 8 is 10 ° C. when propane and butane are used as raw materials. At this time, combustion air was supplied to the combustor 4 from the combustion air supply device 5 at 1.6 mol / min.

  As shown in FIG. 2, when the heating temperature of the CO reducer 2 starts to be increased by the heater 8, the gas adsorbed on the CO reducer 2 is gradually desorbed, and the flow rate of the desorbed gas reaches the maximum value within a few minutes. After that, it gradually decreases.

  In the hydrogen generator 101 in the present embodiment, the combustible gas concentration of the mixed gas of butane and air formed in the combustor 4 is 0.2 minutes after the start of the operation of the heater 8, and the lower limit of the butane combustible range. It became the state which can be ignited exceeding 1.9% which is.

  The combustible gas concentration of the mixed gas of propane and air formed in the combustor 4 is 1.9 minutes from the start of the operation of the heater 8, and ignites exceeding 2.1% which is the lower limit of the combustible range of propane. It was ready.

  Therefore, in the present embodiment using LP gas which is a mixed gas of propane and butane, the ignition time takes any value from 0.2 minutes to 1.9 minutes depending on the composition ratio of the raw material.

  This is because if the combustion is stopped when the combustion starts before 1.9 minutes, the combustion amount of the desorbed gas burned in the combustor 4 is 10 ° C. at the internal temperature of the CO reducer 2. Since it does not become more than that of propane desorbing, it means that deterioration due to overheating of the reforming catalyst of the reformer 1 due to excessive heat being applied from the combustor 4 to the reformer 1 can be prevented. ing. Therefore, in the present embodiment, the first time is 1.9 minutes.

  Next, a method for starting the hydrogen generator 101 will be described with reference to FIG.

  FIG. 3 is a flowchart showing a startup method of the hydrogen generator 101 according to Embodiment 1 of the present invention. Note that the gas flow path from the reformer 1 to the combustor 4 is purged with the raw material before the hydrogen generator 101 is activated (when the hydrogen generator 101 is stopped last time).

When the hydrogen generator 101 is activated, the controller 20 operates the combustion air supply device 5 to supply combustion air to the combustor 4 at 1.6 mol / min (step S101). Subsequently, the controller 20 opens the switch 9 (step S102) and then the igniter 6 (step S103) in order to desorb the gas from the CO reducer 2, introduce it into the combustor 4, and burn it. ) And the heater 8 (step S104) are sequentially operated.

  Next, the controller 20 checks whether or not 1.9 minutes (first time) has elapsed since the operation start of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) have elapsed since the start of the operation of the heater 8, the process proceeds to step S141. On the other hand, if it is determined in step S105 that 1.9 minutes (first time) has not yet elapsed from the start of operation of the heater 8, the process proceeds to step S106.

  In step S106, it is confirmed whether or not the flame has been detected by the flame detector 7. If the flame has been detected by the flame detector 7, the process proceeds to step S107. Conversely, the flame is detected by the flame detector 7. If not, the process returns to step S105.

  Hereinafter, an operation when a flame is detected by the flame detector 7 in step S106 will be described.

  First, the controller 20 detects the flame with the flame detector 7, so the igniter 6 is stopped (step S 107), and then the desorption of gas from the CO reducer 2 is stopped and the combustor 4 is stopped. In order to stop the combustion, the heater 8 is stopped (step S108). Subsequently, the supply of gas from the CO reducer 2 to the combustor 4 is shut off, and the combustion in the combustor 4 is stopped reliably. The switch 9 is closed (step S109).

  Further, when the switch 9 is opened in the subsequent step S121, the combustion air supply device 5 is connected in advance to the combustor 4 so that the combustible gas concentration formed in the combustor 4 does not exceed the lower limit of the combustible range. Is increased (step S110).

  In step S110, the flow rate of the combustion air was increased from 1.6 mol / min to 3.2 mol / min. Next, the controller 20 stands by until the flame detector 7 can no longer detect the flame (step S111). If the flame detector 7 cannot detect the flame in step S111, the controller 20 proceeds to step S121.

  Next, the operation from step S121 to step S125 will be described.

  First, in order to make the internal pressure of the hydrogen generator 101 substantially the same as the atmospheric pressure, the switch 9 is opened again (step S121). Next, the controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 with the first temperature, and when the internal temperature of the CO reducer 2 is lower than the first temperature, The process proceeds to step S123 (step S122). Conversely, if the internal temperature of the CO reducer 2 is equal to or higher than the first temperature, the process proceeds to step S161.

  Here, the first temperature is a temperature at which water vapor contained in the hydrogen-containing gas generated in the reformer 1 is not condensed in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature drop after the operation stop of the heater 8 (step S108).

  Next, in step S123, the controller 20 compares the internal temperature of the reformer 1 acquired from the reformer temperature detector 10 with the second temperature, and the internal temperature of the reformer 1 is lower than the second temperature. If so, the process proceeds to step S124. Conversely, if the internal temperature of the reformer 1 is not lower than the second temperature, the process waits until it becomes lower than the second temperature.

  Here, the second temperature is a temperature sufficiently lower than a temperature (400 ° C.) at which the performance of the catalyst, which is deteriorated due to the deposition of carbon generated by the thermal decomposition of the raw material on the catalyst inside the reformer 1, cannot be ignored. In the present embodiment, the second temperature is set to 200.degree.

  Next, in step S124, the controller 20 performs an operation of waiting for a predetermined non-burning time. The predetermined non-combustion time is the total time after shifting to step S121. Even after the operation to stop desorption from the CO reducer 2 is performed in step S108, unburned gas remains in the combustor 4. For this reason, when the ignition operation is started without scavenging the unburned gas, the unburned gas is ignited, and the combustor 4 may be damaged due to an increase in pressure and temperature due to the ignition.

  Therefore, the unburned gas inside the combustor 4 is replaced with air. Since the volume of the combustor 4 of the present embodiment is 7.2 L, 10 times 72 L of air is supplied. Since the flow rate of the combustion air supplied from the combustion air supply device 5 to the combustor 4 is 3.2 mol / min (= 72 L / min), the non-combustion time is set to 1 minute.

  In step S124, when the time from the time of moving to step S121 to the time of reaching step S124 exceeds 1 minute, the process moves to step S125. On the other hand, if the time from the point of transition to step S121 to the step S124 does not exceed 1 minute, the process waits until 1 minute elapses.

  In step S125, in preparation for the next ignition, the flow rate of the combustion air is adjusted to 1.6 mol / min. Through the above operation, the controller 20 returns to step S103 to desorb the gas from the CO reducer 2 in order to further increase the internal temperature of the reformer 1 and the internal temperature of the CO reducer 2.

  Next, an operation when 1.9 minutes have elapsed from the start of the operation of the heater 8 in step S105 will be described.

  First, after stopping the operation of the igniter 6 (step S141), the controller 20 checks whether or not a flame has been detected by the flame detector 7 (step S142). In step S142, when the flame is detected by the flame detector 7, the controller 20 completes the desorption of the raw material from the CO reducer 2, and the desorbed gas is not supplied to the combustor 4. Since the combustion of the gas cannot be continued, the flame detector 7 waits until the flame cannot be detected.

  As shown in FIG. 2, the flow rate of the desorbed gas gradually decreases after reaching the maximum value within a few minutes from the start of the operation of the heater 8, so that the combustion in the combustor 4 stops. And if a flame becomes impossible to detect, it will transfer to step S143. Conversely, in step S142, if the flame detector 7 cannot detect a flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms whether or not the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) from the CO reducer temperature detector 11 (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature 150 ° C., the step S143 is repeated and the CO reducer 2 is heated by the heater 8. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature 150 ° C., the operation of the heater 8 is stopped (step 144), and the process proceeds to step S161.

  Next, the operation after step S161 will be described. The controller 20 executes the operations after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reformer 1 can perform a reforming reaction. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed by the combustor 4 when the raw material supplier 3 is operated in the subsequent step S163 falls within the combustible range ( Step S161).

  Next, the igniter 6 is operated (step S162), the raw material supplier 3 is operated (step S163), the raw material is supplied to the combustor 4 via the reformer 1 and the CO reducer 2, and the combustor 4 Burn the raw material. Subsequently, the controller 20 waits until the flame can be detected by the flame detector 7 (step S164). When the flame is detected by the flame detector 7, the operation of the igniter 6 is stopped (step S165), and step S166. Migrate to

  In step S166, the controller 20 confirms whether or not the internal temperature of the reformer 1 acquired from the reformer temperature detector 10 is lower than the third temperature, and the internal temperature of the reformer 1 is the third temperature. When the temperature is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has become equal to or higher than the third temperature. When the reformer temperature detector 10 confirms that the internal temperature of the reformer 1 has become equal to or higher than the third temperature, the process proceeds to the end.

  Here, the third temperature is a temperature higher than a temperature at which the water vapor does not condense in the reformer 1 when the gas flowing through the reformer 1 contains water vapor. In the present embodiment, the third temperature is the third temperature. Was set to 120 ° C.

  With the above operation, the operation of raising the temperature of the hydrogen generator 101 to a temperature at which the reforming reaction can be performed without being affected by the flow rate and composition fluctuation of the gas desorbed from the CO reducer 2 is completed.

  Subsequently, a reforming water supply unit (not shown) is operated to supply reforming water to the reforming unit 1, and generation of a hydrogen-containing gas in the reforming unit 1 is started by a steam reforming reaction, thereby reducing CO. The gas discharged from the vessel 2 is supplied to a hydrogen utilization device (not shown).

