JP2013227163A - Hydrogen generating apparatus and operation method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen generating apparatus that operates at a temperature of hydrodesulfurization within a proper range without depending on a power generation load, and a starting method of the same.SOLUTION: A hydrogen generating apparatus, provided with a desulfurization temperature detector that detects a temperature of a hydrodesulfurizer, controls the temperature of a reformed gas exhausted from a reformer to lower when the temperature detected by the desulfurization temperature detector exceeds a first preset temperature, and controls it to rise when the temperature detected by the desulfurization temperature detector becomes lower than a second preset temperature.

Description

  The present invention relates to a hydrogen generator and an operation method thereof.

  Development of a fuel cell capable of high-efficiency power generation even with a small device is being developed as a power generator for a distributed energy supply source. Hydrogen gas used as fuel for fuel cell power generation has not been developed as a general infrastructure. Therefore, when used as a distributed device, for example, a configuration may be adopted in which a hydrogen generation device for generating a hydrogen-containing gas by reacting a raw material obtained from an existing fossil raw material infrastructure such as city gas and LPG with a steam reforming reaction is used. Many. The existing fossil raw material infrastructure such as city gas and LPG contains sulfur as an odorant or as a component derived from the raw material, but the sulfur needs to be desulfurized in order to reduce the reforming performance and the like.

  Examples of the desulfurization method include an adsorption removal method at normal temperature using an adsorbent and a hydrodesulfurization method performed by adding hydrogen. The hydrodesulfurization method has a large sulfur adsorption capacity and can be desulfurized without exchanging the catalyst for a long time. In addition, there is an advantage that even a trace component that is difficult to be adsorbed and desulfurized at room temperature can be removed. On the other hand, the adsorption capacity of sulfur is higher as the temperature is higher, so that the hydrodesulfurization catalyst functions, and generally it is necessary to heat to about 200 ° C. or higher, and it is necessary to keep the temperature at about 300 ° C. or lower from the viewpoint of catalyst heat resistance temperature is there.

  As a temperature control method for hydrodesulfurization catalyst, a method of adjusting the heating temperature by using a cylindrical steam reformer and placing a hydrodesulfurization catalyst layer on the outer periphery of the hydrothermal desulfurization catalyst layer through a heat-insulating material with a controlled thickness is proposed. (For example, refer to Patent Document 1). Further, a method has been proposed in which part of the raw fuel gas is branched into a branch circuit to control the temperature of the desulfurizer to a predetermined temperature (for example, Patent Document 2).

JP 2010-58995 A Japanese Patent Laid-Open No. 11-189401

  As described above, in order for the hydrodesulfurization catalyst to function, it is necessary to keep the catalyst temperature at a predetermined temperature. However, there is a problem that the raw material flow rate is large and the temperature in the hydrodesulfurization unit varies, making it difficult to keep the temperature appropriate.

  In addition, the method of controlling the temperature of the desulfurizer to a predetermined temperature by branching a part of the raw fuel gas into the branch circuit has a problem that the number of components that are branched increases and the apparatus becomes complicated.

  An object of the present invention is to provide a hydrogen generator capable of keeping the temperature of a hydrodesulfurization catalyst within an appropriate range.

In order to solve the above-described problems, a hydrogen generator according to the present invention includes a reformer that generates a reformed gas by reforming a raw material containing hydrocarbon and water, and supplies the raw material to the reformer. A raw material supplier, a water supplier that supplies water to the reformer, a combustion gas that is a raw material or a reformed gas, and air, and that heats the reformer; and the combustor An air supply device for supplying air to the gas generator, a reformed gas flow path for discharging the reformed gas reformed by the reformer, and a configuration that is heated by the heat of the reformed gas flowing through the reformed gas flow path A hydrodesulfurizer that removes sulfur content in the raw material by hydrogenation, a desulfurization temperature detector that detects the temperature of the hydrodesulfurizer, and a controller, wherein the controller includes the desulfurization temperature. The temperature detected by the detector is controlled so as to change the temperature of the reformed gas discharged from the reformer. Configuration to be.

  In the hydrogen generator of the present invention, the temperature of the reformed gas can be raised or lowered when the hydrodesulfurization temperature deviates from the set range, so that the temperature of the hydrodesulfurization catalyst can be maintained within an appropriate range, Since it can be operated at a higher temperature within the heat-resistant temperature, the adsorption capacity can be maintained high, so that the catalyst capacity can be reduced and the durability of the catalyst can be ensured.

