An ammonia-nitrogen and nitrate-nitrogen integrated online detection method and a detection device thereof

Abstract

An ammonia nitrogen and nitrate nitrogen integrated online detection method and a detection device thereof, the accuracy and reliability of subsequent water quality testing are ensured through electrode correction, thereby improving the accuracy of subsequent water quality analysis; after the correction is completed, the liquid remaining in the detection pool can be flushed away, and the pipeline through which the liquid passes can be flushed and cleaned by flushing the pipeline through which the detection pool and the ammonia nitrogen and nitrate nitrogen standard solution pass; then the water sample is extracted into the detection pool for detection, the ammonia nitrogen and nitrate nitrogen concentration content results detected by the full solid ammonia nitrogen and nitrate nitrogen composite electrode after electrode correction are used, and the water sample is discharged after the detection is completed; finally, the detection pool and the pipeline through which the water sample passes are flushed again, so that the detection pool and the pipeline through which the water sample passes are in the best state before being used next time, thereby ensuring the accuracy and reliability of the detection effect.

Description

Technical Field

[0001] This invention relates to the field of water quality testing technology, specifically to an integrated online detection method and device for ammonia nitrogen and nitrate nitrogen. Background Technology

[0002] Ammonia nitrogen and nitrate nitrogen are the main indicators for total pollutant control in my country's water bodies. They are also important monitoring indicators for water environmental quality and the operational effectiveness of wastewater treatment facilities. Real-time and accurate acquisition of ammonia nitrogen and nitrate nitrogen monitoring data plays an important guiding and prompting role in wastewater treatment, aquaculture, agricultural planting, and environmental remediation.

[0003] Existing methods for ammonia nitrogen detection mainly include spectrophotometry, titration, and ion chromatography; methods for nitrate nitrogen detection mainly include spectrophotometry and ion chromatography. Spectrophotometry involves a colorimetric reaction between the analyte and a reagent, followed by calculation of the analyte concentration using the absorbance at a specific wavelength. Titration indirectly titrates distilled NH3 with a reagent to calculate the ammonia nitrogen content in the water sample. Ion chromatography involves an exchange process between the analyte and the chromatographic column, allowing the analyte to enter the detector and generate an electrical signal related to the ion concentration, thus enabling the detection of ammonia nitrogen and nitrate nitrogen concentrations.

[0004] Among the aforementioned detection methods, spectrophotometric methods involve complex reagent preparation and contain toxic reagents, such as Nessler's reagent and phenoldisulfonic acid; titration methods have complex pretreatment steps, a small detection range, and the titration results are affected by operator error, resulting in significant detection errors; ion chromatography methods involve complex instrument structures, high costs, and expensive purchases. Furthermore, the detection of ammonia nitrogen and nitrate nitrogen generally relies on manual sampling, allowing for separate detection of ammonia nitrogen and nitrate nitrogen content, resulting in lengthy analysis times, delayed results, and difficulty in achieving real-time online monitoring of ammonia nitrogen and nitrate nitrogen. Summary of the Invention

[0005] The technical problem to be solved by the present invention is that the detection of ammonia nitrogen and nitrate nitrogen in the prior art mostly adopts manual sampling, which cannot be detected simultaneously. The analysis and detection are time-consuming and the detection results are delayed, making it difficult to achieve simultaneous real-time online monitoring of ammonia nitrogen and nitrate nitrogen. Therefore, the present invention provides an integrated online detection method and device for ammonia nitrogen and nitrate nitrogen.

[0006] To solve the above-mentioned technical problems, the present invention proposes the following technical solution:

[0007] An integrated online detection method for ammonia nitrogen and nitrate nitrogen includes the following steps:

[0008] S1: Electrode calibration: Ammonia nitrogen and nitrate nitrogen standard solutions are pumped into the detection cell. The ammonia nitrogen and nitrate nitrogen standard solutions are passed through the all-solid ammonia nitrogen and nitrate nitrogen composite electrode to measure the potential difference between the ammonium ion selective electrode and the reference electrode, and between the nitrate ion selective electrode and the reference electrode. The measured potential difference results are output. The all-solid ammonia nitrogen and nitrate nitrogen composite electrode is then calibrated. Finally, the calibrated solution is discharged.

