Atomic fluorescence and micro plasma emission spectrum all-in-one machine detection system

Abstract

The invention discloses an atomic fluorescence and micro-plasma emission spectrum all-in-one machine detection system, which relates to the technical field of atomic spectrum application, and comprises a sample introduction system, a data processing system, a hydride reaction system, an atomization system and a micro-plasma excitation device, the sample introduction system is connected with the atomization system through the hydride reaction system, a reducing agent and a sample enter the atomization system through the sample introduction system and the hydride reaction system to complete atomization of elements to be detected, and the atomic fluorescence detection system completes detection of a fluorescence spectrum; and the micro-plasma excitation device is connected with the sampling system, the micro-plasma excitation power supply and the emission spectrum detection system. The atomic fluorescence and the emission spectrum can be simultaneously measured by one instrument, the application of direct sample injection detection of a metal solution can be realized while heavy metals in a hydride generation atomic fluorescence test solution can be met, and respective measurement can be performed according to actual use requirements, so that the instrument cost and the space are effectively saved.

Description

Technical Field

[0001] The present invention relates to the technical field of atomic spectroscopy applications, and in particular to an atomic fluorescence and microplasma emission spectroscopy integrated detection system. Background Art

[0002] Pollution by heavy metal elements is widely present in the atmosphere, soil, and food. It is easy to accumulate in the human body and difficult to be excreted, which seriously endangers people's health. At present, different fields such as environment, disease control, and geology and mining attach great importance to the monitoring of heavy metals.

[0003] Common methods for heavy metal detection in atomic spectroscopy laboratories include atomic fluorescence spectrometry and atomic emission spectrometry. Atomic fluorescence spectrometry has gained widespread application in scientific research and production in numerous fields, including geology, the environment, food, and biology, due to its numerous advantages in elemental analysis, including high sensitivity, good accuracy, strong selectivity, low interference, fast analysis speed, simple structure, and low maintenance costs. However, hydride generation atomic fluorescence spectrometry (HG-AFS) is primarily used for heavy metals that readily form hydrides, such as arsenic, mercury, selenium, antimony, bismuth, tin, lead, cadmium, and zinc. The HG-AFS method, when used to measure elements like lead, cadmium, and zinc, has extremely high requirements for the pH of the reagents and the solution matrix. Sensitivity is also problematic, requiring the addition of special reagents to enhance sensitivity. Furthermore, byproducts can easily adsorb into the piping, leading to higher test blanks and reduced test accuracy. Furthermore, metal elements such as copper, nickel, potassium, sodium, and lithium cannot be detected by AFS, requiring specialized spectrometers for detection, increasing costs.

[0004] In atomic emission spectrometry, a microplasma is generated by liquid cathode discharge, and detection is performed using a direct-reading emission spectrometer. This method features low power consumption, a small size, simple reagents, and low cost. While it can achieve comparable analytical sensitivity, dynamic linear range, and multi-element analysis capabilities to ICP-AES, its sensitivity cannot meet detection requirements when testing heavy metals such as arsenic, mercury, and selenium.

[0005] In summary, there is an urgent need to provide an analysis and detection system that combines atomic fluorescence spectrometry analysis and atomic emission spectrometry analysis to solve the above problems. Summary of the Invention

[0006] The purpose of the present invention is to provide an atomic fluorescence and microplasma emission spectrometry integrated detection system to solve the problems mentioned in the above background technology.

[0007] The present invention adopts the following technical solutions:

[0008] The present invention provides an atomic fluorescence and microplasma emission spectrometry integrated detection system, comprising a sample introduction system, a data processing system, a hydride reaction system, an atomization system and a microplasma excitation device;

[0009] The atomization system is connected to the sampling system via the hydride reaction system. The reducing agent and the sample enter the hydride reaction system simultaneously through the sampling system. The atomization of the element to be measured is completed in the atomization system. Finally, the fluorescence spectrum is detected by the atomic fluorescence detection system. The atomic fluorescence detection system is data-connected to the data processing system.

[0010] The microplasma excitation device is connected to the sampling system. The sample enters the microplasma excitation device through the sampling system, participates in the discharge reaction in the microplasma excitation device to generate microplasma, and the emission spectrum detection system completes the emission spectrum signal collection of the relevant elements. The emission spectrum detection system is data-connected to the data processing system.

