Hydrogen generation device, fuel cell system, and method for operating hydrogen generation device

Abstract

A hydrogen generation device (1) according to the present invention is provided with a reformer (10), a raw fuel feeder (11), a detector (12), a measuring instrument (13) and a control unit (14). The reformer (10) produces a hydrogen-containing gas from a raw fuel gas. The raw fuel feeder (11) supplies the raw fuel gas to the reformer (10). The detector (12) detects a first measurement value that is settled in accordance with the flow rate of the raw fuel gas. The measuring instrument (13) detects a second measurement value that is changed in accordance with the quantitative mixing state of a hydrogen gas in the raw fuel gas, and determines a characteristic value that indicates the quantitative mixing state of the hydrogen gas on the basis of the second measurement value. The control unit (14) adjusts an operational parameter on the basis of the first measurement value and the characteristic value. The operational parameter is a parameter for controlling the production of the hydrogen-containing gas in the reformer (10).

Description

[Technical field]

[0001] The present disclosure relates to a hydrogen generation device, a fuel cell system, and a method for operating a hydrogen generation device. [Background technology]

[0002] Conventionally, there is known a technology for producing hydrogen from a raw fuel gas mainly composed of hydrocarbons in a fuel cell system. For example, Patent Document 1 discloses a hydrogen production device equipped with a steam reformer that produces hydrogen from a raw fuel gas containing hydrocarbons by reacting the raw fuel gas with steam. This hydrogen production device includes a mass flow meter and a control means.

[0003] The mass flow meter measures the mass flow rate of the raw fuel gas. The control means calculates the mass flow rate of the carbon content contained in the raw fuel gas based on the mass flow rate measured by the mass flow meter, and controls the flow rate of the steam supplied to the steam reformer based on the calculated value. As the raw fuel gas, for example, saturated hydrocarbon gas such as natural gas and liquefied petroleum gas (LPG), and unsaturated hydrocarbon gas are used. The mass flow meter is, for example, a thermal flow sensor. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2004-59354 A Summary of the Invention

[0005] Patent Document 1 does not consider the case where the raw fuel gas contains hydrogen. For example, a flow meter adjusted for natural gas used as the raw fuel gas cannot detect the mixed state of hydrogen in the raw fuel gas. Therefore, a discrepancy occurs between the flow rate detected by the flow meter and the actual flow rate. This may cause the operation balance of the hydrogen generation device and the fuel cell system to be lost. In addition, the concentration of hydrogen contained in the raw fuel gas may change over time. For this reason, it has been difficult to grasp the mixed state of hydrogen in the raw fuel gas in advance.

[0006] The present disclosure provides a technique for appropriately controlling the generation of hydrogen-containing gas in accordance with the quantitative mixed state of hydrogen in a raw fuel gas.

[0007] The present disclosure provides a hydrogen generation device including a reformer that generates a hydrogen-containing gas from a raw fuel gas, a raw fuel supplier that supplies the raw fuel gas to the reformer, a detector that detects a first measurement value determined according to a flow rate of the raw fuel gas supplied by the raw fuel supplier, a measuring instrument that detects a second measurement value that changes according to a quantitative mixed state of hydrogen gas in the raw fuel gas and determines a characteristic value that indicates the quantitative mixed state based on the second measurement value, and a control unit that adjusts operating parameters for controlling the generation of the hydrogen-containing gas in the reformer based on the first measurement value and the characteristic value.

[0008] According to the present disclosure, the generation of hydrogen gas in the reformer can be appropriately controlled according to the quantitative mixing state of hydrogen gas in the raw fuel gas. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a configuration diagram showing an example of a hydrogen generation device according to the present disclosure. [Diagram 2] FIG. 2 is a flowchart showing an example of a process in the hydrogen generation device. [Diagram 3] FIG. 3 is a graph showing the relationship between the heat dissipation coefficient of each gas and the temperature of the heating resistor. [Figure 4]FIG. 4 is a configuration diagram showing an example of a measuring device of the hydrogen generation device of the present disclosure. [Diagram 5] FIG. 5 is a configuration diagram showing an example of a fuel cell system according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] (Findings on which this disclosure is based) For example, attempts are being made to supply hydrogen gas generated by Power to Gas to a natural gas pipeline. In this case, it is assumed that hydrogen gas is mixed into the raw fuel gas when hydrogen-containing gas is generated from the raw fuel gas in the reformer. In this case, it is assumed that the concentration of hydrogen gas in the raw fuel gas varies depending on the region or time. When hydrogen gas is mixed into the raw fuel gas, if a thermal mass flowmeter is used to measure the flow rate of the raw fuel gas as in the technology described in Patent Document 1, the actual flow rate of the raw fuel gas may be larger than the measured flow rate. This may make it difficult to maintain a heat balance suitable for generating hydrogen-containing gas in the reformer, making it difficult to stably generate hydrogen-containing gas in the reformer.

[0011] Therefore, the inventors of the present invention have been working day and night to develop a technique for appropriately controlling the generation of hydrogen gas depending on the quantitative mixture state of hydrogen gas in the raw fuel gas, and have devised the hydrogen generation device of the present disclosure.

[0012] (Summary of one aspect of the present disclosure) The hydrogen generation apparatus of the present disclosure includes a reformer that generates a hydrogen-containing gas from a raw fuel gas, a raw fuel supplier that supplies the raw fuel gas to the reformer, a detector that detects a first measurement value determined according to the flow rate of the raw fuel gas supplied by the raw fuel supplier, a measuring instrument that detects a second measurement value that changes according to the quantitative mixed state of hydrogen gas in the raw fuel gas and determines a characteristic value that indicates the quantitative mixed state based on the second measurement value, and a control unit that adjusts operating parameters for controlling the generation of hydrogen-containing gas in the reformer based on the first measurement value and the characteristic value.