[0009] S2: Flushing: Flushing the detection cell and the pipeline through which the ammonia nitrogen and nitrate nitrogen standard solutions pass in step S1;

[0010] S3: Concentration detection: The water sample to be tested is pumped into the detection tank through a water pump. The concentrations of ammonia nitrogen and nitrate nitrogen in the water sample after sedimentation in the detection tank are detected by a solid-state ammonia nitrogen and nitrate nitrogen composite electrode. After the detection is completed, the water sample is discharged.

[0011] S4: Flushing: Flushing the detection pool and the pipeline through which the water sample passes in step S2.

[0012] Furthermore, in step S1, two copies of the ammonia nitrogen and nitrate nitrogen standard solutions are prepared. The potential difference between the two copies of the ammonia nitrogen and nitrate nitrogen standard solutions is measured sequentially using the composite electrode, thereby performing two electrode calibrations.

[0013] Furthermore, in step S3, after the water sample to be tested is pumped into the testing pool, it needs to be allowed to settle.

[0014] Furthermore, in step S3, the water sample after settling is filtered to remove impurities using a filtration structure, and the filtered water sample is then pumped into the detection pool for ammonia nitrogen and nitrate nitrogen concentration detection.

[0015] An integrated online detection device for ammonia nitrogen and nitrate nitrogen includes a multi-port valve, a water sample extraction mechanism, a standard solution tank, a washing solution tank, a detection mechanism, and a first waste liquid tank. The multi-port valve has multiple inlets, and a peristaltic pump is connected to the outlet of the multi-port valve. A first drain valve is provided between the waste liquid tank and the detection mechanism. The water sample extraction mechanism, the standard solution tank, and the washing solution tank are respectively connected to multiple inlets of the multi-port valve, and the detection mechanism is connected to the peristaltic pump. The water sample extraction mechanism is suitable for extracting water samples to be tested for ammonia nitrogen and nitrate nitrogen concentrations. The standard solution tank is suitable for holding ammonia nitrogen and nitrate nitrogen standard solutions. The washing solution tank contains a cleaning solution. The detection mechanism is suitable for detecting the water sample from the water sample extraction mechanism and the standard solution in the standard solution tank. The first waste liquid tank is connected to the end of the detection mechanism furthest from the multi-port valve.

[0016] Furthermore, the water sampling mechanism includes an inlet pump and an inlet pool connected to the outlet of the inlet pump. The inlet pool is connected to the first inlet of the multi-way valve. A filter is provided between the inlet pump and the inlet pool. An inlet valve is connected to the inlet of the inlet pump. A second waste liquid pool is connected to the inlet pool. A second drain valve is provided between the inlet pool and the second waste liquid pool.

[0017] Furthermore, at least two standard solution pools are provided, and the two standard solution pools are respectively connected to the second inlet and the third inlet of the multi-way valve.

[0018] Furthermore, the washing solution tank is connected to the fourth inlet of the multi-way valve, and the cleaning solution contained in the washing solution tank is purified water.

[0019] Furthermore, the detection mechanism includes a detection pool and a detection component disposed within the detection pool. The detection component is a solid-state ammonia nitrogen and nitrate nitrogen composite electrode. A transmitter is electrically connected to the solid-state ammonia nitrogen and nitrate nitrogen composite electrode. The transmitter is adapted to output the detection results of the solid-state ammonia nitrogen and nitrate nitrogen composite electrode. A waste liquid pool No. 1 is connected to the detection pool, and a drain valve No. 1 is disposed between the detection pool and the waste liquid pool No. 1.

[0020] Furthermore, the all-solid-state ammonia nitrogen and nitrate nitrogen composite electrode includes an electrode housing, an electrode chip located within the electrode housing, a reference electrode, an ammonium ion selective electrode, and a nitrate ion selective electrode. The reference electrode, the ammonium ion selective electrode, and the nitrate ion selective electrode are all electrically connected to corresponding input points at one end of the electrode chip, and the other end of the electrode chip is electrically connected to the transmitter via three signal lines.