  As described above, in the present embodiment, in the hydrogen generator 101 using a raw material mainly composed of at least one of propane and butane, the increase rate of the desorbed gas flow rate is slow, and the combustor 4 The ignition time that takes the longest time for the gas concentration to enter the combustible range and ignite is set as the first time (1.9 minutes), and after the ignition operation and the heating operation, from the first time (1.9 minutes) When the flame detector 7 detects a flame before, the operation of the heater 8 is terminated and the supply of the desorbed gas to the combustor 4 by the operation of the switch 9 is shut off, and the combustion in the combustor 4 is performed. Therefore, the desorption of gas from the catalyst is stopped by stopping the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped, so that deterioration due to excessive temperature rise of the catalyst can be prevented.

  Further, after repeating the above series of operations until the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C.), the raw material is supplied to the combustor 4 via the reformer 1 and the CO reducer 2. Since the reformer 1 is heated and heated to the third temperature (120 ° C.) by combustion, the reformer 1 is not affected by changes in the composition and flow rate of the desorbed gas from the CO reducer 2. Degradation of the reforming catalyst due to excessive temperature rise can be prevented, and the reformer 1 can be heated to a temperature at which the reforming reaction can be performed.

  In this embodiment, LP gas is used as a raw material for the hydrogen generator 101. However, not only LP gas but also hydrocarbons having 2 to 4 carbon atoms such as ethane, ethylene, propylene, and butene are used. A mixed gas having a main component may be used as a raw material for the hydrogen generator 101.

  The hydrogen generator 101 of the present embodiment includes a raw material supplier 3 that supplies a raw material mainly composed of hydrocarbons, a reformer 1 that generates a hydrogen-containing gas from the raw material using a reforming catalyst, and a reformer 1 The carbon monoxide concentration of the hydrogen-containing gas produced in step 1 is reduced by the carbon monoxide reduction catalyst, and the gas discharged from the CO reduction device 2 is burned to reform the reformer 1 and the CO reduction device 2. Among them, at least a combustor 4 for heating the reformer 1, a combustion air supply device 5 for supplying combustion air to the combustor 4, an igniter 6 for performing an ignition operation in the combustor 4, and a flame of the combustor 4. A flame detector 7 that detects the presence or absence of the gas, a heater 8 that heats the CO reducer 2, and a controller 20.

  When the controller 20 starts up the hydrogen generator 101, first, the heater is used in a state where the raw material supplier 3 is stopped and the combustion air supplier 5 is supplying air to the combustor 4. 8, the igniter 6 is ignited, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. When a flame is detected, the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set, the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane in this embodiment) after the hydrogen generator 101 has stopped operating. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

  The raw material of the hydrogen generator 101 of the present embodiment is LP gas containing at least one of propane and butane as a main component, and reaches the combustor 4 from the reformer 1 after the hydrogen generator 101 is stopped. The gas flow path is purged with the raw material (LP gas).

  Then, in the first time (1.9 minutes in the present embodiment), when the desorption gas desorbed from the carbon monoxide reduction catalyst by the heating operation of the heater 8 is propane, the combustion in the combustor 4 is performed. It was time to start.

  Thereby, when butane is contained in addition to propane in the desorption gas desorbed from the carbon monoxide reduction catalyst of the CO reducer 2 by the heating operation of the heater 8, the heating time by the heater 8 is stopped early. Therefore, since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the temperature increase of the carbon monoxide reduction catalyst and the combustion in the combustor 4 is stopped, the reforming catalyst and the carbon monoxide reduction catalyst are stopped. Of these, at least deterioration of the reforming catalyst due to excessive temperature rise can be more reliably prevented.

  Further, the hydrogen generator 101 of the present embodiment includes a switch 9 on the generated gas flow path that guides the gas discharged from the CO reducer 2 to the combustor 4, and the controller 20 activates the hydrogen generator 101. When the switch 9 is opened, the heating operation of the heater 8 is started, and the flame detection is performed within the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. When the device 7 detects a flame, the heating operation of the heater 8 is terminated and the switch 9 is closed.

  Thereby, since the inflow to the combustor 4 of the desorbed gas desorbed from the carbon monoxide reducing catalyst by the heating operation of the heater 8 is blocked by the switch 9, the combustion in the combustor 4 is stopped. Of the reforming catalyst and the carbon monoxide reduction catalyst, it is possible to more reliably prevent at least the reforming catalyst from being deteriorated due to excessive temperature rise.

  Further, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is within the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. After the heating operation of the heater 8 is finished by detecting the flame and the switch 9 is closed, when the flame detector 7 no longer detects the flame of the combustor 4, the switch 9 is opened again. To do.

  As a result, even if the temperature of the hydrogen generator 101 changes, the pressure inside the hydrogen generator 101 becomes substantially the same as the atmospheric pressure, so the structure of the hydrogen generator 101 needs to have a structure that can withstand excessive pressure. Therefore, the hydrogen generator 101 can be configured at low cost.

  Further, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is within the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. When a flame is detected, the flow rate of combustion air supplied from the combustion air supply device 5 to the combustor 4 is increased so that the combustible gas concentration of the mixed gas formed in the combustor 4 is outside the combustible range. To do.

  Thereby, since the combustible gas concentration of the mixed gas formed in the combustor 4 is lower than the lower limit of the combustible range, the gas released out of the system of the hydrogen generator 101 has an ignition source. However, it does not burn and the safety of the hydrogen generator 101 is high.

  Further, the hydrogen generator 101 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and And the controller 20 detects the flame within the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. After the heating operation is completed, after the flame detector 7 stops detecting the flame of the combustor 4, the internal temperature of the CO reducer 2 is changed to the first temperature (the hydrogen-containing gas generated in the reformer 1). The temperature at which the contained water vapor does not condense in the CO reducer 2, which is lower than 150 ° C. in the present embodiment, and the internal temperature of the reformer 1 is the second temperature (on the catalyst inside the reformer 1). The performance of the catalyst, which deteriorates due to the deposition of carbon generated by pyrolysis of the raw material, cannot be ignored. The igniter 6 is ignited after a predetermined non-combustion time (1 minute in the present embodiment) has elapsed, which is sufficiently lower than the predetermined temperature and lower than 200 ° C. in the present embodiment. The heating operation of the heater 8 is resumed.

  As a result, the combustor 4 burns the desorbed gas desorbed from the carbon monoxide reducing catalyst, and after the combustion of the combustor 4 is stopped, the combustor 4 does not burn the desorbed gas, and the combustion air Since the process of supplying air from the supply device 5 and cooling the combustor 4 is repeated, the hydrogen-containing gas is prevented while preventing at least the reforming catalyst from deteriorating due to overheating of the reforming catalyst and the carbon monoxide reduction catalyst. The temperature of the reforming catalyst and the carbon monoxide reducing catalyst of the hydrogen generator 101 can be increased to a temperature suitable for the production of hydrogen.

  Further, the hydrogen generator 101 of the present embodiment includes a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and the controller 20 starts the heating operation of the heater 8 after the start of the heating operation. If the flame detector 7 does not detect a flame before 1 hour (1.9 minutes in the present embodiment) elapses, the internal temperature of the CO reducer 2 is the first temperature (this embodiment). The heating operation of the heater 8 is continued until the temperature reaches 150 ° C. or higher. When the internal temperature of the CO reducer 2 becomes equal to or higher than the first temperature (150 ° C. in the present embodiment), the heating of the heater 8 is continued. The operation ends.

  Thereby, when the flame detector 7 does not detect the flame before the first time (1.9 minutes in the present embodiment), the heater 8 is continuously operated, so that it is generated by the reformer 1. The water vapor contained in the hydrogen-containing gas can be raised in a short time to a temperature at which the water vapor does not condense in the CO reducer 2.

Further, the hydrogen generator 101 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and The controller 20 is formed by the combustor 4 when the raw material supplier 3 is operated when the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment). Combustion air is supplied from the combustion air supply device 5 to the combustor 4 and the igniter 6 is ignited so that the combustible gas concentration of the mixed gas falls within the combustible range. Raw material until it exceeds a third temperature (when the gas flowing through the reformer 1 contains water vapor, the temperature is higher than the temperature at which the water vapor does not condense in the reformer 1 and is 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is combusted by the combustor 4 and the temperature inside the hydrogen generator 101 is heated so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). Hydrogen generation to a temperature suitable for generating a hydrogen-containing gas (temperature at which the supply of reforming water to the reformer 1 starts) with only a small amount of desorbed gas desorbed from the carbon reduction catalyst and combustion with the desorbed gas Even when the inside of the apparatus 101 cannot be heated and heated, the inside of the hydrogen generating apparatus 101 can be heated and heated to a temperature suitable for generating a hydrogen-containing gas (a temperature at which the supply of reforming water to the reformer 1 is started).

  In the operation method of the hydrogen generator 101 according to the present embodiment, when the hydrogen generator 101 is started, first, the raw material supplier 3 is stopped, and the combustion air supplier 5 supplies air to the combustor 4. In the supplied state, the heating operation of the heater 8 is started and the first step (steps S103 and S104) for causing the igniter 6 to perform the ignition operation, and the heating operation of the heater 8 is started in step S104. If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set, the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane in this embodiment) after the hydrogen generator 101 has stopped operating. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

(Embodiment 2)
The block diagram of the hydrogen generator 101 according to the second embodiment of the present invention is the same as the hydrogen generator 101 according to the first embodiment shown in FIG. 1, and the same components as those in the first embodiment are denoted by the same reference numerals. The detailed description is omitted. The operation of the hydrogen generator 101 of the second embodiment is partly different from that of the hydrogen generator 101 of the first embodiment.

  Next, a method for starting the hydrogen generator 101 according to the present embodiment will be described with reference to FIG.