[0013] In this manner, the operation parameters for controlling the generation of the hydrogen-containing gas in the reformer are adjusted based on the first measurement value determined according to the flow rate of the raw fuel gas and the characteristic value indicating the quantitative mixed state of the hydrogen gas in the raw fuel gas, so that the generation of the hydrogen-containing gas in the reformer can be appropriately controlled according to the quantitative mixed state of the hydrogen gas in the raw fuel gas, and the hydrogen-containing gas can be stably generated in the reformer.

[0014] In the hydrogen generation apparatus of the present disclosure, the measurement device may determine the characteristic value based on a second measurement value related to the average molecular weight of the raw fuel gas.

[0015] This makes it possible to determine a characteristic value indicative of the quantitative mixing state of hydrogen gas in the raw fuel gas based on the second measurement value relating to the average molecular weight of the raw fuel gas.

[0016] In the hydrogen generation apparatus of the present disclosure, the measurement device may determine the characteristic value based on a second measurement value related to the thermal conductivity of the raw fuel gas.

[0017] This makes it possible to determine a characteristic value indicative of the quantitative mixing state of hydrogen gas in the raw fuel gas based on the second measured value relating to the thermal conductivity of the raw fuel gas.

[0018] The hydrogen generation apparatus of the present disclosure may have a first flow meter and a second flow meter for measuring the flow rate of the raw fuel gas, and the measurement sensitivity of the second flow meter to hydrogen gas may be different from the measurement sensitivity of the first flow meter to hydrogen gas. In addition, the measurement device may determine a characteristic value based on a difference between a first flow rate measured by the first flow meter and a second flow rate measured by the second flow meter.

[0019] This makes it possible to determine a characteristic value that indicates the quantitative mixed state of hydrogen gas in the raw fuel gas based on the flow rates measured by the first flow meter and the second flow meter, which have different measurement sensitivities to hydrogen gas.

[0020] The hydrogen generation apparatus of the present disclosure may further include a water supplier that supplies water to the reformer, and the control unit may control the water supplier based on the first measurement value and the characteristic value so that the molar ratio of water supplied to the reformer to carbon atoms contained in the raw fuel gas supplied to the reformer is within a predetermined range.

[0021] This allows the molar ratio of water supplied to the reformer to the carbon atoms contained in the raw fuel gas to be adjusted within a predetermined range based on the first measurement value and the characteristic value indicating the quantitative mixing state of hydrogen gas in the raw fuel gas, thereby enabling the hydrogen-containing gas to be stably produced in the reformer.

[0022] The hydrogen generation apparatus of the present disclosure may further include a combustor that burns fuel gas with air to heat the reformer, and an air supplier that supplies air for combustion to the combustor, and the control unit may control the air supplier based on the first measurement value and the characteristic value so that the ratio of the flow rate of the air supplied to the combustor to the flow rate of the fuel gas supplied to the combustor, or the ratio of the flow rate of the air supplied to the combustor to the flow rate of the raw fuel gas supplied to the reformer, is within a predetermined range.

[0023] This allows the ratio of the flow rate of the air supplied to the combustor to the flow rate of the fuel gas supplied to the combustor to be adjusted within a predetermined range based on the first measurement value and the characteristic value indicating the quantitative mixing state of hydrogen gas in the raw fuel gas.Alternatively, the ratio of the flow rate of the air supplied to the combustor to the flow rate of the raw fuel gas supplied to the reformer can be adjusted within a predetermined range based on the first measurement value and the characteristic value indicating the quantitative mixing state of hydrogen gas in the raw fuel gas.As a result, hydrogen-containing gas can be stably generated in the reformer.

[0024] The fuel cell system of the present disclosure includes a hydrogen generation device and a fuel cell that generates electricity using hydrogen-containing gas generated by the hydrogen generation device.

[0025] This allows the reformer to stably generate hydrogen-containing gas, and the fuel cell to stably generate power.

[0026] The fuel cell system of the present disclosure may further include a calculation unit that determines a target output of the fuel cell system based on the characteristic value.

[0027] This makes it possible to determine the target output of the fuel cell system according to the quantitative mixture state of hydrogen gas in the raw fuel gas, and to operate the fuel cell system according to the target output.

[0028] The method of operating a hydrogen generation apparatus disclosed herein is a method of operating a hydrogen generation apparatus that generates a hydrogen-containing gas from a raw fuel gas in a reformer, and includes adjusting an operating parameter for controlling the generation of the hydrogen-containing gas in the reformer in accordance with the quantitative mixing state of hydrogen gas in the raw fuel gas.

[0029] This makes it possible to adjust the operation parameters for controlling the production of hydrogen-containing gas in the reformer in accordance with the quantitative mixing state of hydrogen gas in the raw fuel gas, thereby enabling the hydrogen-containing gas to be stably produced in the reformer.

[0030] The operating method of the present disclosure may include detecting a first measurement value determined according to a flow rate of raw fuel gas supplied to the reformer, detecting a second measurement value that varies according to a quantitative mixed state of hydrogen gas in the raw fuel gas, determining a characteristic value indicating the quantitative mixed state based on the second measurement value, and adjusting an operating parameter for controlling the generation of hydrogen-containing gas in the reformer based on the first measurement value and the characteristic value.