[0021] The technical solution of this invention has the following advantages:

[0022] 1. The integrated online detection method for ammonia nitrogen and nitrate nitrogen provided by this invention performs electrode calibration in step S1 to ensure the accuracy and reliability of subsequent water quality testing, thereby improving the accuracy of subsequent water quality analysis; step S2 flushes the detection pool and the pipeline through which the ammonia nitrogen and nitrate nitrogen standard solutions passed in step S1, which removes residual liquid in the detection pool and cleans the pipeline through which the liquid passes; step S3 extracts a water sample into the detection pool for testing, and uses the all-solid-state ammonia nitrogen and nitrate nitrogen composite electrode after electrode calibration to detect the ammonia nitrogen and nitrate nitrogen concentration results. After the test, the water sample is discharged; finally, the detection pool and the pipeline through which the water sample passed are flushed again to ensure that the detection pool and the pipeline through which the water sample passed are in optimal condition before the next use, thereby ensuring the accuracy and reliability of the detection effect.

[0023] 2. The integrated online detection method for ammonia nitrogen and nitrate nitrogen provided by this invention, in step S1, involves preparing two sets of ammonia nitrogen and nitrate nitrogen standard solutions. The potential difference between the two sets of ammonia nitrogen and nitrate nitrogen standard solutions is measured sequentially using a composite electrode, thus performing two electrode calibrations. This setup effectively ensures the accuracy and reliability of water quality testing, thereby improving the accuracy of subsequent water quality analysis. Through two calibrations, potential errors during the detection process can be effectively reduced, ensuring that the detection results match the actual values, thereby improving the accuracy and efficiency of the detection.

[0024] 3. The integrated online detection method for ammonia nitrogen and nitrate nitrogen provided by this invention requires flushing the detection cell and the pipeline through which the ammonia nitrogen and nitrate nitrogen standard solutions pass after each electrode calibration. This setup removes residual liquid from the ammonia nitrogen and nitrate nitrogen standard solutions in the detection cell and the pipeline through which they pass, preventing cross-contamination and ensuring the electrode is in optimal condition before the next use.

[0025] 4. The integrated online detection method for ammonia nitrogen and nitrate nitrogen provided by this invention, in step S3, involves filtering the settled water sample using a filtration structure to remove impurities. The filtered water sample is then pumped into a detection tank for ammonia nitrogen and nitrate nitrogen concentration detection. This setup removes suspended solids from the water sample through sedimentation and fixed substances through filtration, thereby improving the accuracy and reliability of the detection.

[0026] 5. The integrated online detection device for ammonia nitrogen and nitrate nitrogen provided by this invention uses a peristaltic pump to extract ammonia nitrogen and nitrate nitrogen standard solutions from the standard solution pool to the detection mechanism for calibration. After calibration, the ammonia nitrogen and nitrate nitrogen standard solutions are discharged into the first waste liquid pool through the first drain valve, ensuring the accuracy and reliability of subsequent water quality testing, thereby improving the accuracy of subsequent water quality analysis. Cleaning liquid is extracted from the washing liquid pool and transferred to the first waste liquid pool, flushing the pipeline route with the cleaning liquid to remove residual liquid and prevent it from causing deviations in the test results. Water samples extracted by the water sample extraction mechanism are then transported to the detection mechanism for testing via a peristaltic pump. After testing, the water sample is discharged into the first waste liquid pool through the first drain valve. After testing, the sample is flushed again with cleaning liquid to ensure the accuracy of subsequent electrode calibration test results.

[0027] 6. The integrated online detection device for ammonia nitrogen and nitrate nitrogen provided by the present invention can effectively remove impurities from water samples by setting up a filter, preventing impurities in the water sample from causing blockage of the inlet and outlet of the water tank, and reducing interference with subsequent detection.

[0028] 7. The integrated online detection device for ammonia nitrogen and nitrate nitrogen provided by the present invention, by setting up two standard solution pools to perform electrode calibration twice, effectively reduces possible errors in the detection process, ensures that the detection results are consistent with the actual values, and thus improves the accuracy and efficiency of detection.

[0029] 8. The integrated online detection device for ammonia nitrogen and nitrate nitrogen provided by the present invention comprises a reference electrode, an ammonium ion selective electrode, and a nitrate ion selective electrode connected to corresponding input points on an electrode chip to form a three-electrode system for detecting the concentration of ammonia nitrogen and nitrate nitrogen in water. The output connection points of the ammonium ion selective electrode, the nitrate ion selective electrode, and the reference electrode on the electrode chip are connected to the corresponding input terminals of the transmitter through their respective signal lines. The potential difference between the ammonium ion selective electrode and the reference electrode, and between the nitrate ion selective electrode and the reference electrode, is measured, and the measurement results are output through the transmitter, thereby facilitating the calibration of the all-solid-state ammonia nitrogen and nitrate nitrogen composite electrode. Attached Figure Description

[0030] A more complete understanding of the invention and its accompanying advantages and features will be more readily apparent from the accompanying drawings and the following detailed description, wherein:

[0031] Figure 1 This is a schematic diagram of the integrated online detection device for ammonia nitrogen and nitrate nitrogen provided in an embodiment of the present invention;

[0032] Figure 2 This is a schematic diagram of the all-solid-state ammonia-nitrogen and nitrate-nitrogen composite electrode in this invention.

