CN114774946A - Two-step water electrolysis hydrogen production device based on three-electrode system and application thereof - Google Patents
Two-step water electrolysis hydrogen production device based on three-electrode system and application thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 181
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 181
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 173
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 168
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000001301 oxygen Substances 0.000 claims abstract description 143
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 143
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 230000007246 mechanism Effects 0.000 claims abstract description 55
- 238000001816 cooling Methods 0.000 claims abstract description 47
- 229910002640 NiOOH Inorganic materials 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000009833 condensation Methods 0.000 claims description 46
- 230000005494 condensation Effects 0.000 claims description 46
- 230000001276 controlling effect Effects 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 230000001105 regulatory effect Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 17
- 239000007789 gas Substances 0.000 abstract description 5
- -1 analysis equipment Substances 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/023—Measuring, analysing or testing during electrolytic production
- C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
- C25B15/027—Temperature
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- C25B15/00—Operating or servicing cells
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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Abstract
The application discloses two-step method electrolysis water hydrogen plant and application based on three electrode system, the device includes at least: the device comprises a single electrolytic tank, a power supply, a first three-way valve, a hydrogen-electrolytic liquid separator, an oxygen-electrolytic liquid separator, a second three-way valve, an electrolyte cooling mechanism and an electrolyte circulating mechanism; the single electrolytic tank is provided with a liquid inlet, a liquid outlet, an oxygen evolution anode, a hydrogen evolution cathode, NiOOH/Ni (OH)2Composite electrode, oxygen evolution anode and hydrogen evolution cathodeNo separator is disposed between the poles. Through the mode, the device adopts the structure of single electrolytic cell to integrate a plurality of components in a single machine body, has small volume, space saving and good effect, is simple to operate in use, has safety and high efficiency, and can meet the requirements of processing gas, analysis equipment, hydrogen for synthesis or other operations in the electronic industry.
Description
Technical Field
The application relates to the technical field of electrolytic hydrogen production, in particular to a two-step water electrolysis hydrogen production device based on a three-electrode system and application thereof.
Background
The operation of preparing hydrogen by electrolyzing water is relatively simple, the technology is relatively mature, and the hydrogen preparation process is pollution-free, so that the method is an important means for realizing large-scale hydrogen production. In the current hydrogen production industrial production, the alkaline water electrolysis technology has early industrialization, mature technology and low equipment cost, so the alkaline water electrolysis is dominant in the water electrolysis industry. But its wide application is limited because of its high energy consumption. More importantly, the conventional water electrolysis technology generates hydrogen and oxygen by the cathode and the anode simultaneously in the electrode process, so that the hydrogen and the oxygen are easily mixed, safety accidents are easily caused, the prepared gas is impure, and the preparation cost is greatly increased by subsequent purification. The use of an ion selective membrane to separate the hydrogen produced at the hydrogen evolution catalytic electrode from the oxygen produced at the oxygen evolution catalytic electrode is an effective solution, but the use of an ion selective membrane also increases the cost significantly and is not suitable for large-scale production.
Disclosure of Invention
The application aims to provide a detailed design scheme of a two-step water electrolysis hydrogen production device based on a three-electrode system, and aims to solve at least one of the technical problems in the related art to a certain extent.
In order to achieve the above purpose, the present application provides a two-step water electrolysis hydrogen production apparatus based on a three-electrode system, the apparatus at least comprises: the device comprises a single electrolytic tank, a power supply, a first three-way valve, a hydrogen-electrolytic liquid separator, an oxygen-electrolytic liquid separator, a second three-way valve, an electrolyte cooling mechanism and an electrolyte circulating mechanism;
the single electrolytic tank is provided with a liquid inlet, a liquid outlet, an oxygen evolution anode, a hydrogen evolution cathode, NiOOH/Ni (OH)2A composite electrode, wherein no separator is disposed between the oxygen evolution anode and the hydrogen evolution cathode, wherein the hydrogen evolution cathode, the NiOOH/Ni (OH)2The composite electrode and the power supply form a first circuit, the oxygen evolution anode, the NiOOH/Ni (OH)2The composite electrode and the power supply form a second circuit;
when the single electrolytic cell is in a hydrogen evolution operating state, the first circuit is closed and the second circuit is open;
when the single electrolytic cell is in an oxygen evolution working state, the second circuit is closed and the first circuit is opened;
the common end a1 of the first three-way valve is connected with the liquid outlet of the single electrolytic cell, the outlet end a2 of the first three-way valve is connected with the hydrogen-electrolytic liquid separator, the outlet end a3 of the first three-way valve is connected with the oxygen-electrolytic liquid separator, the lower outlet end of the hydrogen-electrolytic liquid separator is connected with the inlet end b2 of the second three-way valve, the lower outlet end of the oxygen-electrolytic liquid separator is connected with the inlet end b3 of the second three-way valve, the common end b1 of the second three-way valve is connected with the electrolyte cooling mechanism, the outlet end of the electrolyte cooling mechanism is connected with the inlet end of the electrolyte circulating mechanism, and the outlet end of the electrolyte circulating mechanism is connected with the liquid inlet of the electrolytic cell;
the hydrogen-electrolyte separator is used for receiving the mixture of the hydrogen and the electrolyte discharged from the liquid outlet, performing gas-liquid separation on the hydrogen and the electrolyte in the mixture, and conveying the separated electrolyte to the electrolyte cooling mechanism;
the oxygen-electrolyte separator is used for receiving the mixture of the oxygen and the electrolyte discharged from the liquid outlet, performing gas-liquid separation on the oxygen and the electrolyte in the mixture, and conveying the separated electrolyte to the electrolyte cooling mechanism;
the electrolyte cooling mechanism is used for regulating and controlling the temperature of the separated electrolyte;
the electrolyte circulating mechanism is used for circulating the electrolyte with the temperature regulated and controlled to the electrolytic cell.
