Water element measurement device and method

Abstract

The present application relates to spectral technology, and specifically provides a water element measuring device and method, the measuring device comprising an enrichment unit and an analysis unit, the enrichment unit comprising a filter membrane and a first driving unit for driving the filter membrane to move; a pretreatment unit for treating a collected water sample and delivering the water sample to a sample chamber; a quantification unit for quantifying the pretreated water sample and delivering the water sample to an atomization unit; a heating unit for making the atomized sample into solid particles; a first pipeline and a second pipeline are respectively arranged on the upper side and the lower side of the filter membrane, and a pump is connected to the output end of the second pipeline; a second driving unit is used for driving the first pipeline and / or the second pipeline, so that the first pipeline and the second pipeline clamp or release the filter membrane; a cleaning unit is used for providing a cleaning liquid, and the cleaning liquid after cleaning the pipeline is delivered to the atomization unit. The present application has the advantages of accurate measurement, etc.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of spectroscopy, and in particular to a device and method for measuring elements in water. BACKGROUND

[0002] Currently, the detection technology of heavy metals in water is mostly in the laboratory stage. The most commonly used methods are atomic absorption spectrophotometry (AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), chemical colorimetry and anodic stripping voltammetry (ASV) and other methods. The disadvantages of these methods are:

[0003] 1. AAS, ICP-AES, ICP-MS and other methods all need to be carried out in the laboratory, and the sample preparation and detection period is long, the detection result is lagging behind, and the equipment cost and operation and maintenance cost are high. The requirements for the operating personnel are also very high. Therefore, the above technologies are not suitable for rapid detection and online monitoring of heavy metal pollutants in water.

[0004] 2. The principle of chemical colorimetry is simple, and it does not require special equipment, and a general spectrophotometer can meet the needs, so it is more common in online monitoring of water quality heavy metals. However, this method has many disadvantages, such as low sensitivity, poor detection limit, weak selectivity of element detection, easy interference from coexisting ions, sometimes the color reagent has response to many metal ions, cannot detect multiple heavy metals at the same time, and the chemical reagent may cause secondary pollution, which cannot meet the detection requirements of low concentration groundwater and complex water samples.

[0005] 3. ASV method can quickly detect very low concentration of metals in the sample, has good sensitivity and selectivity, and the detection limit can reach ug / L, and can simultaneously realize multiple heavy metal elements such as lead, cadmium, copper and the like. However, the detection mechanism of this method is complex, the method is sensitive, and the repeatability is worse than that of photometry. The instrument maintenance requirement is high, especially the electrode polishing maintenance, which requires that the maintenance personnel need to undergo professional training and long-term practice to master.

[0006] X-ray fluorescence spectrometry (XRF) is a non-destructive analysis technique, and energy dispersive XRF technology can simultaneously measure dozens of elements. However, XRF method cannot directly measure water quality samples, and needs to enrich the metal elements in the water quality sample on the filter membrane for XRF measurement.

[0007] The currently commonly used membrane filtration retention and drying technology has selective limitations on the types of elements, cannot measure the total composition of heavy metal elements, and also has problems such as uneven distribution of element concentration. Direct drying of the filter membrane adsorbed with the water quality sample, and then performing XRF element analysis, can measure the total composition of elements, but the water quality sample adsorbed by the filter membrane is limited and also has the problem of uneven concentration. SUMMARY

[0008] To solve the above problems in the prior art, the application provides a water element measuring device.

[0009] The application aims to realize the following technical solutions.