[0011] Preferably, the microplasma excitation device includes a discharge reaction chamber, a metal electrode is provided at the upper portion of the discharge reaction chamber, a graphite electrode tube is provided at the lower portion of the discharge reaction chamber, and the metal electrode and the graphite electrode tube are respectively connected to the anode and cathode of the microplasma excitation power supply;

[0012] A ceramic tube is provided in the graphite electrode tube, and the upper end of the ceramic tube extends into the discharge reaction chamber cavity, and the lower end of the ceramic tube is connected to the sampling system through a sampling capillary;

[0013] A lens positioning window is provided on the side wall of the discharge reaction chamber, and the emission spectrum detection system is provided on one side of the lens positioning window;

[0014] A waste liquid receiving tank is provided at the bottom end of the discharge reaction chamber;

[0015] The sample injection system includes a peristaltic pump and a liquid inlet switching valve;

[0016] The peristaltic pump is provided with two pump tubes, the reducing agent is connected to the hydride reaction system through the first pump tube, and the sample is connected to the liquid inlet switching valve through the second pump tube;

[0017] The liquid inlet switching valve is provided with a liquid inlet end, a first liquid outlet end and a second liquid outlet end, the liquid inlet end is connected to the second pump tube of the peristaltic pump, the first liquid outlet end is connected to the hydride reaction system, and the second liquid outlet end is connected to the injection capillary.

[0018] Preferably, the hydride reaction system comprises a four-way mixer, and the four-way mixer is provided with a first inlet, a second inlet, a third inlet and an outlet;

[0019] The first inlet is connected via a first pump tube of the peristaltic pump;

[0020] The second inlet is connected to the first liquid outlet;

[0021] The third inlet is connected to the first air outlet of the three-way air source switching valve, and the three-way air source switching valve is also provided with an air source inlet connected to an external air source;

[0022] The outlet is connected to a gas-liquid separation device, and an exhaust end of the gas-liquid separation device is connected to the atomization system.

[0023] Preferably, the gas source three-way switching valve is further provided with a second gas outlet, a through vent hole is provided in the metal electrode, and the second gas outlet is connected to the vent hole of the metal electrode.

[0024] Preferably, the gas-liquid separation device includes a primary gas-liquid separator and a secondary gas-liquid separator;

[0025] The first-stage gas-liquid separator is provided with a first feed port, a first gas separation port and a first liquid separation port, and the second-stage gas-liquid separator is provided with a second feed port, a second gas separation port and a second liquid separation port;

[0026] The first feed port is connected to the outlet, the first gas separation port is connected to the second feed port, and the first liquid separation port is connected to a waste discharge system;

[0027] The second gas separation port is connected to the atomization system, and the second liquid separation port is connected to the waste discharge system.

[0028] Preferably, a waste liquid outlet is provided at the bottom of the waste liquid receiving tank;

[0029] The waste discharge system includes a waste discharge solenoid valve, which is provided with a first waste liquid inlet, a second waste liquid inlet and a first waste liquid outlet, wherein the first waste liquid inlet is connected to the first liquid separation port, the first waste liquid outlet is connected to the feed port of the first waste discharge device, and the second waste liquid inlet is connected to the waste liquid outlet;

[0030] The waste discharge system further includes a second waste discharge device, and the second liquid separation port is connected to the feed port of the second waste discharge device;

[0031] The discharge ports of the first waste discharge device and the second waste discharge device are connected to the outside world through a three-way pipe.

[0032] Preferably, the discharge reaction chamber is a structure with an open side wall, and a discharge reaction cavity is provided in the discharge reaction chamber;

[0033] The metal electrode, the graphite electrode tube, and the ceramic tube are arranged vertically coaxially, the metal electrode and the graphite electrode tube are close to each other with a certain gap between them, and the upper end of the ceramic tube passes through the graphite electrode tube and is located between the metal electrode and the graphite electrode tube;

[0034] The metal electrode is fixedly connected to the top wall of the discharge reaction chamber by a first locking device, and the graphite electrode tube is fixedly connected to the bottom wall of the discharge reaction chamber by a second locking device;

[0035] The discharge reaction chamber is connected to the emission spectrum detection system via a fixing plate;

[0036] The bottom wall of the discharge reaction chamber is provided with a through waste liquid channel, and the waste liquid channel connects the waste liquid receiving tank and the discharge reaction chamber;

[0037] A capillary fixing hole is provided on the side wall of the waste liquid receiving tank, and the sampling capillary passes through the capillary fixing hole and is connected to the ceramic tube.

[0038] Preferably, an electrode positioning device is provided on the inner bottom wall of the discharge reaction chamber, a connection end is provided at the lower end of the electrode positioning device, and the connection end is provided on the inner bottom wall of the discharge reaction chamber. A rotatable swing rod is provided at the waist of the electrode positioning device, the top surface of the swing rod contacts and cooperates with the bottom end of the metal electrode, and the bottom surface of the swing rod contacts and cooperates with the top end of the graphite electrode tube;

[0039] The gap area between the metal electrode and the graphite electrode tube corresponds to the lens positioning window.

