JP2020117412A - Hydrogen production system and operation method thereof - Google Patents

Abstract

To provide a hydrogen production system for stably producing high-purity hydrogen.SOLUTION: A hydrogen generation system 1 is configured such that, when gas supply means 7 supplies a hydrogen-containing gas to a first electrode 14 and a power source 4 flows an electric current, the hydrogen-containing gas exhausted from the first electrode 14 is supplied to an anode 10 and a hydrogen-containing off-gas exhausted from the anode 10 is exhausted via a second electrode 15, in which an electric current of a current value calculated based on the supply amount of the hydrogen-containing gas from the gas supply means 7 is passed to an electrochemical device 2 to measure a voltage between the first electrode 14 and the second electrode 15, and when the measured value V does not satisfy a predetermined condition, the current value of the electric current is changed (corrected) based on the measured value V, whereby high-purity hydrogen can be stably generated.SELECTED DRAWING: Figure 1

Description

The present invention relates to a hydrogen generation system for generating high-purity hydrogen from a hydrogen-containing gas using an electrochemical device and a method for operating the same.

This type of hydrogen generation system utilizes an electrochemical reaction from a hydrogen-containing gas using an electrochemical device having an electrolyte membrane-electrode assembly in which a proton-permeable electrolyte membrane is arranged between an anode and a cathode. , A system that produces high-purity hydrogen.

When a hydrogen-containing gas is supplied to the anode of the electrochemical device so that the anode side has a higher potential than the cathode side, and a current in a predetermined direction is passed between the anode and the cathode, An oxidation reaction occurs in which hydrogen shown is dissociated into protons (H ⁺ ) and electrons, and a reduction reaction occurs in the cathode, where hydrogen is produced from the protons (H ⁺ ) shown in (Formula ² ) and electrons.

以上の反応により、アノードに供給された水素含有ガスから、カソードで水素を生成させることができる。

Through the above reaction, hydrogen can be generated at the cathode from the hydrogen-containing gas supplied to the anode.

Here, when the value of the current flowing between the anode and the cathode is increased, the amount of hydrogen generated at the cathode is increased, and conversely, when the value of the current flowing between the anode and the cathode is decreased, the hydrogen is generated at the cathode. The amount of hydrogen decreases.

The hydrogen-containing gas supplied to the hydrogen generation system is obtained by steam reforming, partial oxidation reforming, or autothermal reforming of a hydrocarbon-based fuel such as 13A gas or propane gas by a fuel processor. Is generated. The hydrogen-containing gas generated here contains impurities such as nitrogen, carbon monoxide, carbon dioxide, and ammonia, and has a low hydrogen purity.

For example, in Patent Document 1, a hydrogen-containing gas having a low purity is supplied to an anode of an electrochemical device, and a direct current in a predetermined direction is flown between the anode and the cathode to derive a hydrogen having a high purity from a hydrogen outlet. A method of doing so is disclosed.

JP-A-60-36302

However, in the above-mentioned conventional configuration, the current value to be applied is not determined based on the required amount of hydrogen. Therefore, when the value of the current passed through the electrochemical device is smaller than the amount of hydrogen contained in the supplied hydrogen-containing gas, there is a problem that the gas containing hydrogen is wastefully discharged from the anode.

Further, when the value of the current flowing through the electrochemical device is large with respect to the amount of hydrogen contained in the hydrogen-containing gas supplied, the hydrogen becomes deficient in the anode because the hydrogen expressed by the reaction formula (Formula 1) is deficient. In order to compensate for the above, the reaction shown in the reaction formula (Formula 3) occurs.

（化３）において、Ｃはアノード触媒を構成するカーボンである。このため、アノード触媒の劣化が進行し、耐久性が低下するという課題を有していた。

In Chemical formula 3, C is carbon that constitutes the anode catalyst. Therefore, there is a problem that the deterioration of the anode catalyst progresses and the durability decreases.

The present invention solves the above-mentioned conventional problems, and suppresses the catalyst deterioration of the anode due to hydrogen deficiency, and it is possible to stably generate high-purity hydrogen without wastefully discharging a mixed gas containing hydrogen. An object of the present invention is to provide a hydrogen generation system that can be performed and a method of operating the hydrogen generation system.

In order to solve the conventional problems, the hydrogen generation system of the present invention has a first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode, and supplies a hydrogen-containing gas to the anode, An electrochemical device that produces hydrogen at the cathode by passing a current from the anode to the cathode through the first electrolyte membrane, and a second electrolyte membrane-electrode in which the second electrolyte membrane is sandwiched between the first electrode and the second electrode. An electrochemical sensor having a joined body, a gas supply means for supplying a hydrogen-containing gas to the first electrode, a voltmeter for measuring the voltage between the first electrode and the second electrode, a power supply for supplying a current, and control And a gas supply means supplies the hydrogen-containing gas to the first electrode and the power source is passing an electric current, the hydrogen-containing gas discharged from the first electrode is supplied to the anode and is supplied to the anode. In a hydrogen generating system configured to discharge hydrogen-containing off gas discharged from the anode without passing through the anode from the anode through the first electrolyte membrane among the hydrogen-containing gas via the second electrode. Therefore, when the controller starts the hydrogen generation operation using the electrochemical device, it is calculated based on the flow rate of the hydrogen-containing gas supplied from the gas supply means after causing the gas supply means to perform the supply operation. When the voltage value measured by the voltmeter does not meet the specified conditions, the current value of the current supplied by the power source is based on the voltage value. It is configured to change.

With this, the current amount (current value) of the current flowing through the electrochemical device is accurately determined (corrected) with respect to the hydrogen amount contained in the hydrogen-containing gas to be supplied, so that highly pure hydrogen is generated with high efficiency. In addition, deterioration of the anode catalyst can be suppressed, and durability can be improved.

This can be explained as follows. A hydrogen-containing gas is supplied to the first electrode of the electrochemical sensor, and a hydrogen-containing off-gas from the electrochemical device is supplied to the second electrode of the electrochemical sensor. The voltage between the first electrode and the second electrode of the electrochemical sensor is generated due to the difference in hydrogen partial pressure between the electrodes, and can be determined by the Nernst equation shown in (Equation 1).

（数１）において、Ｖは電気化学センサーの第１電極と第２電極との間の電圧、Ｒは気
体定数、Ｔは電気化学センサーの絶対温度、Ｆはファラデー定数、ＰＨ_２（２）は第２電極の水素分圧、ＰＨ_２（１）は第１電極の水素分圧である。

In (Equation 1), V is the voltage between the first electrode and the second electrode of the electrochemical sensor, R is the gas constant, T is the absolute temperature of the electrochemical sensor, F is the Faraday constant, and PH ₂ (2) is The hydrogen partial pressure of the second electrode, PH ₂ (1) is the hydrogen partial pressure of the first electrode.

Therefore, if the hydrogen concentration contained in the hydrogen-containing off gas changes, the voltage between the first electrode and the second electrode of the electrochemical sensor changes. By detecting the change in this voltage and determining (correcting) the current value of the current flowing through the electrochemical device, the hydrogen concentration contained in the hydrogen-containing off-gas is controlled, so that high-purity hydrogen is generated with high efficiency. In addition, it is possible to suppress deterioration of the anode catalyst and improve durability.

Further, another hydrogen generating system of the present invention has a first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode, and supplies a hydrogen-containing gas to the anode, It has an electrochemical device that produces hydrogen at the cathode by passing a current through the electrolyte membrane to the cathode, and a second electrolyte membrane-electrode assembly in which the second electrolyte membrane is sandwiched between the first electrode and the second electrode. An electrochemical sensor, a gas supply means for supplying a hydrogen-containing gas to the anode, an air supply means for supplying air to the first electrode, and a voltmeter for measuring the voltage between the first electrode and the second electrode, A first power supply for supplying an electric current and a controller are provided, and when the gas supply unit supplies the hydrogen-containing gas to the anode and the power supply is supplying the electric current, the first hydrogen-containing gas from the anode is supplied from the anode. A hydrogen generation system configured such that a hydrogen-containing gas discharged from an anode without permeating to a cathode through an electrolyte membrane is discharged via a second electrode, wherein a controller controls an electrochemical device. When the hydrogen generating operation is started using the gas supply means and the air supply means, the current is calculated based on the flow rate of the hydrogen-containing gas supplied from the gas supply means. When the voltage is measured by the voltmeter while being supplied to the power supply and the voltage value measured by the voltmeter does not satisfy the predetermined condition, the current value of the current supplied by the power supply is changed based on the voltage value. Is what

As a result, the current value of the current flowing through the electrochemical device relative to the amount of hydrogen contained in the supplied hydrogen-containing gas is determined (corrected) with higher accuracy by using the oxidant gas, so that highly pure hydrogen can be produced with high efficiency. It is possible to improve the durability as well as to be produced by.

