Electric control system based on inorganic proton conductor hydrogen pump array

Abstract

The invention discloses an electric control system based on an inorganic proton conductor hydrogen pump array. The electric control system comprises the proton conductor hydrogen pump array and a main driving circuit, the proton conductor hydrogen pump array comprises a plurality of proton conductor hydrogen pump sets which are connected in parallel, and each proton conductor hydrogen pump set comprises proton conductor hydrogen pumps which are connected in series; the main driving circuit provides a constant current source for each proton conductor hydrogen pump set; for each proton conductor hydrogen pump group, the anode of each proton conductor hydrogen pump group is connected with the anode of the main driving circuit, and the cathode of each proton conductor hydrogen pump group is connected with the cathode of the main driving circuit; each proton conductor hydrogen pump comprises an anode side and a cathode side, and for each proton conductor hydrogen pump group, the cathode side of the previous proton conductor hydrogen pump is electrically connected with the anode side of the next proton conductor hydrogen pump. Hydrogen and helium separation / hydrogen isotope extraction is carried out in a proton conductor hydrogen array mode, the array is formed in a series-parallel combination mode, the main driving circuit provides a constant current source, and the utilization rate of the proton conductor hydrogen pump is increased.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen isotope separation, and in particular to an electric control system based on an inorganic proton conductor hydrogen pump array. Background Art

[0002] The tritium fuel cycle system primarily recovers hydrogen isotopes from mixed gases, primarily involving hydrogen-helium separation technology. Traditional hydrogen-helium separation technologies suffer from high costs and complex equipment. Proton conductor hydrogen pumps, which selectively extract hydrogen from hydrogen-containing mixed gases, have emerged as a promising technology for hydrogen-helium separation. This system selectively extracts hydrogen isotopes from mixed gases containing hydrogen isotopes by applying an electrical signal to electrodes on either side of the proton conductor hydrogen pump. This system utilizes a DC electric field to induce anodic and cathodic reactions at the electrolyte interface, respectively, to achieve hydrogen isotope migration. This technology holds great promise for hydrogen separation and purification. Research on proton conductor hydrogen pumps for hydrogen-helium separation has primarily focused on extracting hydrogen from mixed gases containing hydrogen at concentrations above 1%, with the cathode typically containing inert gases or mixed gases. Current methods typically increase the current density or membrane area to boost the hydrogen extraction rate. This technology can also be used for the separation of hydrogen isotopes in the removal of tritium from nuclear wastewater. When the tritium concentration on one side is higher than that on the other side, hydrogen can pass through the proton conductor hydrogen pump more easily than tritium, so it has a certain separation ratio. The hydrogen isotopes in the hydrogen isotope mixture gas are separated by applying electrical signals to the electrodes on both sides of the proton conductor hydrogen pump.

[0003] In the prior art, for the multi-component form of proton conductor hydrogen pumps, constant voltage control is mostly adopted, that is, the voltage source always maintains a constant voltage output: (1) For the direct series form, when a proton conductor hydrogen pump has a short circuit fault, its voltage drop will be further distributed to other proton conductor hydrogen pumps, which will cause the current of the entire circuit to increase. When there are too many proton conductor hydrogen pumps with short circuit faults in this branch, the current of the entire circuit will rise sharply. At the same time, the voltage at both ends of the proton conductor hydrogen pump will also increase sharply. When the proton conductor hydrogen pump is in an overvoltage state for a long time, although the hydrogen extraction rate of the proton conductor hydrogen pump can be increased, it will cause irreversible effects on the electrolyte of the proton conductor hydrogen pump; (2) For the direct parallel form, if the proton conductor hydrogen pumps of the same material are selected, the hydrogen extraction rate of each proton conductor hydrogen pump can be guaranteed to be the same as much as possible. However, in the actual production process, it is impossible to ensure that the electrical characteristics of each proton conductor hydrogen pump are exactly the same. Therefore, there will definitely be a situation where the hydrogen extraction rate of each proton conductor hydrogen pump is not equal. Summary of the Invention

[0004] The purpose of the present invention is to overcome the deficiencies of the prior art and provide an electronic control system based on an inorganic proton conductor hydrogen pump array.

[0005] The object of the present invention is achieved through the following technical solutions: In a first aspect of the present invention, an electric control system based on an inorganic proton conductor hydrogen pump array is provided, comprising a proton conductor hydrogen pump array and a main drive circuit; The proton conductor hydrogen pump array includes multiple groups of proton conductor hydrogen pump groups connected in parallel, and each group of proton conductor hydrogen pump groups includes proton conductor hydrogen pumps connected in series; the main drive circuit provides a constant current source to each group of proton conductor hydrogen pump groups; For each proton conductor hydrogen pump group, the anode of each proton conductor hydrogen pump group is connected to the positive electrode of the main drive circuit, and the cathode of each proton conductor hydrogen pump group is connected to the negative electrode of the main drive circuit; Each proton conductor hydrogen pump includes an anode side and a cathode side. For the proton conductor hydrogen pumps connected along the current direction in each group of proton conductor hydrogen pumps, the cathode side of the previous proton conductor hydrogen pump is electrically connected to the anode side of the next proton conductor hydrogen pump.

[0006] Furthermore, the anode side of the proton conductor hydrogen pump is connected to the raw material input pipeline, and the cathode side of the proton conductor hydrogen pump is connected to the separation output pipeline.

[0007] Furthermore, the current of the constant current source provided by the main driving circuit is set in the working range where the Faraday efficiency of the proton conductor hydrogen pump is 1; the hydrogen extraction rate of the proton conductor hydrogen pump is directly calculated from the current in the working range where the Faraday efficiency is 1; the current of the constant current source is less than the limiting current of the proton conductor hydrogen pump, where the limiting current is the maximum current when the Faraday efficiency is 1.

