A gas storage library elution efficiency detection sensor and a manufacturing method thereof

Abstract

The application discloses a kind of gas storage library washing efficiency detection sensor and its manufacturing method, belong to gas storage operation monitoring and gas sensing technical field;The method is by mixing 2,2'-dipyridyl-5,5'-diamine with 1,3,5-triformylphloroglucinol, dispersed in 1,4-dioxane, m-trimethylbenzene and volume fraction 5%-15% acetic acid mixed solvent, solvent hot reaction, washing, drying, grinding and liquid phase stripping obtain COF nanosheet;COF nanosheet is reacted with metal ion modified material again, and Fe-COF, Zn-COF or FeZn-COF modified nanosheet is prepared;Subsequently, different modified nanosheets are loaded on different areas of the surface of a micro-hotplate chip, forming a combined gas-sensitive membrane composed of multiple gas-sensitive units, and assembled with a data acquisition board, a PCB board and a shell with an air inlet window to form a sensor;The sensor can detect H2S, CO2, CO, SO2, NO2 and other gases online, and can continuously and quantitatively characterize the washing efficiency of the gas storage library according to the concentration change of the target gas.

Description

Technical Field

[0001] This invention belongs to the field of gas monitoring and sensing technology for gas storage facilities, specifically relating to a sensor for detecting the rinsing efficiency of a gas storage facility and its manufacturing method. Background Technology

[0002] Gas storage tank sifting efficiency refers to the degree to which the target residual gas is displaced, diluted, or removed relative to the initial state during the gas storage tank sifting process. It can be characterized by the magnitude, rate, or comprehensive concentration change characteristics of the target gas. The target residual gas includes one or more of H2S, CO2, CO, SO2, and NO2.

[0003] During the purging process of gas storage facilities, continuous replacement, purging, or ventilation operations are typically required to gradually displace, dilute, and discharge residual acidic gases, associated impurities, or polluting gases to meet the requirements for subsequent safe operation or process switching. In acidic gas reservoirs, during injection and production operations, commissioning switching, wellbore replacement, and the start-up and shutdown of surface gathering and transportation systems, the migration, dilution, and discharge of acidic or toxic gases such as H2S, CO2, and associated CO, SO2, and NO2 are common. When residual impurities, acidic media, or abnormal leaks exist at wellheads, valve chambers, pipe racks, or surface manifolds, these gases can easily accumulate in localized spaces, potentially leading to personnel poisoning, equipment corrosion, and operational safety risks. Therefore, multiple gas sensors are needed for gas detection; however, existing gas storage sensors have the following technical problems: (1) Existing gas storage gas sensors have problems such as low sampling frequency, delayed feedback, and inability to continuously characterize the concentration change process of multiple target gases, making it difficult to achieve real-time and quantitative evaluation of washing efficiency.

[0004] (2) Under the working conditions of gas storage, the cross-interference of multiple gases is significant. Traditional single gas sensors are difficult to accurately distinguish and detect under mixed gas conditions. Usually, sensors need to be deployed separately for different gases, which leads to high deployment difficulty and detection cost. Moreover, the detection results are easily affected by cross-sensitivity.

[0005] (3) Traditional gas sensors are susceptible to temperature, humidity, pressure and dust, oil mist and other factors, which can cause the output data to drift and the detection stability to be insufficient.

[0006] (4) When traditional gas sensors are in acidic, high-humidity and corrosive environments for a long time, the internal components are prone to rust, corrosion or short circuit, resulting in poor long-term reliability.

[0007] Therefore, there is a need for a sensor and its manufacturing method that can adapt to acidic, high-humidity and corrosive environments and enable online detection of multiple target gases and quantitative characterization of rinsing efficiency during the gas storage rinsing process. Summary of the Invention

[0008] The purpose of this invention is to provide a gas storage tank rinsing efficiency detection sensor and its manufacturing method, so as to solve the problems in the prior art that the gas storage tank rinsing process relies on offline sampling and analysis, is difficult to achieve continuous online monitoring, and is difficult to quantitatively determine the rinsing efficiency, while taking into account the anti-cross-interference ability and adaptability to complex working conditions in the detection process of multi-component target gases.