[0033] Explanation of reference numerals in the attached diagram: 1. Waste liquid tank No. 2; 2. Drain valve No. 2; 3. Inlet tank; 4. Inlet valve; 5. Inlet pump; 6. Filter; 7. Multi-way valve; 8. Peristaltic pump; 9. Transmitter; 10. All-solid-state ammonia nitrogen and nitrate nitrogen composite electrode; 11. Detection cell; 12. Drain valve No. 1; 13. Waste liquid tank No. 1; 14. Washing solution tank; 15. Standard solution tank No. 2; 16. Standard solution tank No. 1; 17. Signal output line; 18. Electrode housing; 19. Electrode chip; 20. Reference electrode; 21. Ammonium ion selective electrode; 22. Nitrate ion selective electrode. Detailed Implementation

[0034] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings.

[0035] The following examples are merely illustrative of the present invention and are not intended to limit the implementation of the present invention.

[0036] In practice, changes and modifications can be made based on the following description according to requirements, but obvious changes or modifications derived from the spirit of this invention are still within the protection scope of this invention.

[0037] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0038] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for simplifying the description, and do not 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 the invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0039] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" 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.

[0040] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0041] This application discloses an integrated online detection method for ammonia nitrogen and nitrate nitrogen, comprising the following steps:

[0042] S1: Electrode calibration: Ammonia nitrogen and nitrate nitrogen standard solutions are pumped into the detection cell. The ammonia nitrogen and nitrate nitrogen standard solutions are passed through the all-solid ammonia nitrogen and nitrate nitrogen composite electrode 10 to measure the potential difference between the ammonium ion selective electrode and the reference electrode, and between the nitrate ion selective electrode and the reference electrode. The measured potential difference results are output. The all-solid ammonia nitrogen and nitrate nitrogen composite electrode 10 is then calibrated, and the calibrated solution is discharged.

[0043] S2: Flushing: Flushing the detection cell and the pipelines through which the ammonia nitrogen and nitrate nitrogen standard solutions pass in step S1;

[0044] S3: Concentration detection: The water sample to be tested is pumped into the detection pool, and the concentrations of ammonia nitrogen and nitrate nitrogen in the water sample after sedimentation in the detection pool are detected by the all-solid ammonia nitrogen and nitrate nitrogen composite electrode 10. After the detection is completed, the water sample is discharged.

[0045] S4: Flushing: Flushing the detection pool and the pipeline through which the water sample passes in step S2.

[0046] This integrated online detection method for ammonia nitrogen and nitrate nitrogen uses step S1 to perform electrode calibration, ensuring accuracy and reliability in subsequent water quality testing and thus improving the accuracy of subsequent water quality analysis. Step S2 flushes the detection tank and the pipelines through which the ammonia nitrogen and nitrate nitrogen standard solutions passed in step S1, removing any residual liquid in the detection tank and cleaning the pipelines. Step S3 extracts a water sample into the detection tank for testing, using the calibrated all-solid-state ammonia nitrogen and nitrate nitrogen composite electrode 10 to detect the ammonia nitrogen and nitrate nitrogen concentrations. After testing, the water sample is discharged. Finally, the detection tank and the pipelines through which the water sample passed are flushed again to ensure they are in optimal condition before the next use, thereby guaranteeing the accuracy and reliability of the detection results.

[0047] In step S1, two sets of ammonia nitrogen and nitrate nitrogen standard solutions are prepared. The potential difference between the two sets of ammonia nitrogen and nitrate nitrogen standard solutions is measured sequentially using a composite electrode, thus performing two electrode calibrations. This setup effectively ensures the accuracy and reliability of water quality testing, thereby improving the accuracy of subsequent water quality analysis. Through two calibrations, potential errors during the detection process can be effectively reduced, ensuring that the test results match the actual values, thereby improving the accuracy and efficiency of the detection.

