JP6688955B2 - Hydrogen generator and its operating method - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a hydrogen generator that reforms a raw material containing hydrocarbon as a main component to generate a hydrogen-containing gas and a method of operating the same, and more specifically, burns a raw material discharged from the hydrogen generator at startup. The present invention relates to a hydrogen generator that heats each catalyst of the hydrogen generator and an operating method thereof.

  Since the hydrogen-containing gas used as a fuel at the time of power generation of the fuel cell is not prepared as a general infrastructure gas, the fuel cell system usually includes a hydrogen generator. This hydrogen generator generates a hydrogen-containing gas by subjecting LP gas, city gas, or natural gas, which is a general infrastructure, to a reforming reaction in a reformer.

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

  Further, the combustor heats the reformer in order to bring the reforming catalyst of the reformer to a temperature required for the steam reforming reaction. Further, since carbon monoxide is generated as a side reaction in the reformer, when carbon monoxide poisons the anode catalyst of the fuel cell and lowers the voltage (for example, in the case of the polymer electrolyte fuel cell), A CO reducer is provided downstream of the reformer.

  This CO reducer includes a CO shift catalyst that reacts carbon monoxide with water vapor to reduce the concentration of carbon monoxide, and a selective oxidation catalyst that reacts carbon monoxide with oxygen to oxidize and remove carbon monoxide. In many cases.

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

  Therefore, when shutting down the hydrogen generator, first stop the supply of the raw material and steam, extinguish the flame of the combustor, and lower the temperature of the hydrogen generator to a predetermined temperature. Purge the hydrogen-containing gas remaining in the path. A fuel cell system has been proposed in which, when the pressure in the gas passage of the hydrogen generator falls below a predetermined pressure, the hydrogen generator is replenished with raw materials to maintain the positive pressure in the gas passage of the hydrogen generator. (For example, refer to Patent Document 1).

  By the way, at the time of starting 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 the reformed gas from the raw material.

  In the method of directly supplying the fuel from the fuel source to the combustor at the time of start-up and burning and heating each catalyst of the hydrogen generator by the combustion heat, a route for directly supplying the fuel from the fuel source to the combustor is provided. Since the cost of installation is high, the raw material is supplied to the hydrogen generator at startup, and the raw material that comes out without being reformed from the hydrogen generator is burned in the combustor, and the combustion heat is used to generate the hydrogen generator. A method of heating each of the catalysts has been proposed (for example, see Patent Document 2).

Japanese Patent No. 4130603 JP, 2008-218355, A

  However, in the conventional hydrogen generator, when the hydrogen-containing gas remaining in the gas passage is purged and the pressure of the gas passage is kept at a predetermined level after the temperature of the stopped hydrogen generator is lowered to a predetermined temperature. When the pressure drops below the pressure of 1, the raw material is supplied to the hydrogen generator, and the raw material is supplied to the reformer and the CO reducer in order to raise the temperature of each catalyst to a temperature suitable for the production of hydrogen during the start-up operation. Since it is supplied to the combustor through the above and burned, there are the following problems.

  That is, as the temperature of each catalyst was lowered while the hydrogen generator was stopped, at least some components of the raw materials were adsorbed on each catalyst, and during startup operation, the components were adsorbed on each catalyst as the temperature of each catalyst increased. Since the components of the raw material are desorbed and burned in the combustor together with the raw material supplied to the hydrogen generator, there is a problem that if the combustion in the combustor becomes excessive, the temperature of the catalyst rises and the catalyst deteriorates.

  In particular, when LP gas containing propane or butane as a main component is used as the raw material for the hydrogen generator, the above-mentioned adsorption and desorption phenomena are more remarkable than when city gas containing methane as the main component is used. Therefore, in the case of LP gas, the phenomenon of adsorption and desorption described above was observed when butane (normal butane, 10 ° C. at 0.05 MPa) was used, as compared with the case where propane (10 ° C. at 0.53 MPa) was used. It is remarkable.

  Therefore, particularly when the butane concentration of the raw material is high, there is a problem that the combustion in the combustor becomes excessive, and the temperature of the catalyst excessively rises and deteriorates.

  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 is desorbed from the catalyst heated at startup and flows to the combustor. An object of the present invention is to provide a hydrogen generator which can be used as a heat source when starting the hydrogen generator and has high energy efficiency and durability.

  In order to solve the above-mentioned conventional problems, the hydrogen generator of the present invention comprises a raw material supplier for supplying a raw material containing hydrocarbon as a main component, and a reformer for producing a hydrogen-containing gas from the raw material with a reforming catalyst. A CO reducer for reducing the carbon monoxide concentration of the hydrogen-containing gas produced by the reformer with a carbon monoxide reducing catalyst; and a gas discharged from the CO reducer for burning the reformer and the CO reducer. Of these, a combustor that heats at least the reformer, a combustion air supply device 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.

  When the hydrogen generator is started, the controller first starts the heating operation of the heater with the raw material supply device stopped and the combustion air supply device supplying air to the combustor. When the flame detector detects a flame before the first time from the start of the heating operation of the heater, the control is such that the heating operation of the heater is terminated. Is.

As a result, the desorbed gas desorbed from the carbon monoxide reduction catalyst due to the heating operation of the heater when the hydrogen generator is activated slows down the rate of increase in the desorbed gas flow rate flowing to the combustor, and the gas concentration in the combustor increases. If the ignition time from the start of the heating operation of the heater to the flame detection is set to the first time in the case of the raw material component that takes the longest time to enter the flammable range and ignite, the hydrogen generator will not operate after the operation is stopped. Even if the raw material is purged, if the flame is detected before the first hour from the start of the heating operation, the operation of the heater is terminated, so the desorption of gas from the catalyst is stopped by stopping the temperature rise of the catalyst. However, since the 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, it is possible to 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 is desorbed from the catalyst heated at startup and flows to the combustor. It can be used as a heat source at the time of starting the hydrogen generator, and a hydrogen generator with high energy efficiency and durability can be realized.

Block diagram showing the configuration of the hydrogen generator in Embodiments 1 and 2 of the present invention The characteristic view which shows the flow rate of the gas desorbed from the CO reducer of the hydrogen generator in Embodiments 1 and 2 of this invention, and the time change of the combustible gas concentration of the mixed gas formed in a combustor. The flowchart which shows the starting method of the hydrogen generator in Embodiment 1 of this invention. Flowchart showing a method for starting a hydrogen generator according to Embodiment 2 of the present invention Block diagram showing the configuration of the hydrogen generator in Embodiments 3 and 4 of the present invention Flowchart showing a method for starting a hydrogen generator according to Embodiment 3 of the present invention The flowchart which shows the starting method of the hydrogen generator in Embodiment 4 of this invention.

  A first aspect of the invention is a raw material supply device for supplying a raw material containing hydrocarbon as a main component, a reformer for producing a hydrogen-containing gas from the raw material by a reforming catalyst, and a hydrogen-containing gas produced 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 to heat at least the reformer of the reformer and the CO reducer; A combustion air supply device 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 a heater that heats the CO reducer. , A controller, and when the controller starts the hydrogen generator, first, the raw material supply device is stopped and the combustion air supply device supplies air to the combustor. The heating operation of the heater is started and the igniter is ignited to heat 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 desorbed gas desorbed from the carbon monoxide reduction catalyst due to the heating operation of the heater when the hydrogen generator is activated slows down the rate of increase in the desorbed gas flow rate flowing to the combustor, and the gas concentration in the combustor increases. If the ignition time from the start of the heating operation of the heater to the flame detection is set to the 1st time in the case of the raw material component that takes the longest time to enter the flammable range and ignite, the hydrogen generator will not operate after the operation is stopped. Even if the raw material is purged, if the flame is detected before the first hour from the start of the heating operation, the operation of the heater is terminated, so the desorption of gas from the catalyst is stopped by stopping the temperature rise of the catalyst. However, since the 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 present invention, in particular, in the first aspect, the raw material contains at least one of propane and butane as a main component, the hydrogen generator is purged with the raw material after the operation is stopped, and the first time is a heater. When the desorbed gas desorbed from the carbon monoxide reduction catalyst by the heating operation of 1 is propane, it 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 the desorption of gas from the catalyst is stopped by stopping the temperature rise of the catalyst, and Since the combustion of the catalyst is stopped, it is possible to more reliably prevent the deterioration of the catalyst due to excessive temperature rise.

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

  As a result, the inflow of the desorbed gas into the combustor is blocked by the switch, so that the combustion in the combustor is stopped, so that it is possible to configure a hydrogen generation device that can more reliably prevent deterioration due to excessive temperature rise of the catalyst.