[0008] Furthermore, the electrolyte of the proton conductor hydrogen pump is selected from barium zirconate-based materials and barium ceria-based materials, and the electrode material is selected from metal nickel electrode.

[0009] Furthermore, the main drive circuit includes: a power supply VCC, an adjustable potentiometer RV, a transistor Q11, and a resistor R11; for each proton conductor hydrogen pump group, the main drive circuit is also correspondingly configured with a transistor Qn and a resistor Rn; The power supply VCC is connected to the base of the transistor Q11, the base of the transistor Qn, and the collector of the transistor Q11 through the adjustable potentiometer RV. The emitter of the transistor Q11 is grounded through the resistor R11, and the emitter of the transistor Qn is grounded through the resistor Rn. The power supply VCC is also connected to the collector of the corresponding transistor Qn through the proton conductor hydrogen pump group. By adjusting the resistance of the adjustable potentiometer RV, the current of each proton conductor hydrogen pump group of the proton conductor hydrogen pump array is simultaneously changed, thereby changing the hydrogen extraction rate of the proton conductor hydrogen pump array.

[0010] Furthermore, the electronic control system also includes a first auxiliary drive circuit for detecting faults, disconnections, and short circuits of the proton conductor hydrogen pump; each proton conductor hydrogen pump is configured with a first auxiliary drive circuit, and each first auxiliary drive circuit includes a first differential operational amplifier, a second differential operational amplifier, a first inverter, a second inverter, and a NOR gate chip; The anode side wire of the proton conductor hydrogen pump is connected to the positive electrode of the first differential operational amplifier, and the cathode side wire of the proton conductor hydrogen pump is respectively connected to the negative electrode of the first differential operational amplifier and the positive electrode of the second differential operational amplifier, and the negative electrode of the second differential operational amplifier is connected to VDD; the output end of the first differential operational amplifier is connected to the first input end of the NOR gate chip through a first inverter, and the output end of the second differential operational amplifier is connected to the second input end of the NOR gate chip through a second inverter, and the output end of the NOR gate chip outputs a short-circuit signal; The output terminal of the second differential operational amplifier outputs a disconnection signal through the second inverter.

[0011] Furthermore, the electronic control system also includes a second auxiliary drive circuit for suppressing reverse diffusion of the proton conductor hydrogen pump in a non-operating state; each group of proton conductor hydrogen pumps is configured with a second auxiliary drive circuit; each second auxiliary drive circuit includes a first switch located on the cathode side of each proton conductor hydrogen pump and an eleventh switch located on the anode side of the proton conductor hydrogen pump group; The common connection point between the cathode side of each proton conductor hydrogen pump and the corresponding first switch is grounded via a thirteenth switch, the common connection point between the anode side of each proton conductor hydrogen pump and the first switch corresponding to the previous proton conductor hydrogen pump is connected to the voltage source VEE via a twelfth switch, and the common connection point between the first proton conductor hydrogen pump and the eleventh switch is also connected to the voltage source VEE via the twelfth switch; When in a non-working state, the first switch and the eleventh switch are disconnected, and the twelfth switch and the thirteenth switch are closed; when in a working state, the first switch and the eleventh switch are closed, and the twelfth switch and the thirteenth switch are disconnected.

[0012] The beneficial effects of the present invention are: In an exemplary embodiment of the present invention, hydrogen separation / hydrogen isotope extraction is performed using a proton conductor hydrogen array, wherein the circuit connection portion forms an array using a series-parallel combination, and the main drive circuit provides a constant current source to each group of proton conductor hydrogen pump groups, thereby improving the utilization rate of the proton conductor hydrogen pumps. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 Schematic diagram of an electrical control system based on an inorganic proton conductor hydrogen pump array provided in an exemplary embodiment of the present invention; Figure 2This is a schematic diagram of the gas circuit connection of a proton conductor hydrogen pump provided in an exemplary embodiment of the present invention; Figure 3 A schematic diagram of a Faraday efficiency experiment provided in an exemplary embodiment of the present invention; Figure 4 A schematic diagram of a main driving circuit provided in an exemplary embodiment of the present invention; Figure 5 Schematic diagram of a first auxiliary driving circuit provided in an exemplary embodiment of the present invention; Figure 6 Schematic diagram of a second auxiliary driving circuit provided in an exemplary embodiment of the present invention; Figure 7 A schematic diagram of a normal working state provided in an exemplary embodiment of the present invention; Figure 8 A schematic diagram of the reverse diffusion phenomenon provided in an exemplary embodiment of the present invention; In the figure, 1-proton conductor hydrogen pump array, 11-proton conductor hydrogen pump group, 111-proton conductor hydrogen pump, 2-main drive circuit, 3-raw material input pipeline, 4-separation output pipeline. DETAILED DESCRIPTION

[0014] The technical solution of the present invention is described clearly and completely below with reference to the accompanying drawings. It is apparent that the embodiments described are only a portion of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are intended to fall within the scope of protection of the present invention.

[0015] In the description of the present invention, it should be noted that the directions or positional relationships indicated by terms such as "center," "up," "down," "left," "right," "vertical," "horizontal," "inside," and "outside" are based on the directions or positional relationships described in the accompanying drawings and are intended solely to facilitate and simplify the description of the present invention. They are not intended to indicate or imply that the devices or components referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on the present invention. Furthermore, terms such as "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0016] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood in a broad sense. For example, they may refer to fixed connections, detachable connections, or integral connections; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; and internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention.