  FIG. 4 is a flowchart showing a startup method of the hydrogen generator 101 according to Embodiment 2 of the present invention. In FIG. 4, the same step numbers are assigned to the same operations (steps) as those in the flowchart showing the activation method of the hydrogen generator 101 in the first embodiment shown in FIG. Detailed description thereof is omitted.

  In the flowchart showing the startup method of the hydrogen generator 101 in the second embodiment shown in FIG. 4, steps S123 to S125 of the flowchart showing the startup method of the hydrogen generator 101 in the first embodiment shown in FIG. To step S226.

Like the hydrogen generator 101 of the first embodiment, the combustor is changed from the reformer 1 before the start of the hydrogen generator 101 of the second embodiment is executed (when the previous hydrogen generator 101 is stopped). 4
The gas flow path leading to is purged with the raw material.

  When the hydrogen generator 101 is activated, the controller 20 operates the combustion air supply device 5 to supply combustion air to the combustor 4 at 1.6 mol / min (step S101). Subsequently, the controller 20 opens the switch 9 (step S102) and then the igniter 6 (step S103) in order to desorb the gas from the CO reducer 2, introduce it into the combustor 4, and burn it. ) And the heater 8 (step S104) are sequentially operated.

  Next, the controller 20 checks whether or not 1.9 minutes (first time) has elapsed since the operation start of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) have elapsed since the start of the operation of the heater 8, the process proceeds to step S141. On the other hand, if it is determined in step S105 that 1.9 minutes (first time) has not yet elapsed from the start of operation of the heater 8, the process proceeds to step S106.

  In step S106, it is confirmed whether or not the flame has been detected by the flame detector 7. If the flame has been detected by the flame detector 7, the process proceeds to step S107. Conversely, the flame is detected by the flame detector 7. If not, the process returns to step S105.

  Hereinafter, an operation when a flame is detected by the flame detector 7 in step S106 will be described.

  First, the controller 20 detects the flame with the flame detector 7, so the igniter 6 is stopped (step S 107), and then the desorption of gas from the CO reducer 2 is stopped and the combustor 4 is stopped. In order to stop the combustion, the heater 8 is stopped (step S108). Subsequently, the supply of gas from the CO reducer 2 to the combustor 4 is shut off, and the combustion in the combustor 4 is stopped reliably. The switch 9 is closed (step S109).

  Further, when the switch 9 is opened in the subsequent step S121, the combustion air supply device 5 is connected in advance to the combustor 4 so that the combustible gas concentration formed in the combustor 4 does not exceed the lower limit of the combustible range. Is increased (step S110).

  In step S110, the flow rate of the combustion air was increased from 1.6 mol / min to 3.2 mol / min. Next, the controller 20 stands by until the flame detector 7 can no longer detect the flame (step S111). If the flame detector 7 cannot detect the flame in step S111, the controller 20 proceeds to step S121.

  Next, operation | movement from step S121, step S122, and step S223 to step S226 is demonstrated.

  First, in order to make the internal pressure of the hydrogen generator 101 substantially the same as the atmospheric pressure, the switch 9 is opened again (step S121). Next, the controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 with the first temperature, and when the internal temperature of the CO reducer 2 is lower than the first temperature, The process proceeds to step S223 (step S122). Conversely, if the internal temperature of the CO reducer 2 is equal to or higher than the first temperature, the process proceeds to step S161.

  Here, the first temperature is a temperature at which water vapor contained in the hydrogen-containing gas generated in the reformer 1 is not condensed in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature drop after the operation stop of the heater 8 (step S108).

Next, an operation when the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C. in the present embodiment) will be described.

  The controller 20 increases the flow rate of the combustion air supplied from the combustion air supply device 5 to the combustor 4 (step S223). Here, the concentration of the raw material flowing into the combustor 4 from the CO reducer 2 is lowered to a concentration lower than the lower limit of the combustible range by increasing the flow rate of the combustion air.

  In the present embodiment, the maximum flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst and flowing into the combustor 4 by heating the CO reducer 2 when the hydrogen generator 101 is started is shown in FIG. As indicated by the solid line, it is 0.10 mol / min, and the lower limit of the flammable range of butane gas is 1.9%. Therefore, the flow rate of combustion air supplied to make the concentration lower than 1.9% is X Then, the flow rate is obtained by (Equation 1).

The combustion air flow rate X obtained by modifying (Equation 1) was 5.16 mol / min. Therefore, in the present embodiment, the controller 20 increases the flow rate of the combustion air to 6.00 mol / min. When supplying combustion air at 6.00 mol / min, the combustible gas concentration is 1.6% as shown in (Equation 2), which is lower than the lower limit of the combustible range (1.9%). Does not burn even if there is an ignition source.

Subsequently, the controller 20 operates the heater 8 again in order to promote desorption of the raw material from the CO reducer 2 (step S224), and heats the CO reducer 2 by heating.

  Next, the controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 with the first temperature (150 ° C. in the present embodiment) (step S225), and the CO reducer. 2 is lower than the first temperature (150 ° C. in the present embodiment), step S225 is performed until the internal temperature of the CO reducer 2 becomes equal to or higher than the first temperature (150 ° C. in the present embodiment). Repeatedly, the heating and heating of the CO reducer 2 by the heater 8 is continued.

  When the internal temperature of the CO reducer 2 becomes higher than the first temperature (150 ° C. in the present embodiment) by the heating operation of the heater 8, the controller 20 stops the operation of the heater 8 (step S226), the process proceeds to step S161.

  Next, an operation when 1.9 minutes have elapsed from the start of the operation of the heater 8 in step S105 will be described.

First, after stopping the operation of the igniter 6 (step S141), the controller 20 checks whether or not a flame has been detected by the flame detector 7 (step S142). In step S142, when the flame is detected by the flame detector 7, the controller 20 completes the desorption of the raw material from the CO reducer 2, and the desorbed gas is not supplied to the combustor 4. Since the combustion of the gas cannot be continued, the flame detector 7 waits until the flame cannot be detected.

  As shown in FIG. 2, the flow rate of the desorbed gas gradually decreases after reaching the maximum value within a few minutes from the start of the operation of the heater 8, so that the combustion in the combustor 4 stops. And if a flame becomes impossible to detect, it will transfer to step S143. Conversely, in step S142, if the flame detector 7 cannot detect a flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms whether or not the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) from the CO reducer temperature detector 11 (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature 150 ° C., the step S143 is repeated and the CO reducer 2 is heated by the heater 8. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature 150 ° C., the operation of the heater 8 is stopped (step 144), and the process proceeds to step S161.

  Next, the operation after step S161 will be described. The controller 20 executes the operations after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reformer 1 can perform a reforming reaction. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed by the combustor 4 when the raw material supplier 3 is operated in the subsequent step S163 falls within the combustible range ( Step S161).

  Next, the igniter 6 is operated (step S162), the raw material supplier 3 is operated (step S163), the raw material is supplied to the combustor 4 via the reformer 1 and the CO reducer 2, and the combustor 4 Burn the raw material. Subsequently, the controller 20 waits until the flame can be detected by the flame detector 7 (step S164). When the flame is detected by the flame detector 7, the operation of the igniter 6 is stopped (step S165), and step S166. Migrate to

  In step S166, the controller 20 confirms whether or not the internal temperature of the reformer 1 acquired from the reformer temperature detector 10 is lower than the third temperature, and the internal temperature of the reformer 1 is the third temperature. When the temperature is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has become equal to or higher than the third temperature. When the reformer temperature detector 10 confirms that the internal temperature of the reformer 1 has become equal to or higher than the third temperature, the process proceeds to the end.

  Here, the third temperature is a temperature higher than a temperature at which the water vapor does not condense in the reformer 1 when the gas flowing through the reformer 1 contains water vapor. In the present embodiment, the third temperature is the third temperature. Was set to 120 ° C.

  With the above operation, the operation of raising the temperature of the hydrogen generator 101 to a temperature at which the reforming reaction can be performed without being affected by the flow rate and composition fluctuation of the gas desorbed from the CO reducer 2 is completed.

  Subsequently, a reforming water supply unit (not shown) is operated to supply reforming water to the reforming unit 1, and generation of a hydrogen-containing gas in the reforming unit 1 is started by a steam reforming reaction, thereby reducing CO. The gas discharged from the vessel 2 is supplied to a hydrogen utilization device (not shown).

As described above, in the present embodiment, in the hydrogen generator 101 using a raw material mainly composed of at least one of propane and butane, the increase rate of the desorbed gas flow rate is slow, and the combustor 4 The ignition time that takes the longest time for the gas concentration to enter the combustible range and ignite is set as the first time (1.9 minutes), and after the ignition operation and the heating operation, from the first time (1.9 minutes) When the flame detector 7 detects a flame before, the operation of the heater 8 is terminated and the supply of the desorbed gas to the combustor 4 by the operation of the switch 9 is shut off, and the combustion in the combustor 4 is performed. Therefore, the desorption of gas from the catalyst is stopped by stopping the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped, so that deterioration due to excessive temperature rise of the catalyst can be prevented.

  When ignited before the first time (1.9 minutes), the combustible gas concentration of the mixed gas formed in the combustor 4 by the gas desorbed from the CO reducer 2 is below the lower limit of the combustible range. The flow rate of combustion air is increased until the concentration reaches the same level, and the CO reducer 2 is heated to the first temperature (150 ° C.) by the operation of the heater 8, and then the reformer 1 and the CO reducer 2. Because the temperature of the reformer 1 is raised to the third temperature (120 ° C.) by combustion of the raw material supplied to the combustor 4 via the gas, it is affected by changes in the composition and flow rate of the desorbed gas from the CO reducer 2. Without deterioration of the catalyst of the reformer 1 due to excessive temperature rise, the reformer 1 can be heated to a temperature at which the reforming reaction can be performed.