  In a fourth aspect of the present invention, in particular, in the third aspect, the controller reopens the switch when the flame detector no longer detects a flame after the switch has been closed.

  As a result, after the combustion in the combustor is stopped, by opening the switch, even if the temperature of the hydrogen generator changes, the pressure inside the hydrogen generator becomes approximately the same as the atmospheric pressure. The structure of the hydrogen generator does not need to have a structure that can withstand excessive pressure, and the hydrogen generator can be constructed at low cost.

  In a fifth aspect of the present invention, in particular, in the fourth aspect, the controller forms a mixture formed in the combustor when the flame detector detects a flame within a first time after starting the heating operation of the heater. The flow rate of the combustion air supplied from the combustion air supplier to the combustor is increased so that the combustible gas concentration of the gas is out of 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 to the outside of the hydrogen generator system, even if there is an ignition source. A highly safe hydrogen generator that does not burn can be configured.

  In a sixth aspect of the invention, particularly in the first or second aspect of the invention, when the controller detects the flame before the first time period after the heating operation of the heater is started, When the heating operation is terminated, 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 is stopped, so that deterioration due to excessive temperature rise of the catalyst can be more reliably prevented. .

  A seventh invention is, 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. A detector, and the controller has an internal temperature of the CO reducer lower than a first temperature and an internal temperature of the reformer lower than a second temperature after terminating the heating operation of the heater, and After the elapse of a predetermined non-combustion time, the igniter is caused to perform an ignition operation and the heating operation of the heater is restarted.

  As a result, the step of burning the desorbed gas in the combustor and the step of supplying the air to cool the combustor without burning the desorbed gas in the combustor after stopping the combustion are repeated. A hydrogen generator capable of increasing the temperature to a temperature suitable for generating a hydrogen-containing gas while preventing deterioration due to excessive temperature rise can be configured.

  An eighth invention is, in any one of the first to sixth inventions, provided with a CO reducer temperature detector that detects an internal temperature of the CO reducer, and the controller detects that the flame detector detects a flame. When the internal temperature of the CO reducer is lower than the first temperature after disappearing, the combustible gas concentration of the mixed gas formed in the combustor is supplied from the combustion air supplier to the combustor so as to be outside the combustible range. The heating operation of the heater is restarted after the flow rate of the combustion air is increased.

  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 to the outside of the hydrogen generator system, even if there is an ignition source. A highly safe hydrogen generator that does not burn can be configured.

  A ninth invention is, in any one of the first to eighth inventions, provided with a CO reducer temperature detector for detecting the internal temperature of the CO reducer, and the controller starts the heating operation of the heater. If the flame detector does not detect the flame during the first time from the start, the heating operation of the heater is continued until the internal temperature of the CO reducer becomes the first temperature or higher, When the internal temperature of the CO reducer becomes equal to or higher than the first temperature, the heating operation of the heater is finished.

  As a result, when the flame detector does not detect a flame before the first time, the heater is continuously operated, so that the temperature is short enough to prevent the water vapor contained in the hydrogen-containing gas generated in the reformer from condensing. A hydrogen generator that can raise the temperature with time can be configured.

  A tenth invention is, in any one of the first to ninth 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. A detector, and the controller controls the combustion air supply unit 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. To supply combustion air to the combustor and to ignite the igniter, and operate the raw material supply device 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 inside of the hydrogen generator is heated and heated so that the internal temperature of the reformer exceeds the third temperature. Even if the inside of the hydrogen generator cannot be heated and raised to a temperature suitable for generation of the contained gas, the hydrogen generator can be configured to heat and raise the inside of the hydrogen generator to a temperature suitable for generation of the hydrogen-containing gas.

  An eleventh aspect of the invention is to provide a raw material supply device for supplying a raw material containing hydrocarbon as a main component, a reformer for producing a hydrogen-containing gas from the raw material with a reforming catalyst, and a hydrogen-containing gas produced 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 to heat at least the reformer of the reformer and the CO reducer; A combustion air supply device 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 a heater that heats the CO reducer. In the method of operating the hydrogen generator, the raw material supplier is first stopped and the combustion air supplier is supplying air to the combustor. , Start the heating operation of the heater and ignite the igniter. A first step of starting the heating operation of the heater in the first step, and a second step of terminating the heating operation of the heater when the flame detector detects a flame before the first time period after starting the heating operation of the heater, Is to have.

  As a result, when the desorption gas flow rate increases slowly and the gas concentration in the combustor enters the combustible range and the raw material component takes the longest time to ignite, 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 stopped. Since the process ends, the desorption of 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 deterioration of the catalyst due to excessive temperature rise.

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

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

  As shown in FIG. 1, a hydrogen generator 101 according to 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.

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

  The CO reducer 2 is provided to remove carbon monoxide generated as a side reaction in the reformer 1, and reduces CO by reacting carbon monoxide and steam in a container having a volume of 2 L. 1.8 L of a shift catalyst (not shown) is filled.

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

  The combustor 4 heats the reformer 1. As the fuel of the combustor 4, at least one of the raw material discharged from the CO reducer 2, the desorbed gas, and the hydrogen-containing gas is used. In addition, when the combustion operation of the CO reducer 2 is started, when the flow rate of desorbed propane is maximum, the combustor 4 is provided with the reformer 1 so that the excessive temperature rise of the reformer 1 does not occur. Thermally coupled

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

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

  The flame detector 7 is a frame rod. The frame rod is to insert a metal rod electrically connected to a flame current detection circuit composed of a power source and a current sensor into the flame and judge the state of the flame based on the magnitude of the current.

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

  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 period 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 a change over time in the flow rate of 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 obtained experimentally 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, the combustion air was supplied from the combustion air supplier 5 to the combustor 4 at 1.6 mol / min.

  As shown in FIG. 2, when the heating temperature of the CO reducer 2 is started 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. And then gradually decrease.

  In the hydrogen generator 101 according to 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 operation of the heater 8 is started, and the lower limit of the combustible range of butane is reached. It became possible to ignite above 1.9%.

  Further, 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 the ignition exceeds the lower limit of 2.1% of the combustible range of propane. Ready to go.

  Therefore, in the present embodiment using the LP gas that 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.

  If the operation of stopping the combustion is performed when the combustion is started before 1.9 minutes, the amount of the desorbed gas burned in the combustor 4 will be the same when the internal temperature of the CO reducer 2 is 10 ° C. Since it does not become larger than when desorbing propane, it means that deterioration due to excessive temperature rise of the reforming catalyst of the reformer 1 due to excessive heat given to the reformer 1 from the combustor 4 can be prevented. ing. Therefore, in the present embodiment, the first time is set to 1.9 minutes.

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

  FIG. 3 is a flowchart showing a method for starting hydrogen generator 101 according to Embodiment 1 of the present invention. The gas flow path from the reformer 1 to the combustor 4 is purged with the raw material before the hydrogen generator 101 is started (when the operation of the hydrogen generator 101 was stopped last time).

When the activation of the hydrogen generator 101 is executed, the controller 20 operates the combustion air supplier 5 and supplies combustion air to the combustor 4 at 1.6 mol / min (step S101). Subsequently, the controller 20 opens the switch 9 (step S102) to desorb the gas from the CO reducer 2 and introduces the gas into the combustor 4 for combustion, and then the igniter 6 (step S103). ) And the heater 8 (step S104) are sequentially operated.

  Next, the controller 20 confirms whether or not 1.9 minutes (first time) has elapsed from the start of operation of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) has elapsed from the start of operation of the heater 8, the process proceeds to step S141. On the contrary, in step S105, if 1.9 minutes (first time) has not yet passed 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 detector 7 can detect the flame. When the flame detector 7 can detect the flame, the process proceeds to step S107, and conversely, the flame detector 7 detects the flame. If not, the process returns to step S105.

  Hereinafter, the operation when the flame detector 7 detects a flame in step S106 will be described.

  First, since the controller 20 detects the flame with the flame detector 7, the controller 20 stops the igniter 6 (step S107), and then stops the desorption of the gas from the CO reducer 2 and In order to stop the combustion, the heater 8 is stopped (step S108), and subsequently, the supply of gas from the CO reducer 2 to the combustor 4 is cut off to surely stop the combustion in the combustor 4. The switch 9 is closed (step S109).

  Further, in the subsequent step S121, when the switch 9 is opened, the combustor gas concentration in the combustor 4 is changed from the combustion air supplier 5 to the combustor 4 in advance so that the combustible gas concentration does not exceed the lower limit of the combustible range. The combustion air flow rate 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 waits until the flame detector 7 cannot detect the flame (step S111), and when 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, the switch 9 is opened again to make the internal pressure of the hydrogen generator 101 substantially equal to the atmospheric pressure (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). On the contrary, 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 the steam contained in the hydrogen-containing gas generated in the reformer 1 does not condense in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature decrease after the operation of the heater 8 is stopped (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. In that case, the process proceeds to step S124. On the contrary, if the internal temperature of the reformer 1 is not lower than the second temperature, it waits until it becomes lower than the second temperature.