[0031] In this manner, the operation parameters for controlling the generation of the hydrogen-containing gas in the reformer are adjusted based on the first measurement value determined according to the flow rate of the raw fuel gas and the characteristic value indicating the quantitative mixed state of the hydrogen gas in the raw fuel gas, so that the generation of the hydrogen-containing gas in the reformer can be appropriately controlled according to the quantitative mixed state of the hydrogen gas in the raw fuel gas, and the hydrogen-containing gas can be stably generated in the reformer.

[0032] In the method of operation of the present disclosure, the characteristic value may be determined based on a second measurement of the average molecular weight of the raw fuel gas.

[0033] This makes it possible to determine a characteristic value indicative of the quantitative mixing state of hydrogen gas in the raw fuel gas based on the second measurement value relating to the average molecular weight of the raw fuel gas.

[0034] In the method of operation of the present disclosure, the characteristic value may be determined based on a second measurement related to the thermal conductivity of the raw fuel gas.

[0035] This makes it possible to determine a characteristic value indicative of the quantitative mixing state of hydrogen gas in the raw fuel gas based on the second measured value relating to the thermal conductivity of the raw fuel gas.

[0036] In the operating method of the present disclosure, detecting the second measurement value may include measuring a flow rate of the raw fuel gas using a first flow meter and a second flow meter. In addition, a measurement sensitivity of the second flow meter to hydrogen gas may be different from a measurement sensitivity of the first flow meter to hydrogen gas, and the characteristic value may be determined based on a difference between the first flow rate measured by the first flow meter and the second flow rate measured by the second flow meter.

[0037] This makes it possible to determine a characteristic value that indicates the quantitative mixed state of hydrogen gas in the raw fuel gas based on the flow rates measured by the first flow meter and the second flow meter, which have different measurement sensitivities to hydrogen gas.

[0038] In the operating method disclosed herein, the molar ratio of water supplied to the reformer to carbon atoms contained in the raw fuel gas supplied to the reformer may be adjusted to within a predetermined range based on the first measurement value and the characteristic value.

[0039] This allows the molar ratio of water supplied to the reformer to the carbon atoms contained in the raw fuel gas to be adjusted within a predetermined range based on the first measurement value and the characteristic value indicating the quantitative mixing state of hydrogen gas in the raw fuel gas, thereby enabling the hydrogen-containing gas to be stably produced in the reformer.

[0040] The operating method disclosed herein may further include burning the fuel gas with air in the combustor to heat the reformer, and may adjust, based on the first measurement value and the characteristic value, the ratio of the flow rate of the air supplied to the combustor to the flow rate of the fuel gas supplied to the combustor, or the ratio of the flow rate of the air supplied to the combustor to the flow rate of the raw fuel gas supplied to the reformer, within a predetermined range.

[0041] This allows the ratio of the flow rate of the air supplied to the combustor to the flow rate of the fuel gas supplied to the combustor to be adjusted within a predetermined range based on the first measurement value and the characteristic value indicating the quantitative mixing state of hydrogen gas in the raw fuel gas.Alternatively, the ratio of the flow rate of the air supplied to the combustor to the flow rate of the raw fuel gas supplied to the reformer can be adjusted within a predetermined range based on the first measurement value and the characteristic value indicating the quantitative mixing state of hydrogen gas in the raw fuel gas.As a result, hydrogen-containing gas can be stably generated in the reformer.

[0042] Hereinafter, the embodiments will be described in detail with reference to the drawings. However, more detailed description than necessary may be omitted. For example, detailed description of already well-known matters or duplicate description of substantially the same configuration may be omitted.

[0043] It should be noted that the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present disclosure, and are not intended to limit the subject matter described in the claims.

[0044] (Embodiment) 1 is a configuration diagram showing a hydrogen generator 1 according to an embodiment of the present disclosure. As shown in FIG. 1, the hydrogen generator 1 includes a reformer 10, a raw fuel supplier 11, a detector 12, a measuring device 13, and a control unit 14.

[0045] The reformer 10 generates a hydrogen-containing gas from a raw fuel gas. The raw fuel supplier 11 supplies the raw fuel gas to the reformer 10. The raw fuel supplier 11 is, for example, a pump such as a booster pump.

[0046] The detector 12 detects a first measurement value M1 determined according to the flow rate of the raw fuel gas supplied by the raw fuel supplier 11. The detector 12 is, for example, a thermal mass flow meter.

[0047] The measuring instrument 13 detects a second measurement value M2 that changes according to the quantitative mixture state of hydrogen gas in the raw fuel gas. The measuring instrument 13 also determines a characteristic value Vc that indicates the quantitative mixture state of hydrogen gas in the raw fuel gas based on the second measurement value M2.

[0048] The control unit 14 adjusts the operation parameter Ps based on the first measurement value M1 and the characteristic value Vc. The operation parameter Ps is a parameter for controlling the generation of hydrogen-containing gas in the reformer 10. A specific method for controlling the generation of hydrogen-containing gas in the reformer 10 using the operation parameter Ps will be described later.

[0049] According to the hydrogen generator 1, the operation parameter Ps for controlling the generation of hydrogen-containing gas in the reformer 10 is adjusted in accordance with the quantitative mixed state of hydrogen gas in the raw fuel gas.

[0050] In the hydrogen generator 1, for example, when a predetermined condition is met, a series of processes shown in FIG. 2 is executed to control the generation of hydrogen-containing gas in the reformer 10.

[0051] First, in step S11, a first measurement value M1 is detected. For example, the first measurement value M1 is detected by the detector 12.

[0052] Next, in step S12, a second measurement value M2 is detected. For example, the second measurement value M2 is detected by the measuring device 13.

