A kind of on-line detection equipment and detection method of heavy metal pollutants in water

Abstract

The invention discloses an online detection device for heavy metal pollutants in water and a detection method thereof. The detection device comprises a reaction pool, a mechanical clamp, an XRF detection component, a processor and a detection diaphragm; the reaction pool is used to accommodate samples to be detected; the mechanical clamp is used to grab the detection diaphragm and place it in the sample to be detected for enrichment, and after the enrichment reaches a preset time, the detection diaphragm is placed in the detection position of the XRF detection component; the detection diaphragm is divided into a standard sample area and a plurality of detection areas, and heavy metals of known concentrations are preset in the standard sample area; the XRF detection component is used to detect the standard sample area and the detection area and generate XRF spectra respectively; the processor is used to receive and process the XRF spectra to obtain the detection results of heavy metal pollutants in water; the invention quickly performs online identification and analysis of heavy metal pollutants by means of detection diaphragm enrichment-online XRF detection, and a single analysis consumes only one detection diaphragm to obtain the contents of multiple heavy metal pollutants.

Description

Technical Field

[0001] The present invention relates to an on-line detection device for heavy metal pollutants in water and a detection method thereof, belonging to the technical field of environmental detection. Background Art

[0002] Heavy metal pollutants in water pose a huge threat to the environment and human health. Currently, there are three main principles for online heavy metal analyzers in water quality: spectrophotometry, electrochemistry, and atomic fluorescence. Spectrophotometry is widely used and low-cost, but a single instrument can only monitor one heavy metal and requires the use of multiple chemical reagents, resulting in a large amount of waste liquid. Electrochemistry has a very low detection limit and can measure a variety of heavy metals, but the electrodes are complex, difficult to maintain, and the monitoring data is prone to drift. Atomic fluorescence is a heavy metal online analysis technology that has emerged in recent years. It miniaturizes large laboratory experimental equipment and makes it suitable for online analyzers. It has the same measurement principle as laboratory analysis methods and is highly accurate, but the instrument structure is complex, maintenance is difficult, and protective gas is required during operation. Summary of the Invention

[0003] The purpose of the present invention is to overcome the shortcomings of the existing technology and provide an online detection device for heavy metal pollutants in water and a detection method thereof. The device can quickly identify and analyze heavy metal pollutants online by detecting membrane enrichment-online XRF detection. A single analysis consumes only one detection membrane to obtain the content of multiple heavy metal pollutants, and simultaneously realizes instrument calibration and parallel sample measurement without consuming chemical reagents.

[0004] To achieve the above object, the present invention is implemented by adopting the following technical solutions:

[0005] In a first aspect, the present invention provides an online detection device for heavy metal pollutants in water quality, comprising a reaction tank, a mechanical gripper, an XRF detection component, a processor and a detection diaphragm; the reaction tank is used to accommodate a sample to be detected; the mechanical gripper is used to grab the detection diaphragm and place it in the sample to be detected for enrichment, and after the enrichment reaches a preset time, the detection diaphragm is placed in the detection position of the XRF detection component; the detection diaphragm is divided into a standard sample area and multiple detection areas, and a known concentration of heavy metals is preset in the standard sample area; the XRF detection component is used to detect the standard sample area and the detection area and generate XRF spectra respectively; the processor is used to receive and process the XRF spectra to obtain the detection results of heavy metal pollutants in water quality.

[0006] Optionally, the detection membrane includes a high-concentration detection membrane, a low-concentration detection membrane and an ultra-low concentration detection membrane; the high-concentration detection membrane and the low-concentration detection membrane both include a filter membrane, a diffusion layer, an adsorption layer and a support layer laminated in sequence; the diffusion layer thickness of the high-concentration detection membrane is greater than the diffusion layer thickness of the low-concentration detection membrane, and the density of the adsorption material in the adsorption layer of the high-concentration detection membrane is less than the density of the adsorption material in the adsorption layer of the low-concentration detection membrane; the ultra-low concentration detection membrane includes an adsorption layer and a filter membrane laminated to both sides of the adsorption layer, and the density of the adsorption material in the adsorption layer of the ultra-low concentration detection membrane is greater than the density of the adsorption material in the adsorption layer of the low-concentration detection membrane.