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

  Next, in step S124, the controller 20 performs an operation of waiting for a predetermined non-combustion time. The predetermined non-combustion time is the total time after the process proceeds to step S121. Even after the operation of stopping the desorption from the CO reducer 2 is performed in step S108, the unburned gas remains inside the combustor 4. Therefore, if the ignition operation is started without scavenging the unburned gas, the unburned gas is ignited, and the combustor 4 may be damaged due to the 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, it was decided to supply ten times as much 72 L of air. Since the flow rate of the combustion air supplied from the combustion air supplier 5 to the combustor 4 was 3.2 mol / min (= 72 L / min), the non-combustion time was 1 minute.

  In step S124, if the time from the time of shifting to step S121 to step S124 exceeds 1 minute, the flow shifts to step S125. On the contrary, if the time from the time of shifting to step S121 to step S124 does not exceed 1 minute, it waits until 1 minute elapses.

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

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

  First, the controller 20 stops the operation of the igniter 6 (step S141), and then confirms whether or not the flame detector 7 can detect a flame (step S142). In step S142, when the flame detector 7 detects the flame, 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, so that the combustor 4 operates. Since the combustion 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 reaches a maximum value within a few minutes from the start of operation of the heater 8, and then gradually decreases, so that the combustion in the combustor 4 is stopped. When the flame cannot be detected, the process proceeds to step S143. On the contrary, in step S142, when the flame detector 7 cannot detect the flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms from the CO reducer temperature detector 11 whether the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature of 150 ° C., step S143 is repeated and the heater 8 heats the CO reducer 2. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature of 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 in and after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reforming reaction is possible in the reformer 1. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed in the combustor 4 when the raw material supply device 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 supply device 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 is used. Burn raw materials. 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. Move to.

  In step S166, the controller 20 confirms whether 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. If it is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has reached the third temperature or higher. When it is confirmed by the reformer temperature detector 10 that the internal temperature of the reformer 1 has reached the third temperature or higher, the process proceeds to the end.

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

  By the above operation, the operation of raising the temperature of the hydrogen generator 101 to a temperature at which the reforming reaction is possible is completed without being affected by the change in the flow rate and composition of the gas desorbed from the CO reducer 2.

  Then, a reforming water supply device (not shown) is operated to supply the reforming water to the reformer 1, and the steam-reforming reaction starts the generation of the hydrogen-containing gas in the reformer 1 to reduce the CO. The gas discharged from the container 2 is supplied to a hydrogen utilizing device (not shown).

  As described above, in the present embodiment, in the hydrogen generator 101 that uses a raw material containing at least one of propane and butane as a main component, the desorption gas flow rate increases slowly and The ignition time, which takes the longest time for the gas concentration to enter the combustible range and to be ignited, is set as the first time (1.9 minutes), and after the ignition operation and the heating operation, the first time (1.9 minutes) When the flame detector 7 detects the flame before, the operation of the heater 8 is terminated, the supply of the desorbed gas to the combustor 4 due to the operation of the switch 9 is cut off, and the combustion in the combustor 4 is performed. Is stopped, the desorption of gas from the catalyst is stopped due to the stop of the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped. Therefore, deterioration due to excessive temperature rise of the catalyst can be prevented.

  Also, 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. However, since the reformer 1 is 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. It is possible to prevent deterioration of the reforming catalyst due to excessive temperature rise, and it is possible to raise the temperature of the reformer 1 to a temperature at which the reforming reaction is possible.

  In this embodiment, LP gas is used as the raw material of the hydrogen generator 101, but not limited to LP gas, hydrocarbons having 2 to 4 carbon atoms such as ethane, ethylene, propylene and butene can be used. The mixed gas containing the main component may be used as the raw material of the hydrogen generator 101.

  A hydrogen generator 101 according to the present embodiment includes a raw material supply device 3 for supplying a raw material containing hydrocarbon as a main component, a reformer 1 for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and a reformer 1. The CO reducer 2 for reducing the carbon monoxide concentration of the hydrogen-containing gas produced in 1) by the carbon monoxide reducing catalyst, and the gas discharged from the CO reducer 2 are burned to reform the reformer 1 and the CO reducer 2. Among them, a combustor 4 that heats at least the reformer 1, a combustion air supplier 5 that supplies combustion air to the combustor 4, an igniter 6 that performs an ignition operation in the combustor 4, and a flame of the combustor 4 The flame detector 7 for detecting the presence or absence of the above, the heater 8 for heating the CO reducer 2, and the controller 20 are provided.

  Then, when the controller 20 activates the hydrogen generator 101, first, the raw material supply device 3 is in a stopped state, and the combustion air supply device 5 is supplying air to the combustor 4 in the heating device. 8 starts the heating operation of the heater 8 and causes the igniter 6 to perform the ignition operation, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) from the start of the heating operation of the heater 8. When the flame is detected, the heating operation of the heater 8 is completed.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the first embodiment), the hydrogen generator 101 is stopped from the reformer 1 to the combustor 4 using the raw material (LP gas which is a mixed gas of propane and butane in the present embodiment) after the operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is 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 operation of the hydrogen generator 101 is stopped. The gas flow path is purged with the raw material (LP gas).

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

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

  Further, the hydrogen generator 101 of the present embodiment is provided with the 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 starts the hydrogen generator 101. When the switch 9 is opened, the heating operation of the heater 8 is started with the switch 9 open, 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 container 7 detects a flame, the heating operation of the heater 8 is completed and the switch 9 is closed.

  As a result, the inflow of desorbed gas desorbed from the carbon monoxide reduction catalyst into the combustor 4 by the heating operation of the heater 8 is blocked by the switch 9, so that the combustion in the combustor 4 is stopped. At least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst can be more reliably prevented from deterioration due to excessive temperature rise.

  In addition, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is turned on within 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 detector 7 stops detecting the flame of the combustor 4 after the heating operation of the heater 8 is ended by detecting the flame and the switch 9 is closed, the switch 9 is opened again. To do.

  As a result, even if the temperature of the hydrogen generator 101 changes, the internal pressure of the hydrogen generator 101 becomes substantially the same as the atmospheric pressure. Therefore, the structure of the hydrogen generator 101 needs to have a structure that can withstand an excessive pressure. Is eliminated, and the hydrogen generator 101 can be constructed at low cost.

  In addition, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is turned on 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 the combustion air supplied from the combustion air supplier 5 to the combustor 4 is increased so that the combustible gas concentration of the mixed gas formed in the combustor 4 is out of the combustible range. To do.

  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 to the outside of the hydrogen generator 101 temporarily 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, and a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2. , 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 of 1 is finished, the flame detector 7 stops detecting the flame of the combustor 4, and then the internal temperature of the CO reducer 2 becomes the first temperature (the hydrogen-containing gas generated in the reformer 1 becomes The steam contained therein is at a temperature at which it does not condense in the CO reducer 2 and 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 precipitation of carbon generated by the thermal decomposition of the raw material, cannot be ignored. The temperature is sufficiently lower than the temperature of 200 ° C. in the present embodiment, and the igniter 6 is caused to perform an ignition operation after a predetermined non-combustion time (1 minute in the present embodiment) has elapsed. The heating operation of the heater 8 is restarted.

  As a result, the process of burning the desorbed gas desorbed from the carbon monoxide reduction catalyst in the combustor 4 and the step of burning the desorbed gas in the combustor 4 after the combustion of the combustor 4 is stopped Since the step of supplying air from the supply device 5 and cooling the combustor 4 is repeated, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is prevented from being deteriorated due to excessive temperature rise, and the hydrogen-containing gas is The temperature of the reforming catalyst and the carbon monoxide reduction catalyst of the hydrogen generator 101 can be raised to a temperature suitable for the production of hydrogen.

  Further, the hydrogen generator 101 of the present embodiment is provided with the 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 before starting the operation. If the flame detector 7 does not detect a flame before 1 hour (in this embodiment, 1.9 minutes) elapses, the internal temperature of the CO reducer 2 becomes the first temperature (in this embodiment). The heating operation of the heater 8 is continued until the internal temperature of the CO reducer 2 reaches the first temperature (150 ° C. in the present embodiment) or more. The operation ends.