[0010] The water element measuring device comprises an enrichment unit and an analysis unit, the enrichment unit comprises a filter membrane and a first driving unit, and the first driving unit is used for driving the filter membrane to move; the measuring device further comprises:

[0011] a pretreatment unit and a sample chamber, the pretreatment unit is used for treating the collected water sample and delivering the water sample to the sample chamber;

[0012] a quantification unit, the quantification unit is used for quantifying the pretreated water sample and delivering the water sample to an atomization unit;

[0013] an atomization unit and a heating unit, the heating unit is used for changing the atomized sample into solid particles;

[0014] a first pipeline, a second pipeline and a pump, the first pipeline and the second pipeline are arranged on the upper side and the lower side of the filter membrane respectively, and the pump is connected to the output end of the second pipeline;

[0015] a second driving unit, the second driving unit is used for driving the first pipeline and / or the second pipeline, so that the first pipeline and the second pipeline clamp or release the filter membrane;

[0016] a cleaning unit, the cleaning unit is used for providing cleaning liquid, and the cleaning liquid after cleaning the pipeline is delivered to the atomization unit.

[0017] The application also aims to provide a water element measuring method, and the application aims to realize the following technical solutions.

[0018] The water element measuring method comprises the following steps:

[0019] A1. The pretreated water sample enters the sample chamber and is delivered to the atomization unit after quantification;

[0020] A2. The atomized water sample is heated to change into solid particles and enters the enrichment unit along with the airflow;

[0021] A3. The gas passes through the first pipeline, the filter membrane and the second pipeline, and the solid particles in the gas are intercepted and enriched by the filter membrane clamped by the first pipeline and the second pipeline;

[0022] A4. The first pipeline and the second pipeline release the filter membrane, and the filter membrane enriched with the solid particles moves to the analysis unit;

[0023] A5. The cleaning liquid provided by the cleaning unit is used to clean the pipeline, and then is transported to the atomization unit and enters step A2;

[0024] A6. The analysis unit outputs the element content in the water sample according to the detection results of the sample and the cleaning liquid.

[0025] Compared with the prior art, the present application has the beneficial effects that:

[0026] The present application provides a method and device for realizing rapid detection and online monitoring of inorganic elements in water quality samples such as groundwater and river water, based on water sample atomization, drying, enrichment and other pretreatment technologies, combined with X-ray fluorescence (XRF) technology.

[0027] The atomization and drying technology can change the water quality sample into solid particles, which are enriched on the air filtration membrane in the form of aerosol with clean background gas, solving the problems of incomplete adsorption caused by the selectivity of water quality filter membrane adsorption on different elements, the unevenness of liquid sample drying directly on the filter membrane, and the limitation of the total amount of water quality sample directly adsorbed by the filter membrane.

[0028] The present application has the characteristics of simple operation and timely measurement, and can realize on-site rapid detection and online monitoring of heavy metal elements in water, solving the problems of complex operation, high cost and time lag of laboratory detection technology. At the same time, the XRF technology also has the advantages of high sensitivity, low detection limit, large linear range, and can simultaneously measure dozens of elements, including special elements such as Te and Tl.

[0029] Compared with colorimetric method and electrochemical method, the present application has significant advantages in sensitivity, repeatability and measured element types, and can meet the requirements of the latest measurement standards.

[0030] The present application can adjust the measured solution dosage, atomization ratio, air pumping flow, enrichment time and XRF excitation time according to the metal element concentration range in groundwater, to obtain different measurement ranges and detection limit levels. BRIEF DESCRIPTION OF DRAWINGS

[0031] The disclosure of the present application will become more apparent with reference to the accompanying drawings. It is easy for those skilled in the art to understand that these drawings are only used to illustrate the technical solutions of the present application, and are not intended to limit the protection scope of the present application. In the drawings:

[0032] Figure 1 is a structural schematic diagram of an analyzer according to an embodiment of the present application;

[0033] Figure 2 is a structural schematic diagram of an analyzer according to embodiment 3 of the present application;

[0034] Figure 3is a structural schematic diagram of an analyzer according to Embodiment 4 of the present application.