Since the hydrogen generation system of the present invention determines (corrects) the current value of the current passed through the electrochemical device based on the voltage of the electrochemical sensor measured by the voltmeter, it does not wastefully discharge the mixed gas containing hydrogen. Thus, high-purity hydrogen can be stably generated.

Further, the hydrogen generation system of the present invention determines (corrects) the current value of the current passed through the electrochemical device based on the voltage of the electrochemical sensor measured by the voltmeter, so that the catalyst deterioration of the anode due to hydrogen deficiency can be suppressed. .. This makes it possible to provide a hydrogen generation system having high durability and low maintenance frequency.

Block diagram showing a schematic configuration of a hydrogen generation system in Embodiments 1, 2 and 3 of the present invention The flowchart which shows the control processing of the hydrogen generation system in Embodiment 1 of this invention. The flowchart which shows the control processing of the hydrogen generation system in Embodiment 2 of this invention. Flowchart showing the control processing of the hydrogen generation system in Embodiment 3 of the present invention Block diagram showing a schematic configuration of a hydrogen generation system in Embodiments 4, 5, and 6 of the present invention The flowchart which shows the control processing of the hydrogen generation system in Embodiment 4 of this invention. 5 is a flowchart showing a control process of the hydrogen generation system according to the fifth embodiment of the present invention. 6 is a flowchart showing a control process of the hydrogen generation system according to the sixth embodiment of the present invention.

A first aspect of the present invention has a first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode, supplies a hydrogen-containing gas to the anode, and from the anode through the first electrolyte membrane. An electrochemical device having an electrochemical device that produces hydrogen at the cathode by passing an electric current through the cathode, and an electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode, The gas supply means comprises a gas supply means for supplying a hydrogen-containing gas to the first electrode, a voltmeter for measuring the voltage between the first electrode and the second electrode, a power supply for supplying an electric current, and a controller. Is supplying a hydrogen-containing gas to the first electrode and the power supply is passing an electric current, the hydrogen-containing gas discharged from the first electrode is supplied to the anode, and the hydrogen-containing gas supplied to the anode is supplied from the anode. A hydrogen generation system configured such that hydrogen-containing off-gas discharged from an anode without permeating to a cathode via a first electrolyte membrane is discharged via a second electrode, wherein the controller is an electrochemical device. When starting the hydrogen generation operation using the device, after the gas supply means is caused to perform a supply operation, a current having a current value calculated based on the flow rate of the hydrogen-containing gas supplied from the gas supply means is supplied to the power supply. In addition, the voltage is measured by the voltmeter, and if the voltage value measured by the voltmeter does not satisfy the predetermined condition, the current value of the current supplied by the power supply is changed based on the voltage value. System.

Thus, the current value of the current flowing through the electrochemical device with respect to the amount of hydrogen contained in the hydrogen-containing gas to be supplied is determined (corrected) with high accuracy, so that highly pure hydrogen can be produced with high efficiency.

In the second aspect of the present invention, in particular, when the controller of the first aspect of the present invention reduces the current value of the current passed by the power source when the voltage value measured by the voltmeter exceeds the first predetermined value, The hydrogen generation system is characterized in that the voltage is measured again by the voltmeter.

Accordingly, the current flowing through the electrochemical device does not become excessive with respect to the amount of hydrogen contained in the hydrogen-containing gas to be supplied, so that the occurrence of hydrogen deficiency can be suppressed. Therefore, the deterioration of the catalyst of the anode can be more reliably suppressed, and the hydrogen generation system with higher durability can be obtained.

In a third aspect of the present invention, in particular, when the voltage value measured by the voltmeter exceeds a predetermined upper limit value, the controller in the first aspect of the present invention reduces the current value of the current passed by the power source and then reduces the voltage. When the voltage value measured by the voltmeter is redone and the voltage value measured by the voltmeter is less than the predetermined lower limit value, the current value of the current flowing from the power supply is increased and then the voltage measurement by the voltmeter is redone. It is a hydrogen generation system that does.

As a result, the current value calculated based on the amount of hydrogen contained in the hydrogen-containing gas supplied to the electrochemical device can be corrected with higher accuracy, and a highly reliable hydrogen generation system can be obtained.

In a fourth aspect of the present invention, particularly, when the voltage value measured by the voltmeter exceeds a second predetermined value, the controller in the first aspect of the present invention reports an abnormality or stops the operation, or A hydrogen generation system characterized by increasing the amount of hydrogen-containing gas supplied from a gas supply means.

With this, when an abnormality occurs, it can be stopped safely, or the abnormal state can be changed to the normal state by increasing the hydrogen-containing gas supply amount from the gas supply means, which is more reliable. It can be a hydrogen generation system.

A fifth aspect of the present invention has a first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode, supplies a hydrogen-containing gas to the anode, and from the anode through the first electrolyte membrane. An electrochemical device having an electrochemical device that produces hydrogen at the cathode by passing an electric current through the cathode, and an electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode, Gas supply means for supplying a hydrogen-containing gas to the anode, air supply means for supplying air to the first electrode, a voltmeter for measuring the voltage between the first electrode and the second electrode, and a power supply for supplying a current. A controller, wherein the gas supply means supplies the hydrogen-containing gas to the anode and the power source is passing an electric current, and among the hydrogen-containing gas supplied to the anode from the anode through the first electrolyte membrane. A hydrogen generation system configured to discharge a hydrogen-containing gas discharged from an anode without passing through a cathode via a second electrode, wherein the controller uses an electrochemical device to generate hydrogen. At the start of, the gas supply means and the air supply means are caused to perform a supply operation, and then a current having a current value calculated based on the flow rate of the hydrogen-containing gas supplied from the gas supply means is caused to flow in the power source. In a hydrogen generation system, the voltage is measured by a voltmeter, and if the voltage value measured by the voltmeter does not satisfy a predetermined condition, the current value of the current supplied by the power supply is changed based on the voltage value. is there.

As a result, the current value of the current flowing through the electrochemical device with respect to the amount of hydrogen contained in the hydrogen-containing gas to be supplied is determined (corrected) with higher accuracy by using the oxidant gas, so that highly pure hydrogen can be produced with high efficiency. Can be generated with.

In a sixth aspect of the present invention, in particular, when the voltage value measured by the voltmeter exceeds the first predetermined value, the controller of the fifth aspect of the present invention reduces the current value of the current supplied by the power source, The hydrogen generation system is characterized in that the voltage is measured again by the voltmeter.

Accordingly, the current flowing through the electrochemical device does not become excessive with respect to the amount of hydrogen contained in the hydrogen-containing gas to be supplied, so that the occurrence of hydrogen deficiency can be suppressed. Therefore, the deterioration of the catalyst of the anode can be more surely suppressed, and the hydrogen generation system having higher durability can be obtained.

In a seventh aspect of the present invention, in particular, when the voltage value measured by the voltmeter exceeds a predetermined upper limit value, the controller in the fifth aspect of the present invention reduces the current value of the current passed by the power source and then reduces the voltage. When the voltage value measured by the voltmeter is redone and the voltage value measured by the voltmeter is less than the predetermined lower limit value, the current value of the current flowing from the power supply is increased and then the voltage measurement by the voltmeter is redone. It is a hydrogen generation system that does.

Accordingly, the current value calculated based on the amount of hydrogen contained in the hydrogen-containing gas supplied to the electrochemical device can be corrected with higher accuracy, so that a more reliable hydrogen generation system can be obtained. ..

According to an eighth aspect of the present invention, in particular, when the voltage value measured by the voltmeter exceeds a second predetermined value, the controller according to the fifth aspect of the present invention notifies the abnormality or stops the operation, or A hydrogen generation system characterized by increasing the amount of hydrogen-containing gas supplied from a gas supply means.

With this, when an abnormality occurs, it can be stopped safely, or an abnormal state can be changed to a normal state by increasing the amount of hydrogen-containing gas supplied from the gas supply means. It can be a generation system.

A ninth aspect of the present invention has a first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode, supplies a hydrogen-containing gas to the anode, and from the anode through the first electrolyte membrane. An electrochemical device having an electrochemical device that produces hydrogen at the cathode by passing an electric current through the cathode, and an electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode, Gas supply means for supplying a hydrogen-containing gas to the first electrode, a voltmeter for measuring the voltage between the first electrode and the second electrode, and a power supply for supplying a current, the gas supply means is the first electrode The hydrogen-containing gas discharged from the first electrode is supplied to the anode when the hydrogen-containing gas is supplied to the anode and the power source is flowing an electric current, and the first electrolyte membrane is supplied from the anode among the hydrogen-containing gas supplied to the anode. A method for operating a hydrogen generation system configured to discharge hydrogen-containing off-gas discharged from an anode via a second electrode without passing through a cathode through a cathode. When starting the generation operation, the gas supply means is caused to perform a supply operation, and then a current having a current value calculated based on the flow rate of the hydrogen-containing gas supplied from the gas supply means is caused to flow through the power supply, and a voltmeter is also provided. Voltage is measured by the voltmeter, and if the voltage value measured by the voltmeter does not satisfy the predetermined condition, the current value of the current supplied by the power supply is changed based on the voltage value. is there.

