JP2016169124A - Hydrogen generator, fuel cell system using the same and operation method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To lengthen a lifetime of a hydrogen generator by setting the lower limit of temperature of a modification catalyst inlet at high when supply speed of a raw material is high.SOLUTION: It has a modifier 100 to which a modification catalyst 101 generating hydrogen-containing gas by modifying a raw material containing at least a sulfide compound and hydrocarbon is filled, a raw material supplier 31 for supplying a raw material to the modifier 100, a heater 20 for heating the modifier 100 and a controller 300 for controlling temperature of a modification catalyst inlet 102 and lifetime of a hydrogen generator can be lengthened by controlling the heater 20 so that lower limit temperature of the modification catalyst inlet 102 when a supply speed of the raw material is relatively high is higher than lower temperature when the supply speed of the raw material is relatively low and the temperature of the modification catalyst inlet 102 becomes the lower limit or higher by a controller 300 and suppressing reduction of hydrogen generation performance of the modification catalyst.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen generator that generates a hydrogen-containing gas, a fuel cell system using the same, and an operation method thereof.

  Development of a fuel cell cogeneration system (hereinafter simply referred to as “fuel cell system”) capable of high-efficiency power generation even with a small device is being developed as a power generator for a distributed energy supply source.

  This fuel cell system includes a fuel cell as a main body of the power generation unit. As this fuel cell, for example, a phosphoric acid fuel cell, a molten carbonate fuel cell, an alkaline aqueous fuel cell, a solid polymer fuel cell, a solid electrolyte fuel cell, or the like is used.

  Among these fuel cells, phosphoric acid fuel cells and polymer electrolyte fuel cells (abbreviated as “PEFC”) have a relatively low operating temperature during power generation operation, and are therefore used as fuel cells constituting a fuel cell system. Preferably used. In particular, solid polymer fuel cells are particularly suitable for applications such as portable electronic devices and electric vehicles because there is less deterioration of the electrode catalyst compared to phosphoric acid fuel cells and no electrolyte dissipation occurs. It is done.

  Many fuel cells, such as phosphoric acid fuel cells and polymer electrolyte fuel cells, use hydrogen as a fuel during power generation operation. However, the means for supplying hydrogen necessary for power generation operation in these fuel cells is not usually provided as an infrastructure.

  Therefore, in order to obtain electric power from a fuel cell system including a phosphoric acid fuel cell or a polymer electrolyte fuel cell, it is necessary to generate hydrogen as a fuel at the place where the fuel cell system is installed. For this reason, the fuel cell system usually includes a hydrogen generator having a reformer.

  In the reformer, a hydrogen-containing gas is generated by a reforming reaction from city gas, natural gas, or LPG which is a general raw material infrastructure gas. For example, a steam reforming reaction is generally used. In this steam reforming reaction, hydrogen is produced by reacting raw material city gas or the like with steam at a high temperature of about 300 ° C. to 700 ° C. using a noble metal-based reforming catalyst such as Ni-based or Ru-based. A hydrogen-containing gas as a main component is generated.

In order to perform the steam reforming reaction stably and efficiently, it is necessary to supply an amount of water suitable for the composition of the feedstock. For example, in a reforming reaction in which methane (CH ₄ ) or ethane (C ₂ H ₆ ) is steam reformed to generate hydrogen and carbon dioxide, theoretically, the water required for 1 mol of methane. Is 2 moles.

  Further, the amount of water required for 1 mol of ethane is 4 mol. Usually, if the amount of water supplied to the reformer is insufficient, problems such as precipitation of carbon in the feedstock will occur, so the theoretical water volume calculated from the feed flow rate of the feedstock will prevent such problems. The water supply flow rate is set so that about 1.5 times as much water is supplied to the reformer. The operation of the hydrogen generator is controlled so that the water supply flow rate becomes a desired value in accordance with the raw material supply flow rate.

In general, when the steam reforming reaction is performed at a high temperature from the inlet of the reforming catalyst layer, carbon species in the raw material are deposited on the reforming catalyst, causing a decrease in performance. In order to suppress this, the temperature distribution is set so that the inlet temperature is lower than the outlet of the reforming catalyst layer. Further, since the steam reforming reaction is an equilibrium reaction in which the amount of hydrogen generation increases as the reaction temperature increases, the amount of hydrogen generation is determined by the temperature in the high temperature region at the outlet of the reforming catalyst layer and the catalyst performance.

  In addition, since the reforming catalyst deteriorates due to poisoning of the sulfur compound contained in the raw material, it is common to remove the sulfur compound by installing a desulfurizer in front of the reformer. However, a small amount of a sulfur compound remains in the raw material that passes through the desulfurizer and is supplied to the reformer, and the reforming catalyst deteriorates due to the sulfur compound.

  Platinum that does not convert nitrogen placed in the high temperature area on the outlet side to ammonia by disposing a ruthenium-based catalyst highly resistant to sulfur compounds in the low temperature area on the inlet side of the reforming catalyst layer and decomposing heavy hydrocarbons -An operation method is provided that suppresses deterioration of hydrogen generation ability due to carbon deposition of a rhodium-based catalyst (see, for example, Patent Document 1).

JP2013-137865A

  However, in the conventional configuration, there is no mention of suppression of deterioration of the reforming catalyst by a sulfur compound.

  Further, the conventional hydrogen generator has the following problems. Since the temperature of the outlet of the reforming catalyst layer of the hydrogen generator is usually set higher than that of the inlet, the hydrogen generating ability is determined by the temperature in the high temperature region of the outlet and the catalyst performance. Therefore, the adsorption of the sulfur compound at the outlet of the reforming catalyst layer greatly affects the performance reduction of the hydrogen generator.

  Further, the hydrogen generator changes the feed rate of the raw material according to the amount of hydrogen-containing gas required. As the feed rate of the raw material to the reforming catalyst packed bed increases, the linear velocity increases. However, the amount of sulfur compound that can be adsorbed per hour in the reforming catalyst is constant, so the sulfur compound removal rate decreases. When the sulfur compound is adsorbed on the latter stage of the reforming catalyst layer in the high temperature region, the hydrogen generating ability is lowered.

  The present invention solves the above-described conventional problems. When the raw material supply rate is higher than that when the raw material supply rate is low, the lower limit temperature of the reforming catalyst layer inlet is increased to maintain the durability of the product. An object of the present invention is to provide a generation device, a fuel cell system, and an operation method thereof.

  In order to solve the above-described conventional problems, a hydrogen generator according to the present invention includes a reformer filled with a reforming catalyst that reforms a raw material containing at least a sulfur compound and a hydrocarbon to generate a hydrogen-containing gas. A raw material supplier for supplying the raw material to the reformer, a heater for heating the reformer, and a controller for controlling the temperature of the reforming catalyst inlet, wherein the lower limit temperature of the reforming catalyst inlet is the raw material The lower limit temperature when the feed rate of the feed is relatively high is higher than the lower limit temperature when the feed rate of the raw material is relatively slow, and the controller sets the heater so that the temperature of the reforming catalyst inlet is equal to or higher than the lower limit temperature. It is something to control.

  As a result, the reforming catalyst layer inlet can be maintained at a temperature not less than a lower limit temperature appropriately set corresponding to the feed rate of the raw material, and even when the feed rate of the raw material is different, the reforming catalyst is sufficiently adsorbed. Since the speed can be maintained, the necessary amount of sulfur compound adsorbed per unit weight of the reforming catalyst can be secured.

  According to the hydrogen generator of the present invention, the temperature at the inlet of the reforming catalyst layer is maintained above the lower limit temperature appropriately set corresponding to the feed rate of the raw material, so that the sulfur compound is sufficiently adsorbed on the reforming catalyst. The speed can be maintained, and a necessary amount of sulfur compound can be secured on the reforming catalyst layer inlet side, so that slip of the sulfur compound toward the reforming catalyst layer outlet side can be suppressed.

  And by suppressing the adsorption of sulfur compounds at the outlet of the reforming catalyst layer, which greatly affects the amount of hydrogen generation, it is possible to suppress a decrease in the hydrogen generation capacity of the reforming catalyst and to suppress a decrease in the performance of the hydrogen generator. Can do. As a result, the lifetime of the hydrogen generator can be extended.