[0007] Optionally, the filter membrane is made of PES / PVDF ultrafiltration membrane, the diffusion layer is made of agarose material, the adsorption material in the adsorption layer is made of ion exchange resin, and the support layer is made of PE material.

[0008] Optionally, the XRF detection assembly includes an X-ray tube and a detector, wherein the X-ray tube is used to emit X-rays to bombard the enriched detection membrane, and the detector is used to record the fluorescence generated by the bombardment and generate an XRF spectrum.

[0009] Optionally, a temperature controller is provided at the bottom of the reaction pool, and the temperature controller is used to maintain the sample to be detected in the reaction pool at a preset constant temperature condition.

[0010] Optionally, a stirrer is provided at the bottom of the reaction pool, and the stirrer is used to maintain the sample to be detected in the reaction pool at a preset flow rate condition.

[0011] Optionally, the detection device also includes an injection component, which includes a switching valve and a first peristaltic pump. The switching valve includes a first valve connected to the sample liquid source, a second valve connected to the standard liquid source, a third valve connected to the cleaning liquid source, and a fourth valve connected to the air. The output ends of the first valve, the second valve, the third valve, and the fourth valve are all connected to the input end of the first peristaltic pump through a pipeline, and the output end of the first peristaltic pump is connected to the top of the reaction pool.

[0012] Optionally, the detection device further includes a sample outlet component, the sample outlet component includes a second peristaltic pump, and the input end of the second peristaltic pump is connected to the bottom of the reaction tank through a pipeline.

[0013] Optionally, the detection equipment also includes a diaphragm storage bin, which includes a chamber and a solution with ionic strength filled in the chamber; a slide is provided at the bottom of the chamber, and a plurality of parallel annular skeletons are embedded in the slide, and the detection diaphragms are encapsulated one by one on the inner wall of the annular skeleton, and the outer wall of the annular skeleton is provided with a groove for facilitating grasping by a mechanical gripper.

[0014] Optionally, a baffle is provided at one end of the slide groove and a feeding mechanism is provided at the other end. The feeding structure includes a telescopic rod, a push plate provided at one end of the telescopic rod, and a spring sleeved on the telescopic rod. The other end of the telescopic rod is connected to the inner wall of the chamber, and the spring is located between the push plate and the inner wall of the chamber.

[0015] In a second aspect, the present invention provides a detection method applicable to the above-mentioned detection device, comprising:

[0016] Injecting the sample to be tested into the reaction cell;

[0017] The detection membrane is grasped by a mechanical gripper and placed in the sample to be detected for enrichment;

[0018] After the enrichment reaches the preset time, the detection membrane is placed in the detection position of the XRF detection component;

[0019] The standard sample area and the detection area of ​​the detection membrane are detected by the XRF detection component and XRF spectra are generated respectively;

[0020] Receive and process XRF spectra to obtain the test results of heavy metal pollutants in water.

[0021] Optionally, the receiving and processing of the XRF spectrum to obtain the detection result of heavy metal pollutants in water includes:

[0022] For the standard sample area and each test area, determine the characteristic element peaks and their channel addresses in their XRF spectra;

[0023] By querying the periodic table and comparing the addresses of the characteristic element peaks, the heavy metal category corresponding to each characteristic element peak is determined;

[0024] For each heavy metal category in the standard sample area and each detection area, the detection concentration is calculated based on the characteristic element peak; the correction coefficient δ is calculated based on the detection concentration and known concentration of each heavy metal category in the standard sample area i :

[0025]

[0026] Where C i , C′ i is the known concentration and detected concentration of the i-th heavy metal category in the standard sample area;

[0027] Calculate the corrected concentration C based on the detection concentration of each heavy metal category in each detection area and the correction factor j_i :

[0028] C j_i =C′ j_i ×δ i

[0029] Where C′j_i is the detection concentration of the i-th heavy metal category in the j-th detection area;

[0030] The heavy metal categories and their corrected concentrations in each detection area are output as detection results.