  Further, since the ignition operation is not repeated, it can be started with the minimum number of ignition operations, so that the life of the igniter 6 can be extended.

  In this embodiment, LP gas is used as a raw material for the hydrogen generator 101. However, not only LP gas but also hydrocarbons having 2 to 4 carbon atoms such as ethane, ethylene, propylene, and butene are used. A mixed gas having a main component may be used as a raw material for the hydrogen generator 101.

  The hydrogen generator 101 of the present embodiment includes a raw material supplier 3 that supplies a raw material mainly composed of hydrocarbons, a reformer 1 that generates a hydrogen-containing gas from the raw material using a reforming catalyst, and a reformer 1 The carbon monoxide concentration of the hydrogen-containing gas produced in step 1 is reduced by the carbon monoxide reduction catalyst, and the gas discharged from the CO reduction device 2 is burned to reform the reformer 1 and the CO reduction device 2. Among them, at least a combustor 4 for heating the reformer 1, a combustion air supply device 5 for supplying combustion air to the combustor 4, an igniter 6 for performing an ignition operation in the combustor 4, and a flame of the combustor 4. A flame detector 7 that detects the presence or absence of the gas, a heater 8 that heats the CO reducer 2, and a controller 20.

  When the controller 20 starts up the hydrogen generator 101, first, the heater is used in a state where the raw material supplier 3 is stopped and the combustion air supplier 5 is supplying air to the combustor 4. 8, the igniter 6 is ignited, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. When a flame is detected, the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set, the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane in this embodiment) after the hydrogen generator 101 has stopped operating. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

  The raw material of the hydrogen generator 101 of the present embodiment is LP gas containing at least one of propane and butane as a main component, and reaches the combustor 4 from the reformer 1 after the hydrogen generator 101 is stopped. The gas flow path is purged with the raw material (LP gas).

Then, in the first time (1.9 minutes in the present embodiment), when the desorption gas desorbed from the carbon monoxide reduction catalyst by the heating operation of the heater 8 is propane, the combustion in the combustor 4 is performed. It was time to start.

  Thereby, when butane is contained in addition to propane in the desorption gas desorbed from the carbon monoxide reduction catalyst of the CO reducer 2 by the heating operation of the heater 8, the heating time by the heater 8 is stopped early. Therefore, since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the temperature increase of the carbon monoxide reduction catalyst and the combustion in the combustor 4 is stopped, the reforming catalyst and the carbon monoxide reduction catalyst are stopped. Of these, at least deterioration of the reforming catalyst due to excessive temperature rise can be more reliably prevented.

  Further, the hydrogen generator 101 of the present embodiment includes a switch 9 on the generated gas flow path that guides the gas discharged from the CO reducer 2 to the combustor 4, and the controller 20 activates the hydrogen generator 101. When the switch 9 is opened, the heating operation of the heater 8 is started, and the flame detection is performed within the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. When the device 7 detects a flame, the heating operation of the heater 8 is terminated and the switch 9 is closed.

  Thereby, since the inflow to the combustor 4 of the desorbed gas desorbed from the carbon monoxide reducing catalyst by the heating operation of the heater 8 is blocked by the switch 9, the combustion in the combustor 4 is stopped. Of the reforming catalyst and the carbon monoxide reduction catalyst, it is possible to more reliably prevent at least the reforming catalyst from being deteriorated due to excessive temperature rise.

  Further, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is within the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. After the heating operation of the heater 8 is finished by detecting the flame and the switch 9 is closed, when the flame detector 7 no longer detects the flame of the combustor 4, the switch 9 is opened again. To do.

  As a result, even if the temperature of the hydrogen generator 101 changes, the pressure inside the hydrogen generator 101 becomes substantially the same as the atmospheric pressure, so the structure of the hydrogen generator 101 needs to have a structure that can withstand excessive pressure. Therefore, the hydrogen generator 101 can be configured at low cost.

  Further, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is within the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. When a flame is detected, the flow rate of combustion air supplied from the combustion air supply device 5 to the combustor 4 is increased so that the combustible gas concentration of the mixed gas formed in the combustor 4 is outside the combustible range. To do.

  Thereby, since the combustible gas concentration of the mixed gas formed in the combustor 4 is lower than the lower limit of the combustible range, the gas released out of the system of the hydrogen generator 101 has an ignition source. However, it does not burn and the safety of the hydrogen generator 101 is high.

  Further, the hydrogen generator 101 of the present embodiment includes a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and the controller 20 starts the heating operation of the heater 8 after the start of the heating operation. The flame detector 7 detects the flame of the combustor 4 after completing the heating operation of the heater 8 because the flame detector 7 detects the flame within 1 hour (1.9 minutes in the present embodiment). In the present embodiment, the internal temperature of the CO reducer 2 is the first temperature (the temperature at which the water vapor contained in the hydrogen-containing gas generated in the reformer 1 is not condensed in the CO reducer 2). When the temperature is lower than 150 ° C., the flow rate of the combustion air supplied from the combustion air supply device 5 to the combustor 4 is set so that the combustible gas concentration of the mixed gas formed in the combustor 4 is out of the combustible range. After the increase, the heating operation of the heater 8 is restarted.

As a result, the combustible gas concentration of the mixed gas formed in the combustor 4 becomes lower than the lower limit of the combustible range, so that the gas released out of the system of the hydrogen generator 101 has an ignition source. Even if it does not combust, hydrogen generator 101 with high safety can be constituted.

  Further, the hydrogen generator 101 of the present embodiment includes a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and the controller 20 starts the heating operation of the heater 8 after the start of the heating operation. If the flame detector 7 does not detect a flame before 1 hour (1.9 minutes in the present embodiment) elapses, the internal temperature of the CO reducer 2 is the first temperature (this embodiment). The heating operation of the heater 8 is continued until the temperature reaches 150 ° C. or higher. When the internal temperature of the CO reducer 2 becomes equal to or higher than the first temperature (150 ° C. in the present embodiment), the heating of the heater 8 is continued. The operation ends.

  Thereby, when the flame detector 7 does not detect the flame before the first time (1.9 minutes in the present embodiment), the heater 8 is continuously operated, so that it is generated by the reformer 1. The water vapor contained in the hydrogen-containing gas can be raised in a short time to a temperature at which the water vapor does not condense in the CO reducer 2.

  Further, the hydrogen generator 101 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and The controller 20 is formed by the combustor 4 when the raw material supplier 3 is operated when the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment). Combustion air is supplied from the combustion air supply device 5 to the combustor 4 and the igniter 6 is ignited so that the combustible gas concentration of the mixed gas falls within the combustible range. Raw material until it exceeds a third temperature (when the gas flowing through the reformer 1 contains water vapor, the temperature is higher than the temperature at which the water vapor does not condense in the reformer 1 and is 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is combusted by the combustor 4 and the temperature inside the hydrogen generator 101 is heated so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). Hydrogen generation to a temperature suitable for generating a hydrogen-containing gas (temperature at which the supply of reforming water to the reformer 1 starts) with only a small amount of desorbed gas desorbed from the carbon reduction catalyst and combustion with the desorbed gas Even when the inside of the apparatus 101 cannot be heated and heated, the inside of the hydrogen generating apparatus 101 can be heated and heated to a temperature suitable for generating a hydrogen-containing gas (a temperature at which the supply of reforming water to the reformer 1 is started).

  In the operation method of the hydrogen generator 101 according to the present embodiment, when the hydrogen generator 101 is started, first, the raw material supplier 3 is stopped, and the combustion air supplier 5 supplies air to the combustor 4. In the supplied state, the heating operation of the heater 8 is started and the first step (steps S103 and S104) for causing the igniter 6 to perform the ignition operation, and the heating operation of the heater 8 is started in step S104. If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set, the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane in this embodiment) after the hydrogen generator 101 has stopped operating. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

(Embodiment 3)
FIG. 5 is a block diagram showing the configuration of the hydrogen generator in Embodiment 3 of the present invention.

  In FIG. 5, the same components as those in FIG. 1 are given the same reference numerals, and detailed description thereof is omitted. The hydrogen generator 103 of Embodiment 3 is the same as that of Embodiment 1 shown in FIG. 1 in that the switch 9 is not provided on the product gas flow path that guides the gas discharged from the CO reducer 2 to the combustor 4. This is different from the hydrogen generator 101 of the second embodiment.

  Next, a method for starting the hydrogen generator 103 will be described with reference to FIG.

  FIG. 6 is a flowchart showing a startup method of the hydrogen generator 103 according to Embodiment 3 of the present invention. About the same operation | movement as the flowchart which shows the starting method of the hydrogen generator 101 in Embodiment 1 shown in FIG. 3, the same code | symbol is provided and detailed description is abbreviate | omitted.

  3 differs from the flowchart showing the start-up method of the hydrogen generator 101 in the first embodiment shown in FIG. 3 in that steps S102, S109, and S121 related to the switch 9 are omitted, and the combustion air in FIG. 3 is increased. Step S110, Step S111 that waits until the flame detector 7 can no longer detect the flame, Step S310 that increases the combustion air, and Step S311 that returns to Step S310 if the flame detector 7 detects the flame. Each of these points is replaced.

  Similarly to the hydrogen generator 101 of the first embodiment, the combustor is changed from the reformer 1 before the start of the hydrogen generator 103 of the third embodiment is executed (when the previous hydrogen generator 103 is stopped). The gas flow path leading to 4 is purged with the raw material.