1 is a block diagram showing an example of the configuration of a hydrogen generator according to Embodiment 1 of the present invention. The block diagram which shows an example of a structure of the reformer concerning the embodiment The graph which shows an example of the relationship between the supply speed | rate of the raw material of the hydrogen generator concerning Example 1 of the embodiment, and the minimum temperature of the reforming catalyst inlet The graph which shows an example of the relationship between the supply speed | rate of the raw material of the hydrogen generator concerning Example 1 of the embodiment, and the minimum temperature of the reforming catalyst inlet The graph which shows an example of the relationship between the minimum temperature of the reforming catalyst inlet of the hydrogen generator concerning Example 3 of the same embodiment, and the feed rate of a raw material The graph which shows an example of the relationship between the feed rate of the raw material of the hydrogen generator concerning Example 4 of Embodiment 2 of this invention, and the upper limit temperature of a reforming catalyst exit The graph which shows an example of the relationship between the supply speed | rate of the raw material of the hydrogen generator concerning Example 5 of the embodiment, and the upper limit temperature of the reforming catalyst outlet The graph which shows an example of the relationship between the feed rate of the raw material of the hydrogen generator concerning Example 6 of the embodiment, and the upper limit temperature of the reforming catalyst outlet Block diagram showing an example of the configuration of a reformer and a heater according to a third embodiment of the present invention FIG. 6 is a block diagram showing an example of the configuration of a hydrogen generator according to Embodiment 4 of the present invention. FIG. 5 is a block diagram showing an example of the configuration of a fuel cell system according to a fifth embodiment of the present invention. FIG. 7 is a block diagram showing an example of the configuration of a fuel cell system according to Embodiment 6 of the present invention.

  A hydrogen generator according to a first aspect of the present invention includes a reformer that is filled with a reforming catalyst that reforms a raw material containing at least a sulfur compound and a hydrocarbon to generate a hydrogen-containing gas, and the raw material in the reformer And a controller for controlling the temperature of the reforming catalyst inlet of the reformer, the lower limit temperature of the reforming catalyst inlet is The lower limit temperature when the feed rate of the raw material is relatively high is higher than the lower limit temperature when the feed rate of the raw material is relatively slow, and the controller has a temperature of the reforming catalyst inlet equal to or higher than the lower limit temperature. It is characterized by controlling the said heater so that it may become.

  According to the hydrogen generator of the present invention, the temperature at the inlet of the reforming catalyst layer is maintained above the lower limit temperature appropriately set corresponding to the feed rate of the raw material, so that the sulfur compound is sufficiently adsorbed on the reforming catalyst. The speed can be maintained, and a necessary amount of sulfur compound can be secured on the reforming catalyst layer inlet side, so that slip of the sulfur compound toward the reforming catalyst layer outlet side can be suppressed.

And by suppressing the adsorption of sulfur compounds at the outlet of the reforming catalyst layer, which greatly affects the amount of hydrogen generation, it is possible to suppress a decrease in the hydrogen generation capacity of the reforming catalyst and to suppress a decrease in the performance of the hydrogen generator. Can do. As a result, the lifetime of the hydrogen generator can be extended.

  In the hydrogen generator according to the second invention, in particular, in the first invention, the temperature when the feed rate of the raw material is relatively high at the temperature of the reforming catalyst outlet of the reformer is the temperature of the raw material. The controller controls the heater so that the temperature is equal to or lower than a temperature when the supply speed is relatively slow.

  According to the hydrogen generator of the present invention, the upper limit temperature of the reforming catalyst outlet when the feed rate of the raw material is high is set to be equal to or lower than the upper limit temperature of the reforming catalyst outlet when the feed rate of the raw material is slow. It is possible to suppress the performance degradation of the generation device.

  This is because the performance degradation due to the sintering of the catalyst is promoted as the reaction temperature is higher, and as the feed rate is increased, the reaction amount is increased by the reforming catalyst. This is because the performance degradation can be suppressed by setting. As a result, the lifetime of the hydrogen generator can be extended.

  In the hydrogen generator according to the third aspect of the invention, in particular, the heater in the first or second aspect of the invention includes a combustor that burns at least the raw material, and the controller has a relatively high supply rate of the raw material. When the speed is high, λ, which is the stoichiometric ratio of the air supply amount to the combustor and the fuel supply amount, is controlled to be larger than when the raw material supply speed is relatively slow.

  According to the hydrogen generator of the present invention, a combustor is used as a heating unit of the reformer, and the temperature of the reforming catalyst layer inlet is supplied to the raw material by controlling λ without providing a new configuration. It can be maintained above the lower limit temperature appropriately set according to the speed.

  As a result, a sufficient speed for adsorbing the sulfur compound to the reforming catalyst can be maintained, and a necessary amount of sulfur compound can be secured on the reforming catalyst layer inlet side. The slip of the compound can be suppressed, and the performance degradation of the hydrogen generator can be suppressed. Therefore, the lifetime of the hydrogen generator can be extended.

  A hydrogen generator according to a fourth aspect of the present invention is the hydrogen generation apparatus according to any one of the first to third aspects of the invention, comprising a water supply unit for supplying water to the reformer, wherein the controller is configured to supply the raw material. Is relatively fast, the S / C, which is the steam / carbon molar ratio between the raw material and the reforming water, is smaller than when the raw material supply rate is relatively slow. It is characterized by controlling the vessel.

  According to the hydrogen generating apparatus of the present invention, the temperature at the reforming catalyst layer inlet corresponds to the feed rate of the raw material without providing a new configuration by controlling S / C as the temperature control means of the reformer. Thus, the temperature can be maintained at a temperature that is appropriately set or lower.

  As a result, a sufficient speed for adsorbing the sulfur compound to the reforming catalyst can be maintained, and a necessary amount of sulfur compound can be secured on the reforming catalyst layer inlet side. The slip of the compound can be suppressed, and the performance degradation of the hydrogen generator can be suppressed. Therefore, the lifetime of the hydrogen generator can be extended.

  A fuel cell system according to a fifth aspect of the invention includes, in particular, a hydrogen generator of at least one of the first to fourth aspects of the invention, and a fuel cell that generates power using a hydrogen-containing gas supplied from the hydrogen generator. It is characterized by that.

  According to the fuel cell system of the present invention, the temperature of the reforming catalyst layer inlet is maintained at the lower limit temperature appropriately set corresponding to the feed rate of the raw material, so that the sulfur compound can be sufficiently adsorbed on the reforming catalyst. The speed can be maintained, and the necessary amount of sulfur compound adsorption can be secured on the reforming catalyst layer inlet side, so that the slip of sulfur compound to the reforming catalyst layer outlet side can be suppressed, and the hydrogen generator Since performance degradation can be suppressed, the life of the fuel cell system can be extended.

  According to a sixth aspect of the present invention, there is provided an operation method of a hydrogen generator, a reformer filled with a reforming catalyst for reforming a raw material containing at least a sulfur compound and a hydrocarbon to generate a hydrogen-containing gas, and the reformer And a controller for controlling the temperature of the reforming catalyst inlet, comprising: a raw material supplier for supplying the raw material to the raw material; a heater for heating the reformer; The lower limit temperature of the reforming catalyst inlet is such that the lower limit temperature when the feed rate of the raw material is relatively high is higher than the lower limit temperature when the feed rate of the raw material is relatively slow, and the temperature of the reforming catalyst inlet is A step of heating so as to be equal to or higher than the lower limit temperature is provided.

  According to the operation method of the hydrogen generator of the present invention, the sulfur compound is adsorbed to the reforming catalyst by maintaining the temperature of the reforming catalyst layer inlet at or above the lower limit temperature appropriately set corresponding to the feed rate of the raw material. A sufficient amount of the sulfur compound can be maintained, and the amount of sulfur compound adsorbed on the reforming catalyst layer inlet side can be secured, so that slip of the sulfur compound toward the reforming catalyst layer outlet side can be suppressed.