[0031] Optionally, calculating the detection concentration of a characteristic element based on its peak includes:

[0032] Calculate the envelope area G of the half-peak width of the characteristic element peak:

[0033]

[0034] Where a and b are the starting and ending values ​​of the half-peak width area of ​​the characteristic element peak, respectively. i is the amplitude of the i-th track address between the starting point and the end point;

[0035] Calculate the concentration C of heavy metal categories based on the envelope area G:

[0036]

[0037] Where G L , G H For the standard low concentration C L , standard high concentration C H The corresponding standard envelope area is shown below.

[0038] Optionally, the detection method further includes:

[0039] Calculate the detection reliability ΔC based on the corrected concentration of each heavy metal type in each detection area i :

[0040]

[0041] Where C n_i is the corrected concentration of the i-th heavy metal category in the n-th detection zone, where n is the number of detection zones;

[0042] If the detection reliability ΔC i If the value is less than or equal to the preset threshold, the corrected concentration of the i-th heavy metal category in each detection area is reliable as the detection result.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] The present invention provides an online detection device for heavy metal pollutants in water and a detection method thereof. 1) Heavy metal pollutants are quickly identified and analyzed online by detecting membrane enrichment-online XRF detection, and the contents of multiple heavy metal pollutants can be obtained in a single analysis; 2) The detection membrane is a multi-layer membrane with a special configuration that can adsorb multiple heavy metals. The detection membrane is divided into a standard sample area and multiple detection areas. After adsorption and enrichment are completed, XRF is directly used for analysis. In a single analysis, the standard sample area and the detection area are detected in sequence, which can calibrate the XRF and ensure the reliability of the analysis through parallel samples; 3) Only one detection membrane is consumed in a single analysis, without the need to consume other chemical agents, and the enriched solution can be directly discharged without generating environmental pollution risks. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is the structure of an online detection device for heavy metal pollutants in water provided by the first embodiment of the present invention;

[0046] Figure 2 This is a schematic diagram of taking out a test membrane from a membrane storage bin provided in the first embodiment of the present invention;

[0047] Figure 3 This is a structural diagram of the annular skeleton provided in Example 1 of the present invention;

[0048] Figure 4 This is a structural diagram of a diaphragm storage bin provided in Example 1 of the present invention;

[0049] Figure 5 This is a flow chart of a detection method for an online detection device for heavy metal pollutants in water provided by the second embodiment of the present invention;

[0050] Figure 6 This is an example diagram of the XRF spectrum provided in Example 2 of the present invention;

[0051] Figure 7 This is a processed diagram of the XRF spectrum provided in Example 2 of the present invention;

[0052] The following are marked in the figure:

[0053] 1. Reaction cell, 2. Mechanical gripper, 3. XRF detection assembly, 31. X-ray tube, 32. Detector, 4. Detection diaphragm, 5. Temperature controller, 6. Agitator, 7. Switching valve, 8. First peristaltic pump, 9. Second peristaltic pump, 10. Diaphragm storage bin, 101. Chamber, 102. Slide, 103. Annular frame, 104. Groove, 105. Baffle, 106. Telescopic rod, 107. Push plate, 108. Spring. DETAILED DESCRIPTION

[0054] The present invention will be further described below in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention.

[0055] Example 1:

[0056] like Figure 1 As shown, an embodiment of the present invention provides an online detection device for heavy metal pollutants in water quality, including a reaction tank 1, a mechanical clamp 2, an XRF detection component 3, a processor and a detection diaphragm 4; the reaction tank 1 is used to accommodate the sample to be detected; the mechanical clamp 2 is used to grab the detection diaphragm 4 and place it in the sample to be detected for enrichment, and after the enrichment reaches a preset time, the detection diaphragm 4 is placed in the detection position of the XRF detection component 3; the detection diaphragm 4 is divided into a standard sample area and multiple detection areas. In this embodiment, the standard sample area is marked as A, and there are 3 detection areas, respectively marked as B, C, and D, and known concentrations of heavy metals are preset in the standard sample area; the XRF detection component 3 is used to detect the standard sample area and the detection area and generate XRF spectra respectively; the processor is used to receive and process the XRF spectra to obtain the detection results of heavy metal pollutants in water quality.