[0035] In the drawings, 11 - pretreatment unit, 12 - ultrapure water container, 21 - sample chamber, 31 - first quantitative unit, 32 - first flow meter, 33 - second flow meter, 34 - second quantitative unit, 35 - third flow meter, 41 - atomization unit, 411 - atomizer, 412 - atomization cavity, 51 - heating unit, 61 - enrichment unit, 611 - first pipeline, 612 - second pipeline, 613 - third pump, 614 - filter membrane, 6141 - sampling spot, 71 - analysis unit, 72 - second pump, 73 - first pump, 81 - waste liquid container, 91 - first switching module, 92 - second switching module, 93 - third switching module. DETAILED DESCRIPTION

[0036] Figures 1-3 The optional embodiments of the present application described in the following description and illustrated in the accompanying drawings are presented by way of example only. The optional embodiments are not intended to limit the scope of the application to these embodiments. Numerous variations and modifications will become apparent to those skilled in the art once the optional embodiments of the present application have been described. The optional embodiments of the present application as described are meant to be illustrative only and are not intended to limit the scope of the present application. As such, the present application is not limited to the optional embodiments described herein which are presented for illustrative purposes only. The scope of the present application is limited only by the claims and the equivalents thereof.

[0037] Embodiment 1.

[0038] The water element measuring device of the embodiments of the present application, as shown in Figure 1 includes the following units.

[0039] The enrichment unit 61 includes a filter membrane 614 and a first driving unit for driving the filter membrane 614 to move horizontally. The analysis unit 71 is an XRF analyzer.

[0040] The pretreatment unit 11 is used to process the collected water sample and deliver to the sample chamber 21.

[0041] The first quantitative unit 31 is used to quantitatively process the pretreated water sample and deliver to the atomization unit 41.

[0042] The atomization unit 41 and the heating unit 51 are used to make the atomized sample into solid particles.

[0043] a first pipe 611 and a second pipe 612 disposed on the upper side and lower side of the filter membrane 614, respectively, and a third pump 613 connected to the output end of the second pipe for extracting the atomized gas so that the gas passes through the first pipe 611, the filter membrane 614 and the second pipe 612.

[0044] a second driving unit for driving the first pipe 611 and / or the second pipe 612 so that the first pipe 611 and the second pipe 612 clamp or release the filter membrane.

[0045] a cleaning unit for providing cleaning liquid, the cleaning liquid after cleaning the pipe being delivered to the atomizing unit 41.

[0046] In order to obtain accurate detection results, further, the analysis unit 71 outputs the concentration C ij of the i-th element in the j-th detection cycle as:

[0047] .

[0048] N is the number of detection cycles of the analysis unit 71 between two adjacent cleanings, j = 1, 2, ··· N, X ij is the surface density of the i-th element on the filter membrane 614 in the j-th detection cycle, V 1j is the quantitative volume of the water sample output by the first quantitative unit 31 in the j-th detection cycle, X i ˊ is the surface density of the i-th element on the filter membrane 614 after cleaning the pipe, and S is the area of the sampling spot 6141 on the filter membrane 614.

[0049] In order to make the measurement more representative, further, as Figure 2 shown, the measuring device further comprises a waste liquid container 81 connected to the sample chamber 21 and the pipe, and a delivery unit for delivering the water sample in the sample chamber 21 to the waste liquid container 81 when the filter membrane 614 moves, and sending the water sample accumulated in the waste liquid container 81 into the pipe.

[0050] The average concentration C i ˊ of the i-th element in M detection cycles.

[0051] .

[0052] M is the number of detection cycles of the analysis unit 71 from the beginning of the water sample entering to the sending of the atomizing unit 41, which is an integer multiple of N, C ikis the concentration of the i-th element in the k-th detection cycle, k = 1, 2, ···, M, V 1k is the volume of water sample entering the atomization unit 41 in the k-th detection cycle, V2 is the cumulative volume of the waste liquid container 81 in M detection cycles; Y i is the surface density of the i-th element on the filter membrane 614 during the waste liquid measurement, Y i ˊ is the surface density of the i-th element on the filter membrane 614 after the cleaning of the waste liquid container and pipeline.

[0053] In order to realize continuous detection, further, as shown in Figure 3 the measuring device further comprises:

[0054] A first switching module 91 is used to selectively connect the outlet of the pretreatment unit 11 to the two sample chambers 21 in parallel.