As a result, it becomes an operating method that determines (corrects) the current value of the current flowing in the electrochemical device with respect to the amount of hydrogen contained in the hydrogen-containing gas to be supplied with high accuracy, so that highly pure hydrogen can be produced with high efficiency. it can.

A tenth aspect of the present invention has a first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode, supplies a hydrogen-containing gas to the anode, and through the first electrolyte membrane from the anode. An electrochemical device having an electrochemical device that produces hydrogen at the cathode by passing an electric current through the cathode, and an electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode, Gas supply means for supplying a hydrogen-containing gas to the anode, air supply means for supplying air to the first electrode, a voltmeter for measuring the voltage between the first electrode and the second electrode, and a power supply for supplying a current. And, when the gas supply means supplies the hydrogen-containing gas to the anode and the power source is passing an electric current, the hydrogen-containing gas supplied to the anode is permeated from the anode to the cathode through the first electrolyte membrane. A method of operating a hydrogen generation system configured such that a hydrogen-containing gas discharged from an anode without being discharged via a second electrode is provided when starting a hydrogen generation operation using an electrochemical device. After making the gas supply means and the air supply means perform the supply operation, a current having a current value calculated based on the flow rate of the hydrogen-containing gas supplied from the gas supply means is caused to flow through the power supply, and the voltage is measured by the voltmeter. Is measured, and when the voltage value measured by the voltmeter does not satisfy the predetermined condition, the current value of the current passed by the power source is changed based on the voltage value.

Accordingly, the current value of the current flowing through the electrochemical device with respect to the amount of hydrogen contained in the supplied hydrogen-containing gas becomes an operating method that determines (corrects) with higher accuracy by using the oxidant gas. Hydrogen can be produced with high efficiency.

Embodiments of the present invention will be described below with reference to the drawings. The present invention is not limited to the embodiments.

(Embodiment 1)
FIG. 1 is a block diagram showing a schematic configuration of a hydrogen generation system according to Embodiment 1 of the present invention. FIG. 2 is a flowchart showing a control process of the hydrogen generation system according to the first embodiment of the present invention.

As shown in FIG. 1, the hydrogen generation system 1 of the present embodiment includes an electrochemical device 2, an electrochemical sensor 3, a gas supply means 7, a voltmeter 6, a power supply 4, and a controller 5. It is configured.

The electrochemical device 2 has a first electrolyte membrane-electrode assembly 9 in which a first electrolyte membrane 8 is sandwiched between an anode 10 and a cathode 11.

The first electrolyte membrane 8 is a perfluorocarbon sulfonic acid-based polymer electrolyte membrane having a sulfonic acid group.

The anode 10 and the cathode 11 are obtained by dispersing carbon particles carrying platinum in an aqueous solution of a perfluorocarbon sulfonic acid-based polymer electrolyte having a sulfonic acid group on both main surfaces of the first electrolyte membrane 8. It is formed by coating.

In the power supply 4, when the hydrogen-containing gas is supplied to the anode 10, an oxidation reaction occurs in the anode 10, and the protons generated by the oxidation reaction pass through the first electrolyte membrane 8 and move to the cathode 11, and the cathode 11 Is a DC power supply for flowing a current from the anode 10 to the cathode 11 through the first electrolyte membrane 8 so that a reduction reaction occurs and hydrogen is generated. , And the negative terminal of the power source 4 is electrically connected to the cathode 11.

The electrochemical sensor 3 has a second electrolyte membrane-electrode assembly 13 in which the second electrolyte membrane 12 is sandwiched between the first electrode 14 and the second electrode 15.

The second electrolyte membrane 12 is a perfluorocarbon sulfonic acid-based polymer electrolyte membrane having a sulfonic acid group.

The first electrode 14 and the second electrode 15 are obtained by dispersing carbon particles carrying platinum in an aqueous solution of a perfluorocarbon sulfonic acid-based polymer electrolyte having a sulfonic acid group in the second electrolyte membrane 12, respectively. It is formed by coating on both main surfaces.

The gas supply means 7 is a fuel reformer that produces a humidified hydrogen-containing gas from a city gas by using a reforming reaction, and hydrogen having a hydrogen content rate of 80% and a carbon dioxide content rate of 20%. The contained gas is supplied to the anode 10 via the hydrogen-containing gas supply primary pipe 16, the first electrode 14, and the hydrogen-containing gas supply secondary pipe 17. The numerical value of the content ratio is a numerical value that does not take into consideration the water vapor contained in the hydrogen-containing gas.

Of the hydrogen-containing gas supplied to the anode 10, the hydrogen-containing off-gas discharged from the anode 10 without moving (permeating) to the cathode 11 is the hydrogen-containing off-gas pipe 18, the second electrode 15, the hydrogen-containing off-gas discharge pipe 20. Is discharged via.

The voltmeter 6 measures the voltage between the first electrode 14 and the second electrode 15 of the electrochemical sensor 3.

The gas supply means 7 and the first electrode 14 of the electrochemical sensor 3 are connected by a hydrogen-containing gas supply primary pipe 16 for supplying a hydrogen-containing gas. Further, the first electrode 14 of the electrochemical sensor 3 and the anode 10 of the electrochemical device 2 are connected by a hydrogen-containing gas supply secondary pipe 17.

The anode 10 of the electrochemical device 2 and the second electrode 15 of the electrochemical sensor 3 are connected by a hydrogen-containing offgas pipe 18. Further, the electrochemical device 2 has a generated hydrogen discharge pipe 19 for discharging hydrogen generated at the cathode 11, and the second electrode 15 of the electrochemical sensor 3 has a hydrogen-containing offgas discharge pipe 20 for discharging hydrogen-containing offgas. Are connected to each other.

The operation and action of the hydrogen generation system 1 of the present embodiment configured as described above will be described with reference to FIG. 1 with reference to FIG.

First, the hydrogen-containing gas is supplied from the gas supply means 7 through the hydrogen-containing gas supply primary pipe 16, the first electrode 14 of the electrochemical sensor 3, and the hydrogen-containing gas supply secondary pipe 17 to the anode of the electrochemical device 2. 10 (S001), and the power supply 4 is turned on (S002).

Next, the amount H (L/min) of hydrogen contained in the hydrogen-containing gas is calculated from the amount F (L/min) of hydrogen-containing gas supplied from the gas supply means 7 and the concentration Y of hydrogen gas. Further, according to Faraday's law of electrolysis, the current value C(A) flowing to the electrochemical device 2 is calculated using (Equation 2) (S003).

次に、電源４により、電気化学デバイス２のアノード１０から第１電解質膜８を介してカソード１１へ、算出された電流値Ｃ（Ａ）の電流を流す（Ｓ００４）。

Next, the power source 4 causes a current of the calculated current value C(A) to flow from the anode 10 of the electrochemical device 2 to the cathode 11 via the first electrolyte membrane 8 (S004).

Next, the voltage between the first electrode 14 and the second electrode 15 of the electrochemical sensor 3 is measured by the voltmeter 6, and the measured value is set to the measured value V (V) (S005).

Next, it is determined whether the measured value V (V) is smaller than the reference voltage V0 (V) (S006). When the measured value V (V) is equal to or lower than the reference voltage V0 (V), the determination of S006 is repeated without changing the current value C of the current that the power supply 4 passes through the electrochemical device 2, and the measured value V( If V) is larger than the reference voltage V0 (V), the process proceeds to S007. In this embodiment, V0 is 30 mV. Next, the current value C set by the power source 4 is reduced by 1% (S007), and the process returns to S005.

As described above, the hydrogen generation system 1 of the present embodiment has the first electrolyte membrane-electrode assembly 9 in which the first electrolyte membrane 8 is sandwiched between the anode 10 and the cathode 11, and the hydrogen-containing gas is contained in the anode 10. Is supplied and an electric current is passed from the anode 10 to the cathode 11 through the first electrolyte membrane 8 to generate hydrogen in the cathode 11, the second electrolyte membrane 12 and the first electrode 14 and the second electrode. The electrochemical sensor 3 having the second electrolyte membrane-electrode assembly 13 sandwiched between the two electrodes 15, the gas supply means 7 for supplying the hydrogen-containing gas to the first electrode 14, the first electrode 14 and the second electrode 15. Between the anode 10 and the power source 4 for supplying a current to the cathode 11 through the first electrolyte membrane 8, the controller 5, and the gas supply means 7 to supply hydrogen to the first electrode 14. A hydrogen-containing gas supply primary pipe 16 that connects the gas supply means 7 and the first electrode 14 so that the contained gas can be supplied, and the first electrode 14 and the anode 10 that can supply the hydrogen-containing gas from the first electrode 14 to the anode 10. A hydrogen-containing gas supply secondary pipe 17 for connection, a hydrogen-containing off-gas pipe 18 for connecting the anode 10 and the second electrode 15 so that the hydrogen-containing off-gas can be supplied from the anode 10 to the second electrode 15, and a cathode 11. The gas supply means 7 is provided with a produced hydrogen discharge pipe 19 for discharging hydrogen from the cathode 11 and a hydrogen-containing offgas discharge pipe 20 for discharging the hydrogen-containing offgas supplied to the second electrode 15 from the second electrode 15. The hydrogen-containing gas discharged from the first electrode 14 is supplied to the anode 10 while the hydrogen-containing gas is supplied to the first electrode 14 and the power supply 4 is flowing an electric current. In the hydrogen generation system 1 configured so that the hydrogen-containing off-gas discharged from the anode 10 without passing through the anode 10 through the first electrolyte membrane 8 to the cathode 11 is discharged through the second electrode 15. is there.