Further, the power supply includes: power supply body and power supply contact c1、c2、c3Said oxygen evolving anodeContact c with power supply1Connection of the hydrogen-evolving cathode to the power supply contact c3Connection, the NiOOH/Ni (OH)2Composite electrode and power contact c2Connecting;
wherein, when the single electrolytic cell is in a hydrogen evolution working state, the power supply contact c2A positive electrode connected to the power supply body, and a power supply contact c3The negative electrode of the power supply body is connected, and the first circuit is closed;
wherein, when the single electrolytic cell is in an oxygen evolution working state, the power supply contact c1A positive electrode connected to the power supply body, and a power supply contact c3And the second circuit is closed when the power supply is connected with the negative electrode of the power supply body.
Further, the apparatus further comprises: the system comprises an oxygen condensation dryer, an oxygen flowmeter, a hydrogen condensation dryer and a hydrogen flowmeter;
the upper outlet end of the oxygen-electrolyte separator is connected with the oxygen condensation dryer, the upper outlet end of the oxygen condensation dryer is connected with the oxygen flowmeter, and the lower outlet end of the oxygen condensation dryer is connected with the oxygen-electrolyte separator;
the upper outlet end of the hydrogen-electrolyte separator is connected with the hydrogen condensation dryer, the upper outlet end of the hydrogen condensation dryer is connected with the hydrogen flowmeter, and the lower outlet end of the hydrogen condensation dryer is connected with the hydrogen-electrolyte separator;
the oxygen separated by the oxygen-electrolyte separator is discharged into the oxygen condensation dryer, the oxygen condensation dryer is used for carrying out cooling and drying treatment on the separated oxygen, moisture contained in the oxygen is condensed and separated out, the separated moisture reflows to the oxygen-electrolyte separator, the cooled and dried oxygen is discharged to the outside, and the oxygen flowmeter is used for metering the volume flow of the corresponding cooled and dried oxygen;
the hydrogen separated by the hydrogen-electrolyte separator is discharged into the hydrogen condensation dryer, the hydrogen condensation dryer is used for carrying out cooling and drying treatment on the separated hydrogen, moisture contained in the hydrogen is condensed and separated out, the separated moisture reflows into the hydrogen-electrolyte separator, the cooled and dried hydrogen is discharged to the outside, and the hydrogen flowmeter is used for metering the volume flow of the corresponding cooled and dried hydrogen.
Further, the apparatus also includes a controller in communication with the oxygen flow meter, the hydrogen flow meter, and the power supply;
the controller is used for acquiring the oxygen volume flow measured by the oxygen flowmeter and the hydrogen volume flow measured by the hydrogen flowmeter, and regulating and controlling the power supply state according to the hydrogen volume flow and the oxygen volume flow;
when the volume flow of the hydrogen measured in the hydrogen evolution working state of the stage is 2-3 times of the volume flow of the oxygen measured in the oxygen evolution working state of the previous stage, the controller is also used for regulating and controlling the power supply state so as to close the second circuit and open the first circuit, so that the single electrolytic cell is switched from the hydrogen evolution working state to the oxygen evolution working state;
when the volume flow of the oxygen measured in the oxygen evolution working state of the stage is 1/3-1/2 times of the volume flow of the hydrogen measured in the hydrogen evolution working state of the previous stage, the controller is also used for regulating and controlling the power state so as to close the first circuit and open the second circuit, so that the single electrolytic cell is switched from the oxygen evolution working state to the hydrogen evolution working state.