[0017] In addition, the technical features involved in different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0018] See also Figure 1 , Figure 1 The electronic control system based on the inorganic proton conductor hydrogen pump array provided in an exemplary embodiment of the present invention is shown, comprising a proton conductor hydrogen pump array 1 and a main drive circuit 2; The proton conductor hydrogen pump array 1 includes a plurality of parallel proton conductor hydrogen pump groups 11, each proton conductor hydrogen pump group 11 includes proton conductor hydrogen pumps 111 connected in series; the main drive circuit 2 provides a constant current source to each proton conductor hydrogen pump group 11; For each proton conductor hydrogen pump group 11, the anode of each proton conductor hydrogen pump group 11 is connected to the positive electrode of the main drive circuit 2, and the cathode of each proton conductor hydrogen pump group 11 is connected to the negative electrode of the main drive circuit 2; Each proton conductor hydrogen pump 111 includes an anode side and a cathode side. For the proton conductor hydrogen pumps 111 connected along the current direction (A) in each group of proton conductor hydrogen pumps 111, the cathode side of the previous proton conductor hydrogen pump 111 is connected to the anode side of the next proton conductor hydrogen pump 111.

[0019] Specifically, in this exemplary embodiment, each proton conductor hydrogen pump 111 is connected in series to form a proton conductor hydrogen pump group 11, which is then connected in parallel to ultimately form a proton conductor hydrogen pump array 1. The number of proton conductor hydrogen pump groups 111 in each proton conductor hydrogen pump group 11 and the number of proton conductor hydrogen pump groups 11 can be adjusted based on specific actual project requirements. In one exemplary embodiment, a 10*10 proton conductor hydrogen pump array 1 is used.

[0020] At the same time, in this exemplary embodiment, the main driving circuit 2 is used to provide a constant current source to each group of proton conductor hydrogen pump groups 11, and the current of each group of proton conductor hydrogen pump groups 11 can be kept consistent. When the size needs to be adjusted, the size of the constant current source can be adjusted to simultaneously change the current size of 10 columns passing through the proton conductor hydrogen pump array 1.

[0021] It should be noted that, compared to the series or parallel connection methods used in the prior art for constant voltage control, the hybrid connection circuit of the proton conductor hydrogen pump array 1 of this exemplary embodiment uses a series-parallel combination. All proton conductor hydrogen pumps 111 are first connected in series and then in parallel. This method combines the advantages of the above two connection methods (series or parallel). In this exemplary embodiment, a short circuit or open circuit in a row of a group does not affect the normal operation of the proton conductor hydrogen pumps 111 in other columns. This is a relatively ideal connection method. Therefore, in the present invention, this connection method is used to form a proton conductor hydrogen pump array. The series-parallel combination and its use in conjunction with the main drive circuit 2 that provides a constant current source can greatly improve its overall efficiency.

[0022] Furthermore, the structure of this exemplary embodiment can be used to separate hydrogen from a hydrogen-helium mixture, where the hydrogen content in the mixture ranges from 0-99.99999%. It can also be used for isotope separation in nuclear wastewater tritium removal. When the tritium concentration on one side of the proton conductor hydrogen pump 111 is higher than the other, hydrogen permeates more easily than tritium, achieving a certain separation ratio. This array electronic control system can also achieve hydrogen isotope separation. This can be used in heavy water reactors, for deuterium-tritium separation, or in water deuterium extraction, for hydrogen-deuterium separation.

[0023] Therefore, in this exemplary embodiment, hydrogen separation / hydrogen isotope extraction is performed using a proton conductor hydrogen array 1, wherein the circuit connection part forms an array using a series-parallel combination, and the main drive circuit 2 provides a constant current source to each group of proton conductor hydrogen pump groups 11, thereby improving the utilization rate of the proton conductor hydrogen pump 111.

[0024] The following contents will describe various preferred exemplary embodiments: More preferably, in an exemplary embodiment, Figure 2 As shown, the anode side of the proton conductor hydrogen pump 111 is connected to the raw material input pipeline 3 , and the cathode side of the proton conductor hydrogen pump 111 is connected to the separation output pipeline 4 .

[0025] Specifically, in this exemplary embodiment, the gas circuit connections are all in parallel connection mode, the anode side of the proton conductor hydrogen pump 111 is connected to the raw material input pipeline 3, and the cathode side of the proton conductor hydrogen pump 111 is connected to the separation output pipeline 4.

[0026] Taking hydrogen-helium separation as an example, the anode side of the proton conductor hydrogen pump 111 is connected to the raw material input pipeline 3 of 0.1% H2 / 99.9% He, and the cathode side of the proton conductor hydrogen pump 111 is connected to the separation output pipeline 4 of high-purity hydrogen to achieve hydrogen-helium separation.

[0027] More preferably, in an exemplary embodiment, the current of the constant current source provided by the main driving circuit 2 is set in the working range of the proton conductor hydrogen pump 111 with a Faraday efficiency of 1; the hydrogen extraction rate of the proton conductor hydrogen pump 111 is directly calculated from the current in the working range with a Faraday efficiency of 1; the current of the constant current source is less than the limiting current of the proton conductor hydrogen pump, where the limiting current is the maximum current with a Faraday efficiency of 1.