[0053] Next, in step S13, a characteristic value Vc indicating the quantitative mixed state of hydrogen gas in the raw fuel gas is determined based on the second measurement value M2. For example, the characteristic value Vc is determined by the measuring device 13.

[0054] Next, in step S14, an operation parameter Ps for controlling the generation of hydrogen-containing gas in the reformer 10 is adjusted based on the first measurement value M1 and the characteristic value Vc. For example, the control unit 14 adjusts the operation parameter Ps based on the first measurement value M1 and the characteristic value Vc.

[0055] Next, in step S15, the reaction in the reformer 10 is controlled based on the operation parameter Ps adjusted in step S14, and the series of processes is terminated. This series of processes is performed periodically or irregularly during the operation of the hydrogen generator 1.

[0056] The operation parameter Ps is adjusted periodically or irregularly, for example, during operation of the hydrogen generator 1. As a result, even if the quantitative mixture state of hydrogen gas in the raw fuel gas fluctuates during operation of the hydrogen generator 1, for example, the operation parameter Ps is adjusted in accordance with the quantitative mixture state of hydrogen gas in the raw fuel gas.

[0057] As described above, the quantitative mixture state of hydrogen gas in the raw fuel gas may vary during operation of the hydrogen generator 1. For example, the quantitative mixture state of hydrogen gas in the raw fuel gas may temporarily become a high-level state or a low-level state that deviates from the standard state. In this case, the operation parameter Ps is adjusted to match the high-level state or the low-level state. Thereafter, when the quantitative mixture state of hydrogen gas in the raw fuel gas returns to the standard state, the operation parameter Ps is returned to match the standard state.

[0058] The operation parameter Ps may be adjusted, for example, before or during start-up of the hydrogen generation apparatus 1. In this case, the operation parameter Ps is adjusted according to the quantitative mixed state of hydrogen gas in the raw fuel gas before or during start-up of the hydrogen generation apparatus 1. Therefore, the hydrogen generation apparatus 1 can be operated according to the desired operation parameter Ps from the beginning of operation of the hydrogen generation apparatus 1.

[0059] The adjusted operational parameter Ps may be stored in the hydrogen generator 1. For example, when the hydrogen generator 1 is stopped, the operational parameter Ps used immediately before the hydrogen generator 1 was stopped is stored. The stored value of the operational parameter Ps can be used, for example, the next time the hydrogen generator 1 is started up.

[0060] According to the hydrogen generation device 1, the operation parameter Ps is adjusted based on the first measurement value M1 and the characteristic value Vc. Therefore, the generation of hydrogen-containing gas in the reformer 10 is appropriately controlled according to the quantitative mixed state of hydrogen gas in the raw fuel gas. As a result, the hydrogen-containing gas is stably generated in the reformer 10. The first measurement value M1 may be a value of the flow rate of the raw fuel gas supplied by the raw fuel supplier 11, or may be a value of a physical quantity having a correlation with the flow rate. The characteristic value Vc may be a value indicating the mixed ratio of hydrogen gas in the raw fuel gas, or may be a value indicating in stages the level of the quantitative mixed state of hydrogen gas in the raw fuel gas.

[0061] When the mixture ratio of hydrogen gas in the raw fuel gas is high, the difference between the first measurement value M1 and the actual value becomes large due to the sensitivity of the detector 12 to hydrogen gas. In this case, the flow rate of the raw fuel gas corresponding to the first measurement value M1 becomes lower than the actual flow rate of the raw fuel gas. For this reason, if the operation parameter Ps is adjusted based only on the first measurement value M1, it is difficult to keep the generation reaction of the hydrogen-containing gas in the reformer 10 in a desired state. However, according to the hydrogen generation device 1, the operation parameter Ps is adjusted based on the characteristic value Vc in addition to the first measurement value M1. Therefore, it is easy to keep the generation reaction of the hydrogen-containing gas in the reformer 10 in a desired state.

[0062] The second measurement value M2 detected by the measuring instrument 13 is not limited to a specific value as long as it changes depending on the quantitative mixing state of hydrogen gas in the raw fuel gas. The measuring instrument 13 determines the characteristic value Vc based on, for example, the second measurement value M2 related to the average molecular weight of the raw fuel gas. The second measurement value M2 may be a value indicating the average molecular weight of the raw fuel gas, or may be a value of a physical quantity having a correlation with the average molecular weight of the raw fuel gas.

[0063] The second measurement value M2 relating to the average molecular weight of the raw fuel gas may be, for example, the speed of sound Vs in the raw fuel gas. The relationship shown in the following formula (1) holds between the speed of sound Vs in the raw fuel gas and the average molecular weight M of the raw fuel gas. In formula (1), γ is the specific heat ratio (=Cp / Cv), R is the universal gas constant, T is the temperature, Cp is the specific heat at constant pressure, and Cv is the specific heat at constant volume.

[0064]

number

[0065] In addition, the sound speed Vm for a gas mixture containing n components can be determined, for example, according to Equation (2): where Cpi is the constant pressure specific heat of the i-th component, Cvi is the constant volume specific heat of the i-th component, Xi is the mole fraction of the i-th component, and Mi is the molecular weight of the i-th component.

[0066]

number

[0067] The raw fuel gas may typically include gases such as hydrocarbon gases such as methane gas, nitrogen gas, carbon dioxide gas, and hydrogen gas. Among these gases, the molecular weight of hydrogen gas is significantly smaller than that of other gases. Therefore, a change in the mixing ratio of hydrogen gas in the raw fuel gas has a large effect on the average molecular weight M of the raw fuel gas.