  When the hydrogen generator 103 is activated, the controller 20 operates the combustion air supply unit 5 to supply combustion air to the combustor 4 at 1.6 mol / min (step S101). Subsequently, the controller 20 sequentially operates the igniter 6 (step S103) and the heater 8 (step S104) in order to desorb the gas from the CO reducer 2, introduce it into the combustor 4, and burn it.

  Next, the controller 20 checks whether or not 1.9 minutes (first time) has elapsed since the operation start of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) have elapsed since the start of the operation of the heater 8, the process proceeds to step S141. On the other hand, if it is determined in step S105 that 1.9 minutes (first time) has not yet elapsed from the start of operation of the heater 8, the process proceeds to step S106.

  In step S106, it is confirmed whether or not the flame has been detected by the flame detector 7. If the flame has been detected by the flame detector 7, the process proceeds to step S107. Conversely, the flame is detected by the flame detector 7. If not, the process returns to step S105.

  Hereinafter, an operation when a flame is detected by the flame detector 7 in step S106 will be described.

  First, the controller 20 detects the flame with the flame detector 7, so the igniter 6 is stopped (step S 107), and then the desorption of gas from the CO reducer 2 is stopped and the combustor 4 is stopped. In order to stop combustion, the heater 8 is stopped (step S108).

After executing step S108, the controller 20 increases the flow rate of combustion air in order to reliably stop the combustion by lowering the combustible gas concentration formed in the combustor 4 below the lower limit of the combustion range. (Step S310). Subsequently, the controller 20 checks whether or not the flame detector 7 has detected a flame (step S311). If the flame detector 7 detects a flame, the flow returns to step S310 to further increase the flow rate of the combustion air. When the flame detector 7 cannot detect the flame, the process proceeds to step S122.

  Next, the operation from step S122 to step S125 will be described.

  The controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 with the first temperature. If the internal temperature of the CO reducer 2 is lower than the first temperature, the controller 20 proceeds to step S123. Transition is made (step S122). Conversely, if the internal temperature of the CO reducer 2 is equal to or higher than the first temperature, the process proceeds to step S161.

  Here, the first temperature is a temperature at which water vapor contained in the hydrogen-containing gas generated in the reformer 1 is not condensed in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature drop after the operation stop of the heater 8 (step S108).

  Next, in step S123, the controller 20 compares the internal temperature of the reformer 1 acquired from the reformer temperature detector 10 with the second temperature, and the internal temperature of the reformer 1 is lower than the second temperature. If so, the process proceeds to step S124. Conversely, if the internal temperature of the reformer 1 is not lower than the second temperature, the process waits until it becomes lower than the second temperature.

  Here, the second temperature is a temperature sufficiently lower than a temperature (400 ° C.) at which the performance of the catalyst, which is deteriorated due to the deposition of carbon generated by the thermal decomposition of the raw material on the catalyst inside the reformer 1, cannot be ignored. In the present embodiment, the second temperature is set to 200.degree.

  Next, in step S124, the controller 20 performs an operation of waiting for a predetermined non-burning time. The predetermined non-combustion time is the total time after moving to step S122. Even after the operation to stop desorption from the CO reducer 2 is performed in step S108, unburned gas remains in the combustor 4. For this reason, when the ignition operation is started without scavenging the unburned gas, the unburned gas is ignited, and the combustor 4 may be damaged due to an increase in pressure and temperature due to the ignition.

  Therefore, the unburned gas inside the combustor 4 is replaced with air. Since the volume of the combustor 4 of the present embodiment is 7.2 L, 10 times 72 L of air is supplied. Since the flow rate of the combustion air supplied from the combustion air supply device 5 to the combustor 4 is 3.2 mol / min (= 72 L / min), the non-combustion time is set to 1 minute.

  In step S124, when the time from the time of moving to step S122 to the time of reaching step S124 exceeds 1 minute, the process moves to step S125. On the other hand, if the time from the point of transition to step S122 to the step S124 does not exceed 1 minute, the process waits until 1 minute elapses.

  In step S125, in preparation for the next ignition, the flow rate of the combustion air is adjusted to 1.6 mol / min. Through the above operation, the controller 20 returns to step S103 to desorb the gas from the CO reducer 2 in order to further increase the internal temperature of the reformer 1 and the internal temperature of the CO reducer 2.

  Next, an operation when 1.9 minutes have elapsed from the start of the operation of the heater 8 in step S105 will be described.

First, after stopping the operation of the igniter 6 (step S141), the controller 20 checks whether or not a flame has been detected by the flame detector 7 (step S142). In step S142, when the flame is detected by the flame detector 7, the controller 20 completes the desorption of the raw material from the CO reducer 2, and the desorbed gas is not supplied to the combustor 4. Since the combustion of the gas cannot be continued, the flame detector 7 waits until the flame cannot be detected.

  As shown in FIG. 2, the flow rate of the desorbed gas gradually decreases after reaching the maximum value within a few minutes from the start of the operation of the heater 8, so that the combustion in the combustor 4 stops. And if a flame becomes impossible to detect, it will transfer to step S143. Conversely, in step S142, if the flame detector 7 cannot detect a flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms whether or not the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) from the CO reducer temperature detector 11 (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature 150 ° C., the step S143 is repeated and the CO reducer 2 is heated by the heater 8. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature 150 ° C., the operation of the heater 8 is stopped (step 144), and the process proceeds to step S161.

  Next, the operation after step S161 will be described. The controller 20 executes the operations after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reformer 1 can perform a reforming reaction. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed by the combustor 4 when the raw material supplier 3 is operated in the subsequent step S163 falls within the combustible range ( Step S161).

  Next, the igniter 6 is operated (step S162), the raw material supplier 3 is operated (step S163), the raw material is supplied to the combustor 4 via the reformer 1 and the CO reducer 2, and the combustor 4 Burn the raw material. Subsequently, the controller 20 waits until the flame can be detected by the flame detector 7 (step S164). When the flame is detected by the flame detector 7, the operation of the igniter 6 is stopped (step S165), and step S166. Migrate to

  In step S166, the controller 20 confirms whether or not the internal temperature of the reformer 1 acquired from the reformer temperature detector 10 is lower than the third temperature, and the internal temperature of the reformer 1 is the third temperature. When the temperature is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has become equal to or higher than the third temperature. When the reformer temperature detector 10 confirms that the internal temperature of the reformer 1 has become equal to or higher than the third temperature, the process proceeds to the end.

  Here, the third temperature is a temperature higher than a temperature at which the water vapor does not condense in the reformer 1 when the gas flowing through the reformer 1 contains water vapor. In the present embodiment, the third temperature is the third temperature. Was set to 120 ° C.

  With the above operation, the operation of raising the temperature of the hydrogen generator 103 to a temperature at which the reforming reaction can be performed without being affected by the flow rate and composition fluctuation of the gas desorbed from the CO reducer 2 is completed.

  Subsequently, a reforming water supply unit (not shown) is operated to supply reforming water to the reforming unit 1, and generation of a hydrogen-containing gas in the reforming unit 1 is started by a steam reforming reaction, thereby reducing CO. The gas discharged from the vessel 2 is supplied to a hydrogen utilization device (not shown).

As described above, in the present embodiment, in the hydrogen generator 103 that uses a raw material mainly composed of at least one of propane and butane, the increase rate of the desorbed gas flow rate is slow, and the combustor 4 The ignition time that takes the longest time for the gas concentration to enter the combustible range and ignite is set as the first time (1.9 minutes), and after the ignition operation and the heating operation, from the first time (1.9 minutes) If the flame detector 7 detects a flame before, the operation of the heater 8 is finished and the flow rate of the combustion air is increased until the concentration becomes lower than the lower limit of the combustible range. Since the combustion of the catalyst is stopped, the desorption of the gas from the catalyst is stopped by stopping the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped. Therefore, the deterioration due to the excessive temperature rise of the catalyst can be prevented.

  Moreover, since the switch 9 in the hydrogen generator 101 of Embodiment 1 is unnecessary, it is cheap and can improve reliability.

  Further, after repeating the above series of operations until the internal temperature of the CO reducer 2 exceeds the first temperature 150 ° C., the raw material is supplied to the combustor 4 via the reformer 1 and the CO reducer 2, Since the reformer 1 is heated to a third temperature of 120 ° C. by combustion, the reforming catalyst of the reformer 1 is not affected by changes in the composition and flow rate of the desorbed gas from the CO reducer 2. Deterioration due to excessive temperature rise can be prevented, and the reformer 1 can be heated to a temperature at which a reforming reaction can be performed.

  In this embodiment, the raw materials are butane and propane. However, the raw material is a mixed gas mainly composed of hydrocarbons having 2 to 4 carbon atoms such as ethane, ethylene, propylene, and butene. Also good.

  The hydrogen generator 103 of the present embodiment includes a raw material supplier 3 that supplies a raw material mainly composed of hydrocarbons, a reformer 1 that generates a hydrogen-containing gas from the raw material using a reforming catalyst, and a reformer 1 The carbon monoxide concentration of the hydrogen-containing gas produced in step 1 is reduced by the carbon monoxide reduction catalyst, and the gas discharged from the CO reduction device 2 is burned to reform the reformer 1 and the CO reduction device 2. Among them, at least a combustor 4 for heating the reformer 1, a combustion air supply device 5 for supplying combustion air to the combustor 4, an igniter 6 for performing an ignition operation in the combustor 4, and a flame of the combustor 4. A flame detector 7 that detects the presence or absence of the gas, a heater 8 that heats the CO reducer 2, and a controller 20.