[0009] This invention is achieved through the following technical solution: A method for manufacturing a gas storage tank sifting efficiency detection sensor includes the following steps: S1: Preparation of COF nanosheets; S2: Modifying COF nanosheets to obtain various modified nanosheets; S3: Various modified nanosheets are respectively coated on different areas of the surface of the micro hot plate chip to form a combined gas-sensitive film; S4: Assemble the gas sensor by inserting the micro-hot plate chip into the gas sensor housing.

[0010] Preferably, in step S1, the specific method for preparing COF nanosheets includes the following steps: S11: Mix the diamine monomer and the trialdehyde monomer in a molar ratio of 1:1 and disperse them in a solvent to obtain mixed solution A; S12: After ultrasonic dispersion of mixed solution A, it is transferred to a reaction vessel and solvothermal reaction is carried out at 110℃-120℃ for 48h-72h to obtain a two-dimensional β-ketoenamine COF containing bipyridine coordination sites. S13: Two-dimensional β-ketoenamine COF was washed sequentially with dioxane, ethanol and acetone, followed by vacuum drying, grinding and liquid phase exfoliation to obtain COF nanosheets.

[0011] Preferably, in step S11, the solvent is 1,4-dioxane, m-trimethylbenzene, and 6 mol·L⁻¹. -1 A mixed solvent of acetic acid, wherein the volume ratio of 1,4-dioxane to m-trimethylbenzene is 1:1, and the volume fraction of acetic acid is 5%–15%.

[0012] Preferably, in step S11, the diamine monomer is 2,2'-bipyridine-5,5'-diamine.

[0013] Preferably, in step S11, the trialdehyde monomer is 1,3,5-tricarboxymethyl phloroglucinol.

[0014] Preferably, in step S2, the specific method for modifying COF nanosheets includes the following steps: S21: COF nanosheets are dispersed in anhydrous ethanol, and metal ion modifying material is added to make the molar ratio of metal ions to bipyridine sites in COF nanosheets 0.2:1–1.0:1 to obtain a mixed solution; S22: Stir and reflux the mixture at 60℃–80℃ for 6h–12h, centrifuge and wash with ethanol to remove uncoordinated metal salts; S23: Vacuum drying at 80℃ yields modified nanosheets.

[0015] Preferably, in step S21, the metal ion modifying material is any one of FeCl3·6H2O and Zn(Ac)2·2H2O or a mixed salt solution of both. When FeCl3·6H2O is selected as the metal ion modifying material, Fe-COF modified nanosheets are obtained. When Zn(Ac)2·2H2O is selected as the metal ion modifying material, Zn-COF modified nanosheets are obtained. When a mixed salt solution of FeCl3·6H2O and Zn(Ac)2·2H2O is used as the metal ion modification material, FeZn-COF modified nanosheets are obtained, wherein the molar ratio of Fe to Zn is 1:3–3:1.

[0016] Preferably, in step S3, the specific operation of covering the modified nanosheets onto the surface of the micro hot plate chip includes the following steps: S31: Each modified nanosheet was individually mixed with polyvinylidene fluoride (PVDF) at a mass ratio of 9:1 to 19:1, and N-methylpyrrolidone (NMP) was added as a dispersion solvent to prepare different slurries. S32: Each slurry is ultrasonically dispersed and then sprayed or spin-coated onto different areas of the micro-hot plate chip surface to form a combined gas-sensitive film; S33: Dry the micro hot plate chip with the combined gas-sensitive membrane at 60℃–100℃ for 1h–4h, and activate it at 100℃–150℃ in an inert atmosphere for 0.5h–2h to remove residual solvent.