Schematic of the hydrogen generator in Embodiment 1 of the present invention Graph showing the relationship between S / C and hydrodesulfurizer temperature Graph showing the relationship between air ratio and hydrodesulfurizer temperature Graph showing the relationship between raw material flow rate and hydrodesulfurizer temperature Schematic of the hydrogen generator in Embodiment 4 of the present invention Schematic of the hydrogen generator in Embodiment 5 of the present invention

  A first invention includes a reformer that generates a reformed gas by reforming a raw material containing hydrocarbon and water, a raw material supplier that supplies the raw material to the reformer, and the reformer A water supply device that supplies water, a combustion gas that is a raw material or a reformed gas, and a combustion device that heats the reformer; an air supply device that supplies air to the combustor; The reformed gas flow path for discharging the reformed gas reformed by the reformer, and the heat of the reformed gas flowing through the reformed gas flow path are arranged to hydrogenate the sulfur content in the raw material. A hydrodesulfurizer to be removed by the desulfurization, a desulfurization temperature detector for detecting the temperature of the hydrodesulfurizer, and a controller. It is a hydrogen generator that controls to change the temperature of the reformed gas discharged from the mass device.

  With this configuration, the hydrodesulfurizer is heated by the heat of the reformed gas, so the temperature of the hydrodesulfurizer can be changed by changing the temperature of the reformed gas, and kept within an appropriate temperature range. Can do. As a result, the catalyst capacity can be reduced because the adsorption capacity can be maintained within the heat-resistant temperature of the catalyst and high.

  In a second aspect of the invention, particularly in the first aspect of the invention, the controller includes a ratio of water to the raw material supplied to the reformer, a ratio of air to a combustion gas supplied to the combustor, and the hydrodesulfurization. It is a hydrogen generator that controls to change the temperature of the reformed gas discharged from the reformer by changing at least one of the flow rate of the raw material supplied to the reactor.

  With this configuration, the ratio of water to the raw material, the ratio of air to the combustion gas, and the flow rate of the raw material can be easily adjusted, so that the temperature of the hydrodesulfurizer can be kept within an appropriate range regardless of operating conditions. it can.

  In a third aspect of the invention, particularly in the second aspect of the invention, the controller discharges from the reformer when the temperature detected by the desulfurization temperature detector is higher than the preset first temperature. When the temperature of the reformed gas is lowered and the temperature detected by the desulfurization temperature detector is lower than the second temperature set in advance at a temperature lower than the first temperature, the reforming is performed. This is a hydrogen generator that controls the temperature of the reformed gas discharged from the mass device to increase.

  With this configuration, by setting the first temperature and the second temperature in advance, the temperature of the hydrodesulfurizer can be strictly maintained within an appropriate range.

  According to a fourth aspect of the invention, particularly in the third aspect of the invention, the controller controls the water supply device when the temperature detected by the desulfurization temperature detector is higher than the first temperature, and controls the modification. When the ratio of water to the raw material supplied to the quality device is increased and the temperature detected by the desulfurization temperature detector becomes lower than the second temperature, the water supply device is controlled to the reformer. This is a hydrogen generator that controls to reduce the ratio of water to the supplied raw material.

  With this configuration, when the water ratio is changed, the temperature of the reformed gas can be changed, so that the temperature of the hydrodesulfurizer can be maintained within an appropriate range.

  In a fifth aspect of the invention, particularly in the third aspect of the invention, the controller controls the air supply to control the combustion when the temperature detected by the desulfurization temperature detector is higher than the first temperature. When the ratio of air to combustion gas supplied to the combustor is increased and the temperature detected by the desulfurization temperature detector is lower than the second temperature, the air supply device is controlled to control the air to the combustor. This is a hydrogen generator that controls to reduce the ratio of air to combustion gas to be supplied.

  With this configuration, when the air ratio is changed, the temperature of the reformed gas can be changed, so that the temperature of the hydrodesulfurizer can be maintained within an appropriate range.

  In a sixth aspect of the invention, particularly in the third aspect of the invention, the controller controls the raw material feeder to control the water supply when the temperature detected by the desulfurization temperature detector is higher than the first temperature. Increasing the flow rate of the raw material supplied to the hydrodesulfurizer and lowering the flow rate of the raw material supplied to the hydrodesulfurizer when the temperature detected by the desulfurization temperature detector is lower than the second temperature. The hydrogen generator is controlled as follows.

  With this configuration, the temperature of the reformed gas and the flow rate of the raw material gas flowing through the hydrodesulfurizer are changed by changing the raw material flow rate, so that the temperature of the hydrodesulfurizer can be changed. The temperature can be kept in an appropriate range.