  When the controller 20 activates the hydrogen generator 103, first, in the state where the raw material supplier 3 is stopped and the combustion air supplier 5 is supplying air to the combustor 4, the heater 8, the igniter 6 is ignited, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. When a flame is detected, the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set to 1.9 minutes), the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane) in the present embodiment after the hydrogen generator 103 stops operation. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

  The raw material of the hydrogen generator 103 of the present embodiment is LP gas containing at least one of propane and butane as a main component, and reaches the combustor 4 from the reformer 1 after the hydrogen generator 103 is stopped. The gas flow path is purged with the raw material (LP gas).

  Then, in the first time (1.9 minutes in the present embodiment), when the desorption gas desorbed from the carbon monoxide reduction catalyst by the heating operation of the heater 8 is propane, the combustion in the combustor 4 is performed. It was time to start.

  Thereby, when butane is contained in addition to propane in the desorption gas desorbed from the carbon monoxide reduction catalyst of the CO reducer 2 by the heating operation of the heater 8, the heating time by the heater 8 is stopped early. Therefore, since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the temperature increase of the carbon monoxide reduction catalyst and the combustion in the combustor 4 is stopped, the reforming catalyst and the carbon monoxide reduction catalyst are stopped. Of these, at least deterioration of the reforming catalyst due to excessive temperature rise can be more reliably prevented.

  Further, in the hydrogen generator 103 of the present embodiment, the flame detector 7 before the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. When the flame is detected, the heating operation of the heater 8 is terminated, and the flow rate of the combustion air supplied from the combustion air supplier 5 to the combustor 4 is decreased until the flame detector 7 no longer detects the flame. To increase.

  Thereby, the combustible gas concentration of the mixed gas formed in the combustor 4 becomes lower than the lower limit of the combustible range, and the combustion in the combustor 4 stops, so that the deterioration due to the excessive temperature rise of the catalyst is more reliably performed. Can be prevented.

  In addition, the hydrogen generator 103 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and And the controller 20 detects the flame within the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. After the heating operation is completed, after the flame detector 7 stops detecting the flame of the combustor 4, the internal temperature of the CO reducer 2 is changed to the first temperature (the hydrogen-containing gas generated in the reformer 1). The temperature at which the contained water vapor does not condense in the CO reducer 2, which is lower than 150 ° C. in the present embodiment, and the internal temperature of the reformer 1 is the second temperature (on the catalyst inside the reformer 1). The performance of the catalyst, which deteriorates due to the deposition of carbon generated by pyrolysis of the raw material, cannot be ignored. The igniter 6 is ignited after a predetermined non-combustion time (1 minute in the present embodiment) has elapsed, which is sufficiently lower than the predetermined temperature and lower than 200 ° C. in the present embodiment. The heating operation of the heater 8 is resumed.

  As a result, the combustor 4 burns the desorbed gas desorbed from the carbon monoxide reducing catalyst, and after the combustion of the combustor 4 is stopped, the combustor 4 does not burn the desorbed gas, and the combustion air Since the process of supplying air from the supply device 5 and cooling the combustor 4 is repeated, the hydrogen-containing gas is prevented while preventing at least the reforming catalyst from deteriorating due to overheating of the reforming catalyst and the carbon monoxide reduction catalyst. The temperature of the reforming catalyst and the carbon monoxide reducing catalyst of the hydrogen generator 103 can be increased to a temperature suitable for the production of hydrogen.

  The hydrogen generator 103 of the present embodiment also includes a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and the controller 20 starts the heating operation of the heater 8 after the start of the heating operation. If the flame detector 7 does not detect a flame before 1 hour (1.9 minutes in the present embodiment) elapses, the internal temperature of the CO reducer 2 is the first temperature (this embodiment). The heating operation of the heater 8 is continued until the temperature reaches 150 ° C. or higher. When the internal temperature of the CO reducer 2 becomes equal to or higher than the first temperature (150 ° C. in the present embodiment), the heating of the heater 8 is continued. The operation ends.

  Thereby, when the flame detector 7 does not detect the flame before the first time (1.9 minutes in the present embodiment), the heater 8 is continuously operated, so that it is generated by the reformer 1. The water vapor contained in the hydrogen-containing gas can be raised in a short time to a temperature at which the water vapor does not condense in the CO reducer 2.

In addition, the hydrogen generator 103 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and The controller 20 is formed by the combustor 4 when the raw material supplier 3 is operated when the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment). Combustion air is supplied from the combustion air supply device 5 to the combustor 4 and the igniter 6 is ignited so that the combustible gas concentration of the mixed gas falls within the combustible range. Raw material until it exceeds a third temperature (when the gas flowing through the reformer 1 contains water vapor, the temperature is higher than the temperature at which the water vapor does not condense in the reformer 1 and is 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is combusted in the combustor 4 and the temperature inside the hydrogen generator 103 is heated so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). Hydrogen generation to a temperature suitable for generating a hydrogen-containing gas (temperature at which the supply of reforming water to the reformer 1 starts) with only a small amount of desorbed gas desorbed from the carbon reduction catalyst and combustion with the desorbed gas Even when the inside of the apparatus 103 cannot be heated and heated, the inside of the hydrogen generating apparatus 103 can be heated and heated to a temperature suitable for generating the hydrogen-containing gas (a temperature at which the supply of reforming water to the reformer 1 is started).

  In the operation method of the hydrogen generator 103 according to the present embodiment, when the hydrogen generator 103 is started, first, the raw material supplier 3 is stopped, and the combustion air supplier 5 supplies air to the combustor 4. In the supplied state, the heating operation of the heater 8 is started and the first step (steps S103 and S104) for causing the igniter 6 to perform the ignition operation, and the heating operation of the heater 8 is started in step S104. If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set to 1.9 minutes), the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane) in the present embodiment after the hydrogen generator 103 stops operation. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

(Embodiment 4)
The block diagram of the hydrogen generator 103 according to the fourth embodiment of the present invention is the same as the hydrogen generator 103 according to the third embodiment shown in FIG. 5, and the same reference numerals are given to the same components as those in the third embodiment. The detailed description is omitted. The operation of the hydrogen generator 103 according to the fourth embodiment is partially different from that of the hydrogen generator 103 according to the third embodiment.

  Next, a method for starting the hydrogen generator 103 according to the present embodiment will be described with reference to FIG.

  FIG. 7 is a flowchart showing a startup method of the hydrogen generator 103 according to Embodiment 4 of the present invention. 7, a flowchart showing a startup method of the hydrogen generator 101 in the first embodiment shown in FIG. 3, a flowchart showing a startup method of the hydrogen generator 101 in the second embodiment shown in FIG. 4, and an implementation shown in FIG. 6. The same steps (steps) as those in the flowchart showing the start-up method of the hydrogen generator 103 in Embodiment 3 are given the same step codes. Detailed description thereof is omitted.

In the flowchart showing the startup method of the hydrogen generator 103 in the fourth embodiment shown in FIG. 7, steps S123 to S125 of the flowchart showing the startup method of the hydrogen generator 103 in the third embodiment shown in FIG. To step S226.

  Similar to the hydrogen generator 103 of the third embodiment, the combustor is changed from the reformer 1 before the start of the hydrogen generator 103 of the fourth embodiment is executed (when the previous hydrogen generator 103 is stopped). The gas flow path leading to 4 is purged with the raw material.

  When the hydrogen generator 103 is activated, the controller 20 operates the combustion air supply unit 5 to supply combustion air to the combustor 4 at 1.6 mol / min (step S101). Subsequently, the controller 20 sequentially operates the igniter 6 (step S103) and the heater 8 (step S104) in order to desorb the gas from the CO reducer 2, introduce it into the combustor 4, and burn it.

  Next, the controller 20 checks whether or not 1.9 minutes (first time) has elapsed since the operation start of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) have elapsed since the start of the operation of the heater 8, the process proceeds to step S141. On the other hand, if it is determined in step S105 that 1.9 minutes (first time) has not yet elapsed from the start of operation of the heater 8, the process proceeds to step S106.

  In step S106, it is confirmed whether or not the flame has been detected by the flame detector 7. If the flame has been detected by the flame detector 7, the process proceeds to step S107. Conversely, the flame is detected by the flame detector 7. If not, the process returns to step S105.

  Hereinafter, an operation when a flame is detected by the flame detector 7 in step S106 will be described.

  First, the controller 20 detects the flame with the flame detector 7, so the igniter 6 is stopped (step S 107), and then the desorption of gas from the CO reducer 2 is stopped and the combustor 4 is stopped. In order to stop combustion, the heater 8 is stopped (step S108).

  After executing step S108, the controller 20 increases the flow rate of combustion air in order to reliably stop the combustion by lowering the combustible gas concentration formed in the combustor 4 below the lower limit of the combustion range. (Step S310). Subsequently, the controller 20 checks whether or not the flame detector 7 has detected a flame (step S311). If the flame detector 7 detects a flame, the flow returns to step S310 to further increase the flow rate of the combustion air. When the flame detector 7 cannot detect the flame, the process proceeds to step S122.

  Next, step S122 and operations from step S223 to step S226 will be described.

  The controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 with the first temperature. If the internal temperature of the CO reducer 2 is lower than the first temperature, the process proceeds to step S223. Transition is made (step S122). Conversely, if the internal temperature of the CO reducer 2 is equal to or higher than the first temperature, the process proceeds to step S161.

  Here, the first temperature is a temperature at which water vapor contained in the hydrogen-containing gas generated in the reformer 1 is not condensed in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature drop after the operation stop of the heater 8 (step S108).

  Next, an operation when the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C. in the present embodiment) will be described.

  The controller 20 increases the flow rate of the combustion air supplied from the combustion air supply device 5 to the combustor 4 (step S223). Here, the concentration of the raw material flowing into the combustor 4 from the CO reducer 2 is lowered to a concentration lower than the lower limit of the combustible range by increasing the flow rate of the combustion air.