[0028] In the prior art, the atmosphere conditions of the cathode chamber of the proton conductor hydrogen pump 111 are not suitable for engineering application scenarios, and the use of high-purity hydrogen as the cathode atmosphere conditions is more conducive to engineering applications. In current research, increasing the current density can effectively increase the hydrogen extraction rate of the proton conductor hydrogen pump 111, but too high a current density will cause irreversible effects on the proton conductor hydrogen pump 111, and there is a limiting current in the proton conductor hydrogen pump 111. Below the limiting current, the actual hydrogen extraction rate is almost the same as the theoretical hydrogen extraction rate, but once the limiting current is exceeded, the actual hydrogen extraction rate will deviate from the theoretical hydrogen extraction rate. Therefore, it is not conducive to controlling the hydrogen extraction rate of the proton conductor hydrogen pump 111 when the current density is too large. Although increasing the diaphragm area can increase the hydrogen extraction rate of the proton conductor hydrogen pump 111, the mechanical properties are significantly reduced. The processing volume of nuclear fusion hydrogen isotopes is huge and specifically involves extracting hydrogen from ultra-low concentration hydrogen-containing mixed gases. The flow channel-type current collecting plate design of the fuel cell will cause some of the proton conductor hydrogen pump 111 diaphragms placed at the initial end of the flow channel to always be in a working state, while some of the proton conductor hydrogen pump 111 diaphragms placed at the end of the flow channel cannot play their role in pumping hydrogen, thereby causing the utilization rate of the proton conductor hydrogen pump 111 diaphragms to decrease.

[0029] In this exemplary embodiment, the proton conductor hydrogen pump 111 extracts hydrogen isotopes using a preferred Faraday efficiency range of 1 (intervals with Faraday efficiencies other than 1 may also be used). If a Faraday efficiency range of 1 is used, the current flowing through the proton conductor hydrogen pump 111 should be less than the limiting current. Because the proton conductor hydrogen pumps 111 in each proton conductor hydrogen pump group 11 are connected in series, the current flowing through the group is consistent, meaning that the current flowing through each proton conductor hydrogen pump 111 is less than the limiting current.

[0030] This limiting current is the core of this exemplary embodiment. In the range where the Faraday efficiency is 1, the number of hydrogen ions passing through the proton conductor hydrogen pump 111 can be directly calculated from the current, which can directly calculate the specific amount of hydrogen passing through per unit time, and the hydrogen concentration in the 0.1% H2-99.9% He gas pipeline can be dynamically adjusted. For example, when the hydrogen concentration in the hydrogen-helium mixture is too high, increasing the current can reduce the hydrogen concentration in the hydrogen-helium mixture. Using a voltage and current below the limiting current or limiting voltage of the proton conductor hydrogen pump 111, the theoretical hydrogen extraction rate is equal to the actual hydrogen extraction rate, and the actual hydrogen extraction rate is directly derived from Faraday's law: Where i is the electrolysis current (A), F is the Faraday constant (96485 C / mol), Z is the number of electrons required for hydrogen formation, and V_th is the theoretical hydrogen evolution rate (in ml / min).

[0031] It should be noted that the operating temperature range of the proton conductor hydrogen pump 111 in this exemplary embodiment varies greatly, specifically 450-600°C. When the temperature changes, the resistance of the device will change, and temperature has a significant impact on the resistance value. One of the purposes of this patent is that when the temperature changes, its hydrogen permeability will not be affected by its temperature fluctuations, and its hydrogen permeability can be directly converted to current in the range where the Faraday efficiency is 1. The specific formula is shown above. Therefore, one of the purposes of the main drive circuit 2 using a constant current source is that when the temperature fluctuates, when the resistance of the proton conductor hydrogen pump 111 changes, the current passing through the proton conductor hydrogen pump 111 remains unchanged, thereby ensuring that the hydrogen permeability of the proton conductor hydrogen pump 111 does not change.

[0032] Furthermore, compared to the existing constant voltage source, which does not use voltage adjustment, experiments have shown that the device has a time-varying characteristic under voltage control, meaning that its current varies over time. However, the voltage across the device remains stable under current control. Therefore, current control is more conducive to the operation of the device.

[0033] Therefore, in this exemplary embodiment, hydrogen isotopes are extracted using an electrical signal below the limiting current of the proton conductor hydrogen pump 111. Within this range, the Faraday efficiency of the proton conductor hydrogen pump 111 is 1. The hydrogen extraction rate of the proton conductor hydrogen pump 111 can be directly calculated by the current, and the hydrogen extraction rate can be precisely controlled in the range below the limiting current.

[0034] More preferably, in an exemplary embodiment, whether the Faraday efficiency is 1 is measured by experiment. In a specific exemplary embodiment, the experimental results are as follows: Figure 3As shown, the interval where the Faraday efficiency is 1 must be a linear interval. The definition of Faraday efficiency of 1 is as follows, and the following formula is Faraday's law: This formula is the theoretical hydrogen extraction rate calculation formula: This formula calculates the actual hydrogen extraction rate, which can also be determined based on the experimentally measured hydrogen isotope-labeled hydrogen content in the cathode. When the theoretical hydrogen extraction rate and the actual hydrogen extraction rate are equal, the Faraday efficiency is 1. When the Faraday efficiency is 1, the hydrogen extraction rate of the proton conductor hydrogen pump can be calculated by varying the current. As the current gradually increases, the Faraday efficiency decreases below 1. The maximum current at which the Faraday efficiency remains at 1 is the limiting current. In this exemplary embodiment, the optimal operating range is one where the Faraday efficiency is 1, meaning the current applied to both sides of the proton conductor hydrogen pump should be less than the limiting current.

[0035] Figure 3 In the figure, the experimental results of the Faraday efficiency of 1 at three operating temperatures (510°C, 530°C, and 550°C) are shown, where: Figure 3 It was found that its volt-ampere characteristic curve is not a straight line. There is an inflection point at around 2V. After the inflection point appears, the current rises rapidly. At this time, it is very likely that a large number of holes are conducting electricity after 2V. Referring to the hydrogen sensor, there is an ohmic region when the current is less than a certain current, and this phenomenon exists in the linear region. Therefore, the interval with a Faraday efficiency of 1 must exist in the linear region.

