JP2017105645A - Hydrogen generation device and fuel cell system therewith and operation method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen generation device which can lower a peak value of ammonia concentration in hydrogen-containing gas when raw material supply is increased.SOLUTION: A hydrogen generation device 100 comprises a CO eliminator 11 reducing carbon monoxide in hydrogen-containing gas produced by a reformer 1 by selective oxidation catalyst, a raw material feeding device 2 feeding raw materials to the reformer 1, and a controller 50. The controller 50 decreases increase speed of the raw material supply in increasing the raw material supply fed to the reformer 1 from the raw material feeding device 2 as operate duration t after start of the operation gets longer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen generator, a fuel cell system using the same, and an operating method thereof.

  Conventionally, a fuel cell cogeneration system (hereinafter simply referred to as “fuel cell system”) that has both high power generation efficiency and overall efficiency has attracted attention as a distributed generator that can effectively use energy. .

  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, a phosphoric acid fuel cell and a polymer electrolyte fuel cell (abbreviated as “PEFC”) have a relatively low operating temperature during a power generation operation. Therefore, the fuel cells constituting the fuel cell system Is 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 and no electrolyte dissipation compared to phosphoric acid fuel cells. Used.

  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.

  A reforming reaction is generally used as a method for generating hydrogen to be supplied to a fuel cell. The reforming reaction includes, for example, hydrogen containing hydrogen as a main component by reacting raw city gas and water vapor at a high temperature of about 600 ° C. to 700 ° C. using a Ni-based or Ru-based reforming catalyst. Generate gas.

  In addition, since carbon monoxide (CO) is generated as a side reaction in the reformer, when CO poisons the fuel cell to lower the voltage (in the case of a polymer electrolyte fuel cell or the like), the CO remover Is provided downstream of the reformer.

  Examples of the CO remover include a CO conversion catalyst that reacts CO with water vapor to reduce CO, and a selective oxidation catalyst that reacts CO with a small amount of oxygen to oxidize and remove CO. Each catalyst functions as a CO remover by setting it to a temperature range suitable for the CO removal reaction.

  By the way, natural gas supplied as a raw material to a reformer of a hydrogen generator usually contains a small amount of nitrogen compound. The content rate of this nitrogen compound changes with the area which supplies natural gas, for example.

  Then, when the natural gas containing the nitrogen compound is supplied to the reformer of the hydrogen generator, the hydrogen produced by the steam reforming reaction and the nitrogen compound on the reforming catalyst provided in the reformer. As the chemical reaction proceeds, ammonia may be generated.

  Here, depending on the catalyst type of the selective oxidation catalyst provided in the CO remover, ammonia generated in the reformer may be adsorbed. The adsorption to the selective oxidation catalyst by ammonia tends to increase the amount of adsorption as the temperature of the CO remover decreases.

  Conversely, when the temperature increases, the adsorbed ammonia is desorbed, and the ammonia concentration in the hydrogen-containing gas increases. This causes poisoning of the electrode catalyst by ammonia in the polymer electrolyte fuel cell, and remarkably deteriorates the power generation performance of the polymer electrolyte fuel cell.

  If the low-load operation in which the selective oxidation reaction amount of the CO remover is low and the temperature is low in the hydrogen generator becomes longer, the ammonia adsorption amount increases in accordance with the operation time. When the load is increased to a high-load operation where the amount of selective oxidation reaction of the CO remover is large and the temperature is high in a state where the amount of adsorption is large, the adsorbed ammonia is released at once.

  In view of this, a method has been proposed in which the raw material supply amount is changed at a constant change rate when the temperature of the CO remover is within a certain range when the load increases (see, for example, Patent Document 1).

JP 2005-209642 A

  However, in the above conventional configuration, ammonia adsorption at low load is not taken into consideration, and when the load is increased, ammonia is rapidly desorbed from the CO remover, which may increase the peak value of the ammonia concentration in the hydrogen-containing gas. there were.

  An object of the present invention is to solve the above-described conventional problems, and to provide a hydrogen generator and a fuel cell system capable of reducing the peak value of the ammonia concentration in the hydrogen-containing gas when the amount of raw material supply is increased. To do.

  In order to solve the above-described conventional problems, a hydrogen generator of the present invention includes a CO remover that reduces carbon monoxide in a hydrogen-containing gas generated by a reformer using a selective oxidation catalyst, and a raw material in the reformer. The controller is supplied from the raw material supplier to the reformer as the operation continuation time or cumulative operation time from the start of operation becomes longer. When the raw material supply amount is increased, the increase rate of the raw material supply amount is decreased.

  Thereby, the temperature rise of the CO remover when the raw material supply amount increases can be moderated, and the peak value of the ammonia concentration in the hydrogen-containing gas when the raw material supply amount increases can be lowered.