[0040] Preferably, the metal electrode is connected to a first electrode conductive block, and the first electrode conductive block passes through the discharge reaction chamber and is connected to the anode of the micro plasma excitation power supply;

[0041] The graphite electrode tube is connected to the second electrode conductive block, and the second electrode conductive block is connected to the cathode of the micro plasma excitation power supply after passing through the discharge reaction chamber.

[0042] Preferably, the first locking device includes a first locking nut and a first locking sleeve, and the top wall of the discharge reaction chamber is provided with a first screw hole;

[0043] The first locking sleeve and the first locking nut are sequentially sleeved on the outer wall of the metal electrode, and the outer wall of the first locking nut is threadedly connected to the first screw hole;

[0044] The first locking sleeve is funnel-shaped, and a small-diameter side wall of the first locking sleeve is provided with a plurality of spaced-apart notches. The small-diameter end of the first locking sleeve is inserted into the interior of the first locking nut, and the large-diameter side of the first locking sleeve abuts against the inner bottom wall of the first screw hole.

[0045] The second locking device includes a second locking sleeve, a second locking nut, and a butt nut, and the bottom wall of the discharge reaction chamber is provided with a second screw hole;

[0046] The second locking sleeve has the same structure as the first locking sleeve, and the second locking nut has the same structure as the first locking nut;

[0047] The connection relationship among the graphite electrode tube, the second locking sleeve, the second locking nut, and the second screw hole is the same as the connection relationship among the metal electrode, the first locking sleeve, the first locking nut, and the first screw hole;

[0048] The inner wall of the lower end of the second locking nut is provided with a thread, the outer wall of the upper end of the docking nut is threadedly connected to the second locking nut, and the sampling capillary is connected to the ceramic tube through the docking nut.

[0049] Compared with the prior art, the present invention has the following beneficial technical effects:

[0050] The present invention also provides an integrated atomic fluorescence and microplasma emission spectrometry testing system, capable of simultaneously testing heavy metals in hydride generation atomic fluorescence solutions and directly injecting metal solutions for detection. This system provides a new solution for expanding the use of atomic fluorescence equipment to detect more elements in samples. Compared with existing technologies, the present invention enables a single instrument to simultaneously measure atomic fluorescence and emission spectra, resulting in a simpler structure and significant savings in instrument cost and space. Furthermore, while simultaneous atomic fluorescence and emission spectra measurements can be achieved through a single injection, separate measurements can also be performed based on actual usage requirements. This effectively reduces sample and reagent consumption, saving analysis time and instrument operation and maintenance costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] The present invention will be further described below with reference to the accompanying drawings.

[0052] Figure 1 This is a schematic diagram of the overall gas and liquid flow path structure of the atomic fluorescence and microplasma emission spectrometry integrated detection system of the present invention;

[0053] Figure 2 This is a detailed schematic diagram of the main reaction gas and liquid flow paths of the sampling system, hydride reaction system and microplasma excitation device in the integrated atomic fluorescence and microplasma emission spectrometry detection system of the present invention;

[0054] Figure 3 Schematic diagram of the structure of the microplasma excitation device in the atomic fluorescence and microplasma emission spectrometry integrated detection system of the present invention;

[0055] Figure 4 A cross-sectional view of a microplasma excitation device in the integrated atomic fluorescence and microplasma emission spectrometry detection system of the present invention;

[0056] Figure 5 Schematic diagram of the structure of a four-way mixer in the integrated atomic fluorescence and microplasma emission spectrometer detection system of the present invention;

[0057] Figure 6 This is a right view of the microplasma excitation device in the atomic fluorescence and microplasma emission spectrometry integrated detection system of the present invention;

[0058] Figure 7 Schematic diagram of the first electrode conductive block and the second electrode conductive block in the atomic fluorescence and microplasma emission spectrometry integrated detection system of the present invention;

[0059] Figure 8 Schematic diagram of the structure of the electrode positioning device in the atomic fluorescence and microplasma emission spectrometry integrated detection system of the present invention;

[0060] Figure 9 This is a schematic structural diagram of the first locking device in the atomic fluorescence and microplasma emission spectrometry integrated detection system of the present invention;

[0061] Figure 10 This is a schematic structural diagram of the second locking device in the atomic fluorescence and microplasma emission spectrometry integrated detection system of the present invention;

[0062] Figure 11 This is a schematic structural diagram of a first-stage gas-liquid separator in the integrated atomic fluorescence and microplasma emission spectrometry detection system of the present invention;

[0063] Figure 12 The atomic fluorescence and emission spectrometer sample test spectrum in the atomic fluorescence and micro plasma emission spectrometer integrated detection system of the present invention Figure 1 ;

[0064] Figure 13 The atomic fluorescence and emission spectrometer sample test spectrum in the atomic fluorescence and micro plasma emission spectrometer integrated detection system of the present invention Figure 2 .