Further, the device further comprises a temperature measuring instrument, the temperature measuring instrument is arranged on the liquid outlet and used for detecting the temperature of the electrolyte flowing out of the liquid outlet, and the controller is further in communication connection with the temperature measuring instrument and the electrolyte cooling mechanism;
when the electrolytic solution cooling mechanism is in an oxygen evolution working state, the controller is also used for obtaining the temperature of the electrolytic solution detected by the thermodetector and regulating and controlling the power of the electrolytic solution cooling mechanism according to the detected temperature of the electrolytic solution so as to enable the temperature of the electrolytic solution detected by the thermodetector to be less than or equal to 110 ℃;
and in the hydrogen evolution working state, the controller is also used for acquiring the temperature of the electrolyte detected by the temperature detector and regulating and controlling the power of the electrolyte cooling mechanism according to the detected temperature of the electrolyte so as to enable the temperature of the electrolyte detected by the temperature detector to be less than or equal to 60 ℃.
Further, the controller is in communication connection with the first three-way valve and the second three-way valve;
when the second circuit is closed and the first circuit is open, the controller is further used for controlling the common end a1 of the first three-way valve to be communicated with the outlet end a3 of the first three-way valve and controlling the inlet end b3 of the second three-way valve to be communicated with the common end b1 of the second three-way valve;
the controller is also configured to control the common port a1 of the first three-way valve to communicate with the outlet port a2 of the first three-way valve and the inlet port b2 of the second three-way valve to communicate with the common port b1 of the second three-way valve when the first circuit is closed and the second circuit is open.
Further, the electrolyte in the single electrolytic cell is a KOH solution with the mass percentage of 30%.
Furthermore, porous nickel electrodes are adopted for the oxygen evolution anode and the hydrogen evolution cathode.
Further, the power supply body is a direct current power supply.
In order to achieve the purpose, the application also provides an application of the water electrolysis hydrogen production device based on the three-electrode system in water electrolysis hydrogen production.
Compared with the prior art, the method has the following advantages:
(1) the device of the application adopts the structure of a single electrolytic cell, only comprises an independent single electrolytic cell, hydrogen production and oxygen production are carried out in the single electrolytic cell, a plurality of parts are integrated in a single machine body, the size is small, the space is saved, the effect is good, the operation is simple and high-efficiency in use, and the requirements of electronic industry process gas, analysis equipment, hydrogen for synthesis or other operations can be met.
(2) The device has the working characteristics that the hydrogen production by electrolyzing water and the oxygen production by electrolyzing water are carried out in two steps, so that the hydrogen and the oxygen can be produced respectively, the high-purity hydrogen and the high-purity oxygen can be produced, the condition of mixing the oxygen and the hydrogen can not occur, and the safety of producing hydrogen by alkaline electrolyzed water is improved.
(3) Because the hydrogen and the oxygen are respectively prepared, the electrolytic cell of the device does not need to be provided with a diaphragm, and compared with the traditional hydrogen production by alkaline electrolysis of water, the electrolytic cell omits the diaphragm, increases OH in electrolyte-The transmission rate of the ions reduces the cost and improves the efficiency and the rate of the electrolytic hydrogen production.
(4) The device of the application utilizes hydrogen-electrolyte separator and hydrogen condensation desicator duplex to construct in order to obtain the recovery of high-purity hydrogen and electrolyte, utilizes oxygen-electrolyte separator and oxygen condensation desicator duplex to construct in order to obtain the recovery of high-purity hydrogen and electrolyte, and its technique is the industry initiative.
(5) Considering that too low temperature of the electrolyte easily causes unstable electrolytic reaction, and too high temperature of the electrolyte easily causes decomposition of the NiOOH electrode into Ni (OH)2And oxygen, this application device utilizes electrolyte cooling body to carry out the control by temperature change to the electrolyte after the separation to in returning the electrolyte circulation after the control by temperature change to single electrolysis trough with the help of electrolyte circulation mechanism, detect the electrolyte temperature with the help of the thermoscope in addition, realized controlling the electrolyte temperature in the target temperature range that suits in real time, thereby ensured the security and the stability of brineelectrolysis hydrogen plant, and improved the utilization efficiency of electrolyte.
Drawings
Fig. 1 is a schematic structural diagram of a two-step water electrolysis hydrogen production apparatus based on a three-electrode system according to an embodiment of the present application.
Detailed description of the preferred embodiment
Reference will now be made in detail to the embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are illustrative and are only for the purpose of explaining the present application and are not to be construed as limiting the present application. On the contrary, the embodiments of the application include all changes, modifications and equivalents coming within the spirit and terms of the claims appended hereto.
Referring to fig. 1, the two-step water electrolysis hydrogen production device based on the three-electrode system comprises: the device comprises a single electrolytic tank, a power supply, a first three-way valve, a hydrogen-electrolytic liquid separator, an oxygen-electrolytic liquid separator, a second three-way valve, an electrolyte cooling mechanism, an electrolyte circulating mechanism, an oxygen condensation dryer, an oxygen flowmeter, a hydrogen condensation dryer, a hydrogen flowmeter, a thermodetector and a controller.