  The present invention can lower the peak value of the ammonia concentration in the hydrogen-containing gas when the raw material supply amount is increased. Therefore, it is possible to suppress the stop of power generation in the fuel cell system due to an increase in the ammonia concentration in the hydrogen-containing gas, and the reliability can be improved.

The block diagram which shows the structure of the hydrogen production | generation apparatus and fuel cell system in Embodiment 1-3 of this invention Explanatory drawing for demonstrating setting the raw material supply amount increase rate from the operation continuation time in the hydrogen generator of Embodiment 1 of this invention and a fuel cell system. Explanatory drawing for demonstrating setting 1st time from the cumulative operation time in the hydrogen generator and fuel cell system of Embodiment 2 of this invention Explanatory drawing for demonstrating setting the raw material supply amount increase rate from the cumulative operation time in the hydrogen generator and fuel cell system of Embodiment 2 of this invention Explanatory drawing for demonstrating setting the electric power generation amount increase rate from the raw material supply amount increase rate in the hydrogen generator and fuel cell system of Embodiment 2 of this invention (A) Explanatory drawing for demonstrating setting the contribution part of the feed rate increase rate from the operation continuation time in the hydrogen generator and fuel cell system of Embodiment 3 of this invention (b) Implementation of this invention Explanatory drawing for demonstrating setting the contribution of the raw material supply amount increase rate from the accumulation operation time in the hydrogen generator of form 3, and a fuel cell system

  A hydrogen generator of a first invention includes a reformer having a reforming catalyst that reforms a raw material containing hydrocarbons and a nitrogen compound to generate a hydrogen-containing gas, and a hydrogen-containing gas generated by the reformer A CO remover for reducing carbon monoxide in the selective oxidation catalyst, a raw material supplier for supplying the raw material to the reformer, and a controller, and the controller starts operation. As the operation continuation time becomes longer, the rate of increase of the raw material supply amount when the raw material supply amount supplied from the raw material supply device to the reformer is increased is decreased.

  As a result, the temperature rise of the CO remover when the raw material supply amount is increased is moderated, and the more adsorbed ammonia is prevented from desorbing rapidly as the operation duration time becomes longer. The peak value of the ammonia concentration in the contained gas can be lowered.

  The hydrogen generator of the second invention includes a reformer having a reforming catalyst for reforming a raw material containing hydrocarbons and a nitrogen compound to generate a hydrogen-containing gas, and a hydrogen-containing gas generated by the reformer A CO remover for reducing carbon monoxide in the selective oxidation catalyst, a raw material supplier for supplying the raw material to the reformer, and a controller, and the controller starts operation. As the cumulative operation time increases, the rate of increase of the raw material supply amount when the raw material supply amount supplied from the raw material supply device to the reformer is increased is decreased.

  As a result, the temperature rise of the CO remover when the raw material supply amount increases is moderated, and the more adsorbed ammonia is prevented from desorbing rapidly as the cumulative operation time becomes longer. The peak value of the ammonia concentration in the contained gas can be lowered.

  A hydrogen generator according to a third aspect of the present invention includes a reformer having a reforming catalyst that reforms a raw material containing a hydrocarbon and a nitrogen compound to generate a hydrogen-containing gas, and a hydrogen-containing gas generated by the reformer A CO remover for reducing carbon monoxide in the selective oxidation catalyst, a raw material supplier for supplying the raw material to the reformer, and a controller, and the controller starts operation. The increase rate of the raw material supply amount is decreased when the raw material supply amount supplied from the raw material supplier to the reformer is increased according to the length of the operation duration and the cumulative operation time. It is.

  As a result, the temperature rise of the CO remover at the time of increasing the raw material supply amount is moderated, and the amount of ammonia adsorbed to the CO remover is prevented from desorbing rapidly as the operation duration time and cumulative operation time become longer. The peak value of the ammonia concentration in the hydrogen-containing gas at the time of increase can be lowered.

According to a fourth aspect of the present invention, there is provided a hydrogen generating apparatus according to any one of the first to third aspects of the invention, wherein the controller is configured such that the raw material supply amount supplied to the reformer is the maximum raw material supply amount. When it reaches, the operation duration time and the accumulated operation time are reset.

  Thereby, the increase rate of the raw material supply amount is reset in consideration of desorption of ammonia adsorbed on the CO remover when the raw material supply amount reaches the maximum raw material supply amount. Therefore, the increasing rate of the raw material supply amount can be set to an increasing rate corresponding to the ammonia adsorption amount of the CO remover.