[0055] A second switching module 92 is used to selectively connect the atomization unit 41 to the two sample chambers 21 in parallel.

[0056] In order to improve the heating effect, further, the gas mixed after being heated by the heating unit 51 is used to atomize the water sample.

[0057] The water element measurement method of the embodiment of the present application comprises the following steps:

[0058] A1. The pretreated water sample enters the sample chamber 21 and is quantitatively delivered to the atomization unit 41.

[0059] A2. The atomized water sample is heated to become solid particles, which enter the enrichment unit 61 with the gas flow.

[0060] A3. The gas passes through the first pipeline 611, the filter membrane 614 and the second pipeline 612, and the solid particles in the gas are intercepted and enriched by the filter membrane 614 clamped by the first pipeline 611 and the second pipeline 612.

[0061] A4. The first pipeline 611 and the second pipeline 612 release the filter membrane 614, and the filter membrane 614 enriched with solid particles moves to the analysis unit 71.

[0062] A5. After several detection cycles according to the above scheme, the cleaning liquid provided by the cleaning unit is used to clean the pipeline, and then is delivered to the atomization unit 41 to enter step A2, and the analysis unit 71 detects the elements in the cleaning liquid.

[0063] A6. The analysis unit 71 outputs the element content in the water sample according to the detection results of the sample and the cleaning liquid.

[0064] To obtain accurate detection results, further, the analysis unit 71 outputs the concentration C of the i-th element in the j-th detection cycle ij is:

[0065] .

[0066] N is the number of detection cycles of the analysis unit 71 between adjacent two cleanings, j=1,2···N, X ij is the surface density of the i-th element on the filter membrane 614 in the j-th detection cycle, V 1j is the water sample quantitative volume output by the first quantitative unit 31 in the j-th detection cycle, X i ˊ is the surface density of the i-th element on the filter membrane 614 after cleaning the pipeline, and S is the area of the sampling spot 6141 on the filter membrane 614.

[0067] When measuring the water quality sample of river water, groundwater, sewage and the like on site, the sample chamber 21 is fed with sample from the first pump 73 on one side, and the sample is sent into the atomization unit 41 and the enrichment unit 61 in real time through the second pump 72 on the other side. When the filter membrane 614 is translated, the atomization needs to be stopped. After the translation of the filter membrane 614 is completed, the structure is compressed to the filter membrane 614, so that the sample atomization can continue. During this period, if the first pump 73 stops feeding the sample, the water quality sample in this period will not be measured in real time, which causes the problem of poor sampling representation. Further, as shown in Figure 2 , a waste liquid container 81 is introduced. When the filter membrane 614 is moved in step A4, the water sample entering the waste liquid container 81; the measurement method further comprises the following steps:

[0068] A7. After M detection cycles, the water sample accumulated in the waste liquid container 81 is sent into the atomization unit 41 through the pipeline, and step A2 is entered to execute steps A2-A6 to detect the waste liquid, and then the waste liquid container 81 and the pipeline are cleaned and the cleaning liquid is detected.

[0069] The average concentration C of the i-th element in M detection cycles i ˊ ;

[0070] ;

[0071] M is the number of detection cycles of the analysis unit 71 from the start of the water sample into the waste liquid container 81 to the water sample into the atomization unit 41, which is an integer multiple of N, C ik is the concentration of the i-th element in the k-th detection cycle, k=1,2···M, V 1k is the volume of the water sample into the atomization unit 41 in the k-th detection cycle, and V2 is the cumulative volume of the waste liquid container 81 in M detection cycles; Y i is the surface density of the i-th element on the filter membrane 614 when measuring the waste liquid, Yi ˊ is the areal density of the i-th element on the filter membrane 614 after the cleaning of the waste liquid container 81 and the pipeline after the measurement of the waste liquid.

[0072] Example 2.

[0073] Application example of the water element measurement device and method according to the embodiment 1 of the present application.