  According to a seventh invention, in particular, in the third to sixth inventions, a storage unit for storing a flow rate of the raw material supplied to the hydrodesulfurizer is provided, and the storage unit has a temperature detected by the desulfurization temperature detector. The first flow rate that is the flow rate of the raw material supplied to the hydrodesulfurizer when the temperature is equal to or higher than the first temperature, and the temperature detected by the desulfurization temperature detector is equal to or lower than the second temperature. At least one of the second flow rates that is the flow rate of the raw material supplied to the hydrodesulfurizer in the case of becoming, and the controller stores the first flow rate in the storage unit In this case, the flow rate of the raw material supplied to the hydrodesulfurizer is controlled so as to be equal to or higher than the first flow rate, and when the storage unit stores the second flow rate, The raw material feeder is controlled so that the flow rate of the raw material to be supplied is equal to or less than the second flow rate. It is the elementary generation device.

  With this configuration, the temperature of the hydrodesulfurizer is stably maintained for an extended period of time and kept in an appropriate range even if there is a temperature difference due to individual equipment differences or a change in temperature of the hydrodesulfurizer over time. be able to.

According to an eighth aspect of the present invention, a reformer that generates a reformed gas by reforming a raw material containing hydrocarbon and water, a combustion gas that is a raw material or a reformed gas, and air are combusted, and the modified Arranged to be heated by the heat of the reformed gas flowing through the reformed gas channel, the combustor for heating the reformer, the reformed gas channel for discharging the reformed gas generated in the reformer, A hydrodesulfurizer that removes sulfur in the raw material by hydrogenation, and the controller changes the temperature of the reformed gas discharged from the reformer according to the temperature detected by the desulfurization temperature detector. Including a temperature adjustment process for controlling
This is an operation method of the hydrogen generator.

  With this operation method, the temperature of the hydrodesulfurizer can be maintained within an appropriate range by changing the temperature of the reformed gas. As a result, the catalyst capacity can be reduced because the adsorption capacity can be maintained within the heat-resistant temperature of the catalyst and high.

  According to a ninth aspect of the invention, in the eighth aspect of the invention, in the eighth aspect, the temperature adjustment step is a modification that is discharged from the reformer when the temperature of the hydrodesulfurizer becomes higher than a preset first temperature. A step of lowering the temperature of the quality gas and increasing the temperature of the reformed gas discharged from the reformer when the temperature of the hydrodesulfurizer becomes lower than a preset second temperature. This is an operation method of the hydrogen generator.

  By setting the first temperature and the second temperature in advance by this operation method, the temperature of the hydrodesulfurizer can be strictly maintained within an appropriate range.

  According to a tenth aspect of the invention, in the ninth aspect of the invention, in the ninth aspect of the invention, in the temperature adjusting step, when the temperature of the hydrodesulfurizer becomes higher than the first temperature, the reformer is controlled by controlling the water supplier. When the ratio of water to the raw material supplied to the fuel is increased and the temperature detected by the desulfurization temperature detector becomes lower than the second temperature, the water supplier is controlled and supplied to the reformer. This is a method for operating a hydrogen generator, which is a step of reducing the ratio of water to raw material.

  According to this operation method, when the ratio of the water is changed, the temperature of the reformed gas can be changed, so that the temperature of the hydrodesulfurizer can be maintained within an appropriate range.

  In an eleventh aspect of the invention, in particular, in the ninth aspect of the invention, the temperature adjustment step includes controlling the air supply device to the combustor when the temperature of the hydrodesulfurizer is higher than the first temperature. Combustion gas supplied to the combustor by controlling the air supplier when the ratio of air to the supplied combustion gas is increased and the temperature of the hydrodesulfurizer becomes lower than the second temperature. It is the operating method of the hydrogen generator which is the process of reducing the ratio of the air with respect to.

  According to this operation method, when the air ratio is changed, the temperature of the reformed gas can be changed, so that the temperature of the hydrodesulfurizer can be maintained within an appropriate range.

  According to a twelfth aspect of the invention, in the ninth aspect of the invention, in the ninth aspect of the invention, in the hydrodesulfurization, the temperature adjustment step controls the raw material supplier when the temperature of the hydrodesulfurizer becomes higher than the first temperature. Increasing the flow rate of the raw material supplied to the vessel, and lowering the flow rate of the raw material supplied to the hydrodesulfurizer when the temperature detected by the hydrodesulfurizer becomes lower than the second temperature. It is the operating method of the hydrogen production | generation apparatus containing.

  According to this operation method, the temperature of the reformed gas and the flow rate of the raw material gas flowing through the hydrodesulfurizer are changed by changing the raw material flow rate, so that the temperature of the hydrodesulfurizer can be changed. The temperature can be kept in an appropriate range.