[0017] A gas storage tank rinsing efficiency detection sensor, prepared according to the aforementioned method, comprises a housing, a micro-hot plate chip, an insulating support, a data acquisition board, a PCB board, and a battery. The micro-hot plate chip, insulating support, data acquisition board, and PCB board are all housed within the housing. An air inlet is provided at one end of the housing, and the micro-hot plate chip is positioned at the air inlet. The micro-hot plate chip is mounted on the insulating support, and the data acquisition board and PCB board are both located at the bottom of the insulating support, with the data acquisition board positioned between the PCB board and the insulating support. The PCB board is connected to the housing. A combined gas-sensitive membrane is disposed on the micro-hot plate chip. A battery compartment is located on the back side of the housing, and the battery is housed within the battery compartment and electrically connected to the micro-hot plate chip, data acquisition board, and PCB board.

[0018] Preferably, a filter protective membrane is provided at the air inlet window of the housing, and the filter protective membrane is used to seal the air inlet window of the housing.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects: 1) This invention improves the ability to differentiate target gases such as H2S, CO2, CO, SO2, and NO2 by leveraging the synergistic effect of COF framework coordination sites and metal active centers. It enables the joint detection of multiple target gases at a single detection point, thereby reducing the difficulty of sensor deployment and detection costs at gas storage sites.

[0020] 2) This invention improves the sensor’s working stability and environmental adaptability in acidic, high-humidity, corrosive and dusty / oil mist environments by combining a gas-sensitive membrane, a filter protection structure and a micro-hot plate chip temperature modulation mechanism.

[0021] 3) This invention can not only realize the real-time detection of multi-component target gases during the gas storage tank washing process, but also continuously and quantitatively characterize the gas storage tank washing efficiency based on the decrease in concentration, rate of change and comprehensive weight of each target gas during the washing process, thereby providing a basis for washing endpoint determination, process optimization and safety management. Attached Figure Description

[0022] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 This is a TEM characterization image of the pure COF nanosheets in this invention.

[0024] Figure 2 This is a bar graph showing the comparison of the adsorption effects of pure COF nanosheets and modified nanosheets on various gases in this invention.

[0025] Figure 3 This is a schematic cross-sectional view of the gas storage tank rinsing efficiency detection sensor in this invention.

[0026] The components are: 1-shell, 2-micro-hot plate chip, 3-combined gas-sensitive membrane, 4-insulating bracket, 5-data acquisition board, 6-PCB board, 7-filter protective membrane, and 8-battery. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. Example 1:

[0028] A method for fabricating a gas storage tank sifting efficiency detection sensor involves first preparing a gas-sensitive layer for the sensor, which is a COF nanosheet with regular channels and coordinating sites. The COF is a covalent organic framework, preferably a two-dimensional COF framework containing β-keto-enamine bonds or imine bonds, to balance chemical stability, processability, and the ability to adsorb and recognize polar gases.

[0029] In the preparation of COF nanosheets, 1,3,5-tricarboxymethyl phloroglucinol (Tp) was used as the trialdehyde monomer, with 0.05 mmol-0.2 mmol of 1,3,5-tricarboxymethyl phloroglucinol and 2,2'-bipyridine-5,5'-diamine (Bpy) as the diamine monomer, with the same amount of 0.05 mmol-0.2 mmol. The two were mixed at a molar ratio of 1:1 and dispersed in 1,4-dioxane / m-trimethylbenzene / 6 mol·L⁻¹. -1 A mixed solution A is obtained by mixing acetic acid in a mixed solvent; wherein the volume ratio of 1,4-dioxane to m-trimethylbenzene is 1:1, the volume fraction of acetic acid is 5%–15%, 4 mL–6 mL of 1,4-dioxane, 4 mL–6 mL of m-trimethylbenzene, and 0.5 mL–1.5 mL of acetic acid.

[0030] In this embodiment, the amount of 1,3,5-tricarboxymethyl phloroglucinol was 0.1 mmol, the amount of 2,2'-bipyridine-5,5'-diamine was 0.1 mmol, 1,4-dioxane was 5 mL, m-trimethylbenzene was 5 mL, and acetic acid was 0.5 mL.