  The hydrogen generator of the fifth invention is the hydrogen generator of any of the first to fourth inventions, in particular, the controller is configured to adjust the supply amount of the raw material until the operation continuation time reaches the first time. The rate of increase is not changed.

  As a result, the temperature of the CO remover is low and ammonia is not easily desorbed immediately after startup, and the ammonia concentration in the hydrogen-containing gas does not increase. Therefore, until the first time, the feed rate increase rate can be maintained at the maximum value. And the load followability of the hydrogen generator can be maintained.

  According to a sixth aspect of the present invention, in the hydrogen generating apparatus of the fifth aspect of the invention, the controller shortens the first time as the cumulative operation time becomes longer.

  Thus, the first time is set in consideration of the amount of ammonia adsorbed to the CO remover accumulated as the accumulated operation time becomes longer. Therefore, it is possible to appropriately set the time for starting to decrease the raw material supply amount increase rate.

  A fuel cell system according to a seventh aspect includes the hydrogen generator according to any one of the first to sixth aspects, and a fuel cell that generates power using the oxidant gas and the hydrogen-containing gas from the hydrogen generator. It is.

  Accordingly, it is possible to reduce the peak value of the ammonia concentration in the hydrogen-containing gas when the supply amount of the raw material is increased, and to suppress deterioration of the fuel cell. Therefore, it is possible to provide a highly reliable fuel cell system. it can.

  In the fuel cell system according to an eighth aspect of the invention, in particular, in the fuel cell system according to the seventh aspect of the invention, the controller changes the increase rate of the generated power of the fuel cell in accordance with the raw material increase rate.

  Thereby, it is possible to reduce the peak value of the ammonia concentration in the hydrogen-containing gas introduced from the hydrogen generator when the amount of generated power is increased, and it is possible to suppress poisoning of the fuel cell due to high concentration ammonia, A highly reliable fuel cell system capable of maintaining power generation can be provided.

  According to a ninth aspect of the present invention, there is provided a method for operating a hydrogen generator comprising a reformer for reforming a raw material containing hydrocarbons to produce a hydrogen-containing gas, and carbon monoxide in the hydrogen-containing gas produced by the reformer. An operation method of a hydrogen generator comprising a CO remover that reduces the amount by a selective oxidation catalyst and a raw material supplier that supplies the raw material to the reformer, and the operation duration time from the start of operation As the length increases, the rate of increase of the raw material supply amount in the case of increasing the raw material supply amount supplied from the raw material supply device to the reformer is decreased.

  As a result, the temperature rise of the CO remover when the raw material supply amount is increased is moderated, and the more adsorbed ammonia is prevented from desorbing rapidly as the operation duration time becomes longer. The peak value of the ammonia concentration in the contained gas can be lowered.

  According to a tenth aspect of the present invention, there is provided a method for operating a hydrogen generator, a reformer for reforming a raw material containing hydrocarbons to generate a hydrogen-containing gas, and carbon monoxide in the hydrogen-containing gas generated by the reformer. Is a method for operating a hydrogen generator comprising a CO remover that reduces the amount of gas by a selective oxidation catalyst and a raw material supplier that supplies the raw material to the reformer, and the cumulative operation time since the start of operation As the length increases, the rate of increase of the raw material supply amount when the raw material supply amount supplied from the raw material supply device to the reformer is increased is decreased.

  As a result, the temperature rise of the CO remover when the raw material supply amount increases is moderated, and the more adsorbed ammonia is prevented from desorbing rapidly as the cumulative operation time becomes longer. The peak value of the ammonia concentration in the contained gas can be lowered.

  According to an eleventh aspect of the present invention, there is provided a method for operating a hydrogen generator, comprising a reformer having a reforming catalyst for reforming a raw material containing hydrocarbons and a nitrogen compound to generate a hydrogen-containing gas, and the reformer. An operation method of a hydrogen generator comprising: a CO remover that reduces carbon monoxide in a hydrogen-containing gas by a selective oxidation catalyst; and a raw material supplier that supplies the raw material to the reformer, Increase in the raw material supply amount in the case of increasing the raw material supply amount supplied from the raw material supplier to the reformer according to the length of operation continuation time from the start and the length of the cumulative operation time It reduces the speed.

  As a result, the temperature rise of the CO remover at the time of increasing the raw material supply amount is moderated, and the amount of ammonia adsorbed to the CO remover is prevented from desorbing rapidly as the operation duration time and cumulative operation time become longer. The peak value of the ammonia concentration in the hydrogen-containing gas at the time of increase can be lowered.

  An operating method of a fuel cell system according to a twelfth aspect of the invention is an operating method of a fuel cell system comprising a hydrogen generator, and a fuel cell that generates electricity using an oxidant gas and a hydrogen-containing gas from the hydrogen generator. Thus, the hydrogen generator is operated by the operation method of the hydrogen generator of any of the ninth to eleventh aspects.