[0065] Explanation of reference numerals: 1, carrier fluid; 2, reducing agent; 3, sample; 4, injection system; 41, peristaltic pump; 42, liquid inlet switching valve; 421, first liquid outlet; 422, liquid inlet; 423, second liquid outlet; 5, data processing system; 6, hydride reaction system; 61, gas source three-way switching valve; 611, second gas outlet; 612, gas source gas inlet; 613, first gas outlet; 62, four-way mixer; 621, first inlet; 622, second inlet; 623, third inlet 624, outlet; 63, primary gas-liquid separator; 631, first feed inlet; 632, first gas separation port; 633, first liquid separation port; 64, secondary gas-liquid separator; 641, second feed inlet; 642, second gas separation port; 643, second liquid separation port; 65, first waste discharge device; 66, waste discharge solenoid valve; 661, first waste liquid inlet; 662, first waste liquid outlet; 663, second waste liquid inlet; 67, second waste discharge device; 68, waste discharge system ;69. Gas-liquid separation device;7. Atomization system;8. Atomic fluorescence detection system;9. Microplasma excitation device;90. Discharge reaction chamber;901. Lens positioning window;902. Electrode positioning device;902-1. Connecting end;902-2. Rocker;903. First locking device;903-1. First locking nut;903-2. First locking sleeve;903-3. First screw hole;904. Second locking device;904-1. Second locking sleeve;904-2. Second locking nut; 904-3, docking nut; 904-4, second screw hole; 905, waste liquid channel; 906, first electrode conductive block; 907, second electrode conductive block; 908, discharge reaction chamber; 91, metal electrode; 92, graphite electrode tube; 93, ceramic tube; 94, injection capillary; 95, waste liquid receiving tank; 951, capillary fixing hole; 952, waste liquid discharge outlet; 10, micro plasma excitation power supply; 11, emission spectrum detection system; 110, fixing plate. DETAILED DESCRIPTION

[0066] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0067] like Figure 1 and Figure 2 As shown, this embodiment discloses an atomic fluorescence and microplasma emission spectrometry integrated detection system, including a sampling system 4, a data processing system 5, a hydride reaction system 6, an atomization system 7, an atomic fluorescence detection system 8, a microplasma excitation device 9, a microplasma excitation power supply 10 and an emission spectrum detection system 11.

[0068] The atomization system 7 is connected to the sampling system 4 through the hydride reaction system 6. The reducing agent 2 and the sample 3 enter the hydride reaction system 6 at the same time through the sampling system 4. The atomization of the element to be measured is completed in the atomization system 7. Finally, the fluorescence spectrum is detected by the atomic fluorescence detection system 8. The atomic fluorescence detection system 8 is data-connected to the data processing system 5, and the data processing system 5 performs data processing.

[0069] The microplasma excitation device 9 is connected to the sampling system 4. The sample 3 enters the microplasma excitation device 9 through the sampling system 4, and participates in the discharge reaction in the microplasma excitation device 9 to generate microplasma. The emission spectrum detection system 11 completes the emission spectrum signal collection of the relevant elements. The emission spectrum detection system 11 is data-connected to the data processing system 5, and the data processing system 5 performs data processing.

[0070] Microplasma excitation device 9 includes a discharge reaction chamber 90. A metal electrode 91 is disposed at the upper portion of discharge reaction chamber 90, and a graphite electrode tube 92 is disposed at the lower portion of discharge reaction chamber 90. Metal electrode 91 is connected to the anode of microplasma excitation power supply 10, and graphite electrode tube 92 is connected to the cathode of microplasma excitation power supply 10. A ceramic tube 93 is disposed within graphite electrode tube 92. The upper end of ceramic tube 93 extends into the cavity of discharge reaction chamber 90, and the lower end of ceramic tube 93 is connected to the sampling system 4 via a sampling capillary 94. In this embodiment, the inner diameter of the sampling capillary 94 is 0.75-2 mm, the outer diameter of the metal electrode 91 is 5-7 mm, the inner diameter of the ventilation tube in the metal electrode 91 is 2-3 mm, the sampling capillary 94 is connected to the ceramic tube 93 through a sealed joint, the inner diameter of the ceramic tube 93 is 0.25-1 mm, the outer diameter of the ceramic tube 93 is 0.5-2 mm, the outer diameter of the graphite electrode tube 92 is 5-7 mm, and the inner diameter of the graphite electrode tube 92 matches the outer diameter of the ceramic tube 93.

[0071] A lens positioning window 901 is provided on the sidewall of the discharge reaction chamber 90, and an emission spectrum detection system 11 is installed on one side of the lens positioning window 901. Driven by the carrier current 1, the sample 3 solution enters the discharge reaction chamber 90 cavity through the sampling system 4, the sampling capillary 94, and the ceramic tube 93. The microplasma excitation power supply 10 is activated, and a discharge reaction occurs between the sample 3 solution and the metal electrode 91 to generate a microplasma. The graphite electrode tube 92 helps the sample 3 solution conduct electricity. The emission spectrum detection system 11 collects the emission spectrum signals of the relevant elements through the lens positioning window 901, and then the data processing system 5 completes the signal processing.