The electrolyte in the single electrolytic cell is alkaline electrolyte. Preferably, the electrolyte in the single electrolytic cell is a sodium hydroxide solution or a potassium hydroxide solution. More preferably, the electrolyte in the single electrolytic cell is a 30% by mass KOH solution.
The oxygen evolution anode and the hydrogen evolution cathode are both porous nickel electrodes. The porous nickel has a catalytic effect on a Hydrogen Evolution Reaction (HER), so that the electrochemical reaction speed of the surface of the electrode is accelerated, and the porous structure of the porous nickel electrode accelerates the transmission speed of electrons and ions, thereby improving the electrochemical dynamics of the electrode and improving the high-rate discharge performance.
The power supply body is a direct current power supply.
Further, the temperature measuring instrument is used for detecting the temperature of the electrolyte after electrolysis.
Furthermore, the first three-way valve and the second three-way valve are used for controlling the flow direction of the electrolyte.
Further, the hydrogen-electrolyte separator is used for separating the electrolyzed electrolyte from the hydrogen.
Further, the oxygen-electrolyte separator is used for separating the electrolyzed electrolyte from oxygen.
Further, the hydrogen condensation dryer is used for further cooling the separated hydrogen to condense and separate out moisture included in the hydrogen so as to achieve the purpose of drying the hydrogen, and simultaneously, the separated moisture flows back to the corresponding hydrogen-electrolytic liquid separator.
Furthermore, the oxygen condensation dryer is used for further cooling the separated oxygen to condense and separate out moisture contained in the oxygen, so that the purpose of drying the oxygen is achieved, and the separated moisture flows back to the corresponding oxygen-electrolyte separator.
Further, the oxygen flow meter and the hydrogen flow meter are used for measuring the corresponding gas flow.
Further, the electrolyte cooling mechanism is used for controlling the temperature of the electrolyte.
Further, an electrolyte circulation mechanism is used for forcing the electrolyte to circulate forcibly.
A liquid inlet and a liquid outlet are arranged on the single electrolytic tank. Oxygen evolution anode, hydrogen evolution cathode, NiOOH/Ni (OH)2The composite electrodes are placed together in a single electrolytic bath, in which NiOOH/Ni (OH)2The electrode is arranged between the oxygen evolution anode and the hydrogen evolution cathode, and a diaphragm is not arranged between the oxygen evolution anode and the hydrogen evolution cathode.
The power supply includes: power supply body and power supply contact c1、c2、c3Oxygen evolution anode and power supply contact c1Connecting, hydrogen evolution cathode to a power supply contact c3Connection, NiOOH/Ni (OH)2Composite electrode and power supply contact c2And (4) connecting.
When the single electrolytic cell is in the hydrogen evolution working state, the power supply contact c2Connecting the positive pole of the power supply body, power supply contact c3The first circuit is closed and the second circuit is open when the negative electrode of the power supply body is connected. Connecting an external direct current power supply of the electrolytic cell, electrochemically reducing water molecules in the electrolyte on the surface of the hydrogen evolution cathode to generate hydrogen, namely H2O+e-→1/2H2↑+OH-And NiOOH/Ni (OH)2The composite electrode undergoes the following reactions: ni (OH)2+OH--e-→NiOOH+H2O。
When the single electrolytic cell is in the oxygen evolution working state, the power supply contact c1Connecting the positive pole of the power supply body, power supply contact c3The second circuit is closed and the first circuit is open when the negative electrode of the power supply body is connected. The direct current power supply outside the electrolytic cell is switched on, and hydroxide ions in the alkaline electrolyte are electrochemically oxidized into oxygen on the surface of the oxygen evolution anode, namely 2 OH-2 e-→1/2O2+H2O, and NiOOH/Ni (OH)2The composite electrode undergoes the following reactions: NiOOH + H2O+e-→-Ni(OH)2+OH-。
In some embodiments, the common end a1 of the first three-way valve is connected with the liquid outlet, the outlet end a2 of the first three-way valve is connected with the hydrogen-electrolytic liquid separator, the outlet end a3 of the first three-way valve is connected with the oxygen-electrolytic liquid separator, the lower outlet end of the hydrogen-electrolytic liquid separator is connected with the inlet end b2 of the second three-way valve, the lower outlet end of the oxygen-electrolytic liquid separator is connected with the inlet end b3 of the second three-way valve, the common end b1 of the second three-way valve is connected with the electrolyte cooling mechanism, the outlet end of the electrolyte cooling mechanism is connected with the inlet end of the electrolyte circulating mechanism, and the outlet end of the electrolyte circulating mechanism is connected with the liquid inlet of the electrolytic cell. The hydrogen-electrolyte separator is used for receiving the mixture of the hydrogen and the electrolyte discharged from the liquid outlet, performing gas-liquid separation on the hydrogen and the electrolyte in the mixture, and conveying the separated electrolyte to the electrolyte cooling mechanism. The oxygen-electrolyte separator is used for receiving the mixture of the oxygen and the electrolyte discharged from the liquid outlet, performing gas-liquid separation on the oxygen and the electrolyte in the mixture, and conveying the separated electrolyte to the electrolyte cooling mechanism. The electrolyte cooling mechanism is used for regulating and controlling the temperature of the separated electrolyte. The electrolyte circulating mechanism is used for circulating the temperature-regulated electrolyte to the electrolytic cell.
