CN117805198A - Method for monitoring service life of PEM (PEM) electrolytic tank in real time - Google Patents
Method for monitoring service life of PEM (PEM) electrolytic tank in real time Download PDFInfo
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- CN117805198A CN117805198A CN202311806525.XA CN202311806525A CN117805198A CN 117805198 A CN117805198 A CN 117805198A CN 202311806525 A CN202311806525 A CN 202311806525A CN 117805198 A CN117805198 A CN 117805198A
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- Prior art keywords
- pem
- concentration
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- monitoring
- service life
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000012544 monitoring process Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000005070 sampling Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a method for monitoring the service life of a PEM electrolytic tank in real time by adding F in a PEM electrolytic water system ‑ Selecting electrodes to realize real-time online or offline monitoring F ‑ According to the concentration of F obtained by monitoring ‑ The concentration is calculated, and the service life of the PEM electrolytic cell is judged. F in the method ‑ The selective electrode monitors F at the water outlet of the cathode gas-liquid separator or in the cathode side waterway pipeline/gas-liquid separator ‑ Concentration or release rate. According to the method, the electrolytic tank is not required to be stopped or disassembled, the service life of the online electrolytic tank is estimated, the detection convenience is improved, and the operation difficulty and the CVM wiring and explosion-proof risks are reduced.
Description
Technical Field
The invention belongs to the field of hydrogen production by water electrolysis of PEM, and particularly relates to a method for monitoring the service life of a PEM electrolytic tank in real time.
Background
Hydrogen energy is a clean energy source, and the development of hydrogen energy has become an important measure for national energy transformation. Proton exchange membrane (Proton Exchange Membrane, PEM) electrolyzed water hydrogen production is receiving increasing attention as a zero emission hydrogen production process. For fluorosulfonic acid proton exchange membranes, the membrane electrode, which is the core component of a PEM electrolyzer, comprises a proton exchange membrane, a perfluorosulfonic acid membrane, and a cathode and anode catalyst layer. Under the action of direct current, water is separated into H protons and oxygen, the protons are conducted from the anode to the cathode through the perfluorosulfonic acid membrane, and the hydrogen protons are combined with electrons on the cathode side to generate hydrogen. Under the condition of hydrogen crossing, hydrogen peroxide and hydroxyl are usually formed on the surface of the catalyst, so that the proton exchange membrane skeleton is degraded, and the proton exchange membrane becomes thin, so that fluorine F and sulfur S are released. When the electrolytic cell works, the electrolytic system is usually stopped or the electrolytic cell is disassembled directly to perform in-situ test, and the proton exchange membrane thickness is measured by SEM (scanning electron microscope) and other methods, so that the service life of the membrane electrode of the core component of the electrolytic cell is deduced, however, the method has insufficient convenience and consumes time and cost. Voltage inspection (CVM) is also commonly adopted in domestic PEM electrolytic water systems to detect and predict the performance, service life and the like of the electrolytic tank, but due to the specificity of the hydrogen production system, the problems of wiring, explosion prevention and the like are required to be considered, and the operation complexity is increased.
Disclosure of Invention
In order to overcome and remedy the above-mentioned deficiencies in the prior art, the present invention provides a method for real-time monitoring of the lifetime of a PEM electrolyzer for timely and convenient reference assessment of the lifetime of the PEM electrolyzer. The technical scheme adopted by the invention is as follows:
a method for monitoring the service life of a PEM electrolytic tank in real time, which is characterized in that F is added in a PEM electrolytic water system - Select electrode real-time monitoring F - Is a concentration of (3).
Further, in the method of the present invention, the PEM electrolyzed water system comprises at least a PEM electrolyzer, a power source, and an anode/cathode gas-liquid separator.
Specifically, in the method of the invention, in a PEM water electrolysis system, a sampling port is added at the water outlet of a cathode gas-liquid separator, and the water electrolysis system is operated in an electrolysis tankIn the process, the sampling port is opened when needed, and the external F is used - Selecting electrode pairs to sample F in water - The concentration was measured.
In another aspect, in the method of the present invention, F is added to the cathode side waterway pipe or gas-liquid separator as close as possible to the PEM electrolyzer in the PEM electrolyzed water system - Selecting electrode, monitoring F in real time - Concentration or release rate of (a).
Preferably, in the method of the present invention, the monitoring F is performed in real time - The concentration mode is online or offline F - And (5) detecting concentration.
Further, in the method of the present invention, F is obtained based on the monitoring - The concentration is calculated, and the service life of the PEM electrolytic cell is judged. And from F - The conversion of the concentration determination PEM electrolyzer life may be referred to as DOI:10.1016/j.ijhydene.2016.07.125; "Investigation on the degradation of MEAs for PEM water electrolysers part I: effects of testing conditions on MEA performances and membrane properties".
The invention has the advantages that:
1. the service life of the online electrolytic tank is evaluated without stopping the electrolytic tank, so that convenience is improved;
2. the non-in-situ nondestructive property sub-exchange membrane thickness test is realized without disassembling an electrolytic cell, so that the test convenience is improved, and the difficulty of the test is reduced;
3. a life assessment mode is added, and CVM wiring and explosion-proof risks are reduced.
Drawings
FIG. 1 is a schematic diagram of the construction of a PEM electrolyzer unit in accordance with the present invention.