[0068] For example, a standard gas that does not contain hydrogen gas is prepared by adjusting the mixing ratio of each gas other than hydrogen gas to a constant value with reference to a representative composition of gas other than hydrogen gas in the raw fuel gas. This standard gas is mixed with hydrogen gas to prepare a plurality of sample gases with different mixing ratios of hydrogen gas. The sonic velocity of each sample gas is measured at a predetermined temperature. Based on the measurement results, data showing a quantitative relationship between the sonic velocity Vs in the raw fuel gas at a predetermined temperature and the average molecular weight M of the raw fuel gas can be obtained based on the formulas (1) and (2). In addition, based on the obtained data, first reference data, which is data showing the relationship between the sonic velocity Vs of the raw fuel gas and the characteristic value Vc, can be created. Here, the value of the sonic velocity Vs of the raw fuel gas corresponds to the second measurement value M2. The measuring device 13 further includes, for example, a memory unit (not shown), and the first reference data is stored in the memory unit.

[0069] The measuring device 13 is disposed, for example, in the supply path 18a of the raw fuel gas, and detects the speed of sound Vs in the raw fuel gas as the second measured value M2. Furthermore, the measuring device 13 determines the characteristic value Vc from the detected second measured value M2 by referring to the first reference data. The measuring device 13 includes, for example, an ultrasonic gas concentration meter.

[0070] The measuring instrument 13 may determine the characteristic value Vc based on, for example, a second measured value M2 related to the thermal conductivity of the raw fuel gas. The second measured value M2 may be a value indicating the thermal conductivity of the raw fuel gas, or may be a value of a physical quantity having a correlation with the thermal conductivity of the raw fuel gas.

[0071] In addition, when determining the characteristic value Vc based on the second measured value M2 related to the thermal conductivity of the raw fuel gas, the measuring device 13 is not limited to a specific configuration as long as it can detect the second measured value M2. The measuring device 13 includes, for example, a heating resistor and a temperature sensor.

[0072] Fig. 3 shows the relationship between the heat dissipation coefficient of each gas and the temperature of the heating resistor when the environment of the heating resistor is filled with gases such as methane gas, propane gas, nitrogen gas, carbon dioxide gas, and hydrogen gas. As shown in Fig. 3, the rate of change between the heat dissipation coefficient of hydrogen gas and the temperature of the heating resistor is significantly larger than the rates of change between the heat dissipation coefficient of other gases and the temperature of the heating resistor. Therefore, the variation in the mixing ratio of hydrogen gas in the raw fuel gas has a large effect on the rate of change between the heat dissipation coefficient of the raw fuel gas and the temperature of the heating resistor.

[0073] For example, a standard gas that does not contain hydrogen gas is prepared by adjusting the mixing ratio of each gas other than hydrogen gas to a constant value with reference to a representative composition of gas other than hydrogen gas in the raw fuel gas. This standard gas is mixed with hydrogen gas to prepare a plurality of sample gases with different mixing ratios of hydrogen gas. The environment of the heating resistor is filled with the sample gas, the heating resistor is caused to generate heat at two different temperatures, and the temperature of the sample gas is measured, and the rate of change between the heat dissipation coefficient of each sample gas and the temperature of the heating resistor is determined based on the measurement result. This makes it possible to create second reference data that is data showing the relationship between the rate of change Rh between the heat dissipation coefficient of the raw fuel gas and the temperature of the heating resistor of the measuring device 13 and the characteristic value Vc. The rate of change Rh is a physical quantity that has a correlation with the thermal conductivity of the raw fuel gas, and its value corresponds to the second measured value M2. The measuring device 13 further includes, for example, a memory unit (not shown), and the second reference data is stored in the memory unit.

[0074] The measuring device 13 is disposed, for example, in the supply path 18a of the raw fuel gas, and has a heating resistor and a temperature sensor. The measuring device 13 causes the heating resistor to generate heat at a predetermined temperature in a state in which the environment of the heating resistor is filled with the raw fuel gas, and measures the temperature of the raw fuel gas using the temperature sensor. Based on the measurement result, the measuring device 13 detects the rate of change Rh as the second measurement value M2. Furthermore, the measuring device 13 determines the characteristic value Vc by referring to the second reference data from the detected second measurement value M2.

[0075] As shown in Fig. 4, the measuring instrument 13 may have, for example, a first flowmeter 13a and a second flowmeter 13b for measuring the flow rate of the raw fuel gas. The measurement sensitivity of the second flowmeter 13b to hydrogen gas is different from the measurement sensitivity of the first flowmeter 13a to hydrogen gas. The measuring instrument 13 determines the characteristic value Vc based on the difference ΔF = |Fs - Ff| between the first flow rate Ff measured by the first flowmeter 13a and the second flow rate Fs measured by the second flowmeter 13b. In this case, the difference ΔF corresponds to the second measurement value M2.

[0076] The measurement sensitivity of the second flowmeter 13b to hydrogen gas differs from the measurement sensitivity of the first flowmeter 13a to hydrogen gas. Therefore, for example, if the mixture ratio of hydrogen gas in the raw fuel gas is high, the value of the difference ΔF is likely to be large.

[0077] For example, a standard gas that does not contain hydrogen gas is prepared by adjusting the mixing ratio of each gas other than hydrogen gas to a constant value with reference to a representative composition of gas other than hydrogen gas in the raw fuel gas. This standard gas is mixed with hydrogen gas to prepare a plurality of sample gases with different mixing ratios of hydrogen gas. While maintaining the flow rate of each sample gas at a predetermined flow rate, the flow rate of the sample gas is measured by the first flow meter 13a and the second flow meter 13b, and the difference ΔF between the first flow rate Ff and the second flow rate Fs is obtained. This makes it possible to create third reference data that is data showing the relationship between the difference ΔF and the characteristic value Vc. The measuring instrument 13 further includes, for example, a memory unit (not shown), and the third reference data is stored in the memory unit.