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

Further, the hydrogen generator 101 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, and a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2. When the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment), the controller 20 is formed in the combustor 4 when the raw material supply device 3 is operated. The air for combustion is supplied from the combustion air supplier 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 the temperature exceeds a third temperature (a temperature higher than the temperature at which the steam does not condense in the reformer 1 when the gas flowing through the reformer 1 contains the steam, 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is burned in the combustor 4 to heat the inside of the hydrogen generator 101 so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). The flow rate of the desorbed gas desorbed from the carbon reduction catalyst is small, and the combustion of the desorbed gas alone produces hydrogen up to a temperature suitable for producing the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started). Even when the inside of the apparatus 101 cannot be heated and heated, the inside of the hydrogen generator 101 can be heated and raised to a temperature suitable for generating the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started).

  Further, in the operating method of the hydrogen generator 101 of the present embodiment, when starting the hydrogen generator 101, first, the raw material supplier 3 is in a stopped state, and the combustion air supplier 5 supplies air to the combustor 4. In the state of supplying, the first step (steps S103, S104) of starting the heating operation of the heater 8 and igniting the igniter 6 and starting the heating operation of the heater 8 in step S104 If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), step S108 of ending the heating operation of the heater 8 is included.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the first embodiment), the hydrogen generator 101 is stopped from the reformer 1 to the combustor 4 using the raw material (LP gas which is a mixed gas of propane and butane in the present embodiment) after the operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is possible to prevent deterioration.

(Embodiment 2)
The block diagram of the hydrogen generator 101 of Embodiment 2 of the present invention is the same as the hydrogen generator 101 of Embodiment 1 shown in FIG. 1, and the same components as those of Embodiment 1 are designated by the same reference numerals. It is given and its detailed description is omitted. The operation of the hydrogen generator 101 according to the second embodiment is partially different from that of the hydrogen generator 101 according to 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 method of starting the hydrogen generator 101 according to Embodiment 2 of the present invention. In FIG. 4, the same operation (step) as that in the flowchart showing the method of starting the hydrogen generator 101 according to the first embodiment shown in FIG. Detailed description thereof will be omitted.

  In the flowchart showing the starting method of the hydrogen generator 101 in the second embodiment shown in FIG. 4, steps S123 to S125 and step S223 in the flowchart showing the starting method of the hydrogen generator 101 in the first embodiment shown in FIG. 3 are performed. To step S226.

Similar to the hydrogen generator 101 of the first embodiment, before starting the hydrogen generator 101 of the second embodiment (when the hydrogen generator 101 was stopped last time), the reformer 1 to the combustor Four
The gas flow path leading to is purged with the raw material.

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

  Next, the controller 20 confirms whether or not 1.9 minutes (first time) has elapsed from the start of operation of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) has elapsed from the start of operation of the heater 8, the process proceeds to step S141. On the contrary, in step S105, if 1.9 minutes (first time) has not yet passed 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 detector 7 can detect the flame. When the flame detector 7 can detect the flame, the process proceeds to step S107, and conversely, the flame detector 7 detects the flame. If not, the process returns to step S105.

  Hereinafter, the operation when the flame detector 7 detects a flame in step S106 will be described.

  First, since the controller 20 detects the flame with the flame detector 7, the controller 20 stops the igniter 6 (step S107), and then stops the desorption of the gas from the CO reducer 2 and In order to stop the combustion, the heater 8 is stopped (step S108), and subsequently, the supply of gas from the CO reducer 2 to the combustor 4 is cut off to surely stop the combustion in the combustor 4. The switch 9 is closed (step S109).

  Further, in the subsequent step S121, when the switch 9 is opened, the combustor gas concentration in the combustor 4 is changed from the combustion air supplier 5 to the combustor 4 in advance so that the combustible gas concentration does not exceed the lower limit of the combustible range. The combustion air flow rate 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 waits until the flame detector 7 cannot detect the flame (step S111), and when the flame detector 7 cannot detect the flame in step S111, the controller 20 proceeds to step S121.

  Next, the operations of step S121, step S122, and steps S223 to S226 will be described.

  First, the switch 9 is opened again to make the internal pressure of the hydrogen generator 101 substantially equal to the atmospheric pressure (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). On the contrary, 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 the steam contained in the hydrogen-containing gas generated in the reformer 1 does not condense in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature decrease after the operation of the heater 8 is stopped (step S108).

Next, the 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 supplier 5 to the combustor 4 (step S223). Here, the concentration of the raw material flowing from the CO reducer 2 into the combustor 4 is reduced 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 that is desorbed from the carbon monoxide reducing catalyst and flows into the combustor 4 by heating the CO reducer 2 at the time of starting the hydrogen generator 101 is indicated by the black circle in FIG. And 0.10 mol / min as shown by the solid line, and the lower limit of the flammable range of butane gas is 1.9%, so the flow rate of combustion air supplied to reduce the concentration below 1.9% is X. Then, the flow rate is calculated by (Equation 1).

The combustion air flow rate X obtained by modifying (Equation 1) was 5.16 mol / min. Therefore, in the present embodiment, controller 20 increases the flow rate of combustion air to 6.00 mol / min. When the combustion air is supplied 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%). Even if there is an ignition source, it will not burn.

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

  Next, the controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 and the first temperature (150 ° C. in the present embodiment) (step S225), and the CO reducer. When the internal temperature of 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 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), and proceeds to step S161.

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

First, the controller 20 stops the operation of the igniter 6 (step S141), and then confirms whether or not the flame detector 7 can detect a flame (step S142). In step S142, when the flame detector 7 detects the flame, 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, so that the combustor 4 operates. Since the combustion 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 reaches a maximum value within a few minutes from the start of operation of the heater 8, and then gradually decreases, so that the combustion in the combustor 4 is stopped. When the flame cannot be detected, the process proceeds to step S143. On the contrary, in step S142, when the flame detector 7 cannot detect the flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms from the CO reducer temperature detector 11 whether the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature of 150 ° C., step S143 is repeated and the heater 8 heats the CO reducer 2. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature of 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 in and after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reforming reaction is possible in the reformer 1. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed in the combustor 4 when the raw material supply device 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 supply device 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 is used. Burn raw materials. 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. Move to.

  In step S166, the controller 20 confirms whether 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. If it is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has reached the third temperature or higher. When it is confirmed by the reformer temperature detector 10 that the internal temperature of the reformer 1 has reached the third temperature or higher, the process proceeds to the end.

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

  By the above operation, the operation of raising the temperature of the hydrogen generator 101 to a temperature at which the reforming reaction is possible is completed without being affected by the change in the flow rate and composition of the gas desorbed from the CO reducer 2.

  Then, a reforming water supply device (not shown) is operated to supply the reforming water to the reformer 1, and the steam-reforming reaction starts the generation of the hydrogen-containing gas in the reformer 1 to reduce the CO. The gas discharged from the container 2 is supplied to a hydrogen utilizing device (not shown).

As described above, in the present embodiment, in the hydrogen generator 101 that uses a raw material containing at least one of propane and butane as a main component, the desorption gas flow rate increases slowly and The ignition time, which takes the longest time for the gas concentration to enter the combustible range and to be ignited, is set as the first time (1.9 minutes), and after the ignition operation and the heating operation, the first time (1.9 minutes) When the flame detector 7 detects the flame before, the operation of the heater 8 is terminated, the supply of the desorbed gas to the combustor 4 due to the operation of the switch 9 is cut off, and the combustion in the combustor 4 is performed. Is stopped, the desorption of gas from the catalyst is stopped due to the stop of the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped. Therefore, deterioration due to excessive temperature rise of the catalyst can be prevented.

  Further, when ignition occurs 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 equal to or lower than the lower limit of the combustible range. The flow rate of the combustion air is increased to reach the concentration of 1.0 and the temperature of the CO reducer 2 is raised to the first temperature (150 ° C.) by the operation of the heater 8, and then the reformer 1 and the CO reducer 2 are used. Since the reformer 1 is heated to the third temperature (120 ° C.) by the combustion of the raw material supplied to the combustor 4 via the CO, it is affected by changes in the composition and flow rate of the desorbed gas from the CO reducer 2. Without this, deterioration of the catalyst of the reformer 1 due to excessive temperature rise can be prevented, and the reformer 1 can be heated to a temperature at which the reforming reaction is possible.

  Further, since the ignition operation is not repeated, the ignition 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 the raw material of the hydrogen generator 101, but not limited to LP gas, hydrocarbons having 2 to 4 carbon atoms such as ethane, ethylene, propylene and butene can be used. The mixed gas containing the main component may be used as the raw material of the hydrogen generator 101.