[0048] Specifically, after each electrode calibration, the detection cell and the pipelines through which the ammonia nitrogen and nitrate nitrogen standard solutions pass need to be flushed. This setup removes residual liquid from the ammonia nitrogen and nitrate nitrogen standard solutions in the detection cell and the pipelines through which they pass, preventing cross-contamination and ensuring the electrodes are in optimal condition before the next use.

[0049] In step S3, the settled water sample is filtered to remove impurities. The filtered water sample is then pumped into a testing tank for ammonia and nitrate nitrogen concentration analysis. This setup removes suspended solids from the water sample through sedimentation and fixed substances through filtration, thereby improving the accuracy and reliability of the testing.

[0050] like Figure 1 , Figure 2The device shown is an integrated online detection device for ammonia nitrogen and nitrate nitrogen, comprising a multi-port valve 7, a water sample extraction mechanism, a standard solution tank, a washing solution tank, a detection mechanism, and a first waste liquid tank. The multi-port valve 7 has multiple outlets, and a peristaltic pump 8 is connected to the outlet of the multi-port valve 7. A first drain valve is provided between the waste liquid tank and the detection mechanism. The water sample extraction mechanism, the standard solution tank, and the washing solution tank are respectively connected to multiple inlets of the multi-port valve 7, and the detection mechanism is connected to the peristaltic pump 8. The water sample extraction mechanism is suitable for extracting water samples to be tested for ammonia nitrogen and nitrate nitrogen concentrations. The standard solution tank is suitable for holding ammonia nitrogen and nitrate nitrogen standard solutions. The washing solution tank contains cleaning solution. The detection mechanism is suitable for testing the water sample from the water sample extraction mechanism and the standard solution in the standard solution tank. The first waste liquid tank is connected to the end of the detection mechanism furthest from the multi-port valve 7.

[0051] This integrated online ammonia nitrogen and nitrate nitrogen detection device uses a peristaltic pump 8 to extract ammonia nitrogen and nitrate nitrogen standard solutions from the standard solution pool to the detection unit for calibration. After calibration, the ammonia nitrogen and nitrate nitrogen standard solutions are discharged into the waste liquid pool through the first drain valve, ensuring the accuracy and reliability of subsequent water quality tests and thus improving the accuracy of subsequent water quality analysis. Cleaning solution is extracted from the washing solution pool and transferred to the waste liquid pool, flushing the pipeline route to remove any residual liquid and prevent it from affecting the test results. Water samples extracted by the water sample extraction unit are then transported to the detection unit via the peristaltic pump 8 for testing. After testing, the water samples are discharged into the waste liquid pool through the first drain valve. After testing, the system is flushed again with cleaning solution to ensure the accuracy of subsequent electrode calibration test results.

[0052] In this embodiment, the water sample extraction mechanism includes an inlet pump 5 and an inlet tank 3 connected to the outlet of the inlet pump 5. The inlet tank 3 is connected to the first inlet of the multi-way valve 7. A filter 6 is installed between the inlet pump 5 and the inlet tank 3. An inlet valve is connected to the inlet of the inlet pump 5. A second waste liquid tank 1 is connected to the inlet tank 3. A second drain valve 2 is installed between the inlet tank 3 and the second waste liquid tank 1. By installing the filter 6, impurities in the water sample can be effectively removed, preventing impurities in the water sample from blocking the inlet and outlet of the inlet tank 3 and reducing interference with subsequent detection.

[0053] In this embodiment, at least two standard solution pools are provided, including a first standard solution pool and a second standard solution pool, which are respectively connected to the second and third inlets of the multi-port valve 7. By setting up two standard solution pools, electrode calibration is performed twice, effectively reducing possible errors during the detection process, ensuring that the detection results match the actual values, and thus improving the accuracy and efficiency of the detection.

[0054] In this embodiment, the washing solution tank is connected to the fourth inlet of the multi-way valve 7, and the cleaning solution contained in the washing solution tank is purified water.