[0036] More preferably, in an exemplary embodiment, the electrolyte of the proton conductor hydrogen pump 111 based on the above method is selected from barium zirconate-based materials and barium ceria-based materials, and the electrode material is a metal nickel electrode.

[0037] Specifically, the barium zirconate-based material of the electrolyte material, namely BaZrO3, contains 0% to 30% of inorganic additives, and the inorganic additives are selected from one or more of yttrium oxide, scandium oxide, cerium oxide, gadolinium oxide, nickel oxide, iron oxide, magnesium oxide, aluminum oxide, and ytterbium oxide; the barium cerate-based material, namely BaCeO3, contains 0% to 30% of inorganic additives, and the inorganic additives are selected from one or more of yttrium oxide, scandium oxide, zirconium oxide, gadolinium oxide, nickel oxide, iron oxide, magnesium oxide, aluminum oxide, and ytterbium oxide.

[0038] More preferably, the proton conductor electrolyte can be selected from barium zirconate-based materials and barium ceria-based materials, wherein the barium zirconate-based (BaZrO3) material may contain 0% to 10% of inorganic additives, and the inorganic additives are selected from one or more of yttrium oxide, scandium oxide, cerium oxide, gadolinium oxide, nickel oxide, iron oxide, magnesium oxide, aluminum oxide, and ytterbium oxide; wherein the barium ceria-based (BaCeO3) material may contain 0% to 10% of inorganic additives, and the inorganic additives are selected from one or more of yttrium oxide, scandium oxide, zirconium oxide, gadolinium oxide, nickel oxide, iron oxide, magnesium oxide, aluminum oxide, and ytterbium oxide.

[0039] More preferably, in an exemplary embodiment, the proton conductor hydrogen pump 111 is composed of a proton conductor membrane and two electrodes, wherein the material of the proton conductor membrane includes BaZr 0.8 Yr 0.16 Ni 0.04 O 3-σ , where 0<σ<1; the material of BZCYYb diaphragm is BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-ð , where 0< ð <1; the electrodes on both sides of the proton conductor membrane are Ni electrodes, and the operating temperature range of a single proton conductor hydrogen permeable component is 300℃~650℃, and its current density does not exceed 0.1A / cm 2 In a specific exemplary embodiment, the constant current source adopts 0-20mA, and the effective working area of ​​the proton conductor hydrogen pump is 314.159mm 2 That is 0-0.063A / cm 2 .

[0040] It should be noted that the aforementioned content mentioned that this exemplary embodiment can be used not only for hydrogen-helium separation, but also for hydrogen isotope separation; the advantage of using this method for hydrogen isotope separation is that the proton conductor hydrogen pump 111 is resistant to radioactivity, and the radioactivity of hydrogen isotopes will not affect the proton conductor hydrogen pump 111.

[0041] More preferably, in an exemplary embodiment, Figure 4 As shown, the main drive circuit 2 includes: a power supply VCC, an adjustable potentiometer RV, a transistor Q11, and a resistor R11; for each proton conductor hydrogen pump group 11, the main drive circuit 2 is also correspondingly configured with a transistor Qn and a resistor Rn; The power supply VCC is connected to the base of the transistor Q11, the base of the transistor Qn, and the collector of the transistor Q11 through the adjustable potentiometer RV. The emitter of the transistor Q11 is grounded through the resistor R11, and the emitter of the transistor Qn is grounded through the resistor Rn. The power supply VCC is also connected to the collector of the corresponding transistor Qn through the proton conductor hydrogen pump group 11. By adjusting the resistance of the adjustable potentiometer RV, the current of each proton conductor hydrogen pump group 11 of the proton conductor hydrogen pump array 1 is simultaneously changed, thereby changing the hydrogen extraction rate of the proton conductor hydrogen pump array 1 .

[0042] Specifically, in this exemplary embodiment, the constant current source circuit is a proportional constant current source, and 10 proton conductor hydrogen pump groups 11 are used for demonstration.

[0043] In such Figure 4 In the illustrated main drive circuit 2, the specific connection between this circuit and the proton conductor hydrogen pump 111 is as follows: HP1 to HP10 represent the first to tenth proton conductor hydrogen pump groups 11, R1 / Q1 corresponds to the transistor Q1 and resistor R1 of the first proton conductor hydrogen pump group 11HP1, and so on. A characteristic of this circuit is that the current in each column can be maintained consistent, and the current level is determined by the adjustable potentiometer RV. When the current level needs to be increased, the adjustable potentiometer RV can be adjusted to simultaneously change the current level through all ten proton conductor hydrogen pump groups 11.

[0044] More specifically, the devices used in the main drive circuit 2 are Q1 to Q10, all of which are 2N1711 transistors. Based on the circuit principle of the proportional constant current source and the relevant requirements of the multi-channel constant current source drive circuit, the input voltage VCC is set to 24V. In order to make the hydrogen extraction rate of the proton conductor hydrogen pump directly calculateable by Faraday's theorem, the current density of a single proton conductor hydrogen pump is generally not greater than 0.1Acm -2 The specific value is obtained from actual measurement. Take the nominal value of R1-R10=150Ω, the nominal value of R11=920Ω, and the value of RV is 0-2.17K.