  A hydrogen generator 101 according to the present embodiment includes a raw material supply device 3 for supplying a raw material containing hydrocarbon as a main component, a reformer 1 for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and a reformer 1. The CO reducer 2 for reducing the carbon monoxide concentration of the hydrogen-containing gas produced in 1) by the carbon monoxide reducing catalyst, and the gas discharged from the CO reducer 2 are burned to reform the reformer 1 and the CO reducer 2. Among them, a combustor 4 that heats at least the reformer 1, a combustion air supplier 5 that supplies combustion air to the combustor 4, an igniter 6 that performs an ignition operation in the combustor 4, and a flame of the combustor 4 The flame detector 7 for detecting the presence or absence of the above, the heater 8 for heating the CO reducer 2, and the controller 20 are provided.

  Then, when the controller 20 activates the hydrogen generator 101, first, the raw material supply device 3 is in a stopped state, and the combustion air supply device 5 is supplying air to the combustor 4 in the heating device. 8 starts the heating operation of the heater 8 and causes the igniter 6 to perform the ignition operation, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) from the start of the heating operation of the heater 8. When the flame is detected, the heating operation of the heater 8 is completed.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the first embodiment), the hydrogen generator 101 is stopped from the reformer 1 to the combustor 4 using the raw material (LP gas which is a mixed gas of propane and butane in the present embodiment) after the operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is 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 operation of the hydrogen generator 101 is stopped. The gas flow path is purged with the raw material (LP gas).

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

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

  Further, the hydrogen generator 101 of the present embodiment is provided with the 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 starts the hydrogen generator 101. When the switch 9 is opened, the heating operation of the heater 8 is started with the switch 9 open, 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 container 7 detects a flame, the heating operation of the heater 8 is completed and the switch 9 is closed.

  As a result, the inflow of desorbed gas desorbed from the carbon monoxide reduction catalyst into the combustor 4 by the heating operation of the heater 8 is blocked by the switch 9, so that the combustion in the combustor 4 is stopped. At least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst can be more reliably prevented from deterioration due to excessive temperature rise.

  In addition, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is turned on within 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 detector 7 stops detecting the flame of the combustor 4 after the heating operation of the heater 8 is ended by detecting the flame and the switch 9 is closed, the switch 9 is opened again. To do.

  As a result, even if the temperature of the hydrogen generator 101 changes, the internal pressure of the hydrogen generator 101 becomes substantially the same as the atmospheric pressure. Therefore, the structure of the hydrogen generator 101 needs to have a structure that can withstand an excessive pressure. Is eliminated, and the hydrogen generator 101 can be constructed at low cost.

  In addition, in the hydrogen generator 101 of the present embodiment, the flame detector 7 is turned on 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 the combustion air supplied from the combustion air supplier 5 to the combustor 4 is increased so that the combustible gas concentration of the mixed gas formed in the combustor 4 is out of the combustible range. To do.

  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 to the outside of the hydrogen generator 101 temporarily 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 is provided with the 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 before starting the operation. The flame detector 7 detects the flame and the flame detector 7 detects the flame of the combustor 4 after the heating operation of the heater 8 is completed within 1 hour (1.9 minutes in the present embodiment). After that, the internal temperature of the CO reducer 2 is the first temperature (a temperature at which the water vapor contained in the hydrogen-containing gas generated in the reformer 1 does not condense in the CO reducer 2, and in the present embodiment, 150 ° C.), the flow rate of the combustion air supplied from the combustion air supplier 5 to the combustor 4 is set so that the combustible gas concentration of the mixed gas formed in the combustor 4 falls outside 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 the gas released to the outside of the hydrogen generator 101 temporarily had an ignition source. As a result, the hydrogen generator 101 with high safety can be configured without burning.

  Further, the hydrogen generator 101 of the present embodiment is provided with the 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 before starting the operation. If the flame detector 7 does not detect a flame before 1 hour (in this embodiment, 1.9 minutes) elapses, the internal temperature of the CO reducer 2 becomes the first temperature (in this embodiment). The heating operation of the heater 8 is continued until the internal temperature of the CO reducer 2 reaches the first temperature (150 ° C. in the present embodiment) or more. The operation ends.

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

  Further, the hydrogen generator 101 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, and a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2. When the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment), the controller 20 is formed by the combustor 4 when the raw material supply device 3 is operated. The air for combustion 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 the temperature exceeds a third temperature (a temperature higher than a temperature at which the steam does not condense in the reformer 1 when the gas flowing through the reformer 1 contains the steam, 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is burned in the combustor 4 to heat the inside of the hydrogen generator 101 so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). The flow rate of the desorbed gas desorbed from the carbon reduction catalyst is small, and the combustion of the desorbed gas alone produces hydrogen up to a temperature suitable for producing the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started). Even when the inside of the apparatus 101 cannot be heated and heated, the inside of the hydrogen generator 101 can be heated and raised to a temperature suitable for generating the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started).

  Further, in the operating method of the hydrogen generator 101 of the present embodiment, when starting the hydrogen generator 101, first, the raw material supplier 3 is in a stopped state, and the combustion air supplier 5 supplies air to the combustor 4. In the state of supplying, the first step (steps S103, S104) of starting the heating operation of the heater 8 and igniting the igniter 6 and starting the heating operation of the heater 8 in step S104 If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), step S108 of ending the heating operation of the heater 8 is included.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the first embodiment), the hydrogen generator 101 is stopped from the reformer 1 to the combustor 4 using the raw material (LP gas which is a mixed gas of propane and butane in the present embodiment) after the operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is 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.

  5, the same components as those in FIG. 1 are designated by the same reference numerals and detailed description thereof will be omitted. The hydrogen generator 103 of the third embodiment is different from that of the first embodiment shown in FIG. 1 in that the switch 9 is not provided on the generated gas flow path for guiding the gas discharged from the CO reducer 2 to the combustor 4. The hydrogen generator 101 of the second embodiment is different.

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

  FIG. 6 is a flowchart showing a method of starting the hydrogen generator 103 according to Embodiment 3 of the present invention. The same operations as those in the flowchart showing the method for starting the hydrogen generator 101 according to the first embodiment shown in FIG. 3 are designated by the same reference numerals, and detailed description thereof will be omitted.

  3 is different from the flowchart showing the method for starting the hydrogen generator 101 according to Embodiment 1 shown in FIG. 3 in that steps S102, S109, and S121 relating to the switch 9 are omitted, and the amount of combustion air in FIG. 3 is increased. Step S110, step S111 that waits until the flame detector 7 cannot detect a flame, step S310 that increases the amount of combustion air, and step S311 that returns to step S310 when the flame detector 7 can detect a flame. , Respectively.

  Similar to the hydrogen generator 101 according to the first embodiment, before starting the hydrogen generator 103 according to the third embodiment (when the hydrogen generator 103 was stopped last time), the reformer 1 to the combustor The gas flow path to 4 is purged with the raw material.

  When the activation of the hydrogen generator 103 is executed, the controller 20 operates the combustion air supplier 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 and introduce the gas into the combustor 4 for combustion.

  Next, the controller 20 confirms whether or not 1.9 minutes (first time) has elapsed from the start of operation of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) has elapsed from the start of operation of the heater 8, the process proceeds to step S141. On the contrary, in step S105, if 1.9 minutes (first time) has not yet passed 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 detector 7 can detect the flame. When the flame detector 7 can detect the flame, the process proceeds to step S107, and conversely, the flame detector 7 detects the flame. If not, the process returns to step S105.

  Hereinafter, the operation when the flame detector 7 detects a flame in step S106 will be described.

  First, since the controller 20 detects the flame with the flame detector 7, the controller 20 stops the igniter 6 (step S107), and then stops the desorption of the gas from the CO reducer 2 and To stop the combustion, the heater 8 is stopped (step S108).

When step S108 is executed, the controller 20 lowers the concentration of the combustible gas formed in the combustor 4 below the lower limit of the combustion range to surely stop the combustion, and thus increases the flow rate of the combustion air. (Step S310). Subsequently, the controller 20 confirms whether or not the flame detector 7 has detected flame (step S311). When the flame detector 7 detects a flame, the flow returns to step S310 to further increase the flow rate of 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. The process moves (step S122). On the contrary, 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 the steam contained in the hydrogen-containing gas generated in the reformer 1 does not condense in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature decrease after the operation of the heater 8 is stopped (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. In that case, the process proceeds to step S124. On the contrary, if the internal temperature of the reformer 1 is not lower than the second temperature, it waits until it becomes lower than the second temperature.