[0031] Mixed solution A was ultrasonically dispersed and then transferred to a sealed reactor. It was then subjected to a solvothermal reaction at 120°C for 48–72 h to obtain two-dimensional β-ketoenamine COFs containing bipyridine coordination sites. The product was washed sequentially with dioxane, ethanol, and acetone, and then vacuum-dried at 80–120°C for 8–12 h. Following gentle grinding or liquid-phase exfoliation, COF nanosheets with diameters of 80 nm–300 nm and thicknesses of 5 nm–50 nm were obtained.

[0032] This type of β-ketoenamine COF material has good acid resistance and hygrothermal stability, making it suitable for use in acidic gas reservoirs. Example 2:

[0033] Next, the COF nanosheets were modified using systems including Fe-COF, Zn-COF, and FeZn-COF. After preparing COF nanosheets with coordination sites, Fe was introduced via a post-coordination mechanism. 3+ Zn 2+ Alternatively, Fe / Zn bimetallic active sites can be used to form a stable coordination structure between the metal center and the N sites in the COF nanosheet framework, which contains bipyridine nitrogen atoms; Fe 3+ or Zn 2+ It will form coordinate bonds with these nitrogen atoms; the formed metal coordination sites will change the gas adsorption behavior and electron transport behavior; thus causing different gases to produce different responses, thereby enhancing the differentiated response to acidic gases and reducing / oxidizing gases.

[0034] COF nanosheets were dispersed in anhydrous ethanol and divided into three groups for modification: The first group was treated with FeCl3·6H2O to obtain the first mixed solution.

[0035] The second group was treated with Zn(Ac)2·2H2O to obtain the second mixture.

[0036] The third group was prepared by adding a mixed salt solution of FeCl3·6H2O and Zn(Ac)2·2H2O, and making the molar ratio of metal ions to bipyridine sites in COF nanosheets 1:1 to obtain the third mixed solution.

[0037] Each mixture was stirred and refluxed at 60–80℃ for 6–12 h, then centrifuged and thoroughly washed with ethanol to remove uncoordinated metal salts. It was then vacuum dried at 80℃ for 6 h to obtain Fe-COF modified nanosheets, Zn-COF modified nanosheets and FeZn-COF modified nanosheets, respectively.

[0038] The metal loading was controlled within the range of 1.0–8.0 wt% to balance conductivity regulation, active site density, and framework stability. The FeZn-COF nanosheet material had a Fe to Zn molar ratio of 1:3, and was used to construct gas-sensitive materials with differentiated adsorption and charge transfer characteristics for H2S, SO2, NO2, and CO2.

[0039] The modified nanosheets were then dried at 100°C for 3 hours and activated at 100–150°C in an inert atmosphere for 2 hours to remove residual solvent without damaging the modified nanosheet framework.

[0040] A surface protective film is prepared on the surface of the combined gas-sensitive membrane using low-temperature atomic layer deposition (ALD). The preferred deposition temperature is 120°C. A 5nm thick Al2O3 or SiO2 surface protective film is grown on the surface of the combined gas-sensitive membrane to improve the corrosion resistance, droplet resistance, particulate contamination resistance, and long-term operational stability of the combined gas-sensitive membrane and the micro-hot plate chip. It also serves as a surface passivation and electrical insulation protection. Therefore, the surface protective film is selected with an ultra-thin structure that allows the target gas to diffuse through, reducing the impact of humidity, condensate, and corrosive media on sensor performance while ensuring gas detection sensitivity.