In some embodiments, the upper outlet end of the oxygen-electrolyte separator is connected with an oxygen condensation dryer, the upper outlet end of the oxygen condensation dryer is connected with an oxygen flow meter, and the lower outlet end of the oxygen condensation dryer is connected with the oxygen-electrolyte separator. The upper outlet end of the hydrogen-electrolytic liquid separator is connected with a hydrogen condensation dryer, the upper outlet end of the hydrogen condensation dryer is connected with a hydrogen flowmeter, and the lower outlet end of the hydrogen condensation dryer is connected with the hydrogen-electrolytic liquid separator. The oxygen separated by the oxygen-electrolyte separator is discharged into an oxygen condensation dryer, the oxygen condensation dryer is used for cooling and drying the separated oxygen, moisture contained in the oxygen is condensed and separated out, the separated moisture flows back into the oxygen-electrolyte separator, the dried oxygen is discharged to the outside, and an oxygen flowmeter is used for metering the volume flow of the corresponding dried oxygen. The hydrogen separated by the hydrogen-electrolyte separator is discharged into a hydrogen condensation dryer, the hydrogen condensation dryer is used for carrying out cooling and drying treatment on the separated hydrogen, moisture contained in the hydrogen is condensed and separated out, the separated moisture flows back into the hydrogen-electrolyte separator, the dried hydrogen is discharged to the outside, and a hydrogen flowmeter is used for metering the volume flow of the corresponding dried hydrogen.
In some embodiments, the apparatus further comprises a controller communicatively coupled to the oxygen flow meter, the hydrogen flow meter, and the power source. The controller is used for acquiring the oxygen volume flow measured by the oxygen flowmeter and the hydrogen volume flow measured by the hydrogen flowmeter, and regulating and controlling the power state according to the hydrogen volume flow and the oxygen volume flow. When the volume flow of the hydrogen measured in the hydrogen evolution working state of the stage is 2-3 times of the volume flow of the oxygen measured in the oxygen evolution working state of the previous stage, the controller is also used for regulating and controlling the power supply state so as to close the second circuit and open the first circuit, so that the single electrolytic cell is switched from the hydrogen evolution working state to the oxygen evolution working state;
when the volume flow of the oxygen measured in the oxygen evolution working state of the stage is 1/3-1/2 times of the volume flow of the hydrogen measured in the hydrogen evolution working state of the previous stage, the controller is also used for regulating and controlling the power state so as to close the first circuit and open the second circuit, so that the single electrolytic cell is switched from the oxygen evolution working state to the hydrogen evolution working state.
Preferably, the conditions for discriminating the switching between the oxygen evolution operating state and the hydrogen evolution operating state are: the volume flow rate of hydrogen measured by the hydrogen flow meter was 2 times the volume flow rate of oxygen measured by the oxygen flow meter.
In some embodiments, the device further comprises a temperature measuring instrument, the temperature measuring instrument is arranged on the liquid outlet, and in the oxygen evolution working state, the controller is further configured to obtain the temperature of the electrolyte detected by the temperature measuring instrument, and regulate and control the power of the electrolyte cooling mechanism according to the detected temperature of the electrolyte, so that the temperature of the electrolyte detected by the temperature measuring instrument is less than or equal to 110 ℃; and in the hydrogen evolution working state, the controller is also used for acquiring the temperature of the electrolyte detected by the thermodetector and regulating and controlling the power of the electrolyte cooling mechanism according to the detected temperature of the electrolyte so as to enable the temperature of the electrolyte detected by the thermodetector to be less than or equal to 60 ℃.
In some embodiments, the controller is further in communication with the first three-way valve and the second three-way valve. When the second circuit is closed and the first circuit is open, the controller is further configured to control the common port a1 of the first three-way valve to communicate with the outlet port a3 of the first three-way valve, and control the inlet port b3 of the second three-way valve to communicate with the common port b1 of the second three-way valve. When the first circuit is closed and the second circuit is open, the controller is further configured to control the common port a1 of the first three-way valve to communicate with the outlet port a2 of the first three-way valve and the inlet port b2 of the second three-way valve to communicate with the common port b1 of the second three-way valve.