The thirteenth invention is the flow rate of the raw material supplied to the hydrodesulfurizer when the temperature of the hydrodesulfurizer is equal to or higher than the first temperature, particularly in the ninth to twelfth inventions. Storing a flow rate of 1 and a second flow rate that is a flow rate of a raw material supplied to the hydrodesulfurizer when the temperature of the hydrodesulfurizer becomes equal to or lower than the second temperature. When at least one of the steps and the first flow rate are stored, the flow rate of the raw material supplied to the hydrodesulfurizer is set to be equal to or higher than the first flow rate, and the second flow rate is set. Is stored in the hydrodesulfurizer, the flow rate of the raw material supplied to the hydrodesulfurizer is limited to the second flow rate or less.

  This operating method ensures that the temperature of the hydrodesulfurizer is stable for an extended period of time and within the proper range even if there is a temperature difference caused by individual equipment differences or the temperature change of the hydrodesulfurizer over time. Can keep.

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

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

  The hydrogen generator includes a reformer 1 that generates hydrogen gas by proceeding mainly with a reforming reaction of steam with a raw material such as natural gas, hydrocarbon components such as LPG, alcohol such as methanol, or naphtha component, and naphtha. A Ru catalyst was used as a quality catalyst.

  Also, a raw material supplier 2 for supplying raw material to the reformer 1, a water supplier 3 for supplying water used for reforming to the reformer 1, a combustion gas that is a raw material or a reformed gas, and Combustor 4 that burns air and heats reformer 1, air supply device 5 that supplies air to combustor 4, and reformed gas flow that discharges reformed gas reformed by reformer 1 The hydrodesulfurizer 7 is disposed so as to be heated by the heat of the reformed gas flowing through the channel 6 and the reformed gas channel 6, and removes sulfur in the raw material by hydrogenation, and the temperature of the hydrodesulfurizer 7 A desulfurization temperature detector 8 for detecting the above, a controller 9 for controlling at least the raw material supplier 2, the water supplier 3, and the air supplier 5, and the reformed gas discharged from the reformer 1, that is, the reformed gas flow And a reforming outlet temperature detector 11 for detecting the temperature of the gas flowing into the passage. The hydrodesulfurizer 7 used was a Cu-Zn hydrodesulfurization catalyst.

  Next, the operation method of the hydrogen generator in the present invention will be described.

  In the hydrogen generator, the raw material is supplied from the raw material supplier 2 by the controller 9 and the water is supplied from the water supplier 3, and the combustion gas and the combustion gas, which is the raw material or reformed gas, are combusted by the combustor 4 and reformed. The reforming gas is generated by causing the steam reforming reaction to proceed in the vessel 1. The controller 9 is an S / C indicating the ratio of water to the number of carbons in the raw material supplied to the reformer 1 (in this embodiment, the set value of S / C is 2.8), and air for the combustion gas The raw material supply device 2, the water supply device 3, and the air supply device 5 are controlled so that the air ratio (the set value of the air ratio is set to 1.5 in this embodiment) indicating the ratio of To do. The raw material flow rate is controlled in proportion to the amount of reformed gas to be generated. Here, the raw material or the reformed gas is combusted in the combustor 4 so that the temperature detected by the reforming outlet temperature detector 11 is about 620 ° C., for example. At that time, the hydrodesulfurizer 7 is heated at least by heat transfer from the reformed gas, that is, the fluid flowing in the reformed gas flow path 6, so that the temperature detected by the desulfurization temperature detector 8 is about 250 ° C. Make it work. This is based on the fact that the hydrodesulfurization catalyst used in the present embodiment is preferably used in a temperature range of 200 to 300 ° C. A heat insulating material may be disposed between the reformed gas channel 6 and the hydrodesulfurizer 7.

  Next, a characteristic operation in the first embodiment will be described.

  Since the hydrodesulfurizer 7 receives heat from the fluid flowing through the reformed gas flow path 6, the temperature of the hydrodesulfurizer 7 is determined by the temperature or the amount of heat. Therefore, in the first embodiment, in order to keep the temperature of the hydrodesulfurizer 7 in an appropriate range, a method of changing the S / C ratio by controlling the water supplier 3 is adopted. Specifically, [1] The water supply device 3 is controlled to lower the set value of S / C, thereby raising the reformed gas temperature and raising the temperature of the hydrodesulfurizer 7, and vice versa. A method of lowering the reformed gas temperature by controlling the water supplier 3 and increasing the set value of S / C and lowering the temperature of the hydrodesulfurizer 7 is adopted.

  That is, it is assumed that the heat input and output of the hydrogen generator is balanced, and when the S / C is changed, for example, when the set value of S / C is increased, the amount of water to be added is increased and the amount of heat necessary for the evaporation of water is reduced. Since it increases, the temperature of the reformed gas can be lowered. On the other hand, the hydrodesulfurizer 7 is disposed at a location that receives heat from the reformed gas channel 6 at least by heat transfer, and the thermal conductivity of the medium between the reformed gas channel 6 and the hydrodesulfurizer 7. If the temperature does not change, for example, when the temperature of the reformed gas decreases, the temperature of the hydrodesulfurizer 7 can be decreased. This is because if the set value of S / C is reduced, the opposite effect can be obtained and the temperature of the hydrodesulfurizer 7 can be increased.