Detailed Description
The technical scheme of the invention is specifically described below with reference to the embodiment and the attached figure 1. The reference numerals in fig. 1 are shown in the following table 1:
table 1 description of the reference numerals
| 1 | Anode circulating water tank liquid level sensor | 11 | PEM electrolytic cell |
| 2 | Anode outlet temperature sensor | 12 | Anode inlet pressure sensor |
| 3 | Anode outlet pressure sensor | 13 | Anode inlet temperature sensor |
| 4 | DC power supply | 14 | One-way valve |
| 5 | Cathode outlet pressure sensor | 15 | Flowmeter for measuring flow rate |
| 6 | Cathode outlet temperature sensor | 16 | Deionizing device |
| 7 | Cathode outlet heat exchanger | 17 | Anode waterway heat exchanger |
| 8 | Cathode gas-liquid separation tank | 18 | Heater |
| 9 | Liquid level sensor of cathode gas-liquid separation tank | 19 | Circulating water pump |
| 10 | F - Selection electrode | 20 | Anode circulating water tank |
Example 1
In the PEM electrolyzer process of the present invention, as shown in fig. 1, direct current is used to electrolyze pure water to produce hydrogen and oxygen. The cathode is a hydrogen generating end, and the anode is an oxygen generating end. In a PEM electrolyzed water system, water is fed at the anode of the electrolyzer and then discharged from the anode outlet of the electrolyzer to an anode gas-water separator, an ion remover (16) is added at the anode side to reduce the conductivity of the electrolyzer feed water by ion exchange in view of the water quality requirements of the PEM electrolyzer, so that F cannot be evaluated at the anode side - The content is as follows. The water on the cathode side permeates to the cathode side through the proton exchange membrane under the actions of permeation, electromigration and the like on the anode side, and the water on the cathode side is directly discharged after being subjected to gas-water separation, so that the fluorine content in the cathode drainage is a reliable index of the service life of the membrane. The invention is well-knownThe amount of fluorine released from the cathode side was collected to determine the degradation and lifetime of the membrane chemistry in the cell.
Specifically, after the deionized water of the anode circulating water tank (20) is heated to the working temperature by the heater (18), a direct-current power supply (4) is started, and anode products, including oxygen and a large amount of water, are returned to the anode circulating water tank; the cathode product, including hydrogen and a small amount of water, flows into a cathode gas-liquid separation tank (8).
The sampling port is added at the water outlet of the cathode gas-liquid separation, and the sampling port is opened when needed in the working process of the electrolytic tank, and the external F is used - Selecting F in the electrode (10) pair sampling water - Detecting to obtain F by an off-line detection mode - The release rate was calculated as the degree of thinning of the proton exchange membrane thickness to evaluate the lifetime of the PEM electrolyzer.
Example 2
In the hydrogen production process of the PEM electrolyzer of the invention as shown in FIG. 1, in addition to the liquid level sensor (9) in the cathode side gas-liquid separator tank, F is added in the position where the cathode side waterway pipeline/gas-water separator tank is as close to the PEM electrolyzer as possible - Selecting electrode (10) for real-time on-line monitoring F - Release Rate, F in gas-Water separation tank with prolonged operation of PEM electrolyzer - The concentration is gradually increased, and the reduction degree of the proton exchange membrane thickness is calculated by utilizing the accumulated F-concentration according to the positive correlation relation between the increase of the online monitoring F-concentration and the reduction of the proton exchange membrane thickness, so that the service life condition of the electrolytic cell is judged.
As can be seen from fig. 1, in the real-time monitoring methods of embodiments 1 and 2, when the F-concentration is abnormally increased, it is considered that the problem occurs in the whole electrolytic cell or a certain electrolytic cell, including thinning, perforation, etc., and the F-concentration is corresponding to the result of CVM, so as to assist in judging the failure of the electrolytic cell or a certain electrolytic cell.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, but not for limiting the same, and although the present invention has been described in detail with reference to the examples, it should be understood by those skilled in the art that modifications and equivalents can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all the modifications and equivalents are intended to be covered by the scope of the claims of the present invention.
Claims (6)
1. A method for monitoring the service life of a PEM electrolytic tank in real time, which is characterized in that F is added in a PEM electrolytic water system - Select electrode real-time monitoring F - Is a concentration of (3).
2. The method for real-time monitoring of PEM electrolyzer life of claim 1 wherein said PEM electrolyzed water system comprises at least a PEM electrolyzer, a power source, and an anode/cathode gas-liquid separator.
3. The method for real-time monitoring of PEM electrolyzer life of claim 2 wherein a sampling port is added at the drain of the cathode gas-liquid separator, and the sampling port is opened as needed during electrolyzer operation, using external F - Selecting electrode pairs to sample F in water - The concentration was measured.
4. The method for real-time monitoring of PEM electrolyzer life of claim 2 wherein F is added in the cathode side waterway piping or gas-liquid separator as close as possible to the PEM electrolyzer - Selecting electrode, monitoring F in real time - Concentration or release rate of (a).
5. The method for real-time monitoring of PEM electrolyser life of claim 1, wherein said real-time monitoring F - The concentration mode is online or offline F - And (5) detecting concentration.
6. The method for real-time monitoring of PEM electrolyser life of claim 1, wherein F based on said monitoring - The concentration is calculated, and the service life of the PEM electrolytic cell is judged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311806525.XA CN117805198A (en) | 2023-12-26 | 2023-12-26 | Method for monitoring service life of PEM (PEM) electrolytic tank in real time |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311806525.XA CN117805198A (en) | 2023-12-26 | 2023-12-26 | Method for monitoring service life of PEM (PEM) electrolytic tank in real time |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117805198A true CN117805198A (en) | 2024-04-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311806525.XA Pending CN117805198A (en) | 2023-12-26 | 2023-12-26 | Method for monitoring service life of PEM (PEM) electrolytic tank in real time |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117805198A (en) |
-
2023
- 2023-12-26 CN CN202311806525.XA patent/CN117805198A/en active Pending
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