  In the present embodiment, the controller 20 increases the flow rate of the combustion air to 6.00 mol / min. When supplying combustion air at 6.00 mol / min, the flammable gas concentration is 1.6%, which is lower than the lower limit of the flammable range (1.9%). Does not burn.

  Subsequently, the controller 20 operates the heater 8 again in order to promote desorption of the raw material from the CO reducer 2 (step S224), and heats the CO reducer 2 by heating.

  Next, the controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 with the first temperature (150 ° C. in the present embodiment) (step S225), and the CO reducer. 2 is lower than the first temperature (150 ° C. in the present embodiment), step S225 is performed until the internal temperature of the CO reducer 2 becomes equal to or higher than the first temperature (150 ° C. in the present embodiment). Repeatedly, the heating and heating of the CO reducer 2 by the heater 8 is continued.

  When the internal temperature of the CO reducer 2 becomes higher than the first temperature (150 ° C. in the present embodiment) by the heating operation of the heater 8, the controller 20 stops the operation of the heater 8 (step S226), the process proceeds to step S161.

  Next, an operation when 1.9 minutes have elapsed from the start of the operation of the heater 8 in step S105 will be described.

  First, after stopping the operation of the igniter 6 (step S141), the controller 20 checks whether or not a flame has been detected by the flame detector 7 (step S142). In step S142, when the flame is detected by the flame detector 7, the controller 20 completes the desorption of the raw material from the CO reducer 2, and the desorbed gas is not supplied to the combustor 4. Since the combustion of the gas cannot be continued, the flame detector 7 waits until the flame cannot be detected.

  As shown in FIG. 2, the flow rate of the desorbed gas gradually decreases after reaching the maximum value within a few minutes from the start of the operation of the heater 8, so that the combustion in the combustor 4 stops. And if a flame becomes impossible to detect, it will transfer to step S143. Conversely, in step S142, if the flame detector 7 cannot detect a flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms whether or not the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) from the CO reducer temperature detector 11 (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature 150 ° C., the step S143 is repeated and the CO reducer 2 is heated by the heater 8. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature 150 ° C., the operation of the heater 8 is stopped (step 144), and the process proceeds to step S161.

Next, the operation after step S161 will be described. The controller 20 executes the operations after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reformer 1 can perform a reforming reaction. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed by the combustor 4 when the raw material supplier 3 is operated in the subsequent step S163 falls within the combustible range ( Step S161).

  Next, the igniter 6 is operated (step S162), the raw material supplier 3 is operated (step S163), the raw material is supplied to the combustor 4 via the reformer 1 and the CO reducer 2, and the combustor 4 Burn the raw material. Subsequently, the controller 20 waits until the flame can be detected by the flame detector 7 (step S164). When the flame is detected by the flame detector 7, the operation of the igniter 6 is stopped (step S165), and step S166. Migrate to

  In step S166, the controller 20 confirms whether or not the internal temperature of the reformer 1 acquired from the reformer temperature detector 10 is lower than the third temperature, and the internal temperature of the reformer 1 is the third temperature. When the temperature is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has become equal to or higher than the third temperature. When the reformer temperature detector 10 confirms that the internal temperature of the reformer 1 has become equal to or higher than the third temperature, the process proceeds to the end.

  Here, the third temperature is a temperature higher than a temperature at which the water vapor does not condense in the reformer 1 when the gas flowing through the reformer 1 contains water vapor. In the present embodiment, the third temperature is the third temperature. Was set to 120 ° C.

  With the above operation, the operation of raising the temperature of the hydrogen generator 103 to a temperature at which the reforming reaction can be performed without being affected by the flow rate and composition fluctuation of the gas desorbed from the CO reducer 2 is completed.

  Subsequently, a reforming water supply unit (not shown) is operated to supply reforming water to the reforming unit 1, and generation of a hydrogen-containing gas in the reforming unit 1 is started by a steam reforming reaction, thereby reducing CO. The gas discharged from the vessel 2 is supplied to a hydrogen utilization device (not shown).

  As described above, in the present embodiment, in the hydrogen generator 103 that uses a raw material mainly composed of at least one of propane and butane, the increase rate of the desorbed gas flow rate is slow, and the combustor 4 The ignition time that takes the longest time for the gas concentration to enter the combustible range and ignite is set as the first time (1.9 minutes), and after the ignition operation and the heating operation, from the first time (1.9 minutes) If the flame detector 7 detects a flame before, the operation of the heater 8 is finished and the flow rate of the combustion air is increased until the concentration becomes lower than the lower limit of the combustible range. Since the combustion of the catalyst is stopped, the desorption of the gas from the catalyst is stopped by stopping the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped. Therefore, the deterioration due to the excessive temperature rise of the catalyst can be prevented.

  When ignited before the first time (1.9 minutes), the combustible gas concentration of the mixed gas formed in the combustor 4 by the gas desorbed from the CO reducer 2 is below the lower limit of the combustible range. The flow rate of the combustion air is increased until the concentration reaches the same temperature, and the CO reducer 2 is heated to the first temperature 150 ° C. by the operation of the heater 8, and then passed through the reformer 1 and the CO reducer 2. Since the reformer 1 is heated to the third temperature 120 ° C. by combustion of the raw material supplied to the combustor 4, the reforming is performed without being affected by changes in the composition and flow rate of the desorbed gas from the CO reducer 2. The deterioration of the catalyst of the mass device 1 due to excessive temperature rise can be prevented, and the temperature of the reformer 1 can be raised to a temperature at which reforming reaction can be performed.

  Moreover, since the switch 9 in the hydrogen generator 101 of Embodiment 1 and Embodiment 2 is unnecessary, it is cheap and can improve reliability.

  Further, since the ignition operation is not repeated, it can be started with the minimum number of ignition operations, so that the life of the igniter 6 can be extended.

In this embodiment, the raw materials are butane and propane. However, the raw material is a mixed gas mainly composed of hydrocarbons having 2 to 4 carbon atoms such as ethane, ethylene, propylene, and butene. Also good.

  The hydrogen generator 103 of the present embodiment includes a raw material supplier 3 that supplies a raw material mainly composed of hydrocarbons, a reformer 1 that generates a hydrogen-containing gas from the raw material using a reforming catalyst, and a reformer 1 The carbon monoxide concentration of the hydrogen-containing gas produced in step 1 is reduced by the carbon monoxide reduction catalyst, and the gas discharged from the CO reduction device 2 is burned to reform the reformer 1 and the CO reduction device 2. Of these, at least a combustor 4 for heating the reformer 1, a combustion air supply device 5 for supplying combustion air to the combustor 4, an igniter 6 for performing an ignition operation in the combustor 4, and a flame of the combustor 4 A flame detector 7 that detects the presence or absence of the gas, a heater 8 that heats the CO reducer 2, and a controller 20.

  When the controller 20 activates the hydrogen generator 103, first, in the state where the raw material supplier 3 is stopped and the combustion air supplier 5 is supplying air to the combustor 4, the heater 8, the igniter 6 is ignited, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) after the heating operation of the heater 8 is started. When a flame is detected, the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set to 1.9 minutes), the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane) in the present embodiment after the hydrogen generator 103 stops operation. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

  The raw material of the hydrogen generator 103 of the present embodiment is LP gas containing at least one of propane and butane as a main component, and reaches the combustor 4 from the reformer 1 after the hydrogen generator 103 is stopped. The gas flow path is purged with the raw material (LP gas).

  Then, in the first time (1.9 minutes in the present embodiment), when the desorption gas desorbed from the carbon monoxide reduction catalyst by the heating operation of the heater 8 is propane, the combustion in the combustor 4 is performed. It was time to start.

  Thereby, when butane is contained in addition to propane in the desorption gas desorbed from the carbon monoxide reduction catalyst of the CO reducer 2 by the heating operation of the heater 8, the heating time by the heater 8 is stopped early. Therefore, since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the temperature increase of the carbon monoxide reduction catalyst and the combustion in the combustor 4 is stopped, the reforming catalyst and the carbon monoxide reduction catalyst are stopped. Of these, at least deterioration of the reforming catalyst due to excessive temperature rise can be more reliably prevented.

  Further, in the hydrogen generator 103 of the present embodiment, the flame detector 7 before the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. When the flame is detected, the heating operation of the heater 8 is terminated, and the flow rate of the combustion air supplied from the combustion air supplier 5 to the combustor 4 is decreased until the flame detector 7 no longer detects the flame. To increase.

Thereby, the combustible gas concentration of the mixed gas formed in the combustor 4 becomes lower than the lower limit of the combustible range, and the combustion in the combustor 4 stops, so that the deterioration due to the excessive temperature rise of the catalyst is more reliably performed. Can be prevented.

  The hydrogen generator 103 of the present embodiment also includes a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and the controller 20 starts the heating operation of the heater 8 after the start of the heating operation. The flame detector 7 detects the flame of the combustor 4 after completing the heating operation of the heater 8 because the flame detector 7 detects the flame within 1 hour (1.9 minutes in the present embodiment). In the present embodiment, the internal temperature of the CO reducer 2 is the first temperature (the temperature at which the water vapor contained in the hydrogen-containing gas generated in the reformer 1 is not condensed in the CO reducer 2). When the temperature is lower than 150 ° C., the flow rate of the combustion air supplied from the combustion air supply device 5 to the combustor 4 is set so that the combustible gas concentration of the mixed gas formed in the combustor 4 is out of the combustible range. After the increase, the heating operation of the heater 8 is restarted.