  In the hydrogen generator, the temperature distribution is set so that the outlet temperature is higher than the inlet of the reforming catalyst layer, and the amount of hydrogen generated is determined by the temperature and catalyst performance in the high temperature region at the outlet of the reforming catalyst layer. By suppressing the adsorption of the sulfur compound at the outlet of the catalyst layer, it is possible to suppress a decrease in the performance of the hydrogen generator. As a result, the lifetime of the hydrogen generator can be extended.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following description, the same or corresponding elements are denoted by the same reference symbols throughout the drawings, and the description thereof is omitted.

(Embodiment 1)
FIG. 1 is a block diagram showing an example of the configuration of the hydrogen generator 400 according to the first embodiment of the present invention, and FIG. 2 shows an example of the configuration of the reformer 100 according to the first embodiment of the present invention. It is a block diagram.

  As shown in FIG. 1, a hydrogen generator 400 according to the present embodiment includes a reformer 100 that is one of reactors that generate a hydrogen-containing gas, and a reformer temperature that detects the temperature of the reformer 100. The detector 80, the raw material supply device 31 for supplying the raw material to the reformer 100, the raw material supply amount detector 30 for detecting the supply amount of the raw material, the desulfurizer 10 for removing sulfur compounds contained in the raw material, A water supply 51 that supplies water to the mass device 100, a water supply amount detector 50 that detects the supply amount of water, a heater 20 that heats the reformer 100, and air that supplies air to the heater 20 A supply device 71, an air supply amount detector 70 for detecting the supply amount of air, a CO reduction device 150 that is one of the reactors for reducing CO in the hydrogen-containing gas produced by the reformer 100, a CO CO reducer temperature detector 90 for detecting the temperature of reducer 150, hydrogen And a controller 300 for controlling the deposition apparatus 400, the hydrogen-containing gas generated in the reformer 100 is supplied to the hydrogen utilizing device 201 via a hydrogen supply line 41.

  As shown in FIG. 2, the reformer 100 generates a hydrogen-containing gas by a steam reforming reaction using raw materials and steam. The reformer 100 is made of a stainless steel structure and is filled with a reforming catalyst 101 that causes a steam reforming reaction to proceed.

Of the reforming catalyst 101, the reforming catalyst 1 filled on the inlet side of the raw material with respect to the flow direction of the raw material.
01 was the reforming catalyst inlet 102, and the reforming catalyst 101 filled on the outlet side of the hydrogen-containing gas was used as the reforming catalyst outlet 103. The reforming catalyst 101 was set to increase in temperature from the inlet to the outlet, and the reforming catalyst inlet 102 was controlled at 350 to 400 ° C. and the reforming catalyst outlet 103 was controlled at 660 ° C.

  In the present embodiment, the reforming catalyst 101 is used in which Ru is supported using alumina beads as a carrier. As a raw material, city gas (13A) supplied from a gas company to each household through piping was used. In order to detect leakage, city gas contains at least one odorant mainly composed of a sulfur compound and is odorized.

  The sulfur compounds included in these odorants will poison and reform the reforming catalyst 101. Therefore, the raw material from which the sulfur compound was removed by the desulfurizer 10 was supplied to the reformer 100 in advance. As the desulfurizer 10, an adsorptive desulfurizer in which a desulfurization vessel having a stainless steel structure was filled with zeolite ion-exchanged with silver, which is an adsorption desulfurization agent for normal temperature, was used at normal temperature.

  The reformer temperature detector 80 is configured by a thermocouple and detects the temperature of the reformer 100. The reformer temperature detector 80 was installed in a sheath tube provided inside the reformer 100, and directly measured the catalyst temperature.

  The raw material supplier 31 supplies the raw material to the reformer 100. For the raw material supplier 31, a combination of a booster and a flow rate adjustment valve was used.

  The water supply unit 51 is configured by a combination of a pump and a flow rate adjustment valve, and supplies water to the reformer 100. The water supply amount was adjusted by the water supply amount detector 50.

  The heater 20 is composed of a fuel device and heats the reformer 100. As the fuel for the heater 20, a raw material discharged without performing the reforming reaction in the reformer 100 or a part or all of the hydrogen-containing gas discharged from the reformer 100 was used.

  The air supply unit 71 is configured by a fan and supplies combustion air to the heater 20.

  The CO reducer 150 reduces CO in the hydrogen-containing gas output from the reformer 100 using at least one of a shift reaction, a selective oxidation reaction, and a methanation reaction. The CO reduction reaction in the CO reducer 150 requires reaction heat of 100 ° C. to 300 ° C. In this embodiment, the CO reduction reaction is performed adjacent to the relatively high temperature reformer 100 and heated by heat transfer. The method used was used.

  The CO reducer temperature detector 90 is constituted by a thermocouple and detects the temperature of the CO reducer 150. The catalyst temperature detector 90 and the CO reducer 150 were installed in a sheath tube provided inside, and the catalyst temperature was directly measured.

  The controller 300 controls the hydrogen generator 400 and includes a calculation unit 301 and a storage unit 302 that stores a control program. An MPU is used as the calculation unit 301, and a memory is used as the storage unit 302. The storage unit 302 stores a program for controlling various operations of the hydrogen generator 400, and the calculation unit 301 reads out a necessary program from the storage unit 302 and executes it to generate hydrogen. Various operations of the apparatus 400 are controlled.

A raw material supply amount detector 30 for detecting the supply amount of the raw material is provided in the middle of the raw material supply path from the raw material supply device 31 to the reformer 100, and its detection output is input to the calculation unit 301. A water supply amount detector 50 that detects the amount of water supply is provided in the middle of the water supply path from the water supply device 51 to the reformer 100, and the detection output is input to the calculation unit 301. Yes. The raw material supply amount detector 30 and the water supply amount detector 50 are composed of flow meters.

  An air supply amount detector 70 for detecting the air supply amount is provided in the middle of the air supply path from the air supply device 71 to the heater 20, and the detection output is input to the calculation unit 301. The air supply amount detector 70 is composed of a flow meter, and the air supply amount detector 70 adjusts the air supply amount.

  Hereinafter, operation | movement and an effect | action of the hydrogen generator 400 of Embodiment 1 are demonstrated. The following operations and actions are performed by the controller 300 controlling the hydrogen generator 400.

  When the hydrogen-using device requires a 4NLM amount of hydrogen, the hydrogen generator 400 supplies the necessary amount of hydrogen with a raw material supply rate of 1NLM.

  When the hydrogen utilization device requires a hydrogen amount of 12 NLM, the supply rate of the raw material is set to 3 NLM, and the necessary hydrogen amount is supplied. The raw material contains a sulfur compound of several tens of ppb or less even after passing through the desulfurizer 10, and when it is supplied to the reforming catalyst 101, poisoning due to sulfur occurs, causing a reduction in the amount of hydrogen produced. .

  In the hydrogen generator 400 of the present embodiment, the reformer is filled with 500 cc of the reforming catalyst 101, the lower limit temperature of the reforming catalyst inlet 102 when the feed rate of the feed is 1 NLM, and the feed of the feed is performed. The lower limit temperature of the reforming catalyst inlet 102 when the speed was 3NLM was controlled to be 400 ° C.

  The raw material that passed through the desulfurizer 10 contained 10 ppb of sulfur compound. Further, since it is assumed that the product life of the hydrogen generator 400 is 60,000 hours and the average raw material supply rate is 2NLM, a total of 100 mg of sulfur compounds are supplied to the reforming catalyst 101 as sulfur atoms after the endurance.

  When the feed rate of the raw material is 3NLM, the temperature of the reforming catalyst inlet 102 is set to 350 ° C. below the lower limit temperature, and even when the feed rate of the raw material is 1 NLM, the temperature of the reforming catalyst inlet 102 is set to 350 ° C., which is the lower limit temperature. In the case where the temperature was set to 0 ° C., sulfur compounds were adsorbed on the reforming catalyst 101 of 390 cc from the reforming catalyst inlet 102 side out of the total reforming catalyst volume of 500 cc after the endurance.

  Since the sulfur compound was also adsorbed at the reforming catalyst outlet 103, the amount of hydrogen produced when the feed rate of the raw material was 3NLM was initially 12NLM, but decreased to 9.6NLM after the endurance.