[0041] In the fabrication of the gas sensor, an existing hot plate chip is selected as the sensing substrate. Pt or Au interdigitated electrodes and a heating unit are integrated on the hot plate chip, with an electrode spacing preferably of 20 μm. The operating temperature of the hot plate chip is 60℃-150℃. Different gases exhibit varying adsorption, desorption, and charge transfer behaviors at different temperatures; therefore, the distinguishing ability can be enhanced by changing the operating temperature to achieve adsorption detection, temperature modulation, and desorption recovery. Fe-COF modified nanosheets, Zn-COF modified nanosheets, or FeZn-COF modified nanosheet powders are added to an NMP mixing system at a mass ratio of 9:1 with PVDF to prepare a uniform slurry. After ultrasonic dispersion, the slurry is loaded onto different areas of the hot plate chip surface using drop-coating, spraying, or spin-coating methods to form a combined gas-sensitive film.

[0042] The combined gas-sensitive membrane includes three gas-sensitive regions, which are respectively composed of Fe-COF modified nanosheets, Zn-COF modified nanosheets and FeZn-COF modified nanosheets, to form differentiated responses to target gases such as H2S, CO2, CO, SO2 and NO2.

[0043] Finally, the micro-hotplate chip with the combined gas-sensitive membrane is installed into the housing and connected to the other components. A filter protective membrane is placed at the air inlet of the housing as the first protective layer; the Al2O3 or SiO2 surface protective film on the surface of the combined gas-sensitive membrane serves as the second protective layer. During the assembly process, using existing micro-hotplate chips, only the partitioned loading, drying and activation, and subsequent packaging and assembly of the combined gas-sensitive membrane need to be completed to complete the sensor fabrication.

[0044] like Figure 1 and Figure 2 As shown, Figure 1 These are TEM images of pure COF nanosheets. Figure 2 This is a bar graph comparing the adsorption effects of pure COF nanosheets and modified nanosheets on various gases.

[0045] Depend on Figure 1 It can be seen that pure COF nanosheets have a layered stacked structure with thinner local edges and wrinkled morphology, indicating that they have nanosheet structure characteristics, which is beneficial to exposing more adsorption sites and improving the diffusion mass transfer capacity of target gas molecules.

[0046] Depend on Figure 2 It is known that while unmodified COF nanosheets possess a certain adsorption capacity for various target gases, the adsorption differences between different gases are relatively small, and cross-sensitivity is quite significant. After Fe, Zn, or Fe / Zn bimetallic coordination modification, the adsorption strength and charge transfer behavior of the material for different target gases are significantly altered, resulting in differentiated responses of different modified nanosheet materials to H2S, CO2, SO2, NO2, and CO. Based on this differentiated response, multiple gas-sensitive units within a single sensing node can be used to identify and detect the concentration of various target gases, thereby reducing the number of field deployments and improving detection accuracy. The other parts of this embodiment are the same as those in the above embodiments and will not be repeated here. Example 3:

[0047] A gas storage tank sifting efficiency detection sensor, such as Figure 3 As shown, the sensor prepared according to the above-described method for manufacturing a gas storage tank washing efficiency detection sensor includes a housing 1, a micro-hot plate chip 2, an insulating bracket 4, a data acquisition board 5, a PCB board 6, and a battery 8. The micro-hot plate chip 2, the insulating bracket 4, the data acquisition board 5, and the PCB board 6 are all disposed in the housing 1. An air inlet window is provided at one end of the housing 1. A combined gas-sensitive membrane 3 is provided on the micro-hot plate chip 2, and the combined gas-sensitive membrane 3 of the micro-hot plate chip 2 is disposed at the air inlet window position.

[0048] The micro hot plate chip 2 is mounted on the insulating bracket 4. The data acquisition board 5 and the PCB board 6 are both mounted at the bottom of the insulating bracket 4. The data acquisition board 5 is positioned between the PCB board 6 and the insulating bracket 4. The PCB board 6 is glued to the housing 1 or connected by bolts.

[0049] A battery compartment is provided on the back side of the housing 1. The battery 8 is placed in the battery compartment and is electrically connected to the micro-hot plate chip 2, the data acquisition board 5 and the PCB board 6.