[0078] The measuring instrument 13 is disposed, for example, in the supply path 18a of the raw fuel gas. The measuring instrument 13 detects, as a second measured value M2, a difference ΔF between a first flow rate Ff of the raw fuel gas measured by the first flow meter 13a and a second flow rate Fs of the raw fuel gas measured by the second flow meter 13b. Furthermore, the measuring instrument 13 determines the characteristic value Vc from the detected second measured value M2 by referring to third reference data.

[0079] In addition, the first flowmeter 13a and the second flowmeter 13b are not limited to specific flowmeters as long as the measurement sensitivity of the second flowmeter 13b to hydrogen gas is different from the measurement sensitivity of the first flowmeter 13a to hydrogen gas. Each of the first flowmeter 13a and the second flowmeter 13b may be, for example, a thermal mass flowmeter. The detector 12 may be a flowmeter provided separately from the first flowmeter 13a and the second flowmeter 13b, or one of the first flowmeter 13a and the second flowmeter 13b may also function as the detector 12.

[0080] 1, the hydrogen generator 1 includes, for example, a temperature sensor 10a. The temperature sensor 10a measures the temperature inside the reformer 10. The control unit 14 is connected to the temperature sensor 10a so as to obtain information indicating the detection result of the temperature sensor 10a.

[0081] The process of step S14 is not limited to a specific process as long as the operation parameter Ps can be adjusted based on the first measured value M1 and the characteristic value Vc. The hydrogen generation device 1 further includes, for example, a storage unit (not shown), which stores, for example, a first table and a second table. As shown in Table 1, the first table is data showing the relationship between the first measured value M1 and the operation parameter Ps. As shown in Table 2, the second table is data showing the relationship between the first measured value M1, the characteristic value Vc, and a correction value for the operation parameter Ps.

[0082] In step S14, the control unit 14 acquires the first measurement value M1 and the characteristic value Vc from the detector 12 and the measuring device 13, respectively. Thereafter, the control unit 14 reads out the first table and the second table from the storage unit, and determines the operation parameter Ps corresponding to the first measurement value M1 and the characteristic value Vc by referring to these tables.

[0083] [Table 1]

[0084] [Table 2]

[0085] The operation parameter Ps is not limited to a specific parameter as long as it is a parameter for controlling the generation of hydrogen-containing gas in the reformer 10. As shown in FIG. 1, the hydrogen generation device 1 further includes a water supplier 15. The water supplier 15 supplies water to the reformer 10. In the reformer 10, for example, the following reactions of steam reforming and hydrogen generation are carried out. The reformer 10 contains a catalyst for promoting the following reactions. The water supplier 15 is, for example, a pump.

[0086] CnHm+nH2O→nCO+(m / 2+n)H2 nCO+nH2O→nCO2+nH2 For example, in step S14, the molar ratio S / C of water supplied to the reformer 10 to carbon atoms contained in the raw fuel gas supplied to the reformer 10 is adjusted to a predetermined range based on the first measured value M1 and the characteristic value Vc. For example, the adjustment of this molar ratio S / C is performed by the control unit 14. The molar ratio S / C is adjusted to exceed 2.5, for example. This suppresses carbon deposition on the catalyst, and the durability of the hydrogen generator 1 can be improved.

[0087] The control unit 14 controls the water supplier 15, for example, so that the molar ratio S / C falls within a predetermined range. The control unit 14 may control the raw fuel supplier 11 so that the molar ratio S / C falls within a predetermined range. The control unit 14 transmits a predetermined control signal to the raw fuel supplier 11 or the water supplier 15 to adjust the molar ratio S / C to fall within the predetermined range.

[0088] 1, the hydrogen generator 1 further includes, for example, a combustor 16 and an air supplier 17. The combustor 16 burns the fuel gas with air to heat the reformer 10. The air supplier 17 supplies the combustor 16 with air for combustion.

[0089] For example, in step S14, the ratio Rfa of the flow rate of the air supplied to the combustor 16 to the flow rate of the fuel gas supplied to the combustor 16 may be adjusted to a predetermined range based on the first measurement value M1 and the characteristic value Vc. In this case, the ratio Rfa is adjusted, for example, by the control unit 14. The ratio Rfa is adjusted to be between 1.3 and 2.0, for example. This suppresses the generation of carbon monoxide in the combustor, enabling stable operation of the hydrogen generator 1.

[0090] In step S14, the ratio Rra of the flow rate of air supplied to the combustor 16 to the flow rate of raw fuel gas supplied to the reformer 10 may be adjusted to a predetermined range based on the first measurement value M1 and the characteristic value Vc. In this case, for example, the control unit 14 adjusts the ratio Rra. This makes it possible to supply a desired flow rate of air to the combustor 16 depending on the quantitative mixture state of hydrogen gas in the raw fuel gas. Therefore, the above reaction is appropriately controlled in the reformer 10. The control unit 14 controls the air supplier 17, for example, so that the ratio Rfa or the ratio Rra falls within a predetermined range.

[0091] The air supplier 17 is, for example, a fan or a blower. In addition, a fuel gas path 16a is connected to the combustor 16. Fuel gas is supplied to the combustor 16 through the fuel gas path 16a. The fuel gas is not limited to a specific gas. The fuel gas may include a raw fuel gas, may include a hydrogen-containing gas generated in the reformer 10, or may include other combustible gases.