  FIG. 2 shows the relationship between the S / C in the first embodiment and the representative temperature of the hydrodesulfurizer 7 detected by the desulfurization temperature detector 8. It is shown that the temperature of the hydrodesulfurizer 7 can be raised when the S / C is lowered, and the temperature of the hydrodesulfurizer 7 can be kept within an appropriate range by changing the S / C. I understand that.

  Specifically, when the temperature detected by the desulfurization temperature detector 8 is higher than a preset first temperature (260 ° C. in the first embodiment), the controller 9 The temperature of the reformed gas discharged from the reformer 1 is lowered by increasing the set value and increasing the amount of water supplied to the reformer 1. Further, when the temperature detected by the desulfurization temperature detector 8 becomes lower than a preset second temperature (240 ° C. in the first embodiment), the set value of S / C is lowered and the reformer 1 The temperature of the reformed gas discharged from the reformer 1 was increased by reducing the amount of water supplied to the reactor. By this operation, the hydrodesulfurization catalyst housed in the hydrodesulfurizer 7 can be used in an appropriate temperature range.

(Embodiment 2)
Next, the hydrogen generator in Embodiment 2 of this invention is demonstrated. Since the second embodiment has the configuration shown in FIG. 1 as in the first embodiment, a detailed description thereof will be omitted. Next, a characteristic operation of the second embodiment which is different from that of the first embodiment will be described.

  Since the hydrodesulfurizer 7 receives heat from the fluid flowing through the reformed gas flow path 6, the temperature of the hydrodesulfurizer 7 is determined by the temperature or the amount of heat. Therefore, in the second embodiment, as a means for raising and lowering the temperature of the reformed gas in order to keep the temperature of the hydrodesulfurizer 7 in an appropriate range, the air that controls the air supply 5 to indicate the ratio of air to combustion gas. Take the method of changing the ratio. Specifically, [1] The reformed gas temperature is lowered by controlling the air supply device 5 to lower the set value of the air ratio, and the temperature of the hydrodesulfurizer 7 is lowered, and vice versa. A method is adopted in which the reformed gas temperature is raised by increasing the set value of the air ratio by controlling the air feeder 5 and the temperature of the hydrodesulfurizer 7 is raised.

  That is, it is assumed that the heat input and output of the hydrogen generator is balanced, and when the air ratio is changed, for example, when the set value of the air ratio is increased, the amount of heat that the combustion gas has increases, so the reformed gas temperature is reduced. Can be raised. On the other hand, as in the first embodiment, the hydrodesulfurizer 7 is disposed at a location that receives heat from the reformed gas channel 6 at least by heat transfer, and the reformed gas channel 6 and the hydrodesulfurizer 7 If the thermal conductivity of the medium in the meantime does not change, for example, when the temperature of the reformed gas rises, the temperature of the hydrodesulfurizer 7 can be raised. This is because when the set value of the air ratio is lowered, the opposite effect is obtained in the same manner, and the temperature of the hydrodesulfurizer 7 can be lowered.

  FIG. 3 shows the relationship between the air ratio and the representative temperature of the hydrodesulfurizer 7 detected by the desulfurization temperature detector 8 in the second embodiment. This shows that the temperature of the hydrodesulfurizer 7 can be increased by increasing the air ratio, and the temperature of the hydrodesulfurizer 7 can be kept within an appropriate range by changing the air ratio. Recognize.

  Specifically, the controller 9 sets the air ratio when the temperature detected by the desulfurization temperature detector 8 is higher than a preset first temperature (260 ° C. in the second embodiment). The temperature of the reformed gas discharged from the reformer 1 is lowered by lowering the value and reducing the amount of air supplied to the combustor 4. Further, when the temperature detected by the desulfurization temperature detector 8 becomes lower than a preset second temperature (240 ° C. in the second embodiment), the set value of the air ratio is increased and supplied to the combustor 4. The amount of air to be increased was controlled to increase the temperature of the reformed gas discharged from the reformer 1. By this operation, the hydrodesulfurization catalyst housed in the hydrodesulfurizer 7 can be used in an appropriate temperature range.

(Embodiment 3)
Next, the hydrogen generator in Embodiment 3 of this invention is demonstrated. Since the third embodiment has the configuration shown in FIG. 1 as in the first and second embodiments, a detailed description thereof will be omitted. Next, characteristic operations in the third embodiment which are different from those in the first and second embodiments will be described.