[0050] A filter membrane 7 is installed at the air inlet window of the housing 1. The filter membrane 7 is located above the combined gas-sensitive membrane 3 and is used to encapsulate the air inlet window of the housing 1. For the high humidity, corrosive, dust and oil mist environment of the acid gas reservoir storage, the filter membrane 7 can be a PTFE waterproof and breathable membrane or a sintered microporous filter sheet. For the high humidity, corrosive, dust and oil mist environment of the acid gas reservoir storage, the filter membrane 7 can allow the target gas to diffuse in, while blocking droplets, dust, oil mist and large particulate impurities from entering the interior of the housing 1. When necessary, a flow stabilizing cavity or buffer cavity can also be set inside the air inlet window to reduce the impact of instantaneous airflow and improve sampling stability.

[0051] When deploying sensors in a gas storage facility, sensor nodes are placed at injection and production wellheads, surface manifolds, valve chambers, and pipe gallery connections to collect relevant signals and environmental parameters such as H2S, CO2, CO, SO2, and NO2.

[0052] The gas to be tested enters the interior of housing 1 through the air inlet window, passes through the filter membrane 7, and reaches the combined gas-sensitive membrane 3 on the surface of the micro-hot plate chip 2. The PCB board 6 controls the micro-hot plate chip 2 to operate at a preset temperature. After the combined gas-sensitive membrane 3 comes into contact with the gas to be tested, its resistance, conductivity, or current signal changes. The data acquisition board 5 amplifies, filters, and performs analog-to-digital conversion on the changed signal and transmits it to the PCB board 6. The PCB board 6 combines the environmental parameters collected by the temperature and humidity sensor to extract the response amplitude, response rate, recovery rate, and other characteristics of each gas-sensitive unit at different temperature points, and outputs the target gas type and its concentration value through a preset discrimination model. Subsequently, the detection results are wirelessly transmitted to a host computer or monitoring platform via LoRaWAN (Lower Power Wide Area Network) or NB-IoT (Narrowband Internet of Things) for alarm, trend analysis, and security management.

[0053] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., used to indicate the orientation or positional relationship are based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship that the product of this invention is usually placed in during use. They are only for the convenience of describing this invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0054] Furthermore, the use of terms such as "horizontal" and "vertical" in the description of this invention does not imply that the components are required to be absolutely horizontal or suspended, but rather that they can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0055] In the description of this invention, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0056] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications or equivalent changes made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A method for manufacturing a gas storage tank rinsing efficiency detection sensor, characterized in that, Includes the following steps: S1: Preparation of COF nanosheets; S2: Modifying COF nanosheets to obtain various modified nanosheets; S3: Various modified nanosheets are respectively coated on different areas of the surface of the micro hot plate chip to form a combined gas-sensitive film; S4: Assemble the gas sensor by inserting the micro-hot plate chip into the gas sensor housing.

2. The method for manufacturing the gas storage tank rinsing efficiency detection sensor as described in claim 1, characterized in that, In step S1, the specific method for preparing COF nanosheets includes the following steps: S11: Mix the diamine monomer and the trialdehyde monomer in a molar ratio of 1:1 and disperse them in a solvent to obtain mixed solution A; S12: After ultrasonic dispersion of mixed solution A, it is transferred to a reaction vessel and solvothermal reaction is carried out at 110℃-120℃ for 48h-72h to obtain a two-dimensional β-ketoenamine COF containing bipyridine coordination sites. S13: Two-dimensional β-ketoenamine COF was washed sequentially with dioxane, ethanol and acetone, followed by vacuum drying, grinding and liquid phase exfoliation to obtain COF nanosheets.

3. The method for manufacturing the gas storage tank rinsing efficiency detection sensor as described in claim 2, characterized in that, In step S11, the solvent is 1,4-dioxane, m-trimethylbenzene, and 6 mol·L⁻¹. -1 A mixed solvent of acetic acid, wherein the volume ratio of 1,4-dioxane to m-trimethylbenzene is 1:1, and the volume fraction of acetic acid is 5%–15%.