[0055] In this embodiment, the detection mechanism includes a detection pool and a detection component disposed in the detection pool. The detection component is a solid-state ammonia nitrogen and nitrate nitrogen composite electrode 10. A transmitter 9 is electrically connected to the solid-state ammonia nitrogen and nitrate nitrogen composite electrode 10. The transmitter 9 is adapted to output the detection results of the solid-state ammonia nitrogen and nitrate nitrogen composite electrode 10. A waste liquid pool No. 1 is connected to the detection pool, and a drain valve No. 1 is disposed between the detection pool and the waste liquid pool No. 1.

[0056] In this embodiment, the all-solid-state ammonia-nitrogen and nitrate-nitrogen composite electrode 10 includes an electrode housing, an electrode chip located within the electrode housing, a reference electrode, an ammonium ion selective electrode, and a nitrate ion selective electrode. The reference electrode, ammonium ion selective electrode, and nitrate ion selective electrode are all electrically connected to corresponding input points at one end of the electrode chip. The other end of the electrode chip is electrically connected to the transmitter 9 via three signal lines. Specifically, one end of the electrode chip has three input points spaced apart. The reference electrode, ammonium ion selective electrode, and nitrate ion selective electrode are electrically connected to the three input points of the electrode chip via three signal lines. The other end of the electrode chip has three output points spaced apart, each corresponding to one of the three input points. Each output point has a signal output line, and the end of each signal output line furthest from the electrode chip is connected to the transmitter 9. The reference electrode, ammonium ion selective electrode, and nitrate ion selective electrode are connected to the corresponding input points on the electrode chip to form a three-electrode system for detecting the concentrations of ammonia nitrogen and nitrate nitrogen in water. The output connection points of the ammonium ion selective electrode, nitrate ion selective electrode, and reference electrode on the electrode chip are connected to the corresponding input terminals of the transmitter 9 through their respective signal lines. The potential difference between the ammonium ion selective electrode and the reference electrode, and between the nitrate ion selective electrode and the reference electrode, is measured. The measurement results are output through the transmitter 9, which facilitates the calibration of the all-solid-state ammonia nitrogen and nitrate nitrogen composite electrode 10.

[0057] In this embodiment, a sedimentation tank 3 is set up in the detection section for sedimentation. The sedimented water sample is then passed through a filter 6 to remove minor impurities. The filtered water sample is then pumped into the detection tank 11 through a multi-way valve 7 and a peristaltic pump 8 for testing. The device of this invention first pumps the water sample to be tested into the inlet storage tank through the inlet valve and inlet pump for sedimentation. The sedimented water sample is then passed through a membrane filtration device to remove minor impurities, resulting in a clear filtrate. This ensures that the subsequent all-solid-state ammonia nitrogen and nitrate nitrogen composite electrode is not contaminated, improving the electrode's lifespan and the accuracy of the detection results.

[0058] The ammonia nitrogen and nitrate nitrogen integrated online detection device provided by this invention has a fully solid-state ammonia nitrogen and nitrate nitrogen composite electrode, which is different from the traditional liquid-connected electrode. It is a fully solid-state electrode, and there is no internal reference solution in the electrode structure. Therefore, there is no leakage problem of internal reference solution during use, and the electrode has better stability.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that within the spirit and principles of the present invention, modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein; and these modifications or substitutions do not cause the corresponding technical solutions to depart from the protection scope of the present invention.

Claims

1. An integrated online detection method for ammonia nitrogen and nitrate nitrogen, characterized in that, Includes the following steps: S1: Electrode calibration: Ammonia nitrogen and nitrate nitrogen standard solutions are pumped into the detection cell. The ammonia nitrogen and nitrate nitrogen standard solutions are passed through the all-solid ammonia nitrogen and nitrate nitrogen composite electrode to measure the potential difference between the ammonium ion selective electrode and the reference electrode, and between the nitrate ion selective electrode and the reference electrode. The measured potential difference results are output. The all-solid ammonia nitrogen and nitrate nitrogen composite electrode is then calibrated. Finally, the calibrated solution is discharged. S2: Flushing: Flushing the detection cell and the pipeline through which the ammonia nitrogen and nitrate nitrogen standard solutions pass in step S1; S3: Concentration detection: The water sample to be tested is pumped into the detection tank through a water pump. The concentrations of ammonia nitrogen and nitrate nitrogen in the water sample after sedimentation in the detection tank are detected by a solid-state ammonia nitrogen and nitrate nitrogen composite electrode. After the detection is completed, the water sample is discharged. S4: Flushing: Flushing the detection pool and the pipeline through which the water sample passes in step S2.