[0045] Therefore, in this exemplary embodiment, the multi-channel constant current circuit in the main driving circuit 2 can change the output current of each proton conductor hydrogen pump group 11 of the entire proton conductor hydrogen pump array 1 by changing the size of the reference current. The sum of the output currents of each proton conductor hydrogen pump group 11 can be calculated by Faraday's law to obtain the hydrogen extraction rate of the entire proton conductor hydrogen pump array 1. The multi-channel constant current circuit can be used to drive the proton conductor hydrogen pump array 1 to work. The circuit principle is simple and the cost is low.

[0046] More preferably, in an exemplary embodiment, Figure 5 As shown, the electronic control system further includes a first auxiliary drive circuit for detecting faults, disconnections, and short circuits of the proton conductor hydrogen pump 111; each proton conductor hydrogen pump 111 is configured with a first auxiliary drive circuit, and each first auxiliary drive circuit includes a first differential operational amplifier, a second differential operational amplifier, a first inverter, a second inverter, and a NOR gate chip; The anode side wire of the proton conductor hydrogen pump 111 is connected to the positive electrode of the first differential operational amplifier, and the cathode side wire of the proton conductor hydrogen pump 111 is respectively connected to the negative electrode of the first differential operational amplifier and the positive electrode of the second differential operational amplifier, and the negative electrode of the second differential operational amplifier is connected to VDD; the output end of the first differential operational amplifier is connected to the first input end of the NOR gate chip through a first inverter, and the output end of the second differential operational amplifier is connected to the second input end of the NOR gate chip through a second inverter, and the output end of the NOR gate chip outputs a short-circuit signal; The output terminal of the second differential operational amplifier outputs a disconnection signal through the second inverter.

[0047] Specifically, in this exemplary embodiment, the first auxiliary drive circuit mainly includes a fault detection circuit (open circuit and short circuit), which samples the fault open circuit and short circuit signals using analog-to-digital conversion, wherein the circuit is connected in parallel with the proton conductor hydrogen pump 111.

[0048] exist Figure 5 In the illustrated exemplary embodiment, the first differential operational amplifier is an A-LM358, the second differential operational amplifier is a B-LM358, the first inverter is an A-74S04, the second inverter is a B-74S04, the NOR gate chip is a 74S02, and HPLOAD1 represents one of the proton conductor hydrogen pumps 111. Specifically, the following connections are made: the anode terminal wire (input 1) of the proton conductor hydrogen pump 111 is connected to the positive terminal of the A-LM358, the cathode terminal wire (input 2) of the proton conductor hydrogen pump 111 is connected to the negative terminal of the A-LM358 and the positive terminal of the B-LM358, respectively; the negative terminal of the A-LM358 is connected to the positive terminal of the B-LM358; the output of the A-LM358 is connected to the input of the A-74LS04; the output of the B-LM358 is connected to the input of the B-74LS04; and the output of the A-74LS04 and the output of the B-74LS04 are connected to the 74LS02. Specifically, the output end of B-74LS04 outputs an open circuit signal, and the output end of 74LS02 outputs a short circuit signal.

[0049] The first auxiliary driving circuit determines the fault type of the faulty proton conductor hydrogen pump by performing signal conversion through the analog-to-digital conversion circuit. The fault detection circuit is connected in parallel with each proton conductor hydrogen pump. Preferably, LM358 is used to form the fault detection circuit and the 8051 single-chip microcomputer is used to locate and display the faulty proton conductor hydrogen pump.

[0050] When the proton conductor hydrogen pump 111 is operating normally, it generates a voltage drop, with the voltage at point a higher than the voltage at point b. If a short circuit occurs, the voltage at point a becomes almost equal to the voltage at point b. The LM358 operates as follows: when 1IN+ is greater than 1IN- or 2IN+ is greater than 2IN-, 1OUT and 2OUT output a high level; when 1IN+ is less than 1IN- or 2IN+ is less than or equal to 2IN-, 1OUT and 2OUT output a low level. A 74LS04 inverter is connected to the output of the LM358. The output signal is processed and then fed into a 74LS02 logic gate for processing. The control logic indicates that when the proton conductor hydrogen pump is operating normally, its open-circuit and short-circuit signal inputs C_X and MCU_X are both low. In the event of a short circuit, only MCU_X is high, and in the event of an open circuit, only C_X is high. Therefore, the short-circuit and open-circuit signal sampling circuit can simultaneously provide feedback on both open-circuit and short-circuit signals. The specific logic is shown in Table 1.

[0051] Table 1 Proton conductor hydrogen pump operating control logic When the proton conductor hydrogen pump 111 is within the operating temperature range, the first auxiliary drive circuit for fault detection is activated to determine whether the proton conductor hydrogen pump array 1 has a fault. If there is no fault, the main drive circuit 2 is activated for operation. If there is a fault, it is repaired. After the proton conductor hydrogen pump array 1 completes operation, the first auxiliary drive circuit is used for testing, which is consistent with the preparatory work. After the faulty hydrogen pump is inspected and repaired, the array enters the non-operating state, and the series-parallel conversion circuit is activated to stabilize the voltage of the proton conductor hydrogen pump.

[0052] Before normal operation, when the temperature is lower than the operating temperature, only a short circuit fault can be detected. Since the proton conductor hydrogen pump 111 is equivalent to an open circuit under conditions lower than the operating temperature, its equivalent resistance is infinite. Therefore, after detecting the short circuit, the faulty proton conductor hydrogen pump is replaced. When the temperature is raised to the operating temperature, an open circuit fault can be detected. At this time, the corresponding proton conductor hydrogen pump group 11 cannot continue to work, but it does not affect the normal operation of other groups. This is the advantage of the proportional constant current source used in the present invention. However, the group that cannot work properly has been marked. It can be replaced and repaired after the proton conductor hydrogen pump array 1 is completed and cooled to room temperature. After the proton conductor hydrogen pump array 1 is completed and cooled to room temperature, a short circuit test is performed again. If it is found that the proton conductor hydrogen pump 111 is short-circuited, it is replaced and repaired.