[0057] (1) The XRF detection assembly 3 includes an X-ray tube 31 and a detector 32. The X-ray tube 31 is used to emit X-rays to bombard the enriched detection membrane 4, and the detector 32 is used to record the fluorescence generated by the bombardment and generate an XRF spectrum.

[0058] (2) To provide a constant temperature and a certain flow rate for the enrichment reaction of the detection membrane 4, a temperature controller 5 is provided at the bottom of the reaction cell 1. The temperature controller 5 is used to maintain the sample to be detected in the reaction cell 1 at a preset constant temperature. A stirrer 6 is provided at the bottom of the reaction cell 1. The stirrer 6 is used to maintain the sample to be detected in the reaction cell 1 at a preset flow rate.

[0059] (3) To facilitate the injection and discharge of samples into the reaction pool 1, the detection device further includes a sample injection assembly, which includes a switching valve 7 and a first peristaltic pump 8. The switching valve 7 includes a first valve connected to a sample liquid source, a second valve connected to a standard liquid source, a third valve connected to a cleaning liquid source, and a fourth valve connected to air. The output ends of the first valve, the second valve, the third valve, and the fourth valve are all connected to the input end of the first peristaltic pump through a pipeline, and the output end of the first peristaltic pump is connected to the top of the reaction pool 1. The detection device further includes a sample output assembly, which includes a second peristaltic pump 9. The input end of the second peristaltic pump 9 is connected to the bottom of the reaction pool 1 through a pipeline.

[0060] The sample to be tested is input into the reaction pool 1 for testing through the first valve, the standard liquid source is input into the reaction pool 1 for calibration through the second valve, the cleaning liquid source is input into the reaction pool 1 through the third valve to clean the reaction pool 1, and air is allowed to enter the reaction pool 1 through the fourth valve to dry the reaction pool 1.

[0061] (4) Figure 2-4 As shown, the detection device also includes a diaphragm storage bin 10, which includes a chamber 101 and a solution with an ionic strength (generally a 0.03M NaCl solution) filled in the chamber 101. A chute 102 is provided at the bottom of the chamber 101, and a plurality of parallel annular frames 103 are embedded in the chute 102. The detection diaphragms 4 are encapsulated one by one on the inner wall of the annular frames 103. The outer wall of the annular frames 103 is provided with grooves 104 to facilitate grasping by the mechanical gripper 2. The mechanical gripper 2 can be a gripper cylinder. A baffle 105 is provided at one end of the chute 102, and a feed mechanism is provided at the other end. The feed mechanism includes a telescopic rod 106, a push plate 107 provided at one end of the telescopic rod 106, and a spring 108 sleeved on the telescopic rod 106. The other end of the telescopic rod 106 is connected to the inner wall of the chamber 101, and the spring 108 is located between the push plate 107 and the inner wall of the chamber 101.

[0062] (5) In order to cope with the detection adaptability of heavy metal pollutants of different concentrations, so that the detection membrane 4 can enrich heavy metal pollutants sufficient for XRF detection in a short time, the composition of the cross-section of the detection membrane will be adjusted accordingly, thereby being divided into a high-concentration detection membrane, a low-concentration detection membrane and an ultra-low concentration detection membrane; the high-concentration detection membrane and the low-concentration detection membrane both include a filter membrane, a diffusion layer, an adsorption layer and a support layer bonded in sequence; the diffusion layer thickness of the high-concentration detection membrane is greater than the diffusion layer thickness of the low-concentration detection membrane, and the density of the adsorption material in the adsorption layer of the high-concentration detection membrane is less than the density of the adsorption material in the adsorption layer of the low-concentration detection membrane; the ultra-low concentration detection membrane includes an adsorption layer and a filter membrane bonded to both sides of the adsorption layer, and the density of the adsorption material in the adsorption layer of the ultra-low concentration detection membrane is greater than the density of the adsorption material in the adsorption layer of the low-concentration detection membrane.

[0063] The thickness of the diffusion layer of the high-concentration detection diaphragm increases and the density of the adsorption material in the adsorption layer decreases, thereby reducing the enrichment efficiency and preventing it from being saturated; the thickness of the diffusion layer of the low-concentration detection diaphragm decreases and the density of the adsorption material in the adsorption layer increases, thereby improving the enrichment efficiency so that it can adsorb sufficient heavy metal pollutants; the ultra-low concentration detection diaphragm omits the diffusion layer and further improves the adsorption efficiency through the double-sided adsorption layer.