[0092] For example, in step S14, the control unit 14 transmits a predetermined control signal to the air supplier 17 to adjust the ratio Rfa or the ratio Rra to a predetermined range. The combustion state of the fuel gas in the combustor 16 may be monitored by a flame detector such as a flame rod.

[0093] 5, a fuel cell system 2 can be provided by using the hydrogen generation device 1. The fuel cell system 2 includes the hydrogen generation device 1 and a fuel cell 20. The fuel cell 20 generates power by using the hydrogen-containing gas generated by the hydrogen generation device 1. The fuel cell 20 may be a polymer electrolyte fuel cell (PEFC) or a solid oxide fuel cell (SOFC).

[0094] A hydrogen-containing gas is supplied to the anode of the fuel cell 20, and an oxidant gas such as air is supplied to the cathode of the fuel cell 20. As a result, in the fuel cell 20, power is generated by a reaction between the hydrogen-containing gas and the oxidant gas. This reaction, i.e., power generation, generates heat. In the fuel cell system 2, the generated heat is used, for example, to generate hot water. For example, in the fuel cell system 2, the heat generated in the fuel cell 20 is recovered by cooling water. Anode off-gas, which is exhaust gas from the anode of the fuel cell 20, may contain hydrocarbon gas and hydrogen gas. In the fuel cell system 2, the anode off-gas discharged from the fuel cell 20 is supplied to the combustor 16 as, for example, fuel gas.

[0095] 5, the fuel cell system 2 further includes a calculation unit 22. The calculation unit 22 determines a target output Pt of the fuel cell system 2 based on the characteristic value Vc. For example, when the characteristic value Vc indicates that the level of the quantitative mixed state of hydrogen gas in the raw fuel gas is relatively high, the target output Pt is determined to be relatively low. This is because when the mixed ratio of hydrogen gas in the raw fuel gas is high, the amount of hydrogen gas generated by the reaction in the reformer 10 from a constant flow rate of raw fuel gas becomes relatively small.

[0096] 5, the control unit 14 of the hydrogen generation device 1 may also function as, for example, the calculation unit 22. For example, a program for determining a target output Pt of the fuel cell system 2 based on the characteristic value Vc may be executed in the control unit 14. The hardware for the calculation unit 22 may be configured separately from the hardware for the control unit 14.

[0097] An example of adjustment of the operational parameter Ps will be described. Table 3 shows an example of operating conditions of the fuel cell system 2 when gas A and gas B are used as raw fuel gases and the operational parameter Ps is not adjusted based on the first measurement value M1 and the characteristic value Vc. In Table 3, NLM stands for normal liters per minute. Gas A is 100% methane gas. Gas B is a mixed gas of 80% methane gas and 20% hydrogen gas by volume.

[0098] As shown in Table 3, when Gas A is used as the raw fuel gas, the temperature and combustion air ratio λ of the reformer 10 are maintained at the target values, and the fuel cell system 2 is operated under the desired conditions. On the other hand, when Gas B is used as the raw fuel gas, the actual flow rate is higher than the flow rate recognized by the flow meter, but the fuel cell system is controlled based on the flow rate recognized by the flow meter. Therefore, the ratio λ of the target air amount, which is the target value of the amount of air actually supplied to the combustor 16 to the required air amount, which is the amount of air necessary to completely combust the raw fuel gas in the combustor 16, is actually low. Because the flow rate of the raw fuel gas is high and the ratio λ is actually low, the temperature of the reformer 10 becomes higher than the target temperature.

[0099] To avoid such a situation, in the fuel cell system 2, for example, the ratio Rfa or the ratio Rra is adjusted to fall within a predetermined range by adjusting the operation parameter Ps based on the first measurement value M1 and the characteristic value Vc. For example, when gas B is used as the raw fuel gas, the operation parameter Ps is adjusted so that the flow rate of air supplied to the combustor 16 becomes larger than the target air amount shown in Table 3.

[0100] In the example shown in Table 3, when gas B is used, the actual flow rate is greater than the flow rate recognized by the flowmeter. As a result, the molar ratio S / C falls below a predetermined range, and carbon may be deposited on the catalyst. To avoid such a situation, in the fuel cell system 2, the molar ratio S / C is actually adjusted to, for example, within a predetermined range by adjusting the operating parameter Ps based on the first measurement value M1 and the characteristic value Vc.

[0101] For example, when gas B is used as the raw fuel gas, the operation parameter Ps is adjusted so that the amount of water supplied to the reformer 10 is greater than the value shown in Table 3. For example, by controlling the water supplier 15 so that the molar ratio S / C exceeds 2.5, carbon deposition on the catalyst is suppressed. As a result, the durability of the hydrogen generator 1 can be improved.

[0102] In the example shown in Table 3, when gas B is used, both the combustion air ratio λ and the molar ratio S / C deviate from the target values. However, it is also possible that only one of the combustion air ratio λ and the molar ratio S / C deviates from the target value. Even in such a case, the generation of hydrogen-containing gas in the reformer 10 can be appropriately controlled by adjusting the operation parameter Ps so that the actual value that is expected to deviate from the target value falls within the target value.

[0103] The operation parameter Ps is adjusted periodically or irregularly, for example, during operation of the fuel cell system 2. As a result, even if the quantitative mixture state of hydrogen gas in the raw fuel gas fluctuates over time during operation of the fuel cell system 2, for example, the operation parameter Ps is adjusted in accordance with the quantitative mixture state of hydrogen gas in the raw fuel gas.