[0053] Therefore, in this exemplary embodiment, the second auxiliary drive circuit serving as a fault detection circuit can classify and display the fault status of the proton conductor hydrogen pump 111 through the open circuit and short circuit detection circuit, effectively reducing the probability of failure of the proton conductor hydrogen pump 111 when it is in operation. The circuit can display the fault in a timely manner and perform fault replacement, effectively improving the overall hydrogen extraction rate of the proton conductor hydrogen pump array 1.

[0054] More preferably, in an exemplary embodiment, Figure 6 As shown, the electronic control system also includes a second auxiliary drive circuit for suppressing the reverse diffusion of the proton conductor hydrogen pump in a non-operating state; each proton conductor hydrogen pump group 11 is configured with a second auxiliary drive circuit; each second auxiliary drive circuit includes a first switch located on the cathode side of each proton conductor hydrogen pump 111 and an eleventh switch located on the anode side of the proton conductor hydrogen pump group 11; The common connection point between the cathode side of each proton conductor hydrogen pump 111 and the corresponding first switch is grounded via a thirteenth switch, the common connection point between the anode side of each proton conductor hydrogen pump 111 and the first switch corresponding to the previous proton conductor hydrogen pump 111 is connected to the voltage source VEE via a twelfth switch, and the common connection point between the first proton conductor hydrogen pump 111 and the eleventh switch is also connected to the voltage source VEE via the twelfth switch; When in a non-working state, the first switch and the eleventh switch are disconnected, and the twelfth switch and the thirteenth switch are closed; when in a working state, the first switch and the eleventh switch are closed, and the twelfth switch and the thirteenth switch are disconnected.

[0055] Specifically, when the proton conductor hydrogen pump 111 is in normal working condition and an electrical signal is applied to both sides, hydrogen can be transported from the ultra-low concentration hydrogen-helium mixed gas to the high-purity hydrogen side. Figure 7 As shown. When the proton conductor hydrogen pump 111 is in a non-operating state, if it is in the operating temperature range of the proton conductor hydrogen pump 111, if no electrical signal is applied to both sides of the proton conductor hydrogen pump 111, the hydrogen on the high-purity hydrogen side will pass through the proton conductor hydrogen pump and enter the 0.1% H2-99.9% He side. At this time, the proton conductor hydrogen pump becomes a concentration cell, and an electromotive force is generated by the concentration gradient. This electromotive force is the reverse diffusion voltage. In this exemplary embodiment, in order to suppress the occurrence of this phenomenon, a voltage of the magnitude of the reverse diffusion voltage should be applied on both sides to prevent the reverse diffusion phenomenon caused by the concentration gradient, as shown. Figure 8 shown.

[0056] The second auxiliary drive circuit is composed of a serial-parallel conversion circuit. The proton conductor hydrogen pumps 111 in each group of proton conductor hydrogen pump groups 11 connected to the main drive circuit 2 are connected in series. In the non-working circuit, the connection mode of the proton conductor hydrogen pumps 111 in each group of proton conductor hydrogen pump groups 11 is changed from series to parallel. Specifically, the cathode side of each proton conductor hydrogen pump 111 is connected to the same low potential point, and the anode side of each proton conductor hydrogen pump 111 is connected to the same high potential point. The potential difference between the two points is the reverse diffusion voltage value of the proton conductor hydrogen pump.

[0057] exist Figure 6 In the specific exemplary embodiment shown, the entire figure shows a situation where a proton conductor hydrogen pump group 11 includes 10 proton conductor hydrogen pumps 111, and HPLOAD1 to HPLOAD10 respectively represent 10 proton conductor hydrogen pumps 111; on this basis, the first switch on the cathode side of each proton conductor hydrogen pump 111 corresponds to SW1 to SW10 ( Figure 5 SW1 in FIG also corresponds here), the eleventh switch located at the anode of the proton conductor hydrogen pump group 11 is SW11, the twelfth switch is SW12, and the thirteenth switch is SW13.

[0058] When the proton conductor hydrogen pump array 11 is in a non-operating state, the switch control signals BACK1-10 corresponding to the first switches SW1 to SW10 and the switch control signal BACK11 corresponding to the eleventh switch are input with a high level to disconnect the switches, while at the same time, the switch control signals BACK12-13 of SW12 and SW13 are input with a low level to close the switches, thereby forming a series-parallel conversion of the proton conductor hydrogen pump 111. The voltage VEE is the reverse diffusion voltage value of the proton conductor hydrogen pump, which can be obtained by actual measurement.

[0059] The reverse diffusion voltage is spontaneously generated by the proton conductor hydrogen pump. Specifically, within the operating temperature range of the proton conductor hydrogen pump (450-600°C), the proton conductor hydrogen pump is converted into a proton conductor hydrogen permeable membrane. The hydrogen on the high-purity hydrogen side passes through the proton conductor hydrogen pump and enters the hydrogen-containing mixed gas side, thereby forming a voltage difference on both sides of the proton conductor hydrogen pump. The specific reverse diffusion voltage value is the voltage value under zero current test.

[0060] In a specific exemplary embodiment, the voltage of VEE can be 0.1 V, and the actual voltage value can be obtained by measuring the reverse diffusion voltage value of the proton conductor hydrogen pump.