Compared with the prior art, the method has the following advantages:
(1) the device of the application adopts the structure of a single electrolytic cell, only comprises an independent single electrolytic cell, hydrogen production and oxygen production are carried out in the single electrolytic cell, a plurality of parts are integrated in a single machine body, the size is small, the space is saved, the effect is good, the operation is simple and high-efficiency in use, and the requirements of electronic industry process gas, analysis equipment, hydrogen for synthesis or other operations can be met.
(2) The device has the working characteristics that the hydrogen production by electrolyzing water and the oxygen production by electrolyzing water are carried out in two steps, so that the hydrogen and the oxygen can be produced respectively, the high-purity hydrogen and the high-purity oxygen can be produced, the condition of mixing the oxygen and the hydrogen can not occur, and the safety of producing hydrogen by alkaline electrolyzed water is improved.
(3) Because the hydrogen and the oxygen are respectively prepared, the electrolytic tank of the device does not need to be provided with a diaphragm, and compared with the traditional hydrogen production by alkaline electrolysis of water, the electrolytic tank saves the diaphragm, increases OH in electrolyte-The transmission rate of the ions reduces the cost and improves the efficiency and the rate of hydrogen production by electrolysis.
(4) The device of the application utilizes the dual mechanism of hydrogen-electrolytic liquid separator and hydrogen condensation desicator in order to obtain the recovery of high-purity hydrogen and electrolyte, utilizes the dual mechanism of oxygen-electrolytic liquid separator and oxygen condensation desicator in order to obtain the recovery of high-purity hydrogen and electrolyte, and its technique is the industrial initiative.
(5) Considering that too low temperature of the electrolyte easily causes unstable electrolytic reaction, and too high temperature of the electrolyte easily causes decomposition of the NiOOH electrode into Ni (OH)2And oxygen, this application device utilizes electrolyte cooling body to carry out the control by temperature change to the electrolyte after the separation to in getting back to single electrolysis trough with the help of the electrolyte circulation mechanism after the control by temperature change, detect the electrolyte temperature with the help of the thermoscope in addition, realized controlling the electrolyte temperature in the target temperature range that suits in real time, thereby ensured the security and the stability of brineelectrolysis hydrogen plant, and improved the utilization efficiency of electrolyte.
The application also provides an application of the two-step water electrolysis hydrogen production device based on the three-electrode system in water electrolysis hydrogen production. The method comprises the following specific steps:
the two-step water electrolysis hydrogen production device based on the three-electrode system comprises two working states of hydrogen evolution and oxygen evolution.
In the hydrogen-evolving operating state, the power supply contact c2Positive pole connected with DC power supply, power supply contact c3And the common end a1 of the first three-way valve is communicated with the outlet end a2 of the first three-way valve, and the common end b1 of the second three-way valve is communicated with the inlet end b2 of the second three-way valve. After direct current is introduced, hydrogen is generated in the electrolytic cell, and meanwhile, the power of the electrolyte cooling mechanism is adjusted by the temperature detected by the temperature detector through the controller, so that the temperature of the electrolyte in the electrolytic cell is controlled within 60 ℃. In the process, the mixture of the hydrogen and the electrolyte generated in the electrolytic cell sequentially passes through the common end a1 and the outlet end a2 of the first three-way valve and then enters the hydrogen-electrolytic liquid separator, the hydrogen and the electrolyte are separated in the hydrogen-electrolytic liquid separator,the hydrogen passes through the hydrogen condensation dryer and then enters the hydrogen flowmeter, and then enters the next stage. And water generated by condensation in the hydrogen cooling process flows back to the hydrogen-electrolyte separator, electrolyte in the separator sequentially enters the electrolyte cooling mechanism through the inlet end b2 and the common end b1 of the second three-way valve and is cooled by the electrolyte cooling mechanism, and the cooled electrolyte is sent to the electrolytic cell by the electrolyte circulating mechanism.
When in the oxygen evolution working state, the power supply contact c1Positive pole connected with DC power supply, power supply contact c3And the common end a1 of the first three-way valve is communicated with the outlet end a3 of the first three-way valve, and the common end b1 of the second three-way valve is communicated with the inlet end b3 of the second three-way valve. After direct current is introduced, oxygen is generated in the electrolytic cell, and meanwhile, the controller adjusts the power of the electrolyte cooling mechanism through the temperature detected by the temperature detector to control the temperature of the electrolyte in the electrolytic cell within 110 ℃. In the process, the mixture of oxygen and electrolyte generated in the electrolytic cell sequentially passes through the common end a1 and the outlet end a3 of the first three-way valve and then enters the oxygen-electrolyte separator, the oxygen and the electrolyte in the oxygen-electrolyte separator are separated, and the oxygen passes through the oxygen condensation dryer and then enters the oxygen flow meter to enter the next stage. And water generated by condensation in the oxygen cooling process flows back to the oxygen-electrolyte separator, electrolyte in the separator sequentially enters the electrolyte cooling mechanism through the inlet end b3 and the common end b1 of the second three-way valve and is cooled by the electrolyte cooling mechanism, and the cooled electrolyte is sent to the electrolytic cell by the electrolyte circulating mechanism.