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

  Next, in step S124, the controller 20 performs an operation of waiting for a predetermined non-combustion time. The predetermined non-combustion time is the total time after the process proceeds to step S122. Even after the operation of stopping the desorption from the CO reducer 2 is performed in step S108, the unburned gas remains inside the combustor 4. Therefore, if the ignition operation is started without scavenging the unburned gas, the unburned gas is ignited, and the combustor 4 may be damaged due to the 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, it was decided to supply ten times as much 72 L of air. Since the flow rate of the combustion air supplied from the combustion air supplier 5 to the combustor 4 was 3.2 mol / min (= 72 L / min), the non-combustion time was 1 minute.

  In step S124, if the time from the time of shifting to step S122 to the step S124 exceeds 1 minute, the flow shifts to step S125. On the contrary, if the time from the time of shifting to step S122 to step S124 does not exceed 1 minute, it waits until 1 minute elapses.

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

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

First, the controller 20 stops the operation of the igniter 6 (step S141), and then confirms whether or not the flame detector 7 can detect a flame (step S142). In step S142, when the flame detector 7 detects the flame, 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, so that the combustor 4 operates. Since the combustion 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 reaches a maximum value within a few minutes from the start of operation of the heater 8, and then gradually decreases, so that the combustion in the combustor 4 is stopped. When the flame cannot be detected, the process proceeds to step S143. On the contrary, in step S142, when the flame detector 7 cannot detect the flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms from the CO reducer temperature detector 11 whether the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature of 150 ° C., step S143 is repeated and the heater 8 heats the CO reducer 2. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature of 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 in and after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reforming reaction is possible in the reformer 1. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed in the combustor 4 when the raw material supply device 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 supply device 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 is used. Burn raw materials. 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. Move to.

  In step S166, the controller 20 confirms whether 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. If it is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has reached the third temperature or higher. When it is confirmed by the reformer temperature detector 10 that the internal temperature of the reformer 1 has reached the third temperature or higher, the process proceeds to the end.

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

  By 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 is completed without being affected by the change in the flow rate and composition of the gas desorbed from the CO reducer 2.

  Then, a reforming water supply device (not shown) is operated to supply the reforming water to the reformer 1, and the steam-reforming reaction starts the generation of the hydrogen-containing gas in the reformer 1 to reduce the CO. The gas discharged from the container 2 is supplied to a hydrogen utilizing device (not shown).

As described above, in the present embodiment, in the hydrogen generator 103 that uses a raw material containing at least one of propane and butane as a main component, the desorption gas flow rate increases slowly, and Set the ignition time, which is the longest time until the gas concentration enters the combustible range and ignites, 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 the flame before, the operation of the heater 8 is terminated, the flow rate of the combustion air is increased until the concentration becomes lower than the lower limit of the combustible range, and the combustor 4 is activated. Since the combustion of the catalyst is stopped, the desorption of the gas from the catalyst is stopped by the stop of the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped, so that the deterioration due to the excessive temperature rise of the catalyst can be prevented.

  Further, since the switch 9 in the hydrogen generator 101 according to the first embodiment is unnecessary, it is inexpensive and the reliability can be improved.

  Also, after repeating the above series of operations until the internal temperature of the CO reducer 2 exceeds the first temperature of 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 the 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. It is possible to prevent deterioration due to excessive temperature rise, and it is possible to raise the temperature of the reformer 1 to a temperature at which the reforming reaction is possible.

  In the present embodiment, the raw materials are butane and propane, but it is a mixed gas containing a hydrocarbon having a carbon number of 2 to 4 such as ethane, ethylene, propylene and butene as a main component. Is also good.

  The hydrogen generator 103 of the present embodiment includes a raw material supply device 3 for supplying a raw material containing hydrocarbon as a main component, a reformer 1 for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and a reformer 1. The CO reducer 2 for reducing the carbon monoxide concentration of the hydrogen-containing gas produced in 1) by the carbon monoxide reducing catalyst, and the gas discharged from the CO reducer 2 are burned to reform the reformer 1 and the CO reducer 2. Among them, a combustor 4 that heats at least the reformer 1, a combustion air supplier 5 that supplies combustion air to the combustor 4, an igniter 6 that performs an ignition operation in the combustor 4, and a flame of the combustor 4 The flame detector 7 for detecting the presence or absence of the above, the heater 8 for heating the CO reducer 2, and the controller 20 are provided.

  Then, when the controller 20 activates the hydrogen generator 103, first, the raw material supply device 3 is in a stopped state, and the combustion air supply device 5 is supplying air to the combustor 4 in the heating device. 8 starts the heating operation of the heater 8 and causes the igniter 6 to perform the ignition operation, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) from the start of the heating operation of the heater 8. When the flame is detected, the heating operation of the heater 8 is completed.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the above embodiment, the hydrogen generator 103 is stopped by 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 operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is 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 operation of the hydrogen generator 103 is stopped. The gas flow path is purged with the raw material (LP gas).

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

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

  In addition, in the hydrogen generator 103 of the present embodiment, the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. Detects a flame, 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 stopped until the flame detector 7 stops detecting the flame. To increase.

  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, and the combustion in the combustor 4 is stopped, so that deterioration due to excessive temperature rise of the catalyst is more reliably performed. It can be prevented.

  Further, the hydrogen generator 103 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, and a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2. , 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 of 1 is finished, the flame detector 7 stops detecting the flame of the combustor 4, and then the internal temperature of the CO reducer 2 becomes the first temperature (the hydrogen-containing gas generated in the reformer 1 becomes The steam contained therein is at a temperature at which it does not condense in the CO reducer 2 and 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 precipitation of carbon generated by the thermal decomposition of the raw material, cannot be ignored. The temperature is sufficiently lower than the temperature of 200 ° C. in the present embodiment, and the igniter 6 is caused to perform an ignition operation after a predetermined non-combustion time (1 minute in the present embodiment) has elapsed. The heating operation of the heater 8 is restarted.

  As a result, the process of burning the desorbed gas desorbed from the carbon monoxide reduction catalyst in the combustor 4 and the step of burning the desorbed gas in the combustor 4 after the combustion of the combustor 4 is stopped Since the step of supplying air from the supply device 5 and cooling the combustor 4 is repeated, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is prevented from being deteriorated due to excessive temperature rise, and the hydrogen-containing gas is The temperature of the reforming catalyst and the carbon monoxide reduction catalyst of the hydrogen generator 103 can be raised to a temperature suitable for the production of hydrogen.

  Further, the hydrogen generator 103 of the present embodiment includes the 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 before starting the operation. If the flame detector 7 does not detect a flame before 1 hour (in this embodiment, 1.9 minutes) elapses, the internal temperature of the CO reducer 2 becomes the first temperature (in this embodiment). The heating operation of the heater 8 is continued until the internal temperature of the CO reducer 2 reaches the first temperature (150 ° C. in the present embodiment) or more. The operation ends.

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

Further, the hydrogen generator 103 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, and a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2. When the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment), the controller 20 is formed by the combustor 4 when the raw material supply device 3 is operated. The air for combustion 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 the temperature exceeds a third temperature (a temperature higher than the temperature at which the steam does not condense in the reformer 1 when the gas flowing through the reformer 1 contains the steam, 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is burned in the combustor 4 to heat the inside of the hydrogen generator 103 so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). The flow rate of the desorbed gas desorbed from the carbon reduction catalyst is small, and the combustion of the desorbed gas alone produces hydrogen up to a temperature suitable for producing the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started). Even when the inside of the apparatus 103 cannot be heated and heated, the inside of the hydrogen generator 103 can be heated and raised to a temperature suitable for generating the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started).

  In addition, in the operating method of the hydrogen generator 103 of the present embodiment, when starting the hydrogen generator 103, first, the raw material supply device 3 is in a stopped state, and the combustion air supply device 5 supplies air to the combustor 4. In the state of supplying, the first step (steps S103, S104) of starting the heating operation of the heater 8 and igniting the igniter 6 and starting the heating operation of the heater 8 in step S104 If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), step S108 of ending the heating operation of the heater 8 is included.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the above embodiment, the hydrogen generator 103 is stopped by 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 operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is possible to prevent deterioration.

(Embodiment 4)
The block diagram of the hydrogen generator 103 of Embodiment 4 of the present invention is the same as the hydrogen generator 103 of Embodiment 3 shown in FIG. 5, and the same components as those of Embodiment 3 are designated by the same reference numerals. It is given and its 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. 7.

  FIG. 7 is a flowchart showing a method of starting the hydrogen generator 103 according to Embodiment 4 of the present invention. 7, a flowchart showing a method for starting the hydrogen generator 101 according to the first embodiment shown in FIG. 3, a flowchart showing a method for starting the hydrogen generator 101 according to the second embodiment shown in FIG. 4, and an embodiment shown in FIG. The same step numbers are assigned to the same operations (steps) as those in the flowchart showing the method for starting the hydrogen generator 103 according to the third embodiment. Detailed description thereof will be omitted.