4. The method for manufacturing the gas storage tank rinsing efficiency detection sensor as described in claim 2, characterized in that, In step S11, the diamine monomer is 2,2'-bipyridine-5,5'-diamine.

5. The method for manufacturing the gas storage tank rinsing efficiency detection sensor as described in claim 2, characterized in that, In step S11, the trialdehyde monomer is 1,3,5-tricarboxymethyl phloroglucinol.

6. The method for manufacturing the gas storage tank rinsing efficiency detection sensor as described in claim 1, characterized in that, In step S2, the specific method for modifying COF nanosheets includes the following steps: S21: COF nanosheets are dispersed in anhydrous ethanol, and metal ion modifying material is added to make the molar ratio of metal ions to bipyridine sites in COF nanosheets 0.2:1–1.0:1 to obtain a mixed solution; S22: Stir and reflux the mixture at 60℃–80℃ for 6h–12h, centrifuge and wash with ethanol to remove uncoordinated metal salts; S23: Vacuum drying at 80℃ yields modified nanosheets.

7. The method for manufacturing the gas storage tank rinsing efficiency detection sensor as described in claim 6, characterized in that, In step S21, the metal ion modifying material is any one of FeCl3·6H2O, Zn(Ac)2·2H2O, or a mixed salt solution of both. When FeCl3·6H2O is selected as the metal ion modifying material, Fe-COF modified nanosheets are obtained. When Zn(Ac)2·2H2O is selected as the metal ion modifying material, Zn-COF modified nanosheets are obtained. When a mixed salt solution of FeCl3·6H2O and Zn(Ac)2·2H2O is used as the metal ion modification material, FeZn-COF modified nanosheets are obtained, wherein the molar ratio of Fe to Zn is 1:3–3:

1.

8. The method for manufacturing the gas storage tank rinsing efficiency detection sensor as described in claim 1, characterized in that, In step S3, the specific operation method of covering the modified nanosheets onto the surface of the micro hot plate chip includes the following steps: S31: Each modified nanosheet was individually mixed with polyvinylidene fluoride at a mass ratio of 9:1-19:1, and N-methylpyrrolidone was added as a dispersion solvent to prepare different slurries. S32: Each slurry is ultrasonically dispersed and then sprayed or spin-coated onto different areas of the micro-hot plate chip surface to form a combined gas-sensitive film; S33: Dry the micro hot plate chip with the combined gas-sensitive membrane at 60℃–100℃ for 1h–4h, and activate it at 100℃–150℃ in an inert atmosphere for 0.5h–2h to remove residual solvent.

9. A sensor for detecting the rinsing efficiency of a gas storage tank, characterized in that, The sensor prepared by the method of manufacturing the gas storage tank rinsing efficiency detection sensor according to any one of claims 1-8 includes a housing, a micro-hot plate chip, an insulating support, a data acquisition board, a PCB board, and a battery. The micro-hot plate chip, insulating support, data acquisition board, and PCB board are all disposed within the housing. An air inlet window is provided at one end of the housing, and the micro-hot plate chip is disposed at the air inlet window position. The micro-hot plate chip is disposed on the insulating support, and the data acquisition board and PCB board are both disposed at the bottom of the insulating support. The data acquisition board is disposed between the PCB board and the insulating support, and the PCB board is connected to the housing. A combined gas-sensitive membrane composed of multiple gas-sensitive units formed by various modified nanosheets is disposed on the micro-hot plate chip. The PCB board is used to control the micro-hot plate chip to operate according to a preset temperature program and to process the multi-gas response signals collected by the data acquisition board to output the target gas concentration and rinsing efficiency evaluation results. A battery compartment is provided on the back side of the housing, and the battery is disposed in the battery compartment and electrically connected to the micro-hot plate chip, data acquisition board, and PCB board.

10. The gas storage tank sifting efficiency detection sensor as described in claim 9, characterized in that, A filter and protective membrane is provided at the air inlet of the housing, and the filter and protective membrane is used to seal the air inlet of the housing.

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