Then, when the controller 5 starts the hydrogen generation operation using the electrochemical device 2, after the gas supply means 7 is caused to perform the supply operation, the supply amount F of the hydrogen-containing gas supplied from the gas supply means 7 A current having a current value C calculated from the amount H of hydrogen contained in the hydrogen-containing gas calculated based on the hydrogen gas concentration Y is passed through the power source 4, and the voltmeter 6 is used to separate the first electrode 14 and the second electrode 15 from each other. When the voltage V measured by the voltmeter 6 is equal to or lower than the reference voltage V0, the voltage measured by the voltmeter 6 is changed by the voltmeter 6 without changing the current value C of the current supplied from the power source 4 to the electrochemical device 2. Returning to the step of measuring, when the measured value V of the voltage by the voltmeter 6 exceeds the reference voltage V0, the current value C of the current passed by the power source 4 to the electrochemical device 2 is reduced by 1%, and then the voltmeter 6 is used. The measurement of the voltage is redone, and this redone is repeated until the voltage measurement value V measured by the voltmeter 6 becomes equal to or lower than the reference voltage V0.

This prevents the current flowing through the electrochemical device 2 from becoming excessive with respect to the amount of hydrogen contained in the supplied hydrogen-containing gas, and suppresses the occurrence of hydrogen deficiency.

Therefore, the deterioration of the catalyst of the anode 10 can be suppressed more reliably, and the hydrogen generation system 1 having higher durability can be provided.

Further, since the mixed gas containing hydrogen is not wastefully discharged, it is possible to provide the hydrogen generation system 1 that stably generates high-purity hydrogen.

(Embodiment 2)
The block diagram showing the schematic configuration of the hydrogen generation system of the second embodiment of the present invention is the same as the block diagram showing the schematic configuration of the hydrogen generation system 1 of the first embodiment shown in FIG. FIG. 3 is a flowchart showing a control process of the hydrogen generation system 1 according to the second embodiment of the present invention.

In addition, in the present embodiment, the same components as those of the hydrogen generation system 1 of the first embodiment are denoted by the same reference numerals, and redundant description may be omitted.

The operation and action of the hydrogen generation system 1 of Embodiment 2 will be described with reference to FIG. 1 with reference to FIG.

First, the hydrogen-containing gas is supplied from the gas supply means 7 through the hydrogen-containing gas supply primary pipe 16, the first electrode 14 of the electrochemical sensor 3, and the hydrogen-containing gas supply secondary pipe 17 to the anode of the electrochemical device 2. 10 (S101), and the power supply 4 is turned on (S102).

Next, the amount H (L/min) of hydrogen contained in the hydrogen-containing gas is calculated from the amount F (L/min) of hydrogen-containing gas supplied from the gas supply means 7 and the concentration Y of hydrogen gas. Further, according to Faraday's law of electrolysis, the current value C(A) flowing into the electrochemical device 2 is calculated using (Equation 2) (S103).

Next, the power source 4 causes a current of the calculated current value C(A) to flow from the anode 10 of the electrochemical device 2 to the cathode 11 via the first electrolyte membrane 8 (S104).

Next, the voltage between the first electrode 14 and the second electrode 15 of the electrochemical sensor 3 is measured by the voltmeter 6, and the measured value is set to the measured value V (V) (S105).

Next, it is determined whether the measured value V(V) falls within the range of the reference voltage V0(V)±α(V) (S106). Here, α(V) is an allowable voltage value. In this embodiment, V0 is 30 mV and α is 3 mV.

When the measured value V(V) falls within the range of the reference voltage V0(V)±α(V), the determination of S106 is made without changing the current value C of the current supplied from the power source 4 to the electrochemical device 2. When it is outside the range of the reference voltage V0(V)±α(V), the process proceeds to S107, and it is determined whether the measured value V(V) is larger than the reference voltage V0+α(V). (S107).

When the measured value V (V) is larger than the reference voltage V0+α (V), the process proceeds to S108, the current value C flowing in the electrochemical device 2 is reduced by 1% (S108), and the process returns to S105. If the measured value V(V) is smaller than the reference voltage V0−α(V) (not larger than the reference voltage V0+α(V)) in the determination of S107, the process proceeds to S109, and the electrochemical device 2 The current value C flowing through is increased by 1% (S109), and the process returns to S105.

As described above, the hydrogen generation system 1 of the present embodiment has the first electrolyte membrane-electrode assembly 9 in which the first electrolyte membrane 8 is sandwiched between the anode 10 and the cathode 11, and the hydrogen-containing gas is contained in the anode 10. Is supplied and an electric current is passed from the anode 10 to the cathode 11 through the first electrolyte membrane 8 to generate hydrogen in the cathode 11, the second electrolyte membrane 12 and the first electrode 14 and the second electrode. The electrochemical sensor 3 having the second electrolyte membrane-electrode assembly 13 sandwiched between the two electrodes 15, the gas supply means 7 for supplying the hydrogen-containing gas to the first electrode 14, the first electrode 14 and the second electrode 15. Between the anode 10 and the power source 4 for supplying a current to the cathode 11 through the first electrolyte membrane 8, the controller 5, and the gas supply means 7 to supply hydrogen to the first electrode 14. A hydrogen-containing gas supply primary pipe 16 that connects the gas supply means 7 and the first electrode 14 so that the contained gas can be supplied, and the first electrode 14 and the anode 10 that can supply the hydrogen-containing gas from the first electrode 14 to the anode 10. A hydrogen-containing gas supply secondary pipe 17 for connection, a hydrogen-containing off-gas pipe 18 for connecting the anode 10 and the second electrode 15 so that the hydrogen-containing off-gas can be supplied from the anode 10 to the second electrode 15, and a cathode 11. The gas supply means 7 is provided with a generated hydrogen discharge pipe 19 for discharging hydrogen from the cathode 11 and a hydrogen-containing offgas discharge pipe 20 for discharging the hydrogen-containing offgas supplied to the second electrode 15 from the second electrode 15. The hydrogen-containing gas discharged from the first electrode 14 is supplied to the anode 10 while the hydrogen-containing gas is supplied to the first electrode 14 and the power supply 4 is flowing an electric current. In the hydrogen generation system 1 configured so that the hydrogen-containing off-gas discharged from the anode 10 without passing through the anode 10 through the first electrolyte membrane 8 to the cathode 11 is discharged through the second electrode 15. is there.

Then, when the controller 5 starts the hydrogen generation operation using the electrochemical device 2, after the gas supply means 7 is caused to perform the supply operation, the supply amount F of the hydrogen-containing gas supplied from the gas supply means 7 A current having a current value C calculated from the amount H of hydrogen contained in the hydrogen-containing gas calculated based on the hydrogen gas concentration Y is passed through the power source 4, and the voltmeter 6 is used to separate the first electrode 14 and the second electrode 15 from each other. When the voltage between them is measured and the measured value V of the voltage by the voltmeter 6 falls within the range of the reference voltage V0±α (V), the current value C of the current supplied from the power source 4 to the electrochemical device 2 is not changed. Then, returning to the step of measuring the voltage by the voltmeter 6, when the measured value V of the voltage by the voltmeter 6 is larger than the reference voltage V0+α (V), the current value C that the power source 4 sends to the electrochemical device 2 is set to 1 %, the voltage is measured again by the voltmeter 6, and when the measured value V of the voltage by the voltmeter 6 is smaller than the reference voltage V0-α (V), the current supplied by the power source 4 to the electrochemical device 2 After the value C is increased by 1%, the voltmeter 6 measures the voltage again.

As a result, the value of the current flowing through the electrochemical device 2 with respect to the amount of hydrogen contained in the hydrogen-containing gas to be supplied is determined with high accuracy, so that it is possible to provide the hydrogen production system 1 that produces highly pure hydrogen with high efficiency. ..

Further, deterioration of the catalyst of the anode 10 due to hydrogen deficiency can be suppressed more reliably, so that the hydrogen generation system 1 having higher durability can be provided.

(Embodiment 3)
The block diagram showing the schematic configuration of the hydrogen generation system of Embodiment 3 of the present invention is the same as the block diagram showing the schematic configuration of the hydrogen generation system 1 of Embodiment 1 shown in FIG. FIG. 4 is a flowchart showing a control process of the hydrogen generation system 1 according to the third embodiment of the present invention.