  As a result, the peak value of the ammonia concentration in the hydrogen-containing gas introduced from the hydrogen generator when the amount of generated power is increased can be reduced, and poisoning of the fuel cell due to high-concentration ammonia can be suppressed. It is possible to provide a highly reliable fuel cell system capable of maintaining the above.

  Hereinafter, the present invention will be described in more detail with reference to embodiments, but it is needless to say that the present invention is not limited to these embodiments.

(Embodiment 1)
FIG. 1 is a block diagram showing the configuration of a hydrogen generator and a fuel cell system according to Embodiment 1 of the present invention.

  In FIG. 1, a reformer 1 generates a hydrogen-containing gas by a reforming reaction using raw materials and steam. The raw material is city gas. City gas refers to gas supplied from a gas company to households through piping. The reforming reaction is a steam reforming reaction. The reformer temperature detector 12 detects the temperature of the reformer 1. The reformer temperature detector 12 is constituted by a thermocouple.

The raw material supplier 2 supplies the raw material to the reformer 1. The raw material supplier 2 is constituted by a booster. The water supplier 3 supplies water to the reformer 1. The water supply device 3 adjusts the flow rate of water and is configured by a pump. The CO remover 11 is a selective oxidation reactor that reduces CO in the hydrogen-containing gas discharged from the reformer 1 by a selective oxidation reaction. The selective oxidation air supply 6 is made of CO.
It is a blower for supplying air for selective oxidation supplied to the remover 11.

  The hydrogen-containing gas generated by the hydrogen generator 100 is supplied to the fuel cell 151 via the hydrogen supply path 8. The hydrogen supply path 8 is connected from the CO remover 11 to the fuel cell 151. There is a sealer 7 in the hydrogen supply path 8. The sealer 7 is composed of a solenoid valve. The fuel cell 151 is a solid polymer fuel cell.

  The heater 4 is a combustor that heats the reformer 1. As the fuel used for the combustion of the heater 4, a hydrogen-containing gas discharged from the reformer 1 is used during the startup of the hydrogen generator. The hydrogen-containing gas supplied to the heater 4 branches from the CO remover 11 to the sealer 7, passes through the sealer 13, and passes through the fuel supply path 10 introduced into the heater 4. 4 is supplied directly.

  After the supply of the hydrogen-containing gas to the fuel cell 151 is started, the gas that has not been used in the fuel cell 151 is supplied from the return channel 15 to the heater 4 through the sealer 14 and the fuel supply channel 10. The The fuel supplier 9 is constituted by a pump. The sealing device 13 and the sealing device 14 are constituted by electromagnetic valves. The air supplier 5 supplies combustion air to the heater 4. The air supply unit 5 is configured by a fan.

  The controller 50 is a control device that can control the entire fuel cell system 200. The controller 50 includes a CPU that is an arithmetic processing unit (not shown) and a memory that is a storage unit (not shown) that stores a control program. The controller 50 is composed of a single controller that performs centralized control.

  About the fuel cell system comprised as mentioned above, the operation | movement and an effect | action are demonstrated below.

  The following operation is performed by the controller 50 controlling the fuel cell system 200.

  When the hydrogen generator 100 is activated, combustion in the heater 4 is started. At this time, the sealing device 7 and the sealing device 14 are closed, the sealing device 13 is opened, the fuel supply passage 10 for combustion extending from the hydrogen supply passage 8 to reach the heater 4 is in a gas-venting state. It has become.

  Therefore, when the raw material is supplied to the reformer 1 by starting the operation of the raw material supplier 2, the raw material that has passed through the reformer 1 is supplied to the heater 4 using the fuel supply passage 10 for combustion. . At the same time, combustion air is supplied to the heater 4 by starting the operation of the air supply device 5.

  In the heater 4, an ignition operation is performed by an ignition electrode (not shown), and combustion of fuel occurs using combustion air. In this way, the reformer 1 is heated by the combustion heat supplied from the heater 4.

  Next, water is supplied to the reformer 1 by starting the operation of the water supplier 3. After the start of water supply, when the composition of the hydrogen-containing gas generated in the reformer 1 becomes a composition suitable for supply to the fuel cell 151, the sealing device 13 is closed and the sealing device 7 is sealed. The container 14 is opened, and the hydrogen-containing gas is supplied to the fuel cell 151. After the supply of the hydrogen-containing gas is started, the operation duration time is started. Let the operation duration be t.