  On the other hand, when the feed rate of the raw material is 3NLM, the temperature of the reforming catalyst inlet 102 is 400 ° C. which is the lower limit temperature, and when the feed rate of the raw material is 1NLM, the temperature of the reforming catalyst inlet 102 is the lower limit temperature. In the case of 350 ° C., the sulfur compound was adsorbed to the 240 cc reforming catalyst 101 from the reforming catalyst inlet 102 side out of the total reforming catalyst volume of 500 cc after the endurance.

  Since the sulfur compound was not adsorbed on the reforming catalyst outlet 103 portion, the hydrogen generation amount was maintained at 10.8 NLM when the feed rate of the raw material was 3 NLM.

  As described above, in the hydrogen generator of the present embodiment, the temperature distribution is set so that the outlet temperature is higher than the inlet of the reforming catalyst layer, and when the feed rate of the raw material is low, Increasing the lower limit temperature of the reforming catalyst inlet 102 can accelerate the chemisorption reaction rate between the sulfur compound and Ru in the reforming catalyst 101.

  Therefore, adsorption of sulfur compounds at the outlet of the reforming catalyst layer can be suppressed, and a decrease in the hydrogen generation amount of the hydrogen generator can be suppressed. As a result, the lifetime of the hydrogen generator can be extended.

  Here, the temperature of the reforming catalyst inlet 102 is 400 ° C. when the feed rate of the raw material is 3 NML, and the temperature of the reforming catalyst inlet 102 is 350 ° C. when the feed rate of the raw material is 1 NML. For example, the temperature of the reforming catalyst inlet 102 may be the same or higher when the feed rate is higher than when the feed rate is low.

  In the present embodiment, the above-described configuration and operation method of the hydrogen generator are used. However, the present invention is not limited to this, and the following configuration and operation method can be used.

  In the present embodiment, the steam reforming reaction is used to generate the hydrogen-containing gas in the reformer 100. However, any reaction may be used as long as the hydrogen-containing gas is generated from the raw material. Other examples include autothermal reaction and partial oxidation reaction, and combinations thereof may be used.

  As the reforming catalyst 101, a catalyst in which Ru is supported using alumina beads as a carrier is used, but any catalyst may be used as long as the reforming reaction can proceed.

  In general, in addition to Ru, it may be suitably used for at least one catalyst metal selected from the group consisting of Pt, Rh, Pd, Ir, Re, and Ni. A plurality of types of catalysts carrying different catalytic metals may be installed in series with respect to the flow direction of the raw material. A honeycomb can also be used as the carrier.

  In the present embodiment, city gas is used as a raw material, but it is sufficient that an organic compound having at least carbon and hydrogen as constituent elements is contained. Specifically, natural gas, city gas, LPG, LNG, etc. Examples are hydrocarbons and alcohols such as methanol and ethanol.

  An adsorptive desulfurizer is used as the desulfurizer 10, but there is another hydrodesulfurization method as a desulfurization method, and recycling for supplying a part of the hydrogen-containing gas generated in the reformer 100 to the desulfurizer 10. Examples of the hydrodesulfurization catalyst provided with a gas path (not shown) and filled in the desulfurizer 10 include a CuZn-based catalyst (including a combination with a CoMo-based catalyst).

  Moreover, the structure using combining a hydrodesulfurization system and an adsorption desulfurization system as a desulfurization system can also be taken. For example, a method of adsorbing and desulfurizing a sulfur compound by circulating a raw material gas through an adsorptive desulfurization type desulfurizer 10 at a start-up or stop step when hydrogen-containing gas cannot be supplied to a hydrodesulfurization type desulfurizer 10 from a recycle gas path. Etc.

  Although the reformer 100 is adjacent to the CO reducer 150 and the CO reducer is heated by heat transfer, the method of directly heating by the heater 20 may be used or may be used in combination. Although the structure which consists of the reformer 100 and the CO reducer 150 is taken, if the hydrogen utilization apparatus 201 does not provide the upper limit of the CO concentration of the hydrogen-containing gas, it is not necessary to provide the CO reducer 150. A configuration consisting of only 100 is also possible.

  Thermocouples are used as the reformer temperature detector 80 and the CO reducer temperature detector 90, but other examples include a thermistor. Although it is desirable to directly measure the catalyst temperature inside the reformer 100 and the CO reducer 150, if the catalyst temperature can be estimated from the detected value, the outside of the reformer 100 and the CO reducer 150 Alternatively, a temperature detector may be installed in the vicinity.

  The raw material supplier 31 uses a combination of a booster and a flow rate adjustment valve, but may be configured by at least one of them. Although the combination of the pump and the flow rate adjusting valve is used for the water supply device 51, it may be configured by at least one of them. Further, although the water supply amount is adjusted by the water supply amount detector 50, the adjustment may be performed based on the operation amount.

  Although the combustor is used as the heater 20, at least the combustor may be included, and a heater may be used in combination. As the fuel for the heater 20, a raw material discharged without performing the reforming reaction in the reformer 100 or a hydrogen-containing gas discharged from the reformer 100 is used. May be used directly.

  The hydrogen-containing gas supplied to the heater 20 may be supplied directly from the reformer 100 to the heater 20, or is discharged from the hydrogen utilization device 201 via the hydrogen utilization device 201 and supplied to the heater 20. May be. In the heater 20, the fuel may be added to the hydrogen-containing gas from a fuel supplier (not shown) and burned.

  In the present embodiment, a fan is used as the air supply unit 71, but it may be configured by at least one of a fan and a pump. Although the air supply amount is adjusted by the air supply amount detector 70, the supply amount may be adjusted based on the operation amount.

  The controller 300 may be any controller that controls the whole or a part of the hydrogen generator 400 as long as it has a control function. As the computing unit 301, a CPU or the like is exemplified in addition to the MPU.

  The controller 300 may be a single controller or a plurality of controllers. That is, each of the controllers 300 may be configured by a single controller that performs centralized control, or may be configured by a plurality of controllers that perform distributed control in cooperation with each other. This also applies to controllers of other embodiments described later.

  FIG. 3 is a diagram illustrating an example of the relationship between the feed rate of the raw material of the hydrogen generator according to Example 1 of the first embodiment and the lower limit temperature of the reforming catalyst inlet.

  In this embodiment, as shown in FIG. 3, a threshold is set for the feed rate of the raw material, and when the feed rate of the raw material is 2 NML or less, the lower limit temperature of the reforming catalyst inlet 102 is set to 350 ° C. When the speed was higher than 2NML, the lower limit temperature of the reforming catalyst inlet 102 was set to 400 ° C.

  As described above, in this embodiment, a threshold value is provided for the feed rate of the raw material, and the lower limit temperature of the reforming catalyst inlet 102 is increased when the feed rate of the raw material is lower than the threshold value than when the feed rate is higher than the threshold value. Thus, the chemisorption reaction rate between the sulfur compound and Ru in the reforming catalyst 101 can be promoted.

  Therefore, adsorption of sulfur compounds at the outlet of the reforming catalyst layer can be suppressed, and a decrease in the hydrogen generation amount of the hydrogen generator can be suppressed. As a result, the lifetime of the hydrogen generator can be extended.

  Here, the threshold value of the raw material supply rate is set to 2 NML, but it is not limited to this rate. Further, the lower limit temperature of the reforming catalyst inlet 102 is not limited to each lower limit temperature of the reforming catalyst inlet 102.

FIG. 4 is a diagram illustrating an example of a relationship between a raw material supply rate of the hydrogen generator 400 according to Example 1 of the first embodiment and a lower limit temperature of the reforming catalyst inlet.

  In this embodiment, as shown in FIG. 4, a plurality of threshold values are set for the feed rate of the raw material, and the lower limit temperature of the reforming catalyst inlet 102 is set to be higher as the feed rate of the raw material is higher. Specifically, when the feed rate of the raw material is higher than 2.6 NML, the lower limit temperature of the reforming catalyst inlet 102 is set to 400 ° C., and the feed rate of the raw material is 2.6 NML or less and faster than 2.2 NML Then, the lower limit temperature of the reforming catalyst inlet 102 is set to 390 ° C., and thereafter, thresholds are set at 1.8 NML and 1.4 NML. When the lower limit temperature is 1.4 NML or lower, the lower limit temperature of the reforming catalyst inlet 102 is set to 350 ° C. The hydrogen generator 400 was set up and operated.