In addition, in the present embodiment, the same components as those of the hydrogen generation system 1 of the first embodiment are denoted by the same reference numerals, and redundant description may be omitted.

The operation and action of the hydrogen generation system 1 according to the third embodiment will be described with reference to FIG. 1 and with reference to FIG.

First, the hydrogen-containing gas is supplied from the gas supply means 7 through the hydrogen-containing gas supply primary pipe 16, the first electrode 14 of the electrochemical sensor 3, and the hydrogen-containing gas supply secondary pipe 17 to the anode of the electrochemical device 2. 10 (S201), and the power supply 4 is turned on (S202).

Next, the amount H (L/min) of hydrogen contained in the hydrogen-containing gas is calculated from the amount F (L/min) of hydrogen-containing gas supplied from the gas supply means 7 and the concentration Y of hydrogen gas. Further, according to Faraday's law of electrolysis, the current value C(A) flowing to the electrochemical device 2 is calculated using (Equation 2) (S203).

Next, the power source 4 causes a current of the calculated current value C(A) to flow from the anode 10 of the electrochemical device 2 to the cathode 11 via the first electrolyte membrane 8 (S204).

Next, the voltage between the first electrode 14 and the second electrode 15 of the electrochemical sensor 3 is measured by the voltmeter 6, and the measured value is set to the measured value V (V) (S205).

Next, it is determined whether the measured value V(V) falls within the range of the reference voltage V0(V)±α(V) (S206). Here, α(V) is an allowable voltage value. In this embodiment, V0 is 30 mV and α is 3 mV.

When the measured value V(V) falls within the range of the reference voltage V0(V)±α(V), the determination in S206 is made without changing the current value C of the current supplied from the power source 4 to the electrochemical device 2. When the voltage is out of the range of the reference voltage V0 (V)±α (V), the current value of the power source 4 is set to 0 (S207), the power source 4 is turned off (S208), and the gas supply means 7 outputs electricity. The supply of the hydrogen-containing gas to the chemical device 2 is stopped (S209).

As described above, the hydrogen generation system 1 of the present embodiment has the first electrolyte membrane-electrode assembly 9 in which the first electrolyte membrane 8 is sandwiched between the anode 10 and the cathode 11, and the hydrogen-containing gas is contained in the anode 10. Is supplied and an electric current is passed from the anode 10 to the cathode 11 through the first electrolyte membrane 8 to generate hydrogen in the cathode 11, the second electrolyte membrane 12 and the first electrode 14 and the second electrode. The electrochemical sensor 3 having the second electrolyte membrane-electrode assembly 13 sandwiched between the two electrodes 15, the gas supply means 7 for supplying the hydrogen-containing gas to the first electrode 14, the first electrode 14 and the second electrode 15. Between the anode 10 and the power source 4 for supplying a current to the cathode 11 through the first electrolyte membrane 8, the controller 5, and the gas supply means 7 to supply hydrogen to the first electrode 14. A hydrogen-containing gas supply primary pipe 16 that connects the gas supply means 7 and the first electrode 14 so that the contained gas can be supplied, and the first electrode 14 and the anode 10 that can supply the hydrogen-containing gas from the first electrode 14 to the anode 10. A hydrogen-containing gas supply secondary pipe 17 for connection, a hydrogen-containing off-gas pipe 18 for connecting the anode 10 and the second electrode 15 so that the hydrogen-containing off-gas can be supplied from the anode 10 to the second electrode 15, and a cathode 11. The gas supply means 7 is provided with a produced hydrogen discharge pipe 19 for discharging hydrogen from the cathode 11 and a hydrogen-containing offgas discharge pipe 20 for discharging the hydrogen-containing offgas supplied to the second electrode 15 from the second electrode 15. The hydrogen-containing gas discharged from the first electrode 14 is supplied to the anode 10 while the hydrogen-containing gas is supplied to the first electrode 14 and the power supply 4 is flowing an electric current. In the hydrogen generation system 1 configured so that the hydrogen-containing off-gas discharged from the anode 10 without passing through the anode 10 through the first electrolyte membrane 8 to the cathode 11 is discharged through the second electrode 15. is there.

Then, when the controller 5 starts the hydrogen generation operation using the electrochemical device 2, after the gas supply means 7 is caused to perform the supply operation, the supply amount F of the hydrogen-containing gas supplied from the gas supply means 7 A current having a current value C calculated from the amount H of hydrogen contained in the hydrogen-containing gas calculated based on the hydrogen gas concentration Y is passed through the power source 4, and the voltmeter 6 is used to separate the first electrode 14 and the second electrode 15 from each other. When the voltage between them is measured and the measured value V of the voltage by the voltmeter 6 falls within the range of the reference voltage V0±α (V), the current value C of the current supplied from the power source 4 to the electrochemical device 2 is not changed. Then, returning to the step of measuring the voltage by the voltmeter 6, when the measured value V of the voltage by the voltmeter 6 is out of the range of the reference voltage V0±α(V), the current by the power source 4 and the gas supply means 7 are supplied. The supply of the hydrogen-containing gas due to is stopped.

As a result, when an abnormality occurs, it can be stopped safely, and the highly reliable hydrogen generation system 1 can be provided.

When the voltage measurement value V measured by the voltmeter 6 is larger than the reference voltage V0+α(V), the hydrogen-containing gas supply amount from the gas supply means 7 is increased, and the voltage measurement value V measured by the voltmeter 6 is changed to the reference voltage. When it is smaller than V0-α (V), even if the abnormal state is changed to the normal state by reducing the hydrogen-containing gas supply amount from the gas supply means 7, a highly reliable hydrogen generation system 1 is provided. can do.

In the present embodiment, the operation is stopped when the voltage value between the first electrode 14 and the second electrode 15 of the electrochemical sensor 3 exceeds a predetermined range, but the first electrode 14 of the electrochemical sensor 3 is stopped. When the voltage value between the second electrode 15 and the second electrode 15 exceeds a predetermined range, the abnormality may be notified.

(Embodiment 4)
FIG. 5 is a block diagram showing a schematic configuration of a hydrogen generation system according to Embodiment 4 of the present invention. FIG. 6 is a flowchart showing a control process of the hydrogen generation system according to the fourth embodiment of the present invention.

As shown in FIG. 5, the hydrogen generation system 101 of the present embodiment includes an electrochemical device 102, an electrochemical sensor 103, a gas supply means 107, an air supply means 120, a voltmeter 106, and a power supply 104. , And a controller 105.

The electrochemical device 102 has a first electrolyte membrane-electrode assembly 109 in which a first electrolyte membrane 108 is sandwiched between an anode 110 and a cathode 111.

The first electrolyte membrane 108 is a perfluorocarbon sulfonic acid-based polymer electrolyte membrane having a sulfonic acid group.

Each of the anode 110 and the cathode 111 is obtained by dispersing carbon particles carrying platinum on a perfluorocarbon sulfonic acid-based polymer electrolyte aqueous solution having a sulfonic acid group on both main surfaces of the first electrolyte membrane 108. It is formed by coating.

In the power supply 104, when the hydrogen-containing gas is supplied to the anode 110, an oxidation reaction occurs in the anode 110, protons generated by the oxidation reaction pass through the first electrolyte membrane 108, move to the cathode 111, and the cathode 111. Is a DC power supply for flowing a current from the anode 110 to the cathode 111 via the first electrolyte membrane 108 so that a reduction reaction occurs and the hydrogen is generated. The positive terminal of the power supply 104 is electrically connected to the anode 110. The negative terminal of the power source 104 is electrically connected to the cathode 111.

The electrochemical sensor 103 has a second electrolyte membrane-electrode assembly 113 in which the second electrolyte membrane 112 is sandwiched between the first electrode 114 and the second electrode 115.

The second electrolyte membrane 112 is a perfluorocarbon sulfonic acid-based polymer electrolyte membrane having a sulfonic acid group.

For the first electrode 114 and the second electrode 115, carbon particles carrying platinum are dispersed in a perfluorocarbon sulfonic acid-based polymer electrolyte aqueous solution having a sulfonic acid group, respectively. It is formed by coating on both main surfaces.

The gas supply unit 107 is a fuel reformer that produces a humidified hydrogen-containing gas from a city gas by utilizing a reforming reaction, and hydrogen having a hydrogen content rate of 80% and a carbon dioxide content rate of 20%. The contained gas is supplied to the anode 110 via the hydrogen-containing gas supply pipe 116. Here, the numerical value of the content ratio is a numerical value that does not consider the water vapor contained in the hydrogen-containing gas.

Of the hydrogen-containing gas supplied to the anode 110, the hydrogen-containing off-gas discharged from the anode 110 without moving (permeating) to the cathode 111 is the hydrogen-containing off-gas pipe 117, the second electrode 115, and the hydrogen-containing off-gas discharge pipe 119. Is discharged via.