[0074] In this application example, as shown in Figure 1 The pre-treatment unit 11 adopts a filter, the filter, the first pump 73, the sample chamber 21, the second pump 72 and the first quantitative unit 31 (adopting a flow meter) are sequentially arranged on the pipeline. The cleaning unit includes an ultrapure water container 12 and a second quantitative unit 34 (adopting a flow meter), the outlet of the second quantitative unit 34 is communicated with a third switching module 93 (adopting a two-position three-way electromagnetic valve), the third switching module 93 is arranged on the pipeline between the first pump 73 and the sample chamber 21, when switching, the sample chamber 21 selectively receives the water sample and the cleaning liquid (ultrapure water).

[0075] The atomization unit 41 includes an atomizer 411 and an atomization cavity 412. The cleaning gas is divided into two paths, one path enters the atomizer 411 after passing through the first flow meter 32, and the other path enters the atomization cavity 412 after sequentially passing through the second flow meter 33 and the heating unit 51, thereby heating the atomized water sample to generate solid particles.

[0076] The enrichment unit 61 includes a first pipeline 611, a filter membrane 614, a second pipeline 612, a third flow meter 35 and a third pump 613, a first driving unit is used to drive the filter membrane 614 to translate, and a second driving unit is used to drive the first pipeline 611 to move vertically up and down, so that the first pipeline 611 and the second pipeline 612 clamp or release the filter membrane 614. By adjusting the working parameters of the third pump 613, the flow rate output by the third flow meter 35 is equal to the sum of the flow rates output by the first flow meter 32 and the second flow meter 33.

[0077] The analysis unit 71 adopts an XRF analyzer and is arranged on the upper side of the filter membrane 614.

[0078] The water element analysis method based on the measurement device of the present embodiment includes the following steps:

[0079] A1. The third switching module 93 is switched to the sampling mode.

[0080] Under the suction of the first pump 73, the water sample passing through the filter enters the sample chamber 21.

[0081] Under the suction of the second pump 72, the water sample in the sample chamber 21 is quantitatively delivered to the atomization unit 41 after passing through the first quantitative unit 31.

[0082] A2. Clean gas enters the atomizer 411, and the water sample is atomized; at the same time, the clean gas is heated by the heating unit 51, and then enters the atomization chamber 412, where the atomized water sample is heated and turns into solid particles.

[0083] A3. Under the suction of the third pump 613, the gas in the atomizing chamber 412 passes through the first pipe 611, the filter membrane 614 and the second pipe 612. The solid particles in the gas are intercepted and enriched by the filter membrane 614 (clamped by the first pipe 611 and the second pipe 612).

[0084] A4. The second pump 72 and the third pump 613 stop working, the second drive unit drives the first pipe 611 to move upward, the first pipe 611 and the second pipe 612 release the filter membrane 614, the first drive unit drives the filter membrane 614 enriched with solid particles to move to the analysis unit 71, and the analysis unit 71 outputs the areal density of the elements in the sampling spot 6141 on the filter membrane 614.

[0085] A5. After running N detection cycles according to the above scheme, the third switching module 93 switches, and the ultrapure water passes through the second quantitative unit 34, the third switching module 93, the sample chamber 21, the second pump 72 and the first quantitative unit 31 in sequence, and then enters the atomization unit 41. Steps A2-A4 are executed, and the analysis unit 71 detects the elements in the cleaning solution to obtain the areal density of the elements in the sampling spot 6141 on the filter membrane 614.

[0086] A6. Analytical unit 71 outputs the elemental content in the water sample based on the detection results of the sample and cleaning solution, specifically:

[0087] The concentration C of the i-th element in the j-th detection period ij (Unit: mg / L) is:

[0088] .

[0089] N is the number of detection cycles of analysis unit 71 between two adjacent cleaning cycles, j=1,2...N, X ij It is the areal density (unit: mg / cm³) of the i-th element on the filter membrane 614 during the j-th detection cycle. 2 V 1j The quantitative volume (in L) of the water sample output by the first quantitative unit 31 in the j-th detection cycle, X i ˊ It is the areal density (unit: mg / cm³) of the i-th element on the filter membrane 614 after cleaning the pipeline. 2 S is the area of ​​sampling spot 6141 on filter membrane 614 (unit: cm²). 2 ).