  As described above, in this embodiment, a plurality of threshold values are provided for the feed rate of the raw material, and the lower limit temperature of the reforming catalyst inlet 102 is set higher when the feed rate of the raw material is faster than the threshold value than when the feed rate is lower than the threshold value. By doing so, adsorption | suction of the sulfur compound to the exit of a reforming catalyst layer can be suppressed, and the hydrogen production amount fall of a hydrogen generator can be suppressed.

  As a result, the lifetime of the hydrogen generator can be extended. Further, since the decrease in the adsorption performance of the sulfur compound of the reforming catalyst 101 can be suppressed for each step at a finer interval with respect to the feed rate of the raw material when the feed rate of the raw material is faster than when the feed rate of the raw material is slow. The lifetime of the generator can be increased.

  However, the set number of threshold values of the raw material supply speed is not limited to the number set in the present embodiment, and the threshold values may not be set at equal intervals. Further, the lower limit temperature of the reforming catalyst inlet 102 is not limited to each lower limit temperature of the reforming catalyst inlet 102.

  FIG. 5 is a diagram illustrating an example of the relationship between the lower limit temperature of the reforming catalyst inlet of the hydrogen generator 400 according to Example 3 of the first embodiment and the feed rate of the raw material.

  In the present embodiment, as shown in FIG. 5, the relationship between the feed rate of the raw material and the lower limit temperature of the reforming catalyst inlet 102 is a function relationship so that the lower limit temperature of the reforming catalyst inlet 102 becomes higher as the feed rate of the raw material becomes higher. The feed rate of the raw material and the lower limit temperature of the reforming catalyst inlet 102 were set continuously.

  Specifically, the lower limit temperature of the reforming catalyst inlet 102 is set so that the feed rate R of the raw material and the lower limit temperature Tin of the reforming catalyst inlet 102 become a linear function represented by Tin = 25 × R + 325, and the result When the feed rate of the raw material is 1 NLM, the lower limit temperature of the reforming catalyst inlet 102 of the hydrogen generator 400 is set to 350 ° C., and in the case of 3 NLM, the lower limit temperature of the reforming catalyst inlet 102 is set to 400 ° C. Then, the hydrogen generator 400 was operated.

  As described above, in this embodiment, the lower limit temperature of the reforming catalyst inlet 102 is continuously set according to the raw material supply rate so that the lower limit temperature of the reforming catalyst inlet 102 becomes higher when the raw material supply rate is high. By doing so, adsorption | suction of the sulfur compound to the exit of a reforming catalyst layer can be suppressed, and the hydrogen production amount fall of a hydrogen generator can be suppressed.

  As a result, the lifetime of the hydrogen generator can be extended. Further, the lowering of the sulfur compound adsorption performance of the reforming catalyst 101, which is increased when the raw material supply rate is higher than that when the raw material supply rate is low, is continuously set with respect to the raw material supply rate. In contrast, since it is possible to suppress the decrease in the adsorption performance of the optimum sulfur compound, the life of the hydrogen generator can be further extended.

  Here, the relationship between the feed rate of the raw material and the lower limit temperature of the reforming catalyst inlet 102 is set by a linear function. However, the present invention is not limited to this, and other functions may be used, and different functions may be set by providing threshold values. May be. Further, the lower limit temperature of the reforming catalyst inlet 102 is not limited to each lower limit temperature of the reforming catalyst inlet 102.

(Embodiment 2)
Since the configuration of the hydrogen generator and the control of the reforming catalyst inlet temperature are the same as those in the first embodiment, the description thereof is omitted.

  Hereinafter, the operation and action of the hydrogen generator 400 of Embodiment 2 will be described. The following operations and actions are performed by the controller 300 controlling the hydrogen generator 400.

  When the hydrogen-using device requires a 4NLM amount of hydrogen, the hydrogen generator 400 supplies the necessary amount of hydrogen with a raw material supply rate of 1NLM. When the hydrogen utilization device requires a hydrogen amount of 12 NLM, the supply rate of the raw material is set to 3 NLM and the necessary hydrogen amount is supplied. In the hydrogen generator 400 of the present embodiment, the reformer 100 is charged with 500 cc of the reforming catalyst 101, the upper limit temperature of the reforming catalyst outlet 103 when the feed rate of the feed is 1 NLM, The upper limit temperature of the reforming catalyst outlet 103 when the supply rate was 3NLM was controlled to be 660 ° C. Since the product life of the hydrogen generator 400 is assumed to be 60,000 hours and the average feed rate of the raw material is 2 NLM, 7200 m 3 is supplied to the reforming catalyst 101 as a total feed amount after the endurance.

When the feed rate of the raw material is 3NLM, the temperature of the reforming catalyst outlet 103 is set to 680 ° C. which is equal to or higher than the upper limit temperature, and when the feed rate of the raw material is 1NLM, the temperature of the reforming catalyst outlet 103 is set to 640 ° C. which is the upper limit temperature. In this case, the CO adsorption amount indicating the surface area of Ru, which was 0.5 cm ³ / g in the initial stage, becomes 0.1 cm ³ / g at the reforming catalyst outlet 103 after endurance, and the Ru surface area necessary for hydrogen generation is Due to the decrease, the amount of hydrogen produced when the feed rate of the raw material was 3NLM was initially 12 NLM, but decreased to 10.3 NLM after the endurance.

In the present embodiment, when the feed rate of the raw material is 3NLM, the temperature of the reforming catalyst outlet 103 is set to the upper limit temperature of 660 ° C., and when the feed rate of the raw material is 1 NLM, the temperature of the reforming catalyst outlet 103 is also set to the upper limit. When the temperature is 660 ° C. or lower, the CO adsorption amount indicating the surface area of Ru, which was 0.5 cm ³ / g in the initial stage, becomes 0.3 cm ³ / g at the reforming catalyst outlet 103 after the endurance, and the Ru surface area Therefore, the hydrogen generation amount was maintained at 10.9 NLM when the feed rate of the raw material was 3 NLM.

  As described above, in the hydrogen generator of the present embodiment, the temperature distribution is set so that the outlet temperature is higher than the inlet of the reforming catalyst layer, and the reforming catalyst outlet 103 when the feed rate of the raw material is high is set. By setting the upper limit temperature to be equal to or lower than the upper limit temperature of the reforming catalyst outlet 103 when it is slow, it is possible to suppress a decrease in performance of the hydrogen generator.

  This is because the sintering of the catalyst is promoted as the reaction temperature is higher, and the reaction rate is increased in the reforming catalyst 101 as the feed rate of the raw material is faster, but the feed rate of the raw material is faster. This is because the sintering of this catalyst can be suppressed by lowering the temperature of the reforming catalyst outlet 103, and the performance degradation can be suppressed. As a result, the lifetime of the hydrogen generator can be extended.

  In the present embodiment, when the feed rate of the raw material is 3 NML and the speed is 1 NML, the temperature of the reforming catalyst outlet 103 is set to 660 ° C. The temperature of the reforming catalyst inlet 102 may be higher or lower when it is faster than when the supply rate is slower.

  FIG. 6 is a diagram illustrating an example of the relationship between the feed rate of the raw material of the hydrogen generator according to Example 4 of the second embodiment and the upper limit temperature of the reforming catalyst outlet.

  In this embodiment, as shown in FIG. 6, a threshold is set for the feed rate of the raw material, and when the feed rate of the raw material is 2 NML or less, the upper limit temperature of the reforming catalyst outlet 103 is set to 700 ° C. When the speed was higher than 2 NML, the upper limit temperature of the reforming catalyst outlet 103 was set to 660 ° C.

  As described above, in this embodiment, a threshold value is provided for the feed rate of the raw material, and the upper limit temperature of the reforming catalyst outlet 103 is increased when the feed rate of the raw material is lower than the threshold value than when the feed rate is higher than the threshold value. Thus, sintering of the catalyst at the reforming catalyst outlet 103 can be suppressed, and a decrease in the hydrogen generation amount of the hydrogen generator can be suppressed. As a result, the lifetime of the hydrogen generator can be extended.

  Here, the threshold value of the raw material supply rate is set to 2 NML, but it is not limited to this rate. Further, the upper limit temperature of the reforming catalyst outlet 103 is not limited to each upper limit temperature of the reforming catalyst outlet 103.