It should be noted that, in the description of the present application, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In addition, in the description of the present application, "a plurality" means two or more unless otherwise specified.
Any process or method descriptions in flow charts or otherwise described herein may be understood as representing modules, segments, or portions of code which include one or more executable instructions for implementing specific logical functions or steps of the process, and the scope of the preferred embodiments of the present application includes other implementations in which functions may be executed out of order from that shown or discussed, including substantially concurrently or in reverse order, depending on the functionality involved, as would be understood by those reasonably skilled in the art of the present application.
In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that variations, modifications, substitutions and alterations may be made to the above embodiments by those of ordinary skill in the art within the scope of the present application.
Claims (9)
1. A two-step water electrolysis hydrogen production device based on a three-electrode system is characterized by at least comprising: the device comprises a single electrolytic tank, a power supply, a first three-way valve, a hydrogen-electrolytic liquid separator, an oxygen-electrolytic liquid separator, a second three-way valve, an electrolyte cooling mechanism and an electrolyte circulating mechanism;
the single electrolytic tank is provided with a liquid inlet, a liquid outlet, an oxygen evolution anode, a hydrogen evolution cathode, NiOOH/Ni (OH)2A composite electrode, wherein no diaphragm is arranged between the oxygen evolution anode and the hydrogen evolution cathode, wherein the hydrogen evolution cathode, the NiOOH/Ni (OH)2The composite electrode and the power supply constitute a first circuit, the oxygen evolution anode, the NiOOH/Ni (OH)2The composite electrode and the power supply form a second circuit;
when the single electrolytic cell is in a hydrogen evolution working state, the first circuit is closed and the second circuit is opened;
when the single electrolytic cell is in an oxygen evolution working state, the second circuit is closed and the first circuit is opened;
a common end a1 of the first three-way valve is connected with a liquid discharge port of the single electrolytic cell, an outlet end a2 of the first three-way valve is connected with the hydrogen-electrolytic liquid separator, an outlet end a3 of the first three-way valve is connected with the oxygen-electrolytic liquid separator, a lower outlet end of the hydrogen-electrolytic liquid separator is connected with an inlet end b2 of the second three-way valve, a lower outlet end of the oxygen-electrolytic liquid separator is connected with an inlet end b3 of the second three-way valve, a common end b1 of the second three-way valve is connected with the electrolyte cooling mechanism, an outlet end of the electrolyte cooling mechanism is connected with an inlet end of the electrolyte circulating mechanism, and an outlet end of the electrolyte circulating mechanism is connected with a liquid inlet of the electrolytic cell;
the hydrogen-electrolyte separator is used for receiving the mixture of the hydrogen and the electrolyte discharged from the liquid outlet, performing gas-liquid separation on the hydrogen and the electrolyte in the mixture, and conveying the separated electrolyte to the electrolyte cooling mechanism;
the oxygen-electrolyte separator is used for receiving the mixture of the oxygen and the electrolyte discharged from the liquid outlet, performing gas-liquid separation on the oxygen and the electrolyte in the mixture, and conveying the separated electrolyte to the electrolyte cooling mechanism;
the electrolyte cooling mechanism is used for regulating and controlling the temperature of the separated electrolyte;
the electrolyte circulating mechanism is used for circulating the temperature-regulated electrolyte to the electrolytic cell.
2. The three-electrode system-based two-step water electrolysis hydrogen production device according to claim 1, wherein the power supply comprises: power supply body and power supply contact c1、c2、c3Said oxygen evolving anode is connected to a power supply contact c1Connection of the hydrogen-evolving cathode to the power supply contact c3Connection, the NiOOH/Ni (OH)2Composite electrode and power contact c2Connecting;
wherein, when the single electrolytic cell is in a hydrogen evolution working state, the power supply contact c2Connecting the positive pole of the power supply body, power supply contact c3The negative electrode of the power supply body is connected, and the first circuit is closed;
wherein, when the single electrolytic cell is in an oxygen evolution working state, the power supply contact c1A positive electrode connected to the power supply body, and a power supply contact c3And the second circuit is closed when the power supply is connected with the negative electrode of the power supply body.