The air supply unit 120 is composed of a blower capable of supplying air, and supplies air to the first electrode 114 via the air supply pipe 121.

The voltmeter 106 measures the voltage between the first electrode 114 and the second electrode 115 of the electrochemical sensor 103.

The gas supply means 107 and the anode 110 of the electrochemical device 102 are connected by a hydrogen-containing gas supply pipe 116 for supplying a hydrogen-containing gas. The air supply means 120 and the first electrode 114 of the electrochemical sensor 103 are connected by an air supply pipe 121 for supplying air.

Further, the anode 110 of the electrochemical device 102 and the second electrode 115 of the electrochemical sensor 103 are connected by a hydrogen-containing offgas pipe 117. Further, the electrochemical device 102 has a produced hydrogen exhaust pipe 118 for exhausting hydrogen produced at the cathode 111, and the second electrode 115 of the electrochemical sensor 103 has a hydrogen-containing offgas exhaust pipe 119 for exhausting hydrogen-containing offgas. Are connected to each other.

The operation and action of the hydrogen generation system 101 of the present embodiment configured as described above will be described with reference to FIG. 5 with reference to FIG.

First, the hydrogen-containing gas is supplied from the gas supply means 107 to the anode 110 of the electrochemical device 102 through the hydrogen-containing gas supply pipe 116 (S301).

Next, air is supplied from the air supply means 120 to the first electrode 114 of the electrochemical sensor 103 (S302), and the power supply 104 is turned on (S303).

Next, the amount H (L/min) of hydrogen contained in the hydrogen-containing gas is calculated from the amount F (L/min) of hydrogen-containing gas supplied from the gas supply means 107 and the concentration Y of hydrogen gas. Further, the current value C(A) flowing to the electrochemical device 102 is calculated by using (Equation 2) according to Faraday's law of electrolysis (S304).

Next, the power supply 104 causes a current of the calculated current value C(A) to flow from the anode 110 of the electrochemical device 102 to the cathode 111 via the first electrolyte membrane 108 (S305).

Next, the voltage between the first electrode 114 and the second electrode 115 of the electrochemical sensor 103 is measured by the voltmeter 106, and the measured value is set to the measured value V (V) (S306).

Next, it is determined whether the measured value V(V) is smaller than the reference voltage V0(V) (S307). Then, when the measured value V (V) is equal to or lower than the reference voltage V0 (V), the determination of S307 is repeated without changing the current value C of the current that the power supply 104 sends to the electrochemical device 102, and the measured value V( If V) is larger than the reference voltage V0 (V), the process proceeds to S308. In this embodiment, V0 is 30 mV. Next, the current value C set by the power supply 104 is reduced by 1% (S308), and the process returns to S306.

As described above, the hydrogen generation system 101 of the present embodiment has the first electrolyte membrane-electrode assembly 109 in which the first electrolyte membrane 108 is sandwiched between the anode 110 and the cathode 111, and the hydrogen-containing gas is contained in the anode 110. Is supplied and an electric current is passed from the anode 110 to the cathode 111 via the first electrolyte membrane 108 to generate hydrogen at the cathode 111, the second electrolyte membrane 112 is connected to the first electrode 114 and the second electrode 112. An electrochemical sensor 103 having a second electrolyte membrane-electrode assembly 113 sandwiched between two electrodes 115, a gas supply means 107 for supplying a hydrogen-containing gas to the anode 110, and an air supply for supplying air to the first electrode 114. A means 120, a voltmeter 106 for measuring the voltage between the first electrode 114 and the second electrode 115, a power source 104 for flowing a current from the anode 110 to the cathode 111 via the first electrolyte membrane 108, and a controller 105. A hydrogen-containing gas can be supplied from the gas supply means 107 to the anode 110, a hydrogen-containing gas supply pipe 116 connecting the gas supply means 107 and the anode 110, and a hydrogen-containing off gas can be supplied from the anode 110 to the second electrode 115. A hydrogen-containing off-gas pipe 117 connecting the anode 110 and the second electrode 115, a generated hydrogen discharge pipe 118 for discharging hydrogen generated at the cathode 111 from the cathode 111, and a hydrogen-containing off-gas supplied to the second electrode 115. A hydrogen-containing off-gas discharge pipe 119 for discharging from the second electrode 115, and the hydrogen supplied to the anode 110 when the gas supply means 107 supplies the hydrogen-containing gas to the anode 110 and the power supply 104 supplies a current. Hydrogen contained in the contained gas such that the hydrogen-containing off-gas discharged from the anode 110 without permeating from the anode 110 to the cathode 111 via the first electrolyte membrane 108 is discharged via the second electrode 115. The generation system 101.

Then, when the controller 105 starts the hydrogen generation operation using the electrochemical device 102, after the gas supply means 107 is caused to perform the supply operation, the supply amount F of the hydrogen-containing gas supplied from the gas supply means 107. A current having a current value C calculated from the hydrogen amount H contained in the hydrogen-containing gas calculated based on the hydrogen gas concentration Y is passed through the power source 104, and the voltmeter 106 causes the first electrode 114 and the second electrode 115 to When the voltage V measured by the voltmeter 106 is equal to or lower than the reference voltage V0, the voltage is measured by the voltmeter 106 without changing the current value C of the current passed by the power source 104 to the electrochemical device 102. Returning to the step of measuring, when the measured value V of the voltage by the voltmeter 106 exceeds the reference voltage V0, the current value C of the current passed through the electrochemical device 102 by the power source 104 is reduced by 1%, and then the voltmeter 106 is used. The measurement of the voltage is redone, and this redone is repeated until the voltage measurement value V measured by the voltmeter 106 becomes equal to or lower than the reference voltage V0.

As a result, the current flowing through the electrochemical device 102 does not become excessive with respect to the amount of hydrogen contained in the supplied hydrogen-containing gas, so that the occurrence of hydrogen deficiency can be suppressed.

Therefore, the deterioration of the catalyst of the anode 110 can be suppressed more reliably, and the hydrogen generation system 101 having higher durability can be provided.

Moreover, since the mixed gas containing hydrogen is not wastefully discharged, it is possible to provide the hydrogen generation system 101 that stably generates high-purity hydrogen.

(Embodiment 5)
The block diagram showing the schematic configuration of the hydrogen generation system of the fifth embodiment of the present invention is the same as the block diagram showing the schematic configuration of the hydrogen generation system 101 of the fourth embodiment shown in FIG. FIG. 7 is a flowchart showing a control process of the hydrogen generation system 101 according to the fifth embodiment of the present invention.

In addition, in the present embodiment, the same components as those of the hydrogen generation system 101 of the fourth embodiment will be denoted by the same reference numerals, and redundant description may be omitted.

The operation and action of the hydrogen generation system 101 of the fifth embodiment will be described with reference to FIG. 5 with reference to FIG. 7.

First, the hydrogen-containing gas is supplied from the gas supply means 107 to the anode 110 of the electrochemical device 102 through the hydrogen-containing gas supply pipe 116 (S401).

Next, air is supplied from the air supply means 120 to the first electrode 114 of the electrochemical sensor 103 (S402), and the power supply 104 is turned on (S403).

Next, the amount H (L/min) of hydrogen contained in the hydrogen-containing gas is calculated from the amount F (L/min) of hydrogen-containing gas supplied from the gas supply means 107 and the concentration Y of hydrogen gas. Further, according to Faraday's law of electrolysis, the current value C(A) flowing to the electrochemical device 102 is calculated using (Equation 2) (S404).

Next, the power supply 104 causes a current of the calculated current value C(A) to flow from the anode 110 of the electrochemical device 102 to the cathode 111 via the first electrolyte membrane 108 (S405).

Next, the voltage between the first electrode 114 and the second electrode 115 of the electrochemical sensor 103 is measured by the voltmeter 106, and the measured value is set to the measured value V (V) (S406).

Next, it is determined whether the measured value V(V) falls within the range of the reference voltage V0(V)±α(V) (S407). Here, α(V) is an allowable voltage value. In this embodiment, V0 is 30 mV and α is 4 mV.

If the measured value V(V) falls within the range of the reference voltage V0(V)±α(V), the determination of S407 is made without changing the current value C of the current that the power supply 104 passes through the electrochemical device 102. If it is outside the range of the reference voltage V0(V)±α(V), the process proceeds to S408, and it is determined whether the measured value V(V) is larger than the reference voltage V0+α(V). (S408).

When the measured value V(V) is larger than the reference voltage V0+α(V), the process proceeds to S409, the current value C flowing through the electrochemical device 102 is reduced by 1% (S409), and the process returns to S406. If the measured value V(V) is smaller than the reference voltage V0−α(V) (not larger than the reference voltage V0+α(V)) in the determination of S408, the process proceeds to S410, and the electrochemical device 102 is operated. The current value C flowing through is increased by 1% (S410), and the process returns to S406.