[0064] The filter membrane adopts PES / PVDF ultrafiltration membrane, the diffusion layer adopts agarose material, the adsorption material in the adsorption layer adopts ion exchange resin, and the support layer adopts PE material.

[0065] Example 2

[0066] like Figure 5 As shown, the embodiment of the present invention provides a detection method applicable to the above-mentioned detection device (Embodiment 1), comprising the following steps:

[0067] 1. Inject the sample to be tested into reaction cell 1;

[0068] 2. Grab the detection membrane 4 with the mechanical gripper 2 and place it in the sample to be detected for enrichment;

[0069] 3. After the enrichment reaches the preset time, the detection membrane 4 is placed in the detection position of the XRF detection component 3;

[0070] 4. Detecting the standard sample area and the detection area of ​​the detection membrane 4 through the XRF detection component 3 and generating XRF spectra respectively;

[0071] 5. Receive and process XRF spectra to obtain the test results of heavy metal pollutants in water.

[0072] Specifically:

[0073] Receive and process XRF spectra to obtain the test results of heavy metal pollutants in water quality, including:

[0074] 5.1. Determine the peaks and locations of each characteristic element in the XRF spectrum of the standard sample area and each test area;

[0075] 5.2. Determine the heavy metal category corresponding to each characteristic element peak by querying the periodic table and comparing the addresses of each characteristic element peak;

[0076] like Figure 6 As shown in the figure, an example of XRF spectrum is given, and its characteristic element peaks and their channel addresses are determined. The heavy metal categories can be obtained by looking up the channel addresses, such as Cr and Pb in the figure.

[0077] 5.3. Calculate the detection concentration of each heavy metal type in the standard sample area and each detection area based on the characteristic element peaks;

[0078] 5.4. Calculate the correction factor δ based on the detected concentration and known concentration of each heavy metal type in the standard sample area i :

[0079]

[0080] Where C i , C′ i is the known concentration and detected concentration of the i-th heavy metal category in the standard sample area;

[0081] 5.5. Calculate the corrected concentration C based on the detected concentration of each heavy metal category in each detection area and the correction factor j_i:

[0082] C j_i =C′ j_i ×δ i

[0083] Where C′ j_i is the detection concentration of the i-th heavy metal category in the j-th detection area;

[0084] 5.6. Output the heavy metal categories and their corrected concentrations in each test area as test results.

[0085] Specifically:

[0086] like Figure 7 As shown, the detection concentration of the characteristic element is calculated based on its peak, including:

[0087] 5.3.1. Calculate the envelope area G of the half-width (FWHM) region of the characteristic element peak:

[0088]

[0089] Where a and b are the starting and ending values ​​of the half-peak width area of ​​the characteristic element peak, respectively. i is the amplitude of the i-th track address between the starting point and the end point;

[0090] 5.3.2. Calculate the concentration G of heavy metal categories based on the envelope area G:

[0091]

[0092] Where G L , G H For the standard low concentration C L , standard high concentration C H The corresponding standard envelope area is shown below.

[0093] Specifically:

[0094] Detection methods also include:

[0095] Calculate the detection reliability ΔC based on the corrected concentration of each heavy metal type in each detection area i :

[0096]

[0097] Where C n_i is the corrected concentration of the i-th heavy metal category in the n-th detection zone, where n is the number of detection zones;

[0098] If the detection reliability ΔC iIf the value is less than or equal to a preset threshold (generally 5%), the corrected concentration of the i-th heavy metal category in each detection zone is reliable as the detection result.

[0099] Those skilled in the art will appreciate that the embodiments of the present application can be provided as methods, systems, or computer program products. Therefore, the present application can adopt the form of a complete hardware embodiment, a complete software embodiment, or an embodiment in combination with software and hardware. Moreover, the present application can adopt the form of a computer program product implemented on one or more computer-usable storage media (including but not limited to magnetic disk storage, CD-ROM, optical storage, etc.) that contain computer-usable program code.