[0072] like Figure 2 and Figure 3 As shown, a waste liquid receiving tank 95 for collecting waste liquid after reaction is provided at the bottom end of the discharge reaction chamber 90 .

[0073] The sampling system 4 includes a peristaltic pump 41 and a liquid inlet switching valve 42. The peristaltic pump 41 is provided with two pump tubes, the reducing agent 2 is connected to the hydride reaction system 6 through the first pump tube, and the sample 3 is connected to the liquid inlet switching valve 42 through the second pump tube.

[0074] The liquid inlet switching valve 42 is provided with a liquid inlet 422, a first liquid outlet 421, and a second liquid outlet 423. The liquid inlet 422 is connected to the second pump tube of the peristaltic pump 41. The sample 3 enters the liquid inlet 422 through the second pump tube of the peristaltic pump 41. The second liquid outlet 423 is connected to the injection capillary 94. The valve of the liquid inlet switching valve 42 is switched to connect the liquid inlet 422 with the second liquid outlet 423. The sample 3 solution passes through the peristaltic pump 41, the liquid inlet 422, the second liquid outlet 423, the injection capillary 94, and the ceramic tube 93 and enters the discharge reaction chamber 90 for reaction. The first liquid outlet 421 is connected to the hydride reaction system 6.

[0075] like Figure 2 and Figure 5 As shown, the hydride reaction system 6 includes a four-way mixer 62, which is provided with a first inlet 621, a second inlet 622, a third inlet 623, and an outlet 624. In this embodiment, the four-way mixer 62 has a four-way piping structure, and the reducing agent 2, the sample 3, and the experimental gas source enter through the first inlet 621, the second inlet 622, and the third inlet 623, respectively, and flow out through the outlet 624.

[0076] Specifically, the first inlet 621 is connected to the first pump tube of the peristaltic pump 41 so as to introduce the reducing agent 2. The second inlet 622 is connected to the first liquid outlet 421.

[0077] It should be noted that by switching the liquid inlet switching valve 42, both the passage between the liquid inlet end 422 and the second liquid outlet end 423 and the passage between the liquid inlet end 422 and the first liquid outlet end 421 can be kept unobstructed, so that two experiments can be carried out simultaneously.

[0078] The third inlet 623 is connected to the first outlet 613 of the three-way gas source switching valve 61. The three-way gas source switching valve 61 is also provided with a second outlet 611 and a gas source inlet 612 connected to an external gas source. A through-hole is provided within the metal electrode 91, and the second outlet 611 is connected to the vent of the metal electrode 91. During the discharge reaction between the sample 3 solution and the metal electrode 91 to generate the microplasma, air or an inert gas (gas flow rate 0-300 mL / min) can be introduced through the gas source inlet 612 according to actual experimental needs. The three-way gas source switching valve 61 is switched to connect the gas source inlet 612 and the second outlet 611. The air or inert gas enters the discharge reaction chamber 90 through the gas source inlet 612, the second outlet 611, and the vent of the metal electrode 91. It should be noted that the introduction of inert gas or air is intended to reduce the temperature of the electrode, thereby achieving different reaction stability and sensitivity. In some experimental scenarios, the introduction of gas can also be omitted.

[0079] The outlet 624 is connected to the gas-liquid separation device 69, and the exhaust end of the gas-liquid separation device 69 is connected to the atomization system 7. In the process of completing the hydride generation atomic fluorescence test of heavy metal elements, the valve is switched so that the liquid inlet end 422 is connected to the first liquid outlet end 421, and the sample 3 solution required for the experiment flows into the four-way mixer 62 through the second pump tube, liquid inlet end 422, first liquid outlet end 421, and second inlet 622 of the peristaltic pump 41. At the same time, the reducing agent 2 flows into the four-way mixer 62 through the first pump tube and first inlet 621 of the peristaltic pump 41. At the same time, the gas source three-way switching valve 61 is switched so that the gas source inlet 612 and the first gas outlet 613 are connected, and the required experimental gas source flows into the four-way mixer 62 through the gas source inlet 612, first gas outlet 613, and third inlet 623. In this experiment, the experimental gas source acts as a carrier gas, that is, the liquid is pushed forward by the flow of the experimental gas source. The reducing agent 2, sample 3 and experimental gas source enter the four-way mixer 62. The carrier gas and the two liquids complete preliminary mixing at the moment of mixing. Under the push of the carrier gas, they enter the subsequent pipeline to complete further mixing reaction. Under the push of the carrier gas, the gas-liquid mixture flows out from the outlet 624 to the gas-liquid separation device 69 for gas-liquid separation. The separated gas enters the atomization system 7 to atomize the elements to be tested. While completing the atomization of the elements to be tested, the fluorescence spectrum is detected by the atomic fluorescence detection system 8, and the separated liquid is discharged through the waste discharge system 68.