[0090] The specific parameters for this embodiment are as follows:

[0091] N=10, S=1cm 2 The element is Cd.

[0092] Other data are shown in Table 1.

[0093] Table 1 shows various detection data and element concentrations.

[0094] .

[0095] Example 3.

[0096] The application example of the water element measuring device and method according to Example 1 of the present application is different from Example 2 in that:

[0097] As shown in Figure 2 , a waste liquid container 81 and a conveying unit are further provided. The waste liquid container 81 is connected to the cleaning unit and the pipeline (connected to the sample chamber 21) through a two-position three-way electromagnetic valve. The conveying unit is used to convey the water sample in the sample chamber 21 to the waste liquid container 81 when the filter membrane 614 moves, and to send the accumulated water sample in the waste liquid container 81 into the pipeline.

[0098] The water element analysis method based on the measuring device of the present embodiment includes the following steps:

[0099] A1. The third switching module 93 is switched to the sampling mode.

[0100] Under the suction of the first pump 73, the water sample passing through the filter enters the sample chamber 21.

[0101] Under the suction of the second pump 72, the water sample in the sample chamber 21 is quantitatively conveyed to the atomization unit 41 after passing through the first quantitative unit 31.

[0102] A2. The cleaning gas enters the atomizer 411, and the water sample is atomized. At the same time, the cleaning gas is heated by the heating unit 51, and then enters the atomization cavity 412, and the atomized water sample is heated to become solid particles.

[0103] A3. Under the suction of the third pump 613, the gas in the atomization cavity 412 passes through the first pipeline 611, the filter membrane 614 and the second pipeline 612, and the solid particles in the gas are intercepted and enriched by the filter membrane 614 (clamped by the first pipeline 611 and the second pipeline 612).

[0104] A4. The second pump 72 and the third pump 613 stop working, the second driving unit drives the first pipe 611 to move upward, the first pipe 611 and the second pipe 612 loosen the filter membrane 614, the first driving unit drives the filter membrane 614 enriched with solid particles to move to the analysis unit 71, and the analysis unit 71 outputs the area density of the element in the sampling spot 6141 on the filter membrane 614. The water sample in the sample chamber 21 enters the waste liquid container 81.

[0105] A5. After the N detection cycles are performed according to the above scheme, the third switching module 93 is switched, the ultrapure water sequentially passes through the second quantitative unit 34, the third switching module 93, the sample chamber 21, the second pump 72 and the first quantitative unit 31, and then enters the atomization unit 41, steps A2-A4 are performed, and the analysis unit 71 detects the element in the cleaning liquid to obtain the area density of the element in the sampling spot 6141 on the filter membrane 614.

[0106] A6. The analysis unit 71 outputs the element content in the water sample according to the detection results of the sample and the cleaning liquid, and specifically:

[0107] The concentration C ij (unit: mg / L) of the i-th element in the j-th detection cycle is:

[0108] .

[0109] N is the number of detection cycles of the analysis unit 71 between adjacent two cleanings, j=1,2···N, X ij is the area density (unit: mg / cm 2 ) of the i-th element on the filter membrane 614 in the j-th detection cycle, V 1j is the water sample quantitative volume (unit: L) output by the first quantitative unit 31 in the j-th detection cycle, X i ˊ is the area density (unit: mg / cm 2 ) of the i-th element on the filter membrane 614 after cleaning the pipeline, and S is the area (unit: cm 2 ) of the sampling spot 6141 on the filter membrane 614.

[0110] A7. After M detection cycles, the water sample accumulated in the waste liquid container 81 enters the pipeline and enters the atomization unit 41, enters step A2, according to steps A2-A4, the analysis unit 71 outputs the area density Y i of the i-th element in the sampling spot 6141 on the filter membrane 614 of the waste liquid.