[0100] The present application is described with reference to the flowcharts and / or block diagrams of the methods, devices (systems), and computer program products according to the embodiments of the present application. It should be understood that each process and / or box in the flowchart and / or block diagram, as well as the combination of the processes and / or boxes in the flowchart and / or block diagram, can be implemented by computer program instructions. These computer program instructions can be provided to a processor of a general-purpose computer, a special-purpose computer, an embedded processor, or other programmable data processing device to produce a machine, so that the instructions executed by the processor of the computer or other programmable data processing device generate instructions for implementing the steps in the flowchart and / or block diagram. Figure 1 a process or multiple processes and / or boxes Figure 1 A device that provides the functions specified in a block or multiple blocks.

[0101] These computer program instructions may also be stored in a computer readable memory that can direct a computer or other programmable data processing device to work in a specific manner, so that the instructions stored in the computer readable memory produce an article of manufacture comprising an instruction device, which implements the process Figure 1 a process or multiple processes and / or boxes Figure 1 The function specified in one or more boxes.

[0102] These computer program instructions can also be loaded onto a computer or other programmable data processing device so that a series of operational steps are executed on the computer or other programmable device to produce a computer-implemented process, thereby providing the instructions executed on the computer or other programmable device for implementing the process. Figure 1 a process or multiple processes and / or boxes Figure 1 A step that specifies a function in one or more boxes.

[0103] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An online detection device for heavy metal pollutants in water, characterized in that: It includes a reaction pool, a mechanical gripper, an XRF detection component, a processor and a detection membrane; the reaction pool is used to accommodate the sample to be detected; the mechanical gripper is used to grab the detection membrane and place it in the sample to be detected for enrichment, and after the enrichment reaches a preset time, the detection membrane is placed in the detection position of the XRF detection component; the detection membrane is divided into a standard sample area and a plurality of detection areas, and a known concentration of heavy metals is preset in the standard sample area; the XRF detection component is used to detect the standard sample area and the detection area and generate XRF spectra respectively; the processor is used to receive and process the XRF spectrum to obtain the detection results of heavy metal pollutants in water quality; The detection membrane includes a high-concentration detection membrane, a low-concentration detection membrane and an ultra-low concentration detection membrane; the high-concentration detection membrane and the low-concentration detection membrane both include a filter membrane, a diffusion layer, an adsorption layer and a support layer that are sequentially bonded; the diffusion layer thickness of the high-concentration detection membrane is greater than the diffusion layer thickness of the low-concentration detection membrane, and the density of the adsorption material in the adsorption layer of the high-concentration detection membrane is less than the density of the adsorption material in the adsorption layer of the low-concentration detection membrane; the ultra-low concentration detection membrane includes an adsorption layer and a filter membrane bonded to both sides of the adsorption layer, and the density of the adsorption material in the adsorption layer of the ultra-low concentration detection membrane is greater than the density of the adsorption material in the adsorption layer of the low-concentration detection membrane.

2. The on-line detection device for heavy metal pollutants in water according to claim 1, characterized in that: The filter membrane is made of PES / PVDF ultrafiltration membrane, the diffusion layer is made of agarose material, the adsorption material in the adsorption layer is ion exchange resin, and the support layer is made of PE material.

3. The on-line detection device for heavy metal pollutants in water according to claim 1 is characterized in that: The XRF detection assembly includes an X-ray tube and a detector. The X-ray tube is used to emit X-rays to bombard the enriched detection membrane, and the detector is used to record the fluorescence generated by the bombardment and generate an XRF spectrum.

4. The on-line detection device for heavy metal pollutants in water according to claim 1, characterized in that: A temperature controller is provided at the bottom of the reaction pool, and the temperature controller is used to maintain the sample to be detected in the reaction pool at a preset constant temperature condition.

5. The on-line detection device for heavy metal pollutants in water according to claim 1, characterized in that: A stirrer is provided at the bottom of the reaction pool, and the stirrer is used to maintain the sample to be detected in the reaction pool at a preset flow rate condition.