  When the raw material supply amount is smaller than the maximum raw material supply amount, the selective oxidation reaction amount in the CO remover 11 is reduced, and the temperature of the CO remover 11 is lowered. Therefore, ammonia produced by the reaction of nitrogen and hydrogen in the raw material is adsorbed on the selective oxidation catalyst. Further, the total amount of ammonia adsorbed on the selective oxidation catalyst increases as the operation duration time increases.

  When the raw material supply amount reaches the maximum raw material supply amount, the selective oxidation reaction amount of the CO remover 11 increases, the CO remover 11 becomes high temperature, and the adsorbed ammonia is desorbed. Reset when the supply amount is reached. The maximum raw material supply amount is 3.5 NLM.

  Hereinafter, the increase rate determination method at the time of increasing the raw material supply amount will be described with the raw material supply amount increase rate as v.

  FIG. 2 is an explanatory diagram for explaining the setting of the raw material supply amount increase rate from the operation continuation time in the hydrogen generator and the fuel cell system according to Embodiment 1 of the present invention.

  As the operation duration time t becomes longer, the total amount of ammonia adsorbed to the CO remover 11 increases, so as shown in FIG. 2, the raw material supply rate increase rate v is reduced as the operation duration time t becomes longer. .

  When a command for increasing the raw material supply amount is input from the controller 50, the raw material supply amount increase speed v corresponding to the operation continuation time t at that time is set from FIG.

  As shown in FIG. 2, if the operation continuation time t is 20 h, the raw material supply amount increase rate v is set to 0.08 NLM / s. When the operation continuation time t becomes 30 h, the raw material supply amount increase rate v is set to 0.06 NLM / s, and the raw material supply amount increase rate v decreases as the operation continuation time t increases. The raw material supply amount starts to increase at the set raw material supply amount increase rate v.

  As a result of the above operation, the operation duration time t becomes longer and the raw material supply amount increase rate v is reduced, whereby the increase in the selective oxidation reaction amount in the CO remover 11 becomes moderate, and the temperature rise in the CO remover 11 increases. Be gentle.

  Therefore, it is possible to prevent a large amount of ammonia adsorbed on the CO remover 11 from desorbing rapidly, and the ammonia concentration in the hydrogen-containing gas gradually increases as the feed rate increases. Can be lowered.

  Therefore, it is possible to provide a highly reliable fuel cell system 200 that can suppress poisoning of the fuel cell 151 due to high-concentration ammonia and can maintain power generation.

  The fuel cell 151 may be a phosphoric acid fuel cell or an alkaline fuel cell.

  The supply of the hydrogen-containing gas to the heater 4 may be discharged from the fuel cell 151 via the fuel cell 151 and supplied to the heater 4. In the heater 4, the hydrogen-containing gas may be supplied from the fuel supplier 9. The fuel may be added to the gas and burned.

(Embodiment 2)
The configuration of the hydrogen generator and fuel cell system of Embodiment 2 of the present invention is the same as that of Embodiment 1, and the block diagram showing the configuration of the hydrogen generator and fuel cell system of Embodiment 2 is shown in FIG. It is shown in

  The difference from the first embodiment is that the raw material supply amount increase rate is not decreased until the time when the total amount of ammonia adsorbed to the CO remover 11 is small, and the raw material supply amount increase rate is based on the cumulative operation time. This is where the rate of increase in the amount of power generated by the fuel cell 151 is changed according to the setting rate and the rate of increase in the amount of raw material supply.

  After the supply of the hydrogen-containing gas is started, the operation duration time and the cumulative operation time are started to be counted. The operation continuation time is t, the cumulative operation time is T, and the feed rate increase rate is V.

  When the raw material supply amount is smaller than the maximum raw material supply amount, the selective oxidation reaction amount in the CO remover 11 is reduced, and the temperature of the CO remover 11 is lowered. Therefore, ammonia produced by the reaction of nitrogen and hydrogen in the raw material is adsorbed on the selective oxidation catalyst. Further, the total amount of ammonia adsorbed on the selective oxidation catalyst increases as the cumulative operation time T increases.

  When the raw material supply amount reaches the maximum raw material supply amount, the selective oxidation reaction amount of the CO remover 11 increases, the CO remover 11 becomes high temperature, and the adsorbed ammonia is desorbed. T is reset when the raw material supply amount reaches the maximum raw material supply amount. The maximum raw material supply amount is 3.3 NLM.

  Also, when the raw material supply amount increase command is input from the controller 50 until the operation continuation time t reaches the first time, the temperature of the CO remover 11 is low immediately after the start-up, so that ammonia is not easily desorbed. The ammonia concentration in the hydrogen-containing gas does not increase.

  Therefore, since the peak value of the ammonia concentration in the hydrogen-containing gas does not increase, the feed rate increase rate V is set to a constant value. The constant value is 0.09 NLM / s.