  FIG. 7 is a diagram illustrating an example of the relationship between the raw material supply speed of the hydrogen generator 400 according to Example 5 of the second embodiment and the upper limit temperature of the reforming catalyst outlet 103.

  In this embodiment, as shown in FIG. 7, a plurality of threshold values are set for the feed rate of the raw material, and the upper limit temperature of the reforming catalyst outlet 103 is set to be higher as the feed rate of the raw material is higher. Specifically, when the feed rate of the raw material is faster than 2.6 NML, the upper limit temperature of the reforming catalyst outlet 103 is set to 660 ° C., and the feed rate of the raw material is 2.6 NML or less and faster than 2.2 NML Then, the upper limit temperature of the reforming catalyst outlet 103 is set to 668 ° C., and a threshold value is set to 1.8 NML and 1.4 NML, and the upper limit temperature of the reforming catalyst outlet 103 is set to 700 ° C. when 1.4 NML or less. The hydrogen generator 400 was set up and operated.

  As described above, in this embodiment, a plurality of threshold values are provided for the feed rate of the raw material, and the upper limit temperature of the reforming catalyst outlet 103 is increased when the feed rate of the raw material is faster than the threshold value, compared to the case where the feed rate is lower than the threshold value. By doing so, the sintering of the catalyst at the reforming catalyst outlet 103 can be suppressed, and the decrease in the hydrogen generation amount of the hydrogen generator can be suppressed.

  As a result, the lifetime of the hydrogen generator can be extended. Furthermore, when the feed rate of the raw material is higher than when the feed rate of the raw material is slow, the sintering of the catalyst at the reforming catalyst outlet 103 can be suppressed step by step at a finer interval than the feed rate of the raw material. The lifetime of the device can be extended.

  However, the set number of threshold values of the raw material supply speed is not limited to the number set in the present embodiment, and the threshold values may not be set at equal intervals. Further, the upper limit temperature of the reforming catalyst outlet 103 is not limited to each upper limit temperature of the reforming catalyst outlet 103.

  FIG. 8 is a diagram illustrating an example of the relationship between the upper limit temperature of the reforming catalyst outlet of the hydrogen generator according to Example 6 of the second embodiment and the feed rate of the raw material.

In this embodiment, as shown in FIG. 8, the relationship between the feed rate of the raw material and the upper limit temperature of the reforming catalyst outlet 103 is a function so that the upper limit temperature of the reforming catalyst outlet 103 becomes higher as the feed rate of the raw material becomes higher. The feed rate of the raw material and the upper limit temperature of the reforming catalyst outlet 103 were set continuously.

  Specifically, the upper limit temperature of the reforming catalyst outlet 103 is set so that the feed rate R of the raw material and the upper limit temperature Tin of the reforming catalyst outlet 103 become a linear function represented by Tin = −20 × R + 720. As a result, when the feed rate of the raw material is 1 NLM, the upper limit temperature of the reforming catalyst outlet 103 of the hydrogen generator 400 is set to 700 ° C., and when 3 NLM, the upper limit temperature of the reforming catalyst outlet 103 is set to 660 ° C. Thus, the operation of the hydrogen generator 400 was performed.

  As described above, in this embodiment, the upper limit temperature of the reforming catalyst outlet 103 is continuously set according to the raw material supply rate so that the upper limit temperature of the reforming catalyst outlet 103 becomes higher when the raw material supply rate is high. By doing so, the sintering of the catalyst at the reforming catalyst outlet 103 can be suppressed, and the decrease in the hydrogen generation amount of the hydrogen generator can be suppressed.

  As a result, the lifetime of the hydrogen generator can be extended. Furthermore, the sintering of the catalyst at the reforming catalyst outlet 103, which is increased when the raw material supply rate is higher than when the raw material supply rate is low, is set continuously with respect to the raw material supply rate. In addition, since the optimum sintering of the catalyst can be suppressed, the life of the hydrogen generator can be further extended.

  Here, the relationship between the feed rate of the raw material and the upper limit temperature of the reforming catalyst outlet 103 is set by a linear function. However, the present invention is not limited to this, and other functions may be used, and different functions may be set by providing threshold values. May be. Further, the upper limit temperature of the reforming catalyst outlet 103 is not limited to each upper limit temperature of the reforming catalyst outlet 103.

(Embodiment 3)
FIG. 9 is a block diagram showing an example of the configuration of the reformer 100 and the heater 20 according to the third embodiment of the present invention. Since the hydrogen generator 400 according to the present embodiment has the same configuration as that of FIG. 1, redundant description will be omitted, and different parts will be described.

  The reaction vessel of the reformer 100 has a concentric double cylindrical shape, and is a vertical type in which the upper and lower end surfaces of the space surrounded by the outer cylinder 111 and the inner cylinder 112 are closed with a hollow double cylindrical upper surface plate 113 and a bottom surface plate 114. The container. The reforming catalyst 101 is filled in a reaction vessel. The raw material and water are supplied from above, and the hydrogen-containing gas generated by the reforming reaction is discharged downward.

  The heater 20 is composed of a combustor, fuel and air are supplied from above, the flame 21 is held downward, a combustion reaction is performed, and the combustion exhaust gas is discharged downward. The heater 20 is configured above the reforming catalyst 101 so as to be able to exchange heat with the reformer 100, the origin of the flame 21 is located above the reforming catalyst 101, and the tip of the flame 21 is the reforming catalyst inlet 102. And the reforming catalyst outlet 103.

  Hereinafter, the operation and action of the hydrogen generator 400 of Embodiment 3 will be described. The following operations and actions are performed by the controller 300 controlling the hydrogen generator 400.

  When the feed rate of the raw material is 3 NLM and 1 NLM, the temperature of the reforming catalyst inlet 102 is 350 ° C. when λ, which is the stoichiometric ratio between the air supply amount and the fuel supply amount, is 1.5. After the endurance, the sulfur compound was adsorbed on the 390 cc reforming catalyst 101 from the reforming catalyst inlet 102 side out of the total reforming catalyst volume of 500 cc. Since the sulfur compound was also adsorbed at the reforming catalyst outlet 103, the amount of hydrogen produced when the feed rate of the raw material was 3NLM was initially 12NLM, but decreased to 9.6NLM after the endurance.

  In the present embodiment, when the feed rate of the raw material is 3NLM, by setting λ to 2.0, the flame 21 becomes shorter than when λ is set to 1.5, and the tip of the flame 21 is modified. Since the reforming catalyst inlet 102 is heated from the quality catalyst outlet 103, the temperature of the reforming catalyst inlet 102 becomes 400 ° C. which is the lower limit temperature. When the feed rate of the raw material was 1 NLM, λ was 1.5, and the temperature of the reforming catalyst inlet 102 was 350 ° C., which is the lower limit temperature.

  After the endurance, sulfur compounds were adsorbed to the 240 cc reforming catalyst 101 from the reforming catalyst inlet 102 side out of the total reforming catalyst volume of 500 cc. Since the sulfur compound was not adsorbed on the reforming catalyst outlet 103 portion, the hydrogen generation amount was maintained at 10.8 NLM when the feed rate of the raw material was 3 NLM.

  As described above, in the hydrogen generator of the present embodiment, the combustor is used as the heater 20 as the heating means of the reformer 100, and the reforming catalyst inlet is not provided by providing a new configuration by controlling λ. The temperature of 102 can be maintained at or above the lower limit temperature appropriately set according to the feed rate of the raw material.

  As a result, a sufficient speed for adsorbing the sulfur compound to the reforming catalyst can be maintained, and a necessary amount of sulfur compound can be secured on the reforming catalyst layer inlet side. The slip of the compound can be suppressed, and the performance degradation of the hydrogen generator can be suppressed. Therefore, the lifetime of the hydrogen generator can be extended.

  In this embodiment, λ is 2.0 when the feed rate of the raw material is 3 NML, and λ is 1.5 when the feed rate of the raw material is 1 NML, but the temperature of the reforming catalyst inlet 102 is the feed rate of the raw material. It is sufficient that the temperature is equal to or higher than the lower limit temperature set by, and is not limited to this value.