As described above, the hydrogen generation system 101 of the present embodiment has the first electrolyte membrane-electrode assembly 109 in which the first electrolyte membrane 108 is sandwiched between the anode 110 and the cathode 111, and the hydrogen-containing gas is contained in the anode 110. Is supplied and an electric current is passed from the anode 110 to the cathode 111 via the first electrolyte membrane 108 to generate hydrogen at the cathode 111, the second electrolyte membrane 112 is connected to the first electrode 114 and the second electrode 112. An electrochemical sensor 103 having a second electrolyte membrane-electrode assembly 113 sandwiched between two electrodes 115, a gas supply means 107 for supplying a hydrogen-containing gas to the anode 110, and an air supply for supplying air to the first electrode 114. A means 120, a voltmeter 106 for measuring the voltage between the first electrode 114 and the second electrode 115, a power source 104 for flowing a current from the anode 110 to the cathode 111 via the first electrolyte membrane 108, and a controller 105. A hydrogen-containing gas can be supplied from the gas supply means 107 to the anode 110, a hydrogen-containing gas supply pipe 116 connecting the gas supply means 107 and the anode 110, and a hydrogen-containing off gas can be supplied from the anode 110 to the second electrode 115. A hydrogen-containing off-gas pipe 117 connecting the anode 110 and the second electrode 115, a generated hydrogen discharge pipe 118 for discharging hydrogen generated at the cathode 111 from the cathode 111, and a hydrogen-containing off-gas supplied to the second electrode 115. A hydrogen-containing off-gas discharge pipe 119 for discharging from the second electrode 115, and the hydrogen supplied to the anode 110 when the gas supply means 107 supplies the hydrogen-containing gas to the anode 110 and the power supply 104 supplies a current. Hydrogen contained in the contained gas such that the hydrogen-containing off-gas discharged from the anode 110 without permeating from the anode 110 to the cathode 111 via the first electrolyte membrane 108 is discharged via the second electrode 115. The generation system 101.

Then, when the controller 105 starts the hydrogen generation operation using the electrochemical device 102, after the gas supply means 107 is caused to perform the supply operation, the supply amount F of the hydrogen-containing gas supplied from the gas supply means 107. A current having a current value C calculated from the hydrogen amount H contained in the hydrogen-containing gas calculated based on the hydrogen gas concentration Y is passed through the power source 104, and the voltmeter 106 causes the first electrode 114 and the second electrode 115 to If the voltage V measured by the voltmeter 106 falls within the range of the reference voltage V0±α (V), the current value C of the current supplied from the power source 104 to the electrochemical device 102 is not changed. Then, returning to the step of measuring the voltage by the voltmeter 106, when the measured value V of the voltage by the voltmeter 106 is larger than the reference voltage V0+α (V), the current value C that the power source 104 sends to the electrochemical device 102 is set to 1 %, the voltage is measured again by the voltmeter 106, and when the voltage measurement value V by the voltmeter 106 is smaller than the reference voltage V0−α(V), the current supplied by the power source 104 to the electrochemical device 102. After the value C is increased by 1%, the voltmeter 106 measures the voltage again.

As a result, the value of the current flowing through the electrochemical device 102 with respect to the amount of hydrogen contained in the hydrogen-containing gas to be supplied is determined with high accuracy, so that it is possible to provide the hydrogen production system 101 that produces highly pure hydrogen with high efficiency. ..

In addition, since the deterioration of the catalyst of the anode 110 due to hydrogen deficiency can be suppressed more reliably, the hydrogen generation system 101 having higher durability can be provided.

(Embodiment 6)
The block diagram showing the schematic configuration of the hydrogen generation system of the sixth embodiment of the present invention is the same as the block diagram showing the schematic configuration of the hydrogen generation system 101 of the fourth embodiment shown in FIG. FIG. 8 is a flowchart showing a control process of the hydrogen generation system 101 according to the sixth embodiment of the present invention.

In addition, in the present embodiment, the same components as those of the hydrogen generation system 101 of the fourth embodiment will be denoted by the same reference numerals, and redundant description may be omitted.

The operation and action of the hydrogen generation system 101 according to the sixth embodiment will be described with reference to FIG. 5 with reference to FIG.

First, the hydrogen-containing gas is supplied from the gas supply means 107 to the anode 110 of the electrochemical device 102 through the hydrogen-containing gas supply pipe 116 (S501).

Next, air is supplied from the air supply means 120 to the first electrode 114 of the electrochemical sensor 103 (S502), and the power supply 104 is turned on (S503).

Next, the amount H (L/min) of hydrogen contained in the hydrogen-containing gas is calculated from the amount F (L/min) of hydrogen-containing gas supplied from the gas supply means 107 and the concentration Y of hydrogen gas. Further, according to Faraday's law of electrolysis, the current value C(A) flowing to the electrochemical device 102 is calculated using (Equation 2) (S504).

Next, the power supply 104 causes a current of the calculated current value C(A) to flow from the anode 110 of the electrochemical device 102 to the cathode 111 via the first electrolyte membrane 108 (S505).

Next, the voltage between the first electrode 114 and the second electrode 115 of the electrochemical sensor 103 is measured by the voltmeter 106, and the measured value is set to the measured value V (V) (S506).

Next, it is determined whether the measured value V(V) falls within the range of the reference voltage V0(V)±α(V) (S507). Here, α(V) is an allowable voltage value. In this embodiment, V0 is 30 mV and α is 4 mV.

When the measured value V(V) falls within the range of the reference voltage V0(V)±α(V), the determination of S507 is made without changing the current value C of the current that the power supply 104 passes through the electrochemical device 102. When it is outside the range of the reference voltage V0 (V)±α (V), the process proceeds to S508, the current value of the power source 104 is set to 0 (S508), the power source 104 is turned off (S509), and the gas The supply of the hydrogen-containing gas from the supply means 107 to the electrochemical device 102 is stopped (S510).

As described above, the hydrogen generation system 101 of the present embodiment has the first electrolyte membrane-electrode assembly 109 in which the first electrolyte membrane 108 is sandwiched between the anode 110 and the cathode 111, and the hydrogen-containing gas is contained in the anode 110. Is supplied and an electric current is passed from the anode 110 to the cathode 111 via the first electrolyte membrane 108 to generate hydrogen at the cathode 111, the second electrolyte membrane 112 is connected to the first electrode 114 and the second electrode 112. An electrochemical sensor 103 having a second electrolyte membrane-electrode assembly 113 sandwiched between two electrodes 115, a gas supply means 107 for supplying a hydrogen-containing gas to the anode 110, and an air supply for supplying air to the first electrode 114. A means 120, a voltmeter 106 for measuring the voltage between the first electrode 114 and the second electrode 115, a power source 104 for flowing a current from the anode 110 to the cathode 111 via the first electrolyte membrane 108, and a controller 105. A hydrogen-containing gas can be supplied from the gas supply means 107 to the anode 110, a hydrogen-containing gas supply pipe 116 connecting the gas supply means 107 and the anode 110, and a hydrogen-containing off gas can be supplied from the anode 110 to the second electrode 115. A hydrogen-containing off-gas pipe 117 connecting the anode 110 and the second electrode 115, a generated hydrogen discharge pipe 118 for discharging hydrogen generated in the cathode 111 from the cathode 111, and a hydrogen-containing off-gas supplied to the second electrode 115. A hydrogen-containing off-gas discharge pipe 119 for discharging from the second electrode 115, and the hydrogen supplied to the anode 110 when the gas supply means 107 supplies the hydrogen-containing gas to the anode 110 and the power supply 104 supplies a current. Hydrogen contained in the contained gas such that the hydrogen-containing off-gas discharged from the anode 110 without permeating from the anode 110 to the cathode 111 via the first electrolyte membrane 108 is discharged via the second electrode 115. The generation system 101.

Then, when the controller 105 starts the hydrogen generation operation using the electrochemical device 102, after the gas supply means 107 is caused to perform the supply operation, the supply amount F of the hydrogen-containing gas supplied from the gas supply means 107. A current having a current value C calculated from the hydrogen amount H contained in the hydrogen-containing gas calculated based on the hydrogen gas concentration Y is passed through the power source 104, and the voltmeter 106 causes the first electrode 114 and the second electrode 115 to If the voltage V measured by the voltmeter 106 falls within the range of the reference voltage V0±α (V), the current value C of the current supplied from the power source 104 to the electrochemical device 102 is not changed. Then, returning to the step of measuring the voltage by the voltmeter 106, if the measured value V of the voltage by the voltmeter 106 is out of the range of the reference voltage V0±α (V), the current by the power source 104 and the gas supply means The supply of the hydrogen-containing gas by 107 is stopped.

As a result, when an abnormality occurs, it can be stopped safely and a highly reliable hydrogen generation system 101 can be provided.

When the voltage measurement value V measured by the voltmeter 106 is larger than the reference voltage V0+α(V), the hydrogen-containing gas supply amount from the gas supply means 107 is increased so that the voltage measurement value V measured by the voltmeter 106 is the reference voltage. When it is smaller than V0-α (V), a highly reliable hydrogen generation system 101 is provided even if the abnormal state is changed to the normal state by reducing the hydrogen-containing gas supply amount from the gas supply means 107. can do.