  The first time is set in consideration of the amount of ammonia adsorbed by the cumulative operation time T. Let the first time be t1.

  FIG. 3 is an explanatory diagram for explaining the setting of the first time from the cumulative operation time in the hydrogen generator and the fuel cell system according to Embodiment 2 of the present invention. As shown in FIG. 3, the first time t1 is shortened as the cumulative operation time T increases.

  If the cumulative operation time T is 2000h, the first time t1 is 30h. If the cumulative operation time T is 3000h, the first time t1 is 25h, and the first time t1 is shortened as the cumulative operation time T becomes longer.

  When the raw material supply amount increase command is input from the controller 50 after the operation continuation time t reaches the first time t1, the total amount of ammonia adsorbed on the CO remover 11 is increased. V is decreased as the cumulative operation time T becomes longer.

  Thereby, the first time t1 can be set in consideration of the ammonia adsorption amount to the CO remover 11 accumulated as the cumulative operation time T becomes longer. Therefore, it is possible to appropriately set the time for starting to decrease the raw material supply amount increase rate V.

  FIG. 4 is an explanatory diagram for explaining the setting of the feed rate increase rate from the cumulative operation time in the hydrogen generator and the fuel cell system according to Embodiment 2 of the present invention. As the cumulative operation time T becomes longer, the amount of ammonia adsorbed to the CO remover 11 increases, so the raw material supply amount increase rate V is reduced as shown in FIG.

  When a command to increase the raw material supply amount is input from the controller 50, the raw material supply amount increase speed V corresponding to the cumulative operation time T at that time is read from FIG.

As shown in FIG. 4, when the cumulative operation time T is 2000 h, the raw material supply amount increase rate V is set to 0.05 NLM / s. Further, if the cumulative operation time T becomes 3000 h, the raw material supply amount increase rate V is set to 0.04 NLM / s, and the raw material supply amount increase rate V decreases as the cumulative operation time T increases.

  The raw material supply amount starts to increase at the set raw material supply amount increase rate V. As the cumulative operation time T becomes longer and the raw material supply rate increase rate V becomes smaller, the increase in the selective oxidation reaction amount in the CO remover 11 becomes moderate, and the temperature rise in the CO remover 11 becomes moderate. Accordingly, it is possible to prevent a large amount of ammonia adsorbed on the CO remover 11 from being abruptly desorbed as the cumulative operation time T becomes longer, and to reduce the peak value of the ammonia concentration in the hydrogen-containing gas.

  FIG. 5 is an explanatory diagram for explaining the setting of the generated power generation rate increase rate from the raw material supply rate increase rate in the hydrogen generator and the fuel cell system according to Embodiment 2 of the present invention.

  As shown in FIG. 5, as the raw material supply amount increase rate V decreases, the generated power amount increase rate decreases. Let W be the rate of increase in the amount of generated power.

  If the raw material supply amount increase rate V is 0.05 NLM / s, the generated power amount increase rate W is set to 0.10 W / s. If the raw material supply amount increase rate V becomes 0.04 NLM / s, the generated power amount increase rate W is set to 0.08 W / s, and the generated power amount increase rate W decreases as the raw material supply amount increase rate V decreases. .

  By the above operation, before the operation continuation time t reaches the first time t1, the temperature of the CO remover 11 is just after the start-up and the temperature of the CO remover 11 is low. Therefore, the raw material supply amount increase speed V can be maintained at the maximum value, and load followability can be maintained.

  After the operation continuation time t reaches the first time t1, the cumulative operation time T becomes longer and the feed rate increase rate V becomes smaller, so that the increase in the selective oxidation reaction amount in the CO remover 11 becomes moderate, The temperature rise of the CO remover 11 becomes moderate.

  Therefore, the amount of ammonia adsorbed to the CO remover 11 is prevented from being rapidly desorbed as the cumulative operation time T becomes longer, and the hydrogen-containing gas introduced from the hydrogen generator 100 when the amount of power generated by the fuel cell 151 increases is increased. Although the ammonia concentration gradually increases, the peak value of the ammonia concentration can be reduced.

  Therefore, it is possible to provide a highly reliable fuel cell system 200 that can suppress poisoning of the fuel cell 151 due to high-concentration ammonia and can maintain power generation.

  In the present embodiment, the raw material supply amount increase speed V is set based on the cumulative operation time T. However, even if the raw material supply amount increase speed V is set based on the cumulative number of activations, the cumulative operation time T Since the cumulative number of activations is proportional, the same effect can be obtained.

(Embodiment 3)
The configuration of the hydrogen generator and fuel cell system of Embodiment 3 of the present invention is the same as that of Embodiment 1, and a block diagram showing the configuration of the hydrogen generator and fuel cell system of Embodiment 3 is shown in FIG. Is.