6. The on-line detection device for heavy metal pollutants in water according to claim 1, characterized in that: The detection device also includes an injection component, which includes a switching valve and a first peristaltic pump. The switching valve includes a first valve connected to a sample liquid source, a second valve connected to a standard liquid source, a third valve connected to a cleaning liquid source, and a fourth valve connected to air. The output ends of the first valve, the second valve, the third valve, and the fourth valve are all connected to the input end of the first peristaltic pump through a pipeline, and the output end of the first peristaltic pump is connected to the top of the reaction pool.

7. The on-line detection device for heavy metal pollutants in water according to claim 1, characterized in that: The detection device also includes a sample output component, which includes a second peristaltic pump, and an input end of the second peristaltic pump is connected to the bottom of the reaction pool through a pipeline.

8. The on-line detection device for heavy metal pollutants in water according to claim 1, characterized in that: The detection equipment also includes a diaphragm storage bin, which includes a chamber and a solution with ionic strength filled in the chamber; a slide groove is provided at the bottom of the chamber, and a plurality of parallel annular skeletons are embedded in the slide groove. The detection diaphragms are encapsulated one by one on the inner wall of the annular skeleton, and the outer wall of the annular skeleton is provided with grooves for facilitating grasping by a mechanical gripper.

9. The on-line detection device for heavy metal pollutants in water according to claim 8, characterized in that: A baffle is provided at one end of the slide groove, and a feeding mechanism is provided at the other end. The feeding structure includes a telescopic rod, a push plate provided at one end of the telescopic rod, and a spring sleeved on the telescopic rod. The other end of the telescopic rod is connected to the inner wall of the chamber, and the spring is located between the push plate and the inner wall of the chamber.

10. A detection method applicable to the detection device according to any one of claims 1 to 9, characterized in that: include: Injecting the sample to be tested into the reaction pool; Grasp the detection membrane by a mechanical gripper and place it in the sample to be detected for enrichment; After the enrichment reaches the preset time, the detection membrane is placed in the detection position of the XRF detection component; The standard sample area and the detection area of ​​the detection membrane are detected by the XRF detection component and XRF spectra are generated respectively; Receive and process XRF spectra to obtain the test results of heavy metal pollutants in water quality.

11. The detection method of the detection device according to claim 10, characterized in that: The receiving and processing of the XRF spectrum to obtain the detection results of heavy metal pollutants in water quality includes: For the standard sample area and each detection area, determine the peaks of each characteristic element and their addresses in the XRF spectrum; Determine the heavy metal category corresponding to each characteristic element peak by querying the periodic table and comparing the addresses of each characteristic element peak; For each heavy metal type in the standard sample area and each detection area, the detection concentration is calculated based on the characteristic element peak; Calculate the correction factor δ based on the detected concentration and known concentration of each heavy metal category in the standard sample area i : In the formula, C i , C i ′ is the known concentration and detection concentration of the i-th heavy metal category in the standard sample area; Calculate the corrected concentration C based on the detected concentration of each heavy metal category in each detection area and the correction factor j _i: C j_i =C′ j_i ×δ i In the formula, C j ′_i is the detection concentration of the i-th heavy metal category in the j-th detection area; The heavy metal categories and their corrected concentrations in each detection area are output as detection results.

12. The detection method of the detection device according to claim 11, characterized in that: The calculation of the detection concentration based on the characteristic element peak comprises: Calculate the envelope area G of the half-peak width of the characteristic element peak: Where a and b are the starting and ending values ​​of the half-peak width area of ​​the characteristic element peak, respectively. i is the amplitude of the ith track address between the starting point and the end point of the track address; Calculate the concentration C of heavy metal categories based on the envelope area G: In the formula, G L , G H For the standard low concentration C L , Standard high concentration C H The corresponding standard envelope area is shown below.

13. The detection method of the detection device according to claim 11, characterized in that: The detection method further comprises: Calculate the detection reliability ΔC based on the corrected concentration of each heavy metal category in each detection area i : In the formula, C n_i is the corrected concentration of the ith heavy metal category in the nth detection zone, where n is the number of detection zones; If the detection reliability ΔC i If it is less than or equal to the preset threshold, the corrected concentration of the i-th heavy metal category in each detection area is reliable as the detection result.

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