[0111] According to step A5, the ultrapure water enters the waste liquid container 81 and the pipeline, and then is atomized, heated, enriched and analyzed, and the analysis unit 71 outputs the area density Y i of the i-th element in the sampling spot 6141 on the filter membrane 614 of the waste liquid.ˊ .

[0112] average concentration of the i-th element in the M detection periods i ˊ (unit: mg / L);

[0113] ;

[0114] M is the number of detection periods of the analysis unit 71 from the start of the water sample entering the waste liquid container 81 to the delivery to the atomization unit 41, and is an integer multiple of N, C ik is the concentration of the i-th element in the k-th detection period, k = 1, 2, ···, M, V 1k is the volume of the water sample entering the atomization unit 41 in the k-th detection period, and V2 is the cumulative volume of the water sample in the waste liquid container 81 in the M detection periods.

[0115] The specific parameters of this embodiment are as follows:

[0116] N = 10, M = 20, S = 1 cm 2 , V2 = 0.081 L, and the element is Cd.

[0117] Other data are shown in Table 2 (V 1j and V 1k , C ij and C ik only differ in the period number, and are actually the same quantity).

[0118] Table 2 shows various detection data and element concentrations.

[0119] .

[0120] Using the above data, the average concentration of the element Cd in the first k = 1-20 is 0.016776 mg / L, and the average concentration of the element Cd in the second k = 1-20 is 0.016655 mg / L.

[0121] In this embodiment, when the first j = 1, k = 1, the water sample in the sample chamber 21 is collected in the waste liquid container 81, when the second j = 10, k = 10, after the water sample detection is completed, the sample chamber 21 and the pipeline are cleaned and detected, until the third j = 10, k = 20, after the water sample detection is completed, the sample chamber 21 and the pipeline are cleaned and detected, and then the waste liquid collected in the waste liquid container 81 is delivered to the downstream for detection, and finally the waste liquid container 81 and the pipeline are cleaned and detected. That is, 10 times of water sample detection, cleaning (sample chamber 21 and pipeline) and detection, 10 times of water sample detection, cleaning (sample chamber 21 and pipeline) and detection, waste liquid detection, cleaning (waste liquid container 81 and pipeline) and detection are experienced.

[0122] Embodiment 4.

[0123] According to the application example of the water element measuring device and method of embodiment 1, different from embodiment 2 is that:

[0124] As shown in Figure 3 The first switching module 91 is used for selectively connecting the outlet of the pretreatment unit 11 with the two sample chambers 21, and the second switching module 92 is used for selectively connecting the atomization unit 41 with the two sample chambers 21.

[0125] In work, when one of the sample chambers 21 receives a water sample, the water sample in the other sample chamber 21 is sent downstream for atomization, enrichment and analysis, realizing continuous measurement.

Claims

1. A device for measuring elements in water, comprising an enrichment unit and an analysis unit, the enrichment unit comprising a filter membrane and a first drive unit for driving the filter membrane to move; characterized in that, The measuring device further comprises: a pre-treatment unit and a sample chamber, the pre-treatment unit being used to treat the collected water sample and deliver it to the sample chamber; a quantification unit, the quantification unit being used to quantitatively treat the pre-treated water sample and deliver it to the atomization unit; an atomization unit and a heating unit, the heating unit being used to make the atomized sample into solid particles; a first pipe and a second pipe, the first pipe and the second pipe being respectively arranged on the upper side and the lower side of the filter membrane, and a pump, the pump being connected to the output end of the second pipe; a second driving unit, the second driving unit being used to drive the first pipe and / or the second pipe so that the first pipe and the second pipe clamp or unclamp the filter membrane; a cleaning unit, the cleaning unit being used to provide cleaning liquid, the cleaning liquid after cleaning the pipeline being delivered to the atomization unit; The concentration C of the i-th element in the j-th detection cycle output from the analysis unit is given by: ij C = (A + B) / 2 ； N is the number of detection cycles of the analysis unit between two consecutive cleaning cycles, j=1,2...N, X ij V is the areal density of the i-th element on the filter membrane during the j-th detection cycle. 1j X is the quantitative volume of water sample output by the quantitative unit in the j-th detection cycle. i ˊ S is the areal density of the i-th element on the filter membrane after cleaning the pipeline, and S is the area of ​​the sampling spot on the filter membrane.