In the flowchart showing the starting method of the hydrogen generator 103 in the fourth embodiment shown in FIG. 7, steps S123 to S125 and step S223 in the flowchart showing the starting method of the hydrogen generator 103 in the third embodiment shown in FIG. To step S226.

  Similar to the hydrogen generator 103 according to the third embodiment, before starting the hydrogen generator 103 according to the fourth embodiment (when the hydrogen generator 103 was stopped last time), the reformer 1 to the combustor The gas flow path to 4 is purged with the raw material.

  When the activation of the hydrogen generator 103 is executed, the controller 20 operates the combustion air supplier 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 and introduce the gas into the combustor 4 for combustion.

  Next, the controller 20 confirms whether or not 1.9 minutes (first time) has elapsed from the start of operation of the heater 8 (step S105). In step S105, if 1.9 minutes (first time) has elapsed from the start of operation of the heater 8, the process proceeds to step S141. On the contrary, in step S105, if 1.9 minutes (first time) has not yet passed 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 detector 7 can detect the flame. When the flame detector 7 can detect the flame, the process proceeds to step S107, and conversely, the flame detector 7 detects the flame. If not, the process returns to step S105.

  Hereinafter, the operation when the flame detector 7 detects a flame in step S106 will be described.

  First, since the controller 20 detects the flame with the flame detector 7, the controller 20 stops the igniter 6 (step S107), and then stops the desorption of the gas from the CO reducer 2 and To stop the combustion, the heater 8 is stopped (step S108).

  When step S108 is executed, the controller 20 lowers the concentration of the combustible gas formed in the combustor 4 below the lower limit of the combustion range to surely stop the combustion, and thus increases the flow rate of the combustion air. (Step S310). Subsequently, the controller 20 confirms whether or not the flame detector 7 has detected flame (step S311). When the flame detector 7 detects a flame, the flow returns to step S310 to further increase the flow rate of combustion air. When the flame detector 7 cannot detect the flame, the process proceeds to step S122.

  Next, the operation of step S122 and steps S223 to 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, and when the internal temperature of the CO reducer 2 is lower than the first temperature, proceeds to step S223. The process moves (step S122). On the contrary, 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 the steam contained in the hydrogen-containing gas generated in the reformer 1 does not condense in the CO reducer 2. In the present embodiment, the first temperature is set to 150 ° C. in consideration of the temperature decrease after the operation of the heater 8 is stopped (step S108).

  Next, the 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 supplier 5 to the combustor 4 (step S223). Here, the concentration of the raw material flowing from the CO reducer 2 into the combustor 4 is reduced 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, controller 20 increases the flow rate of combustion air to 6.00 mol / min. When the combustion air was supplied at 6.00 mol / min, the combustible gas concentration was 1.6%, which was lower than the lower limit of the combustible range (1.9%), so even if there was an ignition source. Does not burn.

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

  Next, the controller 20 compares the internal temperature of the CO reducer 2 acquired from the CO reducer temperature detector 11 and the first temperature (150 ° C. in the present embodiment) (step S225), and the CO reducer. When the internal temperature of 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 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), and proceeds to step S161.

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

  First, the controller 20 stops the operation of the igniter 6 (step S141), and then confirms whether or not the flame detector 7 can detect a flame (step S142). In step S142, when the flame detector 7 detects the flame, 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, so that the combustor 4 operates. Since the combustion 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 reaches a maximum value within a few minutes from the start of operation of the heater 8, and then gradually decreases, so that the combustion in the combustor 4 is stopped. When the flame cannot be detected, the process proceeds to step S143. On the contrary, in step S142, when the flame detector 7 cannot detect the flame from the beginning, the process immediately proceeds to step S143.

  Next, the controller 20 confirms from the CO reducer temperature detector 11 whether the internal temperature of the CO reducer 2 is lower than the first temperature (150 ° C.) (step S143). When the internal temperature of the CO reducer 2 is lower than the first temperature of 150 ° C., step S143 is repeated and the heater 8 heats the CO reducer 2. If the internal temperature of the CO reducer 2 is equal to or higher than the first temperature of 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 in and after step S161 in order to raise the temperature of the reformer 1 to a temperature at which the reforming reaction is possible in the reformer 1. First, the controller 20 adjusts the flow rate of the combustion air so that the combustible gas concentration of the mixed gas formed in the combustor 4 when the raw material supply device 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 supply device 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 is used. Burn raw materials. 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. Move to.

  In step S166, the controller 20 confirms whether 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. If it is lower, the process waits until it is confirmed that the internal temperature of the reformer 1 has reached the third temperature or higher. When it is confirmed by the reformer temperature detector 10 that the internal temperature of the reformer 1 has reached the third temperature or higher, the process proceeds to the end.

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

  By 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 is completed without being affected by the change in the flow rate and composition of the gas desorbed from the CO reducer 2.

  Then, a reforming water supply device (not shown) is operated to supply the reforming water to the reformer 1, and the steam-reforming reaction starts the generation of the hydrogen-containing gas in the reformer 1 to reduce the CO. The gas discharged from the container 2 is supplied to a hydrogen utilizing device (not shown).

  As described above, in the present embodiment, in the hydrogen generator 103 that uses a raw material containing at least one of propane and butane as a main component, the desorption gas flow rate increases slowly, and The ignition time, which takes the longest time for the gas concentration to enter the combustible range and to be ignited, is set as the first time (1.9 minutes), and after the ignition operation and the heating operation, the first time (1.9 minutes) When the flame detector 7 detects the flame before, the operation of the heater 8 is terminated, the flow rate of the combustion air is increased until the concentration becomes lower than the lower limit of the flammable range, and the combustor 4 Since the combustion of the catalyst is stopped, the desorption of gas from the catalyst is stopped by the stop of the temperature rise of the catalyst, and the combustion in the combustor 4 is stopped, so that the deterioration due to the excessive temperature rise of the catalyst can be prevented.

  Further, when ignition occurs 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 equal to or lower than the lower limit of the combustible range. While increasing the flow rate of the combustion air until the CO concentration reaches a first temperature of 150 ° C. by the operation of the heater 8, the CO reduction device 2 is heated through the reformer 1 and the CO reduction device 2. Since the reformer 1 is heated to the third temperature 120 ° C. by the combustion of the raw material supplied to the combustor 4 by means of the combustion, the composition of the desorbed gas from the CO reducer 2 and the change in the flow rate are not affected, and It is possible to prevent deterioration of the catalyst of the pouch 1 due to excessive temperature rise, and it is possible to raise the temperature of the reformer 1 to a temperature at which the reforming reaction is possible.

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

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

In the present embodiment, the raw materials are butane and propane, but it is a mixed gas containing a hydrocarbon having a carbon number of 2 to 4 such as ethane, ethylene, propylene and butene as a main component. Is also good.

  The hydrogen generator 103 of the present embodiment includes a raw material supply device 3 for supplying a raw material containing hydrocarbon as a main component, a reformer 1 for generating a hydrogen-containing gas from the raw material with a reforming catalyst, and a reformer 1. The CO reducer 2 for reducing the carbon monoxide concentration of the hydrogen-containing gas produced in 1) by the carbon monoxide reducing catalyst, and the gas discharged from the CO reducer 2 are burned to reform the reformer 1 and the CO reducer 2. Among them, a combustor 4 that heats at least the reformer 1, a combustion air supplier 5 that supplies combustion air to the combustor 4, an igniter 6 that performs an ignition operation in the combustor 4, and a flame of the combustor 4 The flame detector 7 for detecting the presence or absence of the above, the heater 8 for heating the CO reducer 2, and the controller 20 are provided.

  Then, when the controller 20 activates the hydrogen generator 103, first, the raw material supply device 3 is in a stopped state, and the combustion air supply device 5 is supplying air to the combustor 4 in the heating device. 8 starts the heating operation of the heater 8 and causes the igniter 6 to perform the ignition operation, and the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) from the start of the heating operation of the heater 8. When the flame is detected, the heating operation of the heater 8 is completed.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the above embodiment, the hydrogen generator 103 is stopped by 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 operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is 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 operation of the hydrogen generator 103 is stopped. The gas flow path is purged with the raw material (LP gas).

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

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

  In addition, in the hydrogen generator 103 of the present embodiment, the flame detector 7 is activated before the first time (1.9 minutes in the present embodiment) after the controller 20 starts the heating operation of the heater 8. Detects a flame, 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 stopped until the flame detector 7 stops detecting the flame. To increase.

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, and the combustion in the combustor 4 is stopped, so that deterioration due to excessive temperature rise of the catalyst is more reliably performed. It can be prevented.