In the present embodiment, the operation is stopped when the voltage value between the first electrode 114 and the second electrode 115 of the electrochemical sensor 103 exceeds a predetermined range, but the first electrode 114 of the electrochemical sensor 103 is stopped. When the voltage value between the second electrode 115 and the second electrode 115 exceeds a predetermined range, it may be configured to notify that there is an abnormality.

As described above, the hydrogen generation system according to the present invention can suppress the catalyst deterioration of the anode due to hydrogen deficiency, and stably generate high-purity hydrogen without wastefully discharging the mixed gas containing hydrogen. Therefore, it is most suitable for a hydrogen generation system that uses an electrochemical device to generate high-purity hydrogen from a hydrogen-containing gas and requires reliability, stability, and durability.

1 Hydrogen Generation System 2 Electrochemical Device 3 Electrochemical Sensor 4 Power Supply 5 Controller 6 Voltmeter 7 Gas Supply Means 8 First Electrolyte Membrane 9 First Electrolyte Membrane-Electrode Assembly 10 Anode 11 Cathode 12 Second Electrolyte Membrane 13 Second Electrolyte membrane-electrode assembly 14 First electrode 15 Second electrode 16 Hydrogen-containing gas supply primary piping 17 Hydrogen-containing gas supply secondary piping 18 Hydrogen-containing off-gas piping 19 Generated hydrogen discharge piping 20 Hydrogen-containing off-gas discharge piping 101 Hydrogen generation system 102 Electrochemical device 103 Electrochemical sensor 104 Power supply 105 Controller 106 Voltmeter 107 Gas supply means 108 First electrolyte membrane 109 First electrolyte membrane-electrode assembly 110 Anode 111 Cathode 112 Second electrolyte membrane 113 Second electrolyte membrane-electrode junction Body 114 First electrode 115 Second electrode 116 Hydrogen-containing gas supply pipe 117 Hydrogen-containing off-gas pipe 118 Generated hydrogen discharge pipe 119 Hydrogen-containing off-gas discharge pipe 120 Air supply means 121 Air supply pipe

Claims (10)

A first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode is provided, a hydrogen-containing gas is supplied to the anode, and a current flows from the anode to the cathode through the first electrolyte membrane. An electrochemical device that produces hydrogen at the cathode by flowing
An electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode,
Gas supply means for supplying a hydrogen-containing gas to the first electrode,
A voltmeter for measuring the voltage between the first electrode and the second electrode,
A power supply for passing the current,
And a controller,
When the gas supply unit supplies the hydrogen-containing gas to the first electrode and the power source is flowing the current, the hydrogen-containing gas discharged from the first electrode is supplied to the anode and supplied to the anode. The hydrogen-containing off gas discharged from the anode without passing through the cathode from the anode through the first electrolyte membrane among the hydrogen-containing gas thus discharged is discharged through the second electrode. A hydrogen production system,
The controller calculates, based on the flow rate of the hydrogen-containing gas supplied from the gas supply means, after the gas supply means performs a supply operation when starting the hydrogen generation operation using the electrochemical device. The current of the current value is made to flow to the power source, the voltage is measured by the voltmeter, and if the voltage value measured by the voltmeter does not satisfy a predetermined condition, A hydrogen generation system, wherein a current value is changed based on the voltage value. When the voltage value measured by the voltmeter exceeds a first predetermined value, the controller reduces the current value of the current passed by the power source and then re-measures the voltage by the voltmeter. The hydrogen generation system according to claim 1, wherein: When the voltage value measured by the voltmeter exceeds a predetermined upper limit value, the controller reduces the current value of the current passed by the power supply, and then re-measures the voltage by the voltmeter, When the voltage value measured by the voltmeter is less than a predetermined lower limit value, the current value of the current passed by the power supply is increased, and then the voltage measurement by the voltmeter is performed again. The hydrogen generation system described in 1. When the voltage value measured by the voltmeter exceeds a second predetermined value, the controller reports an abnormality, stops the operation, or changes the amount of hydrogen-containing gas supplied from the gas supply means. The hydrogen generation system according to claim 1, wherein the hydrogen generation system is increased. A first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode is provided, a hydrogen-containing gas is supplied to the anode, and a current flows from the anode to the cathode through the first electrolyte membrane. An electrochemical device that produces hydrogen at the cathode by flowing
An electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode,
Gas supply means for supplying a hydrogen-containing gas to the anode,
Air supply means for supplying air to the first electrode,
A voltmeter for measuring the voltage between the first electrode and the second electrode,
A power supply for passing the current,
And a controller,
When the gas supply means supplies a hydrogen-containing gas to the anode and the power source is flowing the current, the hydrogen-containing gas supplied to the anode is passed from the anode through the first electrolyte membrane. A hydrogen generation system configured such that a hydrogen-containing gas discharged from the anode without passing through a cathode is discharged via the second electrode,
The controller, when starting a hydrogen generation operation using the electrochemical device, causes the gas supply means and the air supply means to perform a supply operation, and then supplies a hydrogen-containing gas from the gas supply means. While causing the current of the current value calculated based on the flow rate to flow into the power source, the voltage is measured by the voltmeter, and the voltage value measured by the voltmeter does not satisfy a predetermined condition, the A hydrogen generation system, wherein a current value of the current supplied by a power source is changed based on the voltage value. When the voltage value measured by the voltmeter exceeds a first predetermined value, the controller reduces the current value of the current passed by the power source and then re-measures the voltage by the voltmeter. The hydrogen generation system according to claim 5, wherein: When the voltage value measured by the voltmeter exceeds a predetermined upper limit value, the controller reduces the current value of the current passed by the power supply, and then re-measures the voltage by the voltmeter, When the voltage value measured by the voltmeter is less than a predetermined lower limit value, the current value of the current passed by the power source is increased, and then the voltage measurement by the voltmeter is repeated. The hydrogen generation system described in 1. When the voltage value measured by the voltmeter exceeds a second predetermined value, the controller reports an abnormality, stops the operation, or changes the amount of hydrogen-containing gas supplied from the gas supply means. The hydrogen generation system according to claim 5, wherein the hydrogen generation system is increased. A first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode is provided, a hydrogen-containing gas is supplied to the anode, and a current flows from the anode to the cathode through the first electrolyte membrane. An electrochemical device that produces hydrogen at the cathode by flowing
An electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode,
Gas supply means for supplying a hydrogen-containing gas to the first electrode,
A voltmeter for measuring the voltage between the first electrode and the second electrode,
A power source for supplying the current,
When the gas supply unit supplies the hydrogen-containing gas to the first electrode and the power source is flowing the current, the hydrogen-containing gas discharged from the first electrode is supplied to the anode and supplied to the anode. The hydrogen-containing off gas discharged from the anode without passing through the cathode from the anode through the first electrolyte membrane among the hydrogen-containing gas thus discharged is discharged through the second electrode. And a method for operating the hydrogen generation system, comprising:
When starting the hydrogen generation operation using the electrochemical device, the current value of the current value calculated based on the flow rate of the hydrogen-containing gas supplied from the gas supply means after the supply operation to the gas supply means is started. While causing the current to flow in the power supply, the voltage is measured by the voltmeter, and when the voltage value measured by the voltmeter does not satisfy a predetermined condition, the current value of the current passed by the power supply is set to the voltage. A method for operating a hydrogen generation system, characterized by changing the value based on a value. A first electrolyte membrane-electrode assembly in which a first electrolyte membrane is sandwiched between an anode and a cathode is provided, a hydrogen-containing gas is supplied to the anode, and a current flows from the anode to the cathode through the first electrolyte membrane. An electrochemical device that produces hydrogen at the cathode by flowing
An electrochemical sensor having a second electrolyte membrane-electrode assembly in which a second electrolyte membrane is sandwiched between a first electrode and a second electrode,
Gas supply means for supplying a hydrogen-containing gas to the anode,
Air supply means for supplying air to the first electrode,
A voltmeter for measuring the voltage between the first electrode and the second electrode,
A power source for supplying the current,
When the gas supply means supplies a hydrogen-containing gas to the anode and the power source is flowing the current, the hydrogen-containing gas supplied to the anode is passed from the anode through the first electrolyte membrane. A method for operating a hydrogen generation system, wherein the hydrogen-containing gas discharged from the anode without permeating to the cathode is discharged via the second electrode,
Based on the flow rate of the hydrogen-containing gas supplied from the gas supply means after the gas supply means and the air supply means are supplied when the hydrogen generation operation is started using the electrochemical device. The current of the calculated current value is caused to flow through the power supply, the voltage is measured by the voltmeter, and if the voltage value measured by the voltmeter does not satisfy a predetermined condition, the current flowed by the power supply. The method for operating a hydrogen generation system, characterized in that the current value of is changed based on the voltage value.

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