[0080] In this embodiment, the data processing system 5 and the atomization system 7 are mature and widely used devices in this industry. The atomic fluorescence detection system 8 (such as the day-blind photomultiplier tube from Hamamatsu, Japan) and the micro plasma excitation power supply 10 are both existing technical means and will not be introduced in detail here.

[0081] like Figure 2As shown, in this embodiment, the gas-liquid separation device 69 includes a primary gas-liquid separator 63 and a secondary gas-liquid separator 64. The primary gas-liquid separator 63 is provided with a first feed port 631, a first gas separation port 632 and a first liquid separation port 633, and the secondary gas-liquid separator 64 is provided with a second feed port 641, a second gas separation port 642 and a second liquid separation port 643. The first feed port 631 is connected to the outlet 624, the first gas separation port 632 is connected to the second feed port 641, and the first liquid separation port 633 is connected to the waste discharge system 68. The second gas separation port 642 is connected to the atomization system 7, and the second liquid separation port 643 is connected to the waste discharge system 68. The primary gas-liquid separator 63 and the secondary gas-liquid separator 64 are both commonly used gas-liquid separators with the same structure. As a conventional technical means, the gas-liquid separator will not be introduced here.

[0082] The gas-liquid mixture flowing out of outlet 624 enters the primary gas-liquid separator 63 through the first feed port 631. The separated gas enters the secondary gas-liquid separator 64 through the first gas separation port 632 and the second feed port 641, while the separated liquid enters the waste system 68 through the first liquid separation port 633. The secondary gas-liquid separator 64 performs further gas-liquid separation. The separated gas enters the atomization system 7 through the second gas separation port 642 for atomization of the element to be measured. Simultaneously with the completion of the atomization of the element to be measured, the fluorescence spectrum is detected by the atomic fluorescence detection system 8. The liquid separated by the secondary gas-liquid separator 64 also enters the waste system 68.

[0083] like Figures 2 to 4 As shown, the discharge reaction chamber 90 has an open sidewall structure. A discharge reaction chamber 908 is disposed within the discharge reaction chamber 90. The discharge reaction chamber 908 communicates with the outside world via the sidewall opening of the discharge reaction chamber 90. A through-hole waste liquid channel 905 is disposed on the bottom wall of the discharge reaction chamber 90. This waste liquid channel 905 connects the discharge reaction chamber 908 with a waste liquid receiving tank 95. A waste liquid outlet 952 is disposed at the bottom of the waste liquid receiving tank 95. Sample 3 solution enters the discharge reaction chamber 908 through the ceramic tube 93, undergoes reaction, and then flows through the waste liquid channel 905 to the waste liquid receiving tank 95. This process is like a fountain, as it sprays out from the upper end of the ceramic tube 93 and flows away directly after completing the reaction.

[0084] The waste discharge system 68 includes a waste discharge solenoid valve 66, which is provided with a first waste liquid inlet 661, a second waste liquid inlet 663, and a first waste liquid outlet 662. The first waste liquid inlet 661 is connected to the first liquid separation port 633 for discharging the liquid separated by the primary gas-liquid separator 63. The first waste liquid outlet 662 is connected to the feed port of the first waste discharge device 65. The second waste liquid inlet 663 is connected to the waste liquid outlet 952 via a pipeline for discharging waste liquid from the microplasma discharge reaction experiment.

[0085] The waste discharge system 68 also includes a second waste discharge device 67. A second liquid separation port 643 is connected to the feed port of the second waste discharge device 67, which is used to discharge the liquid separated by the secondary gas-liquid separator 64. The discharge ports of the first and second waste discharge devices 65 and 67 are connected to the outside world through a tee pipe for unified treatment. Both the first and second waste discharge devices 65 and 67 are peristaltic pumps.

[0086] like Figures 3 and 4 As shown, the discharge reaction chamber 90 is connected to the emission spectrum detection system 11 through a fixing plate 110 .

[0087] A capillary fixing hole 951 is provided on the side wall of the waste liquid receiving tank 95 , and the sampling capillary 94 passes through the capillary fixing hole 951 and is connected to the ceramic tube 93 .