  The difference from the first embodiment is that the raw material supply amount increase rate is set based on both the operation continuation time and the cumulative operation time.

  After the supply of the hydrogen-containing gas is started, the operation duration time and the cumulative operation time are started to be counted.

  The operation duration time is t, and the cumulative operation time is T.

  When the raw material supply amount is smaller than the maximum raw material supply amount, the selective oxidation reaction amount in the CO remover 11 is reduced, and the temperature of the CO remover 11 is lowered. Therefore, ammonia produced by the reaction of nitrogen and hydrogen in the raw material is adsorbed on the selective oxidation catalyst. Further, the total amount of ammonia adsorbed on the selective oxidation catalyst increases as the operation duration time and the accumulated operation time become longer.

  When the raw material supply amount reaches the maximum raw material supply amount, the selective oxidation reaction amount of the CO remover 11 increases, the CO remover 11 becomes high temperature, and the adsorbed ammonia is desorbed. T is reset when the raw material supply amount reaches the maximum raw material supply amount. The maximum raw material supply amount is 3.6 NLM.

  The feed rate increase rate is obtained as the sum of the contribution due to the operation duration time t and the contribution due to the cumulative operation time T.

  The contribution due to the operation continuation time of the raw material supply rate increase rate is v, and the contribution due to the cumulative operation time is V.

  FIG. 6 (a) is an explanatory diagram for explaining setting of the contribution rate of the raw material supply amount increase rate from the operation continuation time in the hydrogen generator and fuel cell system of Embodiment 3 of the present invention.

  As the operation duration time t becomes longer, the amount of ammonia adsorbed to the CO remover 11 increases, so as shown in FIG. 6A, the contribution v due to the operation duration time of the raw material supply rate increase rate is reduced.

  FIG. 6B is an explanatory diagram for explaining setting of the contribution of the raw material supply amount increase rate from the cumulative operation time in the hydrogen generator and the fuel cell system according to Embodiment 3 of the present invention.

  As the cumulative operation time T becomes longer, more ammonia is adsorbed to the CO remover 11, so that the contribution V due to the cumulative operation time of the raw material supply rate increase rate is reduced as shown in FIG. 6B.

  When a command for increasing the raw material supply amount is input from the controller 50, the contribution v of the raw material supply amount increase speed corresponding to the operation continuation time t and the cumulative operation time T at that time and the raw material supply amount increase speed The contribution V due to the accumulated operation time is read from FIGS. 6 (a) and 6 (b).

  As shown in FIG. 6A, if the operation continuation time t is 200 h, the contribution v due to the operation continuation time of the raw material supply rate increase rate is 0.05 NLM / s. If the operation duration t is 400h, the contribution v due to the operation duration time of the raw material supply rate increase rate is 0.03 NLM / s, and the contribution of the raw material supply rate increase rate due to the operation duration time as the operation duration time t increases. Shorten the minute v.

  As shown in FIG. 6B, if the cumulative operation time T is 3000 h, the contribution V due to the cumulative operation time of the raw material supply rate increase rate is 0.08 NLM / s. If the cumulative operation time T is 4000 h, the contribution V due to the cumulative operation time of the raw material supply rate increase rate is 0.04 NLM / s, and as the cumulative operation time T becomes longer, it depends on the cumulative operation time of the raw material supply rate increase rate. The contribution V is reduced.

The feed rate increase rate is set by the contribution v due to the operation duration of the feed rate increase rate + the contribution V due to the cumulative run time of the feed rate increase rate, 7 if the run duration t is 200h and the cumulative run time T is 3000h. 0.05NLM / s + 0.08NLM / s = 0.13NLM / s. If the operation duration time t is 400h and the cumulative operation time T is 4000h, 0.03NLM / s + 0.04NLM / s = 0.07NLM / s. Start increasing the feed rate at the set speed.

  By the above operation, the operation continuation time t and the cumulative operation time T are lengthened, and the increase in the selective oxidation reaction amount in the CO remover 11 is moderated by decreasing the raw material supply rate increase rate. The temperature rise is moderate.

  Therefore, as the operation duration time t and the cumulative operation time T become longer in the CO remover 11, the more adsorbed ammonia is prevented from rapidly desorbing, and the ammonia concentration in the hydrogen-containing gas when the feed rate is increased gradually. However, the peak value of the ammonia concentration can be lowered.

  Therefore, it is possible to provide a highly reliable fuel cell system 200 that can suppress poisoning of the fuel cell 151 due to high-concentration ammonia and can maintain power generation.

  From the above 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. The details of the structure and / or function may be substantially changed without departing from the spirit of the invention.