  The temperature of the hydrodesulfurizer 7 is determined at least by the heat capacity of the gas flowing in the hydrodesulfurizer and the temperature of the reformed gas discharged from the reformer. Therefore, in the present third embodiment, the raw material supplied to the reformer 1 by controlling the raw material supplier 2 as means for raising and lowering the temperature of the reformed gas in order to keep the temperature of the hydrodesulfurizer 7 in an appropriate range. Take a method to change the flow rate. Specifically, [1] The temperature of the hydrodesulfurizer 7 is decreased by controlling the raw material supplier 2 to increase the flow rate of the raw material, and conversely, [2] controlling the raw material supplier 2. And the method of raising the temperature of the hydrodesulfurizer 7 is taken by reducing the flow rate of the raw material.

  That is, when the raw material flow rate is changed, for example, when the set value of the raw material flow rate is increased, the heat capacity of the raw material flow rate is increased and more heat is taken out from the hydrodesulfurizer 7, but on the other hand, the amount of heat received by the hydrodesulfurizer 7 is increased. Since the change is small relative to the change in the raw material flow rate, the temperature of the hydrodesulfurizer 7 can be lowered. This is because when the set value of the raw material flow rate is lowered, the opposite effect is obtained and the temperature of the hydrodesulfurizer 7 can be raised.

  FIG. 4 shows the relationship between the raw material flow rate and the representative temperature of the hydrodesulfurizer 7 detected by the desulfurization temperature detector 8 in the third embodiment. It shows that the temperature of the hydrodesulfurizer 7 can be increased by lowering the raw material flow rate, and it is possible to keep the temperature of the hydrodesulfurizer 7 within an appropriate range by changing the raw material flow rate. Recognize.

  Specifically, when the temperature detected by the desulfurization temperature detector 8 is higher than a preset first temperature (260 ° C. in the present embodiment), the controller 9 causes the raw material supplier 2 to When the flow rate of the raw material supplied to the hydrodesulfurizer 7 is increased and the temperature detected by the desulfurization temperature detector 8 becomes lower than a preset second temperature (240 ° C. in the present embodiment), The flow rate of the raw material supplied to the hydrodesulfurizer 7 by the raw material supplier 2 was controlled to decrease. By this operation, the hydrodesulfurization catalyst housed in the hydrodesulfurizer 7 can be used in an appropriate temperature range.

(Embodiment 4)
Next, a hydrogen generation apparatus according to Embodiment 4 of the present invention will be described. FIG. 5 is a schematic diagram showing the configuration of the hydrogen generator in Embodiment 4 of the present invention. In addition to the configurations of the first to third embodiments, the storage unit 10 that stores the flow rate of the raw material supplied to the hydrodesulfurizer 7 is used. The rest of the configuration is the same as that of the hydrogen generator in Embodiment 1, and other detailed description is omitted. As in the first embodiment, a heat insulating material may be disposed between the reformed gas flow path 6 and the hydrodesulfurizer 7.

  Next, a characteristic operation in the fourth embodiment, which is different from the third embodiment, will be described.

  During operation of the hydrogen generator, the storage unit 10 performs hydrodesulfurization when the temperature detected by the desulfurization temperature detector 8 is equal to or higher than a preset first temperature (260 ° C. in the present embodiment). The first flow rate that is the flow rate of the raw material supplied to the vessel 7 and the temperature detected by the desulfurization temperature detector 8 are equal to or lower than a preset second temperature (240 ° C. in the present embodiment). In this case, at least one of the second flow rates that are the flow rates of the raw materials supplied to the hydrodesulfurizer 7 is stored. When the storage unit 10 stores the first flow rate, the controller 9 controls the flow rate of the raw material supplied to the hydrodesulfurizer 7 to be equal to or higher than the first flow rate, and the storage unit 10 stores the second flow rate. Is stored, the raw material supply device 2 can be controlled so that the flow rate of the raw material supplied to the hydrodesulfurizer 7 is equal to or lower than the second flow rate.

  By limiting the flow rate range of the raw material by the storage unit 10 in this way, even if there is a temperature difference due to individual differences due to, for example, manufacturing variations or a temperature change with time of the hydrodesulfurizer, It is possible to stably maintain the temperature of the addition desulfurizer 7 in an appropriate range for a long time.

(Embodiment 5)
Next, a hydrogen generation apparatus according to Embodiment 5 of the present invention will be described. FIG. 6 is a schematic diagram showing the configuration of the hydrogen generator in Embodiment 5 of the present invention. The same or corresponding parts as those in the embodiment shown in FIG. 1 or FIG.