[0088] like Figures 6 and 7 As shown, the metal electrode 91, graphite electrode tube 92, and ceramic tube 93 are arranged vertically and coaxially. The metal electrode 91 and graphite electrode tube 92 are close together with a certain gap. The upper end of the ceramic tube 93 is located between the metal electrode 91 and the graphite electrode tube 92. An electrode positioning device 902 is provided on the inner bottom wall of the discharge reaction chamber 908. The lower end of the electrode positioning device 902 is provided with a connecting end 902-1, which is fixed to the inner bottom wall of the discharge reaction chamber 908. A rotatable rocker 902-2 is mounted on the waist of the electrode positioning device 902. The top surface of the rocker 902-2 contacts the bottom end of the metal electrode 91, and the bottom surface of the rocker 902-2 contacts the top end of the graphite electrode tube 92. The rocker 902-2 is provided with a notch to avoid the ceramic tube 93. When installing the metal electrode 91 and graphite electrode tube 92, rotate the pendulum 902-2 between them and adjust their depth within the discharge reaction chamber 908 so that they contact the top and bottom surfaces of the pendulum 902-2, respectively, ensuring the discharge gap meets experimental requirements. After securing both the metal electrode 91 and the graphite electrode tube 92, rotate the pendulum 902-2 away from them to prevent any interference during the discharge reaction.

[0089] The gap area between the metal electrode 91 and the graphite electrode tube 92 corresponds to the lens positioning window 901. In this embodiment, the center position of the gap between the metal electrode 91 and the graphite electrode tube 92 and the center position of the lens positioning window 901 are located on the same horizontal plane.

[0090] In this embodiment, the discharge distance between the lower end of the metal electrode 91 and the upper end of the graphite electrode tube 92 is 2 mm-6.5 mm, which is the height of the rocker 902 - 2 . The discharge distance is adjusted by positioning the rocker 902 - 2 .

[0091] In this embodiment, the metal electrode 91 is fixedly connected to the top wall of the discharge reaction chamber 90 by a first locking device 903 , and the graphite electrode tube 92 is fixedly connected to the bottom wall of the discharge reaction chamber 90 by a second locking device 904 .

[0092] like Figures 6 to 8 As shown, the metal electrode 91 is connected to the first electrode conductive block 906, which passes through the discharge reaction chamber 90 and is connected to the anode of the micro plasma excitation power supply 10; the graphite electrode tube 92 is connected to the second electrode conductive block 907, which passes through the discharge reaction chamber 90 and is connected to the cathode of the micro plasma excitation power supply 10.

[0093] like Figures 9 and 10 As shown, the first locking device 903 includes a first locking nut 903-1 and a first locking sleeve 903-2, and a first screw hole 903-3 is provided on the top wall of the discharge reaction chamber 90; the first locking sleeve 903-2 and the first locking nut 903-1 are sequentially sleeved on the outer wall of the metal electrode 91, and the outer wall of the first locking nut 903-1 is threadedly connected to the first screw hole 903-3.

[0094] The first locking sleeve 903-2 is funnel-shaped, with multiple spaced-apart notches on the smaller-diameter side of the first locking sleeve 903-2. The smaller-diameter end of the first locking sleeve 903-2 is inserted into the first locking nut 903-1, while the larger-diameter end of the first locking sleeve 903-2 rests against the inner bottom wall of the first threaded hole 903-3. During the tightening process of the first locking nut 903-1, the first locking nut 903-1 moves downward within the first threaded hole 903-3, squeezing and contracting the first locking sleeve 903-2. The smaller-diameter end of the first locking sleeve 903-2 is then tightly clamped against the outer wall of the metal electrode 91, securing it.

[0095] The second locking device 904 includes a second locking sleeve 904-1, a second locking nut 904-2, and a butt nut 904-3. A second threaded hole 904-4 is provided on the bottom wall of the discharge reaction chamber 90. The second locking sleeve 904-1 is structurally identical to the first locking sleeve 903-2, and the second locking nut 904-2 is structurally identical to the first locking nut 903-1. The connection between the graphite electrode tube 92, the second locking sleeve 904-1, the second locking nut 904-2, and the second threaded hole 904-4 is similar to the connection between the metal electrode 91, the first locking sleeve 903-2, the first locking nut 903-1, and the first threaded hole 903-3. By tightening the second locking nut 904-2 into the second threaded hole 904-4, the second locking nut 904-2 compresses the second locking sleeve 904-1, which then tightly grips the outer wall of the graphite electrode tube 92, securing it.

[0096] In this embodiment, the inner wall of the lower end of the second locking nut 904-2 is also provided with a thread, and the outer wall of the upper end of the docking nut 904-3 is threadedly connected to the second locking nut 904-2. The sampling capillary 94 passes through the docking nut 904-3, and the lower end of the docking nut 904-3 tightly clamps the outer wall of the sampling capillary 94. Thus, the sampling capillary 94 is connected to the ceramic tube 93 in the graphite electrode tube 92 through the docking nut 904-3.