  Further, the hydrogen generator 103 of the present embodiment includes the 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 before starting the operation. The flame detector 7 detects the flame and the flame detector 7 detects the flame of the combustor 4 after the heating operation of the heater 8 is completed within 1 hour (1.9 minutes in the present embodiment). After that, the internal temperature of the CO reducer 2 is the first temperature (a temperature at which the water vapor contained in the hydrogen-containing gas generated in the reformer 1 does not condense in the CO reducer 2, and in the present embodiment, 150 ° C.), the flow rate of the combustion air supplied from the combustion air supplier 5 to the combustor 4 is set so that the combustible gas concentration of the mixed gas formed in the combustor 4 falls outside 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 the gas released to the outside of the hydrogen generator 103 had an ignition source. However, the hydrogen generator 103 with high safety can be configured without burning.

  Further, the hydrogen generator 103 of the present embodiment includes the 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 before starting the operation. If the flame detector 7 does not detect a flame before 1 hour (in this embodiment, 1.9 minutes) elapses, the internal temperature of the CO reducer 2 becomes the first temperature (in this embodiment). The heating operation of the heater 8 is continued until the internal temperature of the CO reducer 2 reaches the first temperature (150 ° C. in the present embodiment) or more. The operation ends.

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

  Further, the hydrogen generator 103 of the present embodiment includes a reformer temperature detector 10 that detects the internal temperature of the reformer 1, and a CO reducer temperature detector 11 that detects the internal temperature of the CO reducer 2. When the internal temperature of the CO reducer 2 exceeds the first temperature (150 ° C. in the present embodiment), the controller 20 is formed by the combustor 4 when the raw material supply device 3 is operated. The air for combustion 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 the temperature exceeds a third temperature (a temperature higher than a temperature at which the steam does not condense in the reformer 1 when the gas flowing through the reformer 1 contains the steam, 120 ° C. in the present embodiment). The feeder 3 is operated.

  As a result, the raw material is burned in the combustor 4 to heat the inside of the hydrogen generator 103 so that the internal temperature of the reformer 1 exceeds the third temperature (120 ° C. in the present embodiment). The flow rate of the desorbed gas desorbed from the carbon reduction catalyst is small, and the combustion of the desorbed gas alone produces hydrogen up to a temperature suitable for producing the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started). Even when the inside of the apparatus 103 cannot be heated and heated, the inside of the hydrogen generator 103 can be heated and raised to a temperature suitable for generating the hydrogen-containing gas (the temperature at which the supply of the reforming water to the reformer 1 is started).

In addition, in the operating method of the hydrogen generator 103 of the present embodiment, when starting the hydrogen generator 103, first, the raw material supply device 3 is in a stopped state, and the combustion air supply device 5 supplies air to the combustor 4. In the state of supplying, the first step (steps S103, S104) of starting the heating operation of the heater 8 and igniting the igniter 6 and starting the heating operation of the heater 8 in step S104 If the flame detector 7 detects a flame before the first time (1.9 minutes in the present embodiment), step S108 of ending the heating operation of the heater 8 is included.

  As a result, the desorbed gas desorbed from the carbon monoxide reducing catalyst of the CO reducer 2 due to the heating operation of the heater 8 has a slow increase rate of the desorbed gas flow rate flowing to the combustor 4, and the gas in the combustor 4 is reduced. The ignition time from the start of the heating operation of the heater 8 to the flame detection by the flame detector 7 in the case of the raw material component (propane) in which the concentration is in the flammable range and the longest time to ignite is the first time (this implementation 1.9 minutes) in the above embodiment, the hydrogen generator 103 is stopped by 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 operation is stopped. Even if the gas flow path leading to the above 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 gas from the carbon monoxide reduction catalyst is stopped by the stop of the rise and the combustion in the combustor 4 is stopped, at least the reforming catalyst of the reforming catalyst and the carbon monoxide reducing catalyst is overheated. It is possible to prevent deterioration.

  Many modifications and other embodiments of the present invention will be apparent to those skilled in the art from the above description of the present embodiment. Therefore, the above description should be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode for carrying out the present invention. The details of structure and / or function may be changed substantially 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 that is desorbed from the catalyst heated at startup and flows to the combustor. Since the gas can be used as a heat source when starting the hydrogen generator, and a hydrogen generator with high energy efficiency and durability can be realized, it can be discharged depending on the remaining amount of the raw material storage container such as the LPG cylinder and the temperature environment. It 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 varies.

1 reformer 2 CO reducer 3 raw material supplier 4 combustor 5 combustion air supplier 6 igniter 7 flame detector 8 heater 9 switch 10 reformer temperature detector 11 CO reducer temperature detector 20 controller 101 hydrogen generator 103 hydrogen generator

Claims (11)

A raw material supplier for supplying a raw material containing hydrocarbon as a main component, a reformer for producing a hydrogen-containing gas from the raw material with a reforming catalyst, and carbon monoxide for the hydrogen-containing gas produced by 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 supply device 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 a CO reduction device. A hydrogen generator comprising a heating device for controlling, and a controller,
When the controller starts the hydrogen generator, first, the raw material supply device is in a stopped state, and the combustion air supply device supplies air to the combustor. When the flame detector detects flame before starting the heating operation of the heater and starting the heating operation of the heater, the heating operation of the heater is started. Hydrogen generator that terminates.   The raw material contains at least one of propane and butane as a main component, the hydrogen generator is purged with the raw material after the operation is stopped, and the carbon monoxide is heated by the heating operation of the heater for the first time. The hydrogen generator according to claim 1, wherein when the desorbed gas desorbed from the reduction catalyst is propane, it is a time until combustion in the combustor starts.   The hydrogen generator includes a switch on a generated gas flow path that guides the gas discharged from the CO reducer to the combustor, and the controller causes the switch to operate when the hydrogen generator is started. When the heating operation of the heater is started in the open state and the flame detector detects a flame within the first time after starting the heating operation of the heater, the heating operation of the heater is ended. The hydrogen generator according to claim 1 or 2, wherein the switch is closed at the same time.   The hydrogen generator according to claim 3, wherein the controller opens the switch again when the flame detector no longer detects a flame after closing the switch.   When 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 supplier to the combustor is increased so as to be out of the range.   When the flame detector detects a flame before the first time period after the heating operation of the heater is started, the controller ends the heating operation of the heater and the flame detector. 3. The hydrogen generator according to claim 1, wherein the flow rate of combustion air supplied from the combustion air supply device to the combustor is increased until no longer detects a flame. A reformer temperature detector that detects the internal temperature of the reformer; and a CO reducer temperature detector that detects the internal temperature of the CO reducer,
The controller, after finishing the heating operation of the heater, has an internal temperature of the CO reducer lower than a first temperature, an internal temperature of the reformer lower than a second temperature, and a predetermined temperature. The hydrogen generator according to any one of claims 1 to 6, wherein after the non-combustion time has elapsed, the igniter is caused to perform an ignition operation 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 stops detecting the flame, the controller determines that the combustible gas concentration of the mixed gas formed in the combustor is combustible. 7. The heating operation of the heater is restarted after increasing the flow rate of the combustion air supplied from the combustion air supplier to the combustor so as to be out of the 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 a flame during the first time period after the heating operation of the heater is started, the controller determines that the internal temperature of the CO reducer is equal to the first temperature. 9. The heating operation of the heater is continued until it becomes a temperature or higher, and when the internal temperature of the CO reducer becomes the first temperature or higher, the heating operation of the heater is ended. The hydrogen generator according to Item 1. A reformer temperature detector that detects the internal temperature of the reformer; and a CO reducer temperature detector that detects the internal temperature of the CO reducer,
When the internal temperature of the CO reducer exceeds a first temperature, the controller controls the combustion air supply unit to perform combustion so that the combustible gas concentration of the mixed gas formed in the combustor falls within a combustible range. 10. The raw material supplier is operated until the internal temperature of the reformer exceeds a third temperature while supplying combustion air to the reactor and igniting the igniter. The hydrogen generator according to item. A raw material supplier for supplying a raw material containing hydrocarbon as a main component, a reformer for producing a hydrogen-containing gas from the raw material with a reforming catalyst, and carbon monoxide for the hydrogen-containing gas produced by 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 supply device 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 a CO reduction device. A method of operating a hydrogen generator comprising:
When starting the hydrogen generator, first, the heating operation of the heater is started in a state where the raw material supply device is stopped and the combustion air supply device is supplying air to the combustor. Together with a first step of causing the igniter to perform an ignition operation, and if the flame detector detects a flame before a first time after starting the heating operation of the heater in the first step, the heating is performed. A second step of terminating the heating operation of the reactor.