  In the fifth embodiment, the reformer 1 is arranged on the outer periphery of the combustor 4, and the reformed gas flow path 6 is arranged on the outer side of the reformer 1 so as to face the gas flow direction of the reformer 1. In addition, a configuration of a multi-cylindrical hydrogen generator in which the hydrodesulfurizer 7 is disposed concentrically on the outer side. A heat insulating material may be disposed between the reformed gas channel 6 and the hydrodesulfurizer 7. Other configurations are omitted.

  Next, the operation in the fifth embodiment of the present invention will be described. The operation of the fifth embodiment can be the same as that of the first to third embodiments, and the temperature of the hydrodesulfurizer is changed by changing at least one of S / C, air ratio, and raw material flow rate. Can be optimized.

  That is, when the temperature detected by the desulfurization temperature detector 8 becomes higher than a preset first temperature (260 ° C. in the present embodiment), the controller 9 at least [1] the water supplier 3. To increase the set value of S / C by controlling [2] to control the air supply unit 5 to decrease the set value of the air ratio, [3] to control the raw material supply unit 2 to increase the flow rate of the raw material, By taking one of the above, the temperature of the hydrodesulfurizer 7 can be lowered.

  Similarly, the controller 9 at least [1] supplies water when the temperature detected by the desulfurization temperature detector 8 becomes lower than a preset second temperature (260 ° C. in the present embodiment). Control device 3 to lower S / C setting value, [2] Control air supply device 5 to increase air ratio setting value, [3] Control raw material supply device 2 to lower raw material flow rate By taking one of the above, the temperature of the hydrodesulfurizer 7 can be raised. Further, similarly to the fourth embodiment, a configuration including the storage unit 10 may be employed.

  Thus, by using a multi-cylindrical hydrogen generator, the size of the apparatus can be made compact, and the effect of increasing the efficiency of hydrogen generation can be obtained because heat is exchanged efficiently.

As described above, when the temperature of hydrodesulfurization deviates from the set range, it is possible to keep the temperature of the hydrodesulfurizer within an appropriate range. Since it can be operated and the adsorption capacity can be maintained high, the catalyst capacity can be reduced and the durability of the catalyst can be ensured.

  The present invention provides a hydrogen generator equipped with a hydrodesulfurizer capable of operating at a high temperature having a high adsorption capacity within the heat resistant temperature range of the hydrodesulfurization catalyst by providing a temperature control mechanism for the hydrodesulfurizer. It is particularly useful for a fuel cell power generation system of a dispersed solid polymer type or solid oxide type that reforms a raw material containing a sulfur content to generate hydrogen.

DESCRIPTION OF SYMBOLS 1 Reformer 2 Raw material supply device 3 Water supply device 4 Combustion device 5 Air supply device 6 Reformation gas flow path 7 Hydrodesulfurization device 8 Desulfurization temperature detector 9 Controller 10 Memory | storage part 11 Reforming outlet temperature detector

Claims (13)