[0104] The operation parameter Ps may be adjusted, for example, before operation or during startup of the fuel cell system 2. In this case, the operation parameter Ps is adjusted according to the quantitative mixture state of hydrogen gas in the raw fuel gas before operation or during startup of the fuel cell system 2. Therefore, the fuel cell system 2 can be operated in accordance with the desired operation parameter Ps from the beginning of operation of the fuel cell system 2.

[0105] The adjusted operational parameter Ps may be stored in the fuel cell system 2. For example, when the hydrogen generation device 1 is stopped, the operational parameter Ps used immediately before the hydrogen generation device 1 was stopped is stored. The stored value of the operational parameter Ps can be used, for example, the next time the fuel cell system 2 is started up.

[0106] [Table 3] [Explanation of symbols]

[0107] 1 Hydrogen generator 2. Fuel Cell System 10 Reformer 11 Raw fuel supply device 12 Detector 13 Measuring instruments 13a First flow meter 13b Second flow meter 14 Control section 15 Water supply 16 Combustor 16a Fuel gas line 17 Air Supply 18a Supply Channel 20 Fuel Cell 22 Arithmetic section M1 First measurement value M2 Second measurement Ps Operation parameters Vc characteristic value

Claims

1. a reformer for generating a hydrogen-containing gas from a raw fuel gas; a raw fuel supplier for supplying the raw fuel gas to the reformer; a detector for detecting a first measurement value determined in accordance with a flow rate of the raw fuel gas supplied by the raw fuel supply device; a measuring device that detects a second measurement value that changes depending on a quantitative mixed state of hydrogen gas in the raw fuel gas, and determines the characteristic value from reference data that indicates a relationship between the second measurement value and a characteristic value that indicates the quantitative mixed state; A control unit that adjusts an operation parameter for controlling the generation of the hydrogen-containing gas in the reformer based on the first measurement value and the characteristic value. Hydrogen generator.

2. The hydrogen generation apparatus according to claim 1 , wherein the measurement device determines the characteristic value based on the second measurement value related to an average molecular weight of the raw fuel gas.

3. The hydrogen generation apparatus according to claim 1 , wherein the measurement device determines the characteristic value based on the second measurement value related to thermal conductivity of the raw fuel gas.

4. the measuring device includes a first flow meter and a second flow meter that measure flow rates of the raw fuel gas, the measurement sensitivity of the second flow meter to hydrogen gas is different from the measurement sensitivity of the first flow meter to hydrogen gas, The hydrogen generation apparatus according to claim 1 , wherein the measuring device determines the characteristic value based on a difference between a first flow rate measured by the first flow meter and a second flow rate measured by the second flow meter.

5. Further comprising a water supplier for supplying water to the reformer; 5. The hydrogen generation device according to claim 1, wherein the control unit controls the water supplier based on the first measurement value and the characteristic value so that a molar ratio of the water supplied to the reformer to the carbon atoms contained in the raw fuel gas supplied to the reformer is within a predetermined range.

6. a combustor that burns fuel gas with air to heat the reformer; An air supplier that supplies air for combustion to the combustor, 6. The hydrogen generation apparatus according to claim 1, wherein the control unit controls the air supplier based on the first measurement value and the characteristic value so that a ratio of a flow rate of the air supplied to the combustor to a flow rate of the fuel gas supplied to the combustor, or a ratio of a flow rate of the air supplied to the combustor to a flow rate of the raw fuel gas supplied to the reformer, is within a predetermined range.

7. The hydrogen generation device according to any one of claims 1 to 6, A fuel cell that generates electricity using the hydrogen-containing gas generated by the hydrogen generation device. Fuel cell system.

8. 8. The fuel cell system according to claim 7, further comprising a calculation unit that determines a target output of the fuel cell system based on the characteristic value.

9. A method for operating a hydrogen generating apparatus for generating a hydrogen-containing gas from a raw fuel gas in a reformer, comprising: Detecting a first measurement value determined in response to a flow rate of the raw fuel gas supplied to the reformer; detecting a second measurement value that changes depending on a quantitative mixed state of hydrogen gas in the raw fuel gas, and determining the characteristic value from reference data that indicates a relationship between the second measurement value and a characteristic value that indicates the quantitative mixed state; and adjusting an operating parameter for controlling the production of the hydrogen-containing gas in the reformer based on the first measurement and the characteristic value. A method for operating a hydrogen generation device.

10. The method of claim 9 , further comprising determining the characteristic value based on the second measurement of an average molecular weight of the raw fuel gas.

11. The method of claim 9 , further comprising determining the characteristic value based on the second measurement related to thermal conductivity of the raw fuel gas.

12. detecting the second measurement value includes measuring a flow rate of the raw fuel gas using a first flow meter and a second flow meter; the measurement sensitivity of the second flow meter to hydrogen gas is different from the measurement sensitivity of the first flow meter to hydrogen gas, The method of claim 9 , further comprising determining the characteristic value based on a difference between a first flow rate measured by the first flow meter and a second flow rate measured by the second flow meter.

13. 13. The operating method according to claim 9, further comprising adjusting a molar ratio of water supplied to the reformer to carbon atoms contained in the raw fuel gas supplied to the reformer within a predetermined range based on the first measurement value and the characteristic value.

14. further comprising combusting a fuel gas with air in a combustor to heat the reformer; 14. The operating method according to claim 9, further comprising adjusting, based on the first measurement value and the characteristic value, a ratio of a flow rate of the air supplied to the combustor to a flow rate of the fuel gas supplied to the combustor, or a ratio of a flow rate of the air supplied to the combustor to a flow rate of the raw fuel gas supplied to the reformer, within a predetermined range.

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