  As a result, the combustible gas concentration of the mixed gas formed in the combustor 4 is lower than the lower limit of the combustible range, so that the gas released out of the system of the hydrogen generator 103 had an ignition source. Even if it does not burn, hydrogen generator 103 with high safety can be constituted.

  The hydrogen generator 103 of the present embodiment also includes a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and the controller 20 starts the heating operation of the heater 8 after the start of the heating operation. If the flame detector 7 does not detect a flame before 1 hour (1.9 minutes in the present embodiment) elapses, the internal temperature of the CO reducer 2 is the first temperature (this embodiment). The heating operation of the heater 8 is continued until the temperature reaches 150 ° C. or higher. When the internal temperature of the CO reducer 2 becomes equal to or higher than the first temperature (150 ° C. in the present embodiment), the heating of the heater 8 is continued. The operation ends.

  Thereby, when the flame detector 7 does not detect the flame before the first time (1.9 minutes in the present embodiment), the heater 8 is continuously operated, so that it is generated by the reformer 1. The water vapor contained in the hydrogen-containing gas can be raised in a short time to a temperature at which the water vapor does not condense in the CO reducer 2.

  In addition, the hydrogen generator 103 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2, and The controller 20 is formed by the combustor 4 when the raw material supplier 3 is operated when the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment). Combustion air is supplied from the combustion air supply device 5 to the combustor 4 and the igniter 6 is ignited so that the combustible gas concentration of the mixed gas falls within the combustible range. Raw material until it exceeds a third temperature (when the gas flowing through the reformer 1 contains water vapor, the temperature is higher than the temperature at which the water vapor does not condense in the reformer 1 and is 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is combusted in the combustor 4 and the temperature inside the hydrogen generator 103 is heated so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). Hydrogen generation to a temperature suitable for generating a hydrogen-containing gas (temperature at which the supply of reforming water to the reformer 1 starts) with only a small amount of desorbed gas desorbed from the carbon reduction catalyst and combustion with the desorbed gas Even when the inside of the apparatus 103 cannot be heated and heated, the inside of the hydrogen generating apparatus 103 can be heated and heated to a temperature suitable for generating the hydrogen-containing gas (a temperature at which the supply of reforming water to the reformer 1 is started).

In the operation method of the hydrogen generator 103 according to the present embodiment, when the hydrogen generator 103 is started, first, the raw material supplier 3 is stopped, and the combustion air supplier 5 supplies air to the combustor 4. In the supplied state, the heating operation of the heater 8 is started and the first step (steps S103 and S104) for causing the igniter 6 to perform the ignition operation, and the heating operation of the heater 8 is started in step S104. If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), the heating operation of the heater 8 is terminated.

  As a result, the increasing rate of the desorbed gas flow rate of the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 by the heating operation of the CO reducer 2 to the combustor 4 is slow, and the gas in the combustor 4 is In the case of a raw material component (propane) having the longest time until the concentration enters the combustible range and ignites, the ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 is the first time (this implementation) (1.9 minutes in this embodiment) is set to 1.9 minutes), the reformer 1 to the combustor 4 with the raw material (LP gas, which is a mixed gas of propane and butane) in the present embodiment after the hydrogen generator 103 stops operation. Even when the gas flow path leading to is purged, if the flame is detected before the first time (1.9 minutes in the present embodiment) from the start of the heating operation, the operation of the heater 8 is terminated. Carbon monoxide reduction catalyst temperature Since the desorption of the gas from the carbon monoxide reduction catalyst is stopped by stopping the increase and the combustion in the combustor 4 is stopped, at least the reforming catalyst or the carbon monoxide reduction catalyst is caused by excessive temperature increase of the reforming catalyst. It becomes possible to prevent deterioration.

  From the above description of the embodiments, many modifications and other embodiments of the present invention will be apparent to persons skilled in the art. Accordingly, the foregoing description should be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the spirit of the invention.

  The hydrogen generator of the present invention can prevent excessive heating of the catalyst due to combustion of the desorbed gas, regardless of the flow rate and composition of the desorbed gas flowing from the catalyst heated at the start and flowing to the combustor. Gas can be used as a heat source at the start of the hydrogen generator, and a hydrogen generator with high energy efficiency and durability can be realized. This is suitable for a household fuel cell system, a portable hydrogen generator, and an in-vehicle hydrogen generator that use a raw material supply infrastructure in which the composition of the raw material to be changed fluctuates.

DESCRIPTION OF SYMBOLS 1 Reformer 2 CO reduction device 3 Raw material supply device 4 Combustion device 5 Combustion air supply device 6 Ignition device 7 Flame detector 8 Heater 9 Switch 10 Reformer temperature detector 11 CO reduction device temperature detector 20 Controller 101 Hydrogen generator 103 Hydrogen generator

Claims (11)

A raw material supplier for supplying a raw material mainly composed of hydrocarbons, a reformer for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and carbon monoxide generated in the reformer A CO reducer that reduces the concentration with a carbon monoxide reducing catalyst; a combustor that burns gas discharged from the CO reducer to heat at least one of the reformer and the CO reducer; A combustion air supplier that supplies combustion air to the combustor, an igniter that performs an ignition operation in the combustor, a flame detector that detects the presence or absence of a flame in the combustor, and the CO reducer A hydrogen generator comprising a heater and a controller,
When the controller starts the hydrogen generator, first, the raw material supply unit is stopped, and the combustion air supply unit supplies air to the combustor. When the flame detector detects a flame before the first time after starting the heating operation and causing the igniter to perform an ignition operation and starting the heating operation of the heater, the heating operation of the heater The hydrogen generator to finish.   The raw material contains at least one of propane and butane as a main component, and the hydrogen generator is purged with the raw material after operation is stopped, and the carbon monoxide is heated by the heating operation of the heater during the first time. 2. The hydrogen generator according to claim 1, wherein when the desorbed gas desorbed from the reduction catalyst is propane, the time until the combustion in the combustor starts.   The hydrogen generation device includes a switch on a generated gas flow path that guides the gas discharged from the CO reducer to the combustor, and when the controller starts the hydrogen generation device, the switch The heating operation of the heater is started in an open state, and when the flame detector detects a flame within the first time after the heating operation of the heater is started, the heating operation of the heater is ended. The hydrogen generator according to claim 1 or 2, wherein the switch is closed.   The hydrogen generation apparatus according to claim 3, wherein the controller opens the switch again when the flame detector stops detecting the flame after the switch is closed.   If the flame detector detects a flame within the first time after starting the heating operation of the heater, the controller determines that the combustible gas concentration of the mixed gas formed in the combustor is combustible. The hydrogen generator according to claim 4, wherein the flow rate of combustion air supplied from the combustion air supply device to the combustor is increased so as to be out of range.   If the flame detector detects a flame before the first time after starting the heating operation of the heater, the controller ends the heating operation of the heater and the flame detector. The hydrogen generating apparatus according to claim 1 or 2, wherein a flow rate of combustion air supplied from the combustion air supply device to the combustor is increased until no flame is detected. A reformer temperature detector for detecting the internal temperature of the reformer, and a CO reducer temperature detector for detecting the internal temperature of the CO reducer,
The controller, after finishing the heating operation of the heater, the internal temperature of the CO reducer is lower than the first temperature, the internal temperature of the reformer is lower than the second temperature, and the predetermined temperature The hydrogen generator according to any one of claims 1 to 6, wherein after the non-burning time has elapsed, the igniter is ignited and the heating operation of the heater is restarted. A CO reducer temperature detector for detecting the internal temperature of the CO reducer;
When the internal temperature of the CO reducer is lower than the first temperature after the flame detector no longer detects the flame, the controller controls the combustible gas concentration of the mixed gas formed in the combustor to be combustible. The heating operation of the heater is restarted after increasing the flow rate of combustion air supplied from the combustion air supply device to the combustor so as to be out of range. The hydrogen generator described in 1. A CO reducer temperature detector for detecting the internal temperature of the CO reducer;
If the flame detector does not detect the flame between the start of the heating operation of the heater and the elapse of the first time, the internal temperature of the CO reducer is set to the first temperature. The heating operation of the heater is continued until the temperature becomes equal to or higher than the temperature, and when the internal temperature of the CO reducer becomes equal to or higher than the first temperature, the heating operation of the heater is terminated. 2. The hydrogen generator according to claim 1. A reformer temperature detector for detecting the internal temperature of the reformer, and a CO reducer temperature detector for detecting the internal temperature of the CO reducer,
When the internal temperature of the CO reducer exceeds the first temperature, the controller controls the combustion air supply from the combustion air supply so that the combustible gas concentration of the mixed gas formed in the combustor falls within a combustible range. 10. The combustion apparatus according to claim 1, wherein combustion air is supplied to the furnace and the igniter is ignited, and the raw material supplier is operated until an internal temperature of the reformer exceeds a third temperature. The hydrogen generator according to item. A raw material supplier for supplying a raw material mainly composed of hydrocarbons, a reformer for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and carbon monoxide generated in the reformer A CO reducer that reduces the concentration with a carbon monoxide reducing catalyst; a combustor that burns gas discharged from the CO reducer to heat at least one of the reformer and the CO reducer; A combustion air supplier that supplies combustion air to the combustor, an igniter that performs an ignition operation in the combustor, a flame detector that detects the presence or absence of a flame in the combustor, and the CO reducer A method of operating a hydrogen generator comprising:
When starting up the hydrogen generator, first, the heating operation of the heater is started in a state where the raw material supplier is in a stopped state and the combustion air supplier is supplying air to the combustor. And a first step for causing the igniter to perform an ignition operation, and when the flame detector detects a flame before the first time after starting the heating operation of the heater in the first step, And a second step of ending the heating operation of the heater.