(Embodiment 4)
FIG. 10 is a block diagram showing an example of the configuration of the hydrogen generator 400 according to Embodiment 4 of the present invention. Since the hydrogen generator 400 according to the present embodiment has the same configuration as that of FIG. 1, description thereof is omitted and only different portions will be described.

  The reaction vessel of the reformer 100 has a concentric double cylindrical shape, and the upper and lower end surfaces of the space surrounded by the inner cylinder 116 and the inner cylinder 112 are closed by a hollow double cylindrical upper surface plate 113 and a bottom surface plate 114. This is a mold container. The reforming catalyst 101 is filled in a reaction vessel.

  The raw material and water are supplied from above, and the hydrogen-containing gas generated by the reforming reaction is discharged downward. A concentric cylindrical outer cylinder 117 is formed outside the outer cylinder 116, and the hydrogen-containing gas is discharged upward along a path surrounded by the outer cylinder 116 and the outer cylinder 117. Further, a CO reducer 150 and an evaporator 52 are formed above the reformer 100.

  The container of the CO reducer 150 is a vertical container in which the upper and lower end surfaces of the space surrounded by the outer cylinder 161 and the inner cylinder outer 162 are closed by a hollow double cylindrical top plate 163 and bottom plate 164. The evaporator 52 includes a space surrounded by the inner cylinder outer 162 and the inner cylinder inner 165. The CO reducer 150 and the evaporator 52 are configured in a concentric cylindrical shape on the outer side and the inner side so that heat can be exchanged.

  A concentric cylindrical combustion cylinder 166 is formed on the side of the inner cylinder 112, and combustion exhaust gas discharged from the heater 20 as a combustor is discharged upward along a path surrounded by the inner cylinder 112 and the combustion cylinder 166. The

  Hereinafter, the operation and action of the hydrogen generator 400 of Embodiment 2 will be described. The following operations and actions are performed by the controller 300 controlling the hydrogen generator 400.

  Regardless of whether the feed rate of the raw material is 3NLM or 1NLM, when the S / C, which is the steam / carbon molar ratio of the raw material and reforming water, is 3.0, the temperature of the reforming catalyst inlet 102 350 ° C. After the endurance, the sulfur compound was adsorbed on the reforming catalyst 101 of 390 cc from the reforming catalyst inlet 102 side in the 500 cc volume of all the reforming catalysts. Since the sulfur compound was also adsorbed at the reforming catalyst outlet 103, the amount of hydrogen produced when the feed rate of the raw material was 3NLM was initially 12NLM, but decreased to 9.6NLM after the endurance.

  In the present embodiment, when the feed rate of the raw material is 3NLM, the S / C is set to 2.7, so that the evaporation of water in the evaporator 52 is made more than when the S / C is set to 3.0. Since the amount decreased, the temperature of the mixed gas of the raw material and steam supplied to the reforming catalyst inlet 102 increased, and the temperature of the reforming catalyst inlet 102 reached 400 ° C., which is the lower limit temperature.

  When the feed rate of the raw material was 1 NLM, S / C was 3.0, and the temperature of the reforming catalyst inlet 102 was 350 ° C., which is the lower limit temperature. After the endurance, sulfur compounds were adsorbed to the 240 cc reforming catalyst 101 from the reforming catalyst inlet 102 side out of the total reforming catalyst volume of 500 cc. Since the sulfur compound was not adsorbed on the reforming catalyst outlet 103 portion, the hydrogen generation amount was maintained at 10.8 NLM when the feed rate of the raw material was 3 NLM.

  As described above, in the hydrogen generator of the present embodiment, the temperature of the reformer 100 is controlled by controlling the S / C so that the temperature at the inlet of the reforming catalyst layer is controlled without providing a new configuration. Can be maintained at a temperature not less than a lower limit temperature appropriately set depending on the supply speed.

  As a result, a sufficient speed for adsorbing the sulfur compound to the reforming catalyst can be maintained, and a necessary amount of sulfur compound can be secured on the reforming catalyst layer inlet side. The slip of the compound can be suppressed, and the performance degradation of the hydrogen generator can be suppressed. Therefore, the lifetime of the hydrogen generator can be extended.

  In the present embodiment, S / C is set to 2.7 when the feed rate of the raw material is 3 NML, and S / C is set to 3.0 when the feed rate of the raw material is 1 NML. It should just be more than the minimum temperature set by the supply rate of a raw material, and is not restricted to this value.

(Embodiment 5)
FIG. 11 is a block diagram showing an example of the configuration of the fuel cell system according to Embodiment 5 of the present invention.

  As shown in FIG. 11, the fuel cell system 500 a of the present embodiment includes a hydrogen generator 400 and a fuel cell 200. The fuel cell 200 generates electricity by reacting the hydrogen-containing gas supplied from the hydrogen generator 400 with the oxidant gas.

  In the present embodiment, a polymer electrolyte fuel cell (PEFC) is used for the fuel cell 200. A sealer 40 is installed in the hydrogen supply path 41 from the hydrogen generator 400 to the fuel cell 200, a bypass path 43 is installed in the fuel supply path 42 and the hydrogen supply path 41 from the fuel cell 200 to the heater 20, A bypass sealer 44 was installed in the bypass path 43.

  The fuel cell system 500 a includes a controller 300. The controller 300 includes a central processing unit (CPU) as a main body of the calculation unit 301 and a storage unit 302. A raw material supply amount detector 30 for detecting the supply amount of the raw material is provided in the middle of the raw material supply path from the raw material supply device 31 to the reformer 100, and the detection output is input to the calculation unit 301.

A water supply amount detector 50 that detects the amount of water supply is provided in the middle of the water supply path from the water supply device 51 to the reformer 100, and the detection output is input to the calculation unit 301. Here, the raw material supply amount detector 30 and the water supply amount detector 50 are each composed of a flow meter such as a mass flow meter.

  The storage unit 302 provided in the controller 300 stores a program for controlling various operations of the fuel cell system 500a. The calculation unit 301 reads out a necessary program from the storage unit 302 and executes it. By doing so, various operations of the fuel cell system 500a are controlled.

  A generated current detector 60 is provided in the current path from the fuel cell 200 to the output controller 61, and the detected output is input to the calculation unit 301. Here, the generated current detector 60 is composed of an ammeter.

  In addition, the calculation unit 301 can detect the power generation amount from the generated current obtained from the generated current detector 60, the generated voltage obtained from the output controller 61, and the generated time. The arithmetic unit 301 included in the controller 300 controls the overall operation of the fuel cell system 500a by inputting various detection outputs including these detection outputs and controlling the above-described components.

  Similarly, the storage unit 302 provided in the controller 300 stores programs for controlling various operations of the fuel cell system 500a. The calculation unit 301 reads out necessary programs from the storage unit 302. By executing this, various operations of the fuel cell system 500a are controlled.

  The operation and action of the fuel cell system 500a according to Embodiment 2 will be described below. The following operations and actions are performed by the controller 300 controlling the hydrogen generator 400.

  When the hydrogen generator 400 is activated, combustion in the heater 20 is started. At this time, the sealer 40 is closed, the bypass sealer 44 is opened, the fuel supply path 42 for combustion reaching the heater 20 is branched from the hydrogen supply path 41 and extending to the heater 20. . Therefore, when the raw material is supplied to the reformer 100 by starting the operation of the raw material supplier 31, the raw material that has passed through the reformer 100 is supplied to the heater 20 using the combustion fuel supply path 42. .

  At the same time, combustion air is supplied to the heater 20 by starting the operation of the air supply device 71. In the heater 20, an ignition operation is performed by an ignition electrode (not shown), and combustion of fuel occurs using combustion air. In this way, the reformer 100 is heated by the combustion heat supplied from the heater 20.

  Next, water is supplied to the reformer 100 when the operation of the water supplier 51 starts. After the start of water supply, when the composition of the hydrogen-containing gas generated in the reformer 100 becomes a composition suitable for supply to the fuel cell 200, the sealer 40 is opened and the bypass sealer 44 is closed. As a result, the hydrogen-containing gas is supplied to the fuel cell 200.