A reformer for generating a reformed gas by reforming a raw material containing hydrocarbon and water;
A raw material supplier for supplying raw material to the reformer;
A water supply for supplying water to the reformer;
A combustor that burns a combustion gas that is a raw material or a reformed gas and air, and heats the reformer;
An air supply for supplying air to the combustor;
A reformed gas flow path for discharging the reformed gas reformed by the reformer;
A hydrodesulfurizer that is arranged to be heated by the heat of the reformed gas flowing through the reformed gas flow path and removes sulfur in the raw material by hydrogenation;
A desulfurization temperature detector for detecting the temperature of the hydrodesulfurizer;
A controller, and
The said controller is a hydrogen generator which controls so that the temperature of the reformed gas discharged | emitted from the said reformer may be changed with the temperature detected by the said desulfurization temperature detector.   The controller includes at least one of a ratio of water to a raw material supplied to the reformer, a ratio of air to a combustion gas supplied to the combustor, and a flow rate of the raw material supplied to the hydrodesulfurizer. The hydrogen generator according to claim 1, wherein one is changed to control the temperature of the reformed gas discharged from the reformer to be changed.   The controller reduces the temperature of the reformed gas discharged from the reformer when the temperature detected by the desulfurization temperature detector is higher than a preset first temperature, When the temperature detected by the desulfurization temperature detector becomes lower than the preset second temperature at a temperature lower than the first temperature, the temperature of the reformed gas discharged from the reformer is set. The hydrogen generator according to claim 2, which is controlled to be raised.   When the temperature detected by the desulfurization temperature detector is higher than the first temperature, the controller increases the ratio of water to the raw material supplied to the reformer by controlling the water supplier. And when the temperature detected by the desulfurization temperature detector becomes lower than the second temperature, the water supply device is controlled so as to reduce the ratio of water to the raw material supplied to the reformer. The hydrogen generator according to claim 3.   When the temperature detected by the desulfurization temperature detector is higher than the first temperature, the controller controls the air supply device to set the ratio of air to combustion gas supplied to the combustor. When the temperature detected by the desulfurization temperature detector is lower than the second temperature, the ratio of air to the combustion gas supplied to the combustor is controlled by controlling the air supply device. The hydrogen generator according to claim 3, which is controlled as follows.   The controller increases the flow rate of the raw material supplied to the hydrodesulfurizer by controlling the raw material supplier when the temperature detected by the desulfurization temperature detector is higher than the first temperature. The hydrogen generation according to claim 3, wherein when the temperature detected by the desulfurization temperature detector becomes lower than the second temperature, control is performed to reduce the flow rate of the raw material supplied to the hydrodesulfurizer. apparatus. A storage unit for storing the flow rate of the raw material supplied to the hydrodesulfurizer;
The storage unit has a first flow rate that is a flow rate of a raw material supplied to the hydrodesulfurizer when the temperature detected by the desulfurization temperature detector is equal to or higher than the first temperature, and Storing at least one of a second flow rate that is a flow rate of the raw material supplied to the hydrodesulfurizer when the temperature detected by the desulfurization temperature detector is equal to or lower than the second temperature;
When the storage unit stores the first flow rate, the controller controls the flow rate of the raw material supplied to the hydrodesulfurizer to be equal to or higher than the first flow rate, and the storage unit The said raw material feeder is controlled so that the flow volume of the raw material supplied to the said hydrodesulfurizer may become the said 2nd flow volume or less when the said 2nd flow volume is memorize | stored. A hydrogen generator according to claim 1. A reformer for generating a reformed gas by reforming a raw material containing hydrocarbon and water;
A combustor that burns a combustion gas that is a raw material or a reformed gas and air, and heats the reformer;
A reformed gas passage for discharging the reformed gas generated by the reformer;
A hydrodesulfurizer that is arranged to be heated by the heat of the reformed gas flowing through the reformed gas flow path and removes sulfur in the raw material by hydrogenation;
A method of operating a hydrogen generator comprising:
The operation method of a hydrogen generator, wherein the controller includes a temperature adjustment step of controlling the temperature of the reformed gas discharged from the reformer to change according to the temperature detected by the desulfurization temperature detector.   In the temperature adjusting step, when the temperature of the hydrodesulfurizer becomes higher than a preset first temperature, the temperature of the reformed gas discharged from the reformer is decreased, and the hydrodesulfurization is performed. The operation of the hydrogen generator according to claim 8, which is a step of increasing the temperature of the reformed gas discharged from the reformer when the temperature of the reformer becomes lower than a preset second temperature. Method.   In the temperature adjustment step, when the temperature of the hydrodesulfurizer becomes higher than the first temperature, the ratio of water to the raw material supplied to the reformer by controlling the water supplier is increased, When the temperature detected by the desulfurization temperature detector is lower than the second temperature, it is a step of controlling the water supply device to reduce the ratio of water to the raw material supplied to the reformer. The operation method of the hydrogen generator according to claim 9.   The temperature adjustment step increases the ratio of air to combustion gas supplied to the combustor by controlling the air supply when the temperature of the hydrodesulfurizer becomes higher than the first temperature. When the temperature of the hydrodesulfurizer becomes lower than the second temperature, the step of controlling the air supply device to reduce the ratio of air to the combustion gas supplied to the combustor. Item 10. The operation method of the hydrogen generator according to Item 9.   The temperature adjusting step increases the flow rate of the raw material supplied to the hydrodesulfurizer by controlling the raw material supplier when the temperature of the hydrodesulfurizer becomes higher than the first temperature, The hydrogen generator according to claim 9, further comprising a step of reducing a flow rate of a raw material supplied to the hydrodesulfurizer when a temperature detected by the hydrodesulfurizer becomes lower than the second temperature. how to drive. Storing a first flow rate that is a flow rate of the raw material supplied to the hydrodesulfurizer when the temperature of the hydrodesulfurizer becomes equal to or higher than the first temperature; and the hydrodesulfurizer At least one of the steps of storing a second flow rate, which is a flow rate of the raw material supplied to the hydrodesulfurizer when the temperature of is lower than the second temperature;
When the first flow rate is stored, the flow rate of the raw material supplied to the hydrodesulfurizer is not less than the first flow rate, and when the second flow rate is stored, the water A flow rate limiting step of limiting a flow rate of the raw material so that a flow rate of the raw material supplied to the desulfurizer is equal to or less than the second flow rate, The method for operating the hydrogen generator according to any one of claims 9 to 12 .

Images