2. The measuring device of claim 1, wherein, The measuring device further comprises a waste liquid container and a delivery unit, the waste liquid container being connected to the sample chamber and the pipeline, the delivery unit being used to deliver the water sample in the sample chamber to the waste liquid container when the filter membrane moves, and to deliver the accumulated water sample in the waste liquid container to the pipeline; average concentration C of the i-th element of M detection periods i ˊ ; ； M is the number of detection periods of the analysis unit between the start of the water sample into the waste liquid container and the sending to the atomization unit, which is an integer multiple of N, C ik is the concentration of the i-th element in the k-th detection period, k = 1, 2, ···, M, V 1k is the volume of the water sample entering the atomization unit in the k-th detection period, V2 is the cumulative volume of the waste liquid container in the M detection periods; Y i is the surface density of the i-th element on the filter membrane when the waste liquid is measured, Y i ˊ is the surface density of the i-th element on the filter membrane after the cleaning liquid is detected.

3. The measuring device of claim 1, wherein, The analysis unit adopts an XRF analyzer.

4. The measuring device of claim 1, wherein, The measuring device further comprises: a first switching module, the first switching module being used to selectively connect the outlet of the pre-treatment unit to the first sample chamber and / or the second sample chamber; a second switching module, the second switching module being used to selectively connect the atomization unit to the first sample chamber and / or the second sample chamber.

5. The measuring device of claim 1, wherein, The gas after being heated by the heating unit atomizes the water sample.

6. A method of measuring elements in water, characterized by, The measuring method comprises the following steps: A1. The pre-treated water sample enters the sample chamber and is delivered to the atomization unit after being quantitatively treated; A2. The atomized water sample is heated to become solid particles and enters the enrichment unit with the airflow; A3. The gas passes through the first pipe, the filter membrane and the second pipe, and the solid particles in the gas are intercepted and enriched by the filter membrane clamped by the first pipe and the second pipe; A4. The first pipe and the second pipe unclamp the filter membrane, and the filter membrane enriched with solid particles moves to the analysis unit; A5. The cleaning liquid provided by the cleaning unit cleans the pipeline and is then delivered to the atomization unit to enter step A2; A6. The analysis unit outputs the element content in the water sample according to the detection results of the sample and the cleaning liquid; The concentration C of the i-th element in the j-th detection cycle output from the analysis unit is given by: ij C = (A + B) / 2 ； N is the number of detection cycles of the analysis unit between two consecutive cleanings, j = 1, 2, ···, N, X ij is the surface density of the i-th element on the filter membrane at the j-th detection cycle, V 1j is the quantitative volume of the water sample output by the quantitative unit at the j-th detection cycle, X i ˊ is the surface density of the i-th element on the filter membrane after cleaning the pipeline, S is the area of the sampling spot on the filter membrane.

7. The measuring method according to claim 6, characterized in that, In step A4, the water sample in the sample chamber is delivered to the waste liquid container; the measuring method further comprises the following steps: A7. After M detection cycles, the accumulated water sample in the waste liquid container is delivered to the atomization unit through the pipeline to enter step A2 and execute steps A2-A6; average concentration C of the i-th element of M detection periods i ˊ ; ； M is the number of detection periods of the analysis unit between the start of the water sample into the waste liquid container and the sending to the atomization unit, which is an integer multiple of N, C ik is the concentration of the i-th element in the k-th detection period, k = 1, 2, ···, M, V 1k is the volume of the water sample entering the atomization unit in the k-th detection period, V2 is the cumulative volume of the waste liquid container in the M detection periods; Y i is the surface density of the i-th element on the filter membrane when the waste liquid is measured, Y i ˊ is the surface density of the i-th element on the filter membrane after the cleaning liquid is detected.

8. The measurement method according to claim 6, characterized by, The analysis unit adopts an XRF analyzer.

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