  The hydrogen generator of the present invention can reduce the peak value of the ammonia concentration in the hydrogen-containing gas when the amount of raw material supply is increased, and thus is suitable for a household cogeneration system.

DESCRIPTION OF SYMBOLS 1 Reformer 2 Raw material supply device 3 Water supply device 4 Heater 5 Air supply device 6 Selective oxidation air supply device 7 Sealing device 8 Hydrogen supply channel 9 Fuel supply device 10 Fuel supply channel 11 CO remover 12 Reformer Temperature detector 13 Sealing device 14 Sealing device 15 Return flow path 50 Controller 100 Hydrogen generator 151 Fuel cell 200 Fuel cell system

Claims (12)

A reformer having a reforming catalyst for reforming a raw material containing a hydrocarbon and a nitrogen compound to generate a hydrogen-containing gas;
A CO remover for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer with a selective oxidation catalyst;
A raw material supplier for supplying the raw material to the reformer;
A controller;
With
The controller increases an increase rate of the raw material supply amount when the raw material supply amount supplied from the raw material supply device to the reformer is increased as the operation continuation time from the start of operation becomes longer. Reduce hydrogen generator. A reformer having a reforming catalyst for reforming a raw material containing a hydrocarbon and a nitrogen compound to generate a hydrogen-containing gas;
A CO remover for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer with a selective oxidation catalyst;
A raw material supplier for supplying the raw material to the reformer;
A controller;
With
The controller increases an increase rate of the raw material supply amount when the raw material supply amount supplied from the raw material supply device to the reformer is increased as the cumulative operation time from the start of operation becomes longer. Reduce hydrogen generator. A reformer having a reforming catalyst for reforming a raw material containing a hydrocarbon and a nitrogen compound to generate a hydrogen-containing gas;
A CO remover for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer with a selective oxidation catalyst;
A raw material supplier for supplying the raw material to the reformer;
A controller;
With
When the controller increases the amount of raw material supplied from the raw material supplier to the reformer according to the length of operation continuation time after starting operation and the length of cumulative operation time A hydrogen generation device that reduces the rate of increase in the amount of raw material supply.   4. The controller according to claim 1, wherein when the raw material supply amount supplied to the reformer reaches a maximum raw material supply amount, the controller resets the operation duration time and the cumulative operation time. 5. The hydrogen generator.   The hydrogen generator according to any one of claims 1 to 4, wherein the controller does not change the increasing rate of the raw material supply amount until an operation continuation time reaches a first time.   The hydrogen generator according to claim 5, wherein the controller shortens the first time as the cumulative operation time becomes longer.   A fuel cell system comprising: the hydrogen generator according to any one of claims 1 to 6; and a fuel cell that generates electric power using an oxidant gas and a hydrogen-containing gas from the hydrogen generator.   The fuel cell system according to claim 7, wherein the controller changes an increase rate of the generated power of the fuel cell according to the raw material increase rate. A reformer that reforms a raw material containing hydrocarbons to produce a hydrogen-containing gas;
A CO remover for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer with a selective oxidation catalyst;
A raw material supplier for supplying the raw material to the reformer;
A method of operating a hydrogen generator comprising:
Hydrogen generation that decreases the rate of increase of the raw material supply amount when increasing the raw material supply amount supplied from the raw material supply device to the reformer as the operation duration time from the start of operation increases. How to operate the device. A reformer that reforms a raw material containing hydrocarbons to produce a hydrogen-containing gas;
A CO remover for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer with a selective oxidation catalyst;
A raw material supplier for supplying the raw material to the reformer;
A method of operating a hydrogen generator comprising:
Hydrogen generation that decreases the rate of increase of the raw material supply amount when the raw material supply amount supplied from the raw material supply device to the reformer is increased as the cumulative operation time from the start of operation becomes longer How to operate the device. A reformer having a reforming catalyst for reforming a raw material containing a hydrocarbon and a nitrogen compound to generate a hydrogen-containing gas;
A CO remover for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer with a selective oxidation catalyst;
A raw material supplier for supplying the raw material to the reformer;
A method of operating a hydrogen generator comprising:
The raw material supply amount in the case of increasing the raw material supply amount supplied from the raw material supplier to the reformer according to the length of the operation continuation time after starting operation and the length of the cumulative operation time A method of operating a hydrogen generator that reduces the rate of increase of the gas. An operation method of a fuel cell system comprising: a hydrogen generator; and a fuel cell that generates electricity using an oxidant gas and a hydrogen-containing gas from the hydrogen generator,
An operation method of a fuel cell system, wherein the hydrogen generation device is operated by the operation method of the hydrogen generation device according to any one of claims 9 to 11.

Images