3. The three-electrode system-based two-step water electrolysis hydrogen production device according to claim 2, characterized by further comprising: the system comprises an oxygen condensation dryer, an oxygen flowmeter, a hydrogen condensation dryer and a hydrogen flowmeter;
the upper outlet end of the oxygen-electrolyte separator is connected with the oxygen condensation dryer, the upper outlet end of the oxygen condensation dryer is connected with the oxygen flowmeter, and the lower outlet end of the oxygen condensation dryer is connected with the oxygen-electrolyte separator;
the upper outlet end of the hydrogen-electrolytic liquid separator is connected with the hydrogen condensation dryer, the upper outlet end of the hydrogen condensation dryer is connected with the hydrogen flowmeter, and the lower outlet end of the hydrogen condensation dryer is connected with the hydrogen-electrolytic liquid separator;
the oxygen separated by the oxygen-electrolyte separator is discharged into the oxygen condensation dryer, the oxygen condensation dryer is used for carrying out cooling and drying treatment on the separated oxygen, moisture contained in the oxygen is condensed and separated out, the separated moisture reflows to the oxygen-electrolyte separator, the cooled and dried oxygen is discharged to the outside, and the oxygen flowmeter is used for metering the volume flow of the corresponding cooled and dried oxygen;
the hydrogen separated by the hydrogen-electrolytic liquid separator is discharged into the hydrogen condensation dryer, the hydrogen condensation dryer is used for carrying out cooling and drying treatment on the separated hydrogen, water contained in the hydrogen is condensed and separated out, the separated water flows back into the hydrogen-electrolytic liquid separator, the cooled and dried hydrogen is discharged to the outside, and the hydrogen flowmeter is used for metering the volume flow of the corresponding cooled and dried hydrogen.
4. The three-electrode system-based two-step water electrolysis hydrogen production device according to claim 3, further comprising a controller, wherein the controller is in communication connection with the oxygen flow meter, the hydrogen flow meter and the power supply;
the controller is used for acquiring the oxygen volume flow measured by the oxygen flowmeter and the hydrogen volume flow measured by the hydrogen flowmeter, and regulating and controlling the power supply state according to the hydrogen volume flow and the oxygen volume flow;
when the volume flow of the hydrogen measured in the hydrogen evolution working state of the stage is 2-3 times of the volume flow of the oxygen measured in the oxygen evolution working state of the previous stage, the controller is also used for regulating and controlling the power supply state so as to close the second circuit and open the first circuit, so that the single electrolytic cell is switched from the hydrogen evolution working state to the oxygen evolution working state;
when the volume flow of the oxygen measured in the oxygen evolution working state of the stage is 1/3-1/2 times of the volume flow of the hydrogen measured in the hydrogen evolution working state of the previous stage, the controller is also used for regulating and controlling the power supply state, so that the first circuit is closed and the second circuit is opened, and the single electrolytic cell is switched to the hydrogen evolution working state from the oxygen evolution working state.
5. The three-electrode system-based two-step water electrolysis hydrogen production device according to claim 4, further comprising a temperature measuring instrument disposed on the liquid outlet, the temperature measuring instrument being configured to detect the temperature of the electrolyte flowing out of the liquid outlet, the controller being further communicatively connected to the temperature measuring instrument and the electrolyte cooling mechanism;
in the oxygen evolution working state, the controller is also used for acquiring the temperature of the electrolyte detected by the temperature detector and regulating and controlling the power of the electrolyte cooling mechanism according to the detected temperature of the electrolyte so as to enable the temperature of the electrolyte detected by the temperature detector to be less than or equal to 110 ℃;
and in the hydrogen evolution working state, the controller is also used for acquiring the temperature of the electrolyte detected by the thermodetector and regulating and controlling the power of the electrolyte cooling mechanism according to the detected temperature of the electrolyte so as to enable the temperature of the electrolyte detected by the thermodetector to be less than or equal to 60 ℃.
6. The three-electrode system-based two-step water electrolysis hydrogen production device according to claim 4 or 5, wherein the controller is further connected with the first three-way valve and the second three-way valve in a communication manner;
when the second circuit is closed and the first circuit is open, the controller is further used for controlling the common end a1 of the first three-way valve to be communicated with the outlet end a3 of the first three-way valve and controlling the inlet end b3 of the second three-way valve to be communicated with the common end b1 of the second three-way valve;
the controller is also configured to control the common port a1 of the first three-way valve to communicate with the outlet port a2 of the first three-way valve and the inlet port b2 of the second three-way valve to communicate with the common port b1 of the second three-way valve when the first circuit is closed and the second circuit is open.
7. The three-electrode system-based two-step water electrolysis hydrogen production device according to claim 1,
the electrolyte in the single electrolytic cell is a KOH solution with the mass percentage of 30%.
8. The two-step water electrolysis hydrogen production device based on the three-electrode system according to claim 1, characterized in that the oxygen evolution anode and the hydrogen evolution cathode both adopt porous nickel electrodes.
9. The three-electrode system-based two-step water electrolysis hydrogen production device according to claim 2,
the power body is a direct current power supply.
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