2. The integrated online detection method for ammonia nitrogen and nitrate nitrogen according to claim 1, characterized in that, In step S1, two copies of the ammonia nitrogen and nitrate nitrogen standard solutions are prepared. The potential difference between the two copies of the ammonia nitrogen and nitrate nitrogen standard solutions is measured sequentially using the composite electrode to perform two electrode calibrations.

3. The integrated online detection method for ammonia nitrogen and nitrate nitrogen according to claim 2, characterized in that, In step S3, after the water sample to be tested is pumped into the testing pool, it needs to be allowed to settle.

4. The integrated online detection method for ammonia nitrogen and nitrate nitrogen according to claim 3, characterized in that, In step S3, the water sample after settling is filtered to remove impurities using a filtration structure. The filtered water sample is then pumped into a detection tank for testing of ammonia nitrogen and nitrate nitrogen concentrations.

5. An integrated online detection device for ammonia nitrogen and nitrate nitrogen, characterized in that, The system includes a multi-port valve (7), a water sample extraction mechanism, a standard solution tank, a washing solution tank, a detection mechanism, and a first waste liquid tank. The multi-port valve (7) has multiple outlets, and a peristaltic pump (8) is connected to the outlet of the multi-port valve (7). A first drain valve is provided between the waste liquid tank and the detection mechanism. The water sample extraction mechanism, the standard solution tank, and the washing solution tank are respectively connected to multiple inlets of the multi-port valve (7), and the detection mechanism is connected to the peristaltic pump (8). The water sample extraction mechanism is suitable for extracting water samples to be tested for ammonia nitrogen and nitrate nitrogen concentrations. The standard solution tank is suitable for holding ammonia nitrogen and nitrate nitrogen standard solutions. The washing solution tank contains cleaning fluid. The detection mechanism is suitable for testing the water sample from the water sample extraction mechanism and the standard solution in the standard solution tank. The first waste liquid tank is connected to the end of the detection mechanism away from the multi-port valve (7).

6. The integrated online detection device for ammonia nitrogen and nitrate nitrogen according to claim 5, characterized in that, The water sampling mechanism includes an inlet pump (5) and an inlet pool (3) connected to the outlet of the inlet pump (5). The inlet pool (3) is connected to the first inlet of the multi-way valve (7). A filter (6) is provided between the inlet pump (5) and the inlet pool (3). An inlet valve is connected to the inlet of the inlet pump (5). A second waste liquid pool (1) is connected to the inlet pool (3). A second drain valve (2) is provided between the inlet pool (3) and the second waste liquid pool (1).

7. The integrated online detection device for ammonia nitrogen and nitrate nitrogen according to claim 5, characterized in that, At least two standard solution pools are provided, and the two standard solution pools are respectively connected to the second inlet and the third inlet of the multi-way valve (7).

8. The integrated online detection device for ammonia nitrogen and nitrate nitrogen according to claim 5, characterized in that, The washing solution tank is connected to the fourth inlet of the multi-way valve (7), and the cleaning solution contained in the washing solution tank is purified water.

9. The integrated online detection device for ammonia nitrogen and nitrate nitrogen according to claim 7, characterized in that, The detection mechanism includes a detection pool and a detection component disposed in the detection pool. The detection component is a solid-state ammonia nitrogen and nitrate nitrogen composite electrode (10). A transmitter (9) is electrically connected to the solid-state ammonia nitrogen and nitrate nitrogen composite electrode (10). The transmitter (9) is adapted to output the detection result of the solid-state ammonia nitrogen and nitrate nitrogen composite electrode (10). A waste liquid pool No. 1 is connected to the detection pool. A drain valve No. 1 is disposed between the detection pool and the waste liquid pool No.

1.

10. The integrated online detection device for ammonia nitrogen and nitrate nitrogen according to claim 9, characterized in that, The all-solid ammonia-nitrogen and nitrate-nitrogen composite electrode (10) includes an electrode housing, an electrode chip located inside the electrode housing, a reference electrode, an ammonium ion selective electrode, and a nitrate ion selective electrode. The reference electrode, the ammonium ion selective electrode, and the nitrate ion selective electrode are all electrically connected to the corresponding input point at one end of the electrode chip, and the other end of the electrode chip is electrically connected to the transmitter (9) through three signal lines.

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