  The fuel cell 200 generates electricity by reacting an oxidant gas supplied from an oxidant supply path (not shown) and a hydrogen-containing gas. Moreover, when stopping the fuel cell system 500a, the raw material supply device 31 and the water supply device 51 are stopped.

When the feed rate of the raw material is 3NLM, the temperature of the reforming catalyst inlet 102 is set to 350 ° C. below the lower limit temperature, and even when the feed rate of the raw material is 1 NLM, the temperature of the reforming catalyst inlet 102 is set to 350 ° C., which is the lower limit temperature. In the case where the temperature was set to 0 ° C., sulfur compounds were adsorbed on the reforming catalyst 101 of 390 cc from the reforming catalyst inlet 102 side out of the total reforming catalyst volume of 500 cc after the endurance.

  Since the sulfur compound was also adsorbed at the reforming catalyst outlet 103, the initial hydrogen generation amount when the feed rate of the raw material was 3NLM was 12NLM and the power generation amount was 750W, but the hydrogen generation amount after the endurance was 9.6NLM The power generation amount dropped to 600W.

  On the other hand, in this embodiment, when the feed rate of the raw material is 3NLM, the controller sets the temperature of the reforming catalyst inlet 102 to 400 ° C., which is the lower limit temperature, and when the feed rate of the raw material is 1NLM, When the temperature of the catalyst inlet 102 was 350 ° C., which is the lower limit temperature, sulfur compounds were adsorbed on the reforming catalyst 101 of 240 cc from the reforming catalyst inlet 102 side out of the total reforming catalyst volume of 500 cc after the endurance. .

  Since the sulfur compound was not adsorbed at the reforming catalyst outlet 103 portion, the hydrogen generation amount was maintained at 10.8 NLM and the power generation amount was 675 W when the feed rate of the raw material was 3 NLM.

  As described above, in the hydrogen generator of the present embodiment, the temperature distribution is set so that the temperature of the reforming catalyst outlet 103 is higher than that of the reforming catalyst inlet 102, and the case where the temperature is higher than when the feed rate of the raw material is low. Furthermore, by increasing the lower limit temperature of the reforming catalyst inlet 102, it is possible to suppress adsorption of sulfur compounds at the outlet of the reforming catalyst layer and to suppress a decrease in the amount of hydrogen generated by the hydrogen generator.

  As a result, the lifetimes of the hydrogen generator 400 and the fuel cell system 500a can be extended.

  Here, the temperature of the reforming catalyst inlet 102 is 400 ° C. when the feed rate of the raw material is 3 NML, and the temperature of the reforming catalyst inlet 102 is 350 ° C. when the feed rate of the raw material is 1 NML. For example, the temperature of the reforming catalyst inlet 102 may be the same or higher when the feed rate is higher than when the feed rate is low.

  In the present embodiment, a polymer electrolyte fuel cell (PEFC) is used as the fuel cell 200. However, any type of fuel cell may be used, and a solid oxide fuel cell, phosphoric acid may be used. A fuel cell or a molten carbonate fuel cell can be used.

(Embodiment 6)
FIG. 12 is a block diagram showing an example of the configuration of the fuel cell system according to Embodiment 6 of the present invention.

  As shown in FIG. 12, the fuel cell 200 is configured to be able to exchange heat with the reformer 100, and is used as the heater 20 of the reformer 100. The polymer electrolyte fuel cell uses a polymer electrolyte membrane and normally operates at 80 to 90 ° C. Further, the operating temperature of the polymer electrolyte fuel cell is limited to about 200 ° C. even at a high temperature, and is not used as the heater 20 of the reformer 100.

  However, the solid oxide fuel cell uses a heat-resistant ceramic-based electrolyte, operates at 700 ° C. to 1000 ° C., and the operating temperature is higher than the set temperature 600 ° C. to 700 ° C. of the reformer 100. It can be used as the heater 20 of the mass device 100. The molten carbonate fuel cell also has an operating temperature of 650 ° C. to 700 ° C. and can be used as the heater 20 of the reformer 100.

The fuel cell system 500b of the present embodiment uses the fuel cell 200 as the heater 20 of the reformer 100, sets the temperature distribution so that the temperature of the reforming catalyst outlet 103 is higher than the reforming catalyst inlet 102, When the feed rate of the raw material is low, the lower limit temperature of the reforming catalyst inlet 102 is increased to suppress the adsorption of sulfur compounds to the outlet of the reforming catalyst layer, and the hydrogen of the reformer 100 is increased. A decrease in the production amount can be suppressed.

  As a result, the life of the reformer 100 and the fuel cell system 500b can be extended.

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

  As described above, the hydrogen generator according to the present invention, the fuel cell system using the hydrogen generator, and the operation method thereof suppress the deterioration of the reforming catalyst due to sulfur when the feed rate of the raw material is high, and reduce the hydrogen generation amount. Can be suppressed, and the life of the hydrogen generator can be extended, so that it can be applied to a hydrogen generator and a fuel cell system having high durability and high commerciality.

DESCRIPTION OF SYMBOLS 10 Desulfurizer 20 Heater 21 Flame 30 Raw material supply amount detector 31 Raw material supply device 40 Sealing device 41 Hydrogen supply path 50 Water supply amount detector 51 Water supply device 52 Evaporator 60 Power generation current detector 61 Output controller 70 Air Supply amount detector 71 Air supply device 80 Reformer temperature detector 100 Reformer 101 Reforming catalyst 102 Reforming catalyst inlet 103 Reforming catalyst outlet 111 Outer cylinder 112 Inner cylinder 113 Top plate 114 Bottom plate 150 CO reducer 161 Outer cylinder 163 Top plate 164 Bottom plate 200 Fuel cell 201 Hydrogen-utilizing device 300 Controller 301 Calculation unit 302 Storage unit 400 Hydrogen generator 500a Fuel cell system 500b Fuel cell system

Claims (6)

A reformer filled with a reforming catalyst that reforms a raw material containing at least a sulfur compound and a hydrocarbon to generate a hydrogen-containing gas;
A raw material supplier for supplying the raw material to the reformer;
A heater for heating the reformer;
A controller for controlling the temperature of the reforming catalyst inlet of the reformer;
With
The lower limit temperature of the reforming catalyst inlet is lower than the lower limit temperature when the feed rate of the raw material is relatively high, and the lower limit temperature when the feed rate of the raw material is relatively slow,
The said controller is a hydrogen generator which controls the said heater so that the temperature of the said reforming catalyst inlet_port | entrance becomes more than the said minimum temperature.   In the controller, the temperature at the reforming catalyst outlet of the reformer is such that the temperature when the feed rate of the raw material is relatively fast is equal to or lower than the temperature when the feed rate of the raw material is relatively slow. The hydrogen generator according to claim 1, wherein the heater is controlled. The heater includes a combustor that burns at least the raw material,
When the feed rate of the raw material is relatively high, the controller has a stoichiometric ratio between the air supply amount and the fuel supply amount supplied to the combustor is λ, which is a relatively slow supply rate of the raw material. The hydrogen generator according to claim 1, wherein the hydrogen generator is controlled to be larger. A water supply for supplying water to the reformer,
In the controller, when the feed rate of the raw material is relatively high, S / C, which is a steam / carbon molar ratio between the raw material and reforming water, is smaller than when the feed rate of the raw material is relatively slow. The hydrogen generator according to any one of claims 1 to 3, further comprising a controller for controlling the raw material supplier and the water supplier.   A fuel cell system comprising the hydrogen generator according to any one of claims 1 to 4 and a fuel cell that generates electric power using a hydrogen-containing gas supplied from the hydrogen generator. A reformer filled with a reforming catalyst that reforms a raw material containing at least a sulfur compound and a hydrocarbon to generate a hydrogen-containing gas;
A raw material supplier for supplying the raw material to the reformer;
A heater for heating the reformer;
A controller for controlling the temperature of the reforming catalyst inlet;
A method of operating a hydrogen generator comprising:
The lower limit temperature of the reforming catalyst inlet is lower than the lower limit temperature when the feed rate of the raw material is relatively high, and the lower limit temperature when the feed rate of the raw material is relatively slow,
Heating the reforming catalyst inlet so that the temperature becomes equal to or higher than the lower limit temperature,
Operation method of hydrogen generator.

Images