[0061] Therefore, in this exemplary embodiment, the second auxiliary driving circuit, which serves as a non-working circuit, can prevent hydrogen from the high-concentration side from diffusing to the low-concentration side, wherein the series-parallel conversion circuit can effectively ensure that the voltage across each proton conductor hydrogen pump 111 is higher than the reverse diffusion voltage of the proton conductor hydrogen pump 111.

[0062] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications can be made based on the above descriptions. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications derived therefrom remain within the scope of protection of the present invention.

Claims

1. An electronic control system based on an inorganic proton conductor hydrogen pump array, characterized by: It includes a proton conductor hydrogen pump array and a main driving circuit; The proton conductor hydrogen pump array includes multiple groups of proton conductor hydrogen pump groups connected in parallel, and each group of proton conductor hydrogen pump groups includes proton conductor hydrogen pumps connected in series; the main drive circuit provides a constant current source to each group of proton conductor hydrogen pump groups; For each proton conductor hydrogen pump group, the anode of each proton conductor hydrogen pump group is connected to the positive electrode of the main drive circuit, and the cathode of each proton conductor hydrogen pump group is connected to the negative electrode of the main drive circuit; Each proton conductor hydrogen pump includes an anode side and a cathode side. For the proton conductor hydrogen pumps connected along the current direction in each group of proton conductor hydrogen pumps, the cathode side of the previous proton conductor hydrogen pump is electrically connected to the anode side of the next proton conductor hydrogen pump.

2. The electronic control system based on the inorganic proton conductor hydrogen pump array according to claim 1, characterized in that: The anode side of the proton conductor hydrogen pump is connected to the raw material input pipeline, and the cathode side of the proton conductor hydrogen pump is connected to the separation output pipeline.

3. The electronic control system based on the inorganic proton conductor hydrogen pump array according to claim 1, characterized in that: The current magnitude of the constant current source provided by the main driving circuit is set within the working range of the proton conductor hydrogen pump with a Faraday efficiency of 1; the hydrogen extraction rate of the proton conductor hydrogen pump in the working range with a Faraday efficiency of 1 is directly calculated from the current; the current magnitude of the constant current source is less than the limiting current of the proton conductor hydrogen pump, where the limiting current is the maximum current with a Faraday efficiency of 1.

4. The electronic control system based on the inorganic proton conductor hydrogen pump array according to claim 3, characterized in that: The electrolyte of the proton conductor hydrogen pump is made of barium zirconate-based materials and barium ceria-based materials, and the electrode material is a metal nickel electrode.

5. The electronic control system based on the inorganic proton conductor hydrogen pump array according to claim 3, characterized in that: The main drive circuit includes: a power supply VCC, an adjustable potentiometer RV, a transistor Q11, and a resistor R11; for each proton conductor hydrogen pump group, the main drive circuit is also configured with a transistor Qn and a resistor Rn; The power supply VCC is connected to the base of the transistor Q11, the base of the transistor Qn, and the collector of the transistor Q11 through the adjustable potentiometer RV. The emitter of the transistor Q11 is grounded through the resistor R11, and the emitter of the transistor Qn is grounded through the resistor Rn. The power supply VCC is also connected to the collector of the corresponding transistor Qn through the proton conductor hydrogen pump group. By adjusting the resistance of the adjustable potentiometer RV, the current of each proton conductor hydrogen pump group of the proton conductor hydrogen pump array is simultaneously changed, thereby changing the hydrogen extraction rate of the proton conductor hydrogen pump array.

6. The electronic control system based on the inorganic proton conductor hydrogen pump array according to claim 1 or 5, characterized in that: The electronic control system also includes a first auxiliary drive circuit for detecting faults, disconnections, and short circuits of the proton conductor hydrogen pump; each proton conductor hydrogen pump is configured with a first auxiliary drive circuit, and each first auxiliary drive circuit includes a first differential operational amplifier, a second differential operational amplifier, a first inverter, a second inverter, and a NOR gate chip; The anode side wire of the proton conductor hydrogen pump is connected to the positive electrode of the first differential operational amplifier, and the cathode side wire of the proton conductor hydrogen pump is respectively connected to the negative electrode of the first differential operational amplifier and the positive electrode of the second differential operational amplifier, and the negative electrode of the second differential operational amplifier is connected to VDD; the output end of the first differential operational amplifier is connected to the first input end of the NOR gate chip through a first inverter, and the output end of the second differential operational amplifier is connected to the second input end of the NOR gate chip through a second inverter, and the output end of the NOR gate chip outputs a short-circuit signal; The output terminal of the second differential operational amplifier outputs a disconnection signal through the second inverter.

7. The electronic control system based on the inorganic proton conductor hydrogen pump array according to claim 1 or 5, characterized in that: The electronic control system also includes a second auxiliary drive circuit for suppressing reverse diffusion of the proton conductor hydrogen pump in a non-operating state; each proton conductor hydrogen pump group is equipped with a second auxiliary drive circuit; each second auxiliary drive circuit includes a first switch located on the cathode side of each proton conductor hydrogen pump and an eleventh switch located on the anode side of the proton conductor hydrogen pump group; The common connection point between the cathode side of each proton conductor hydrogen pump and the corresponding first switch is grounded via a thirteenth switch, the common connection point between the anode side of each proton conductor hydrogen pump and the first switch corresponding to the previous proton conductor hydrogen pump is connected to the voltage source VEE via a twelfth switch, and the common connection point between the first proton conductor hydrogen pump and the eleventh switch is also connected to the voltage source VEE via the twelfth switch; When in a non-working state, the first switch and the eleventh switch are disconnected, and the twelfth switch and the thirteenth switch are closed; when in a working state, the first switch and the eleventh switch are closed, and the twelfth switch and the thirteenth switch are disconnected.

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