[0097] like Figure 11 As shown, it is a simplified schematic diagram of the inlet and outlet of the first-stage gas-liquid separator 63. The gas-liquid separator is a conventional technical means, and its structure and working principle are not introduced here.

[0098] In the present invention, the two detection systems share the sample injection system 4, the waste discharge system 68, and the data processing system 5. The data processing system 5 is connected, communicated or controlled with the peristaltic pump 41, various valves, and other equipment in the present invention through pipelines.

[0099] The present invention provides a detection method for an atomic fluorescence and microplasma emission spectrometer, comprising the following steps:

[0100] Method 1: Complete the process of hydride generation atomic fluorescence testing of heavy metal elements:

[0101] Step 1: Connection of the liquid circuit: by switching the liquid inlet switching valve 42, the liquid outlet end of the second pump tube connecting the peristaltic pump 41 to the sample 3 is connected to the second inlet 622 of the four-way mixer 62 through the liquid inlet end 422 and the first liquid outlet end 421; the first pump tube connecting the peristaltic pump 41 to the reducing agent 2 is connected to the first inlet 621 of the four-way mixer 62; the outlet 624 is connected to the first feed port 631, the first gas separation port 632 is connected to the second feed port 641, and the second gas separation port 642 is connected to the atomization system 7; the first liquid separation port 633 is connected to the first waste liquid inlet 661, the first waste liquid outlet 662 is connected to the feed port of the first waste discharge device 65, the second liquid separation port 643 is connected to the feed port of the second waste discharge device 67, and the outlets of the first waste discharge device 65 and the second waste discharge device 67 are connected to the outside world through a three-way pipe; switch the waste discharge solenoid valve 66 so that the first waste liquid inlet 661 is connected to the first waste liquid outlet 662;

[0102] Step 2: Connecting the gas circuit: Switch the gas source three-way switching valve 61 so that the gas source inlet 612 and the first gas outlet 613 are connected, and the first gas outlet 613 is connected to the third inlet 623 of the four-way mixer 62 through a pipeline;

[0103] Step 3: Start the test: The peristaltic pump 41 starts working. The sample 3, driven by the carrier fluid 1, completes a mixing reaction with the reducing agent 2 and the experimental gas source in the four-way mixer 62. The sample then enters the first gas-liquid separator 63 from the outlet 624 through the first feed port 631, completing the first step of gas-liquid separation. The liquid portion enters the waste system 68 through the first liquid separation port 633. The separated gas enters the second gas-liquid separator 64 through the first gas separation port 632 and the second feed port 641 for further gas-liquid separation. The separated gas enters the atomization system 7 through the second gas separation port 642 for atomization of the element to be tested. While the atomization of the element to be tested is completed, the fluorescence spectrum is detected by the atomic fluorescence detection system 8. The liquid separated by the second gas-liquid separator 64 also enters the waste system 68.

[0104] Method 2: Complete the process of microplasma discharge emission spectrum test:

[0105] Step 1: Connecting the liquid flow path: Switch the liquid inlet switching valve 42 so that the liquid inlet end 422 is connected to the second liquid outlet end 423. The liquid inlet end 422 is connected to the sample 3 through the second pump tube of the peristaltic pump 41, and the second liquid outlet end 423 is connected to the injection capillary 94. The sample 3 solution can enter the ceramic tube 93 through the injection capillary 94 and then enter the discharge reaction chamber 908 for reaction;

[0106] Step 2: Connecting the gas source: Switch the gas source three-way switching valve 61 so that the gas source inlet 612 is connected to the second gas outlet 611, and the second gas outlet 611 is connected to the vent hole of the metal electrode 91 via a gas pipeline;

[0107] Step 3: Microplasma Discharge Emission Spectroscopy Test for Heavy Metal Elements: Peristaltic pump 41 begins operation. Driven by carrier current 1, sample 3 solution passes through peristaltic pump 41, liquid inlet 422, second liquid outlet 423, injection capillary 94, and ceramic tube 93 into discharge reaction chamber 908. Air or inert gas is introduced from gas source inlet 612 and enters discharge reaction chamber 908 through second outlet 611 and the vent of metal electrode 91.

[0108] The microplasma excitation power supply 10 starts working, and a discharge occurs between the sample 3 solution entering the discharge reaction chamber 908 and the metal electrode 91 to generate microplasma. The emission spectrum detection system 11 completes the acquisition of the emission spectrum signal of the relevant elements through the lens positioning window 901, and the data processing system 5 completes the signal processing.

[0109] Step 4: Discharge of waste liquid during the experiment: After participating in the experimental reaction, the sample 3 solution enters the waste liquid receiving tank 95 from the waste liquid channel 905. At this time, the waste liquid discharge outlet 952 of the waste liquid receiving tank 95 is connected to the second waste liquid inlet 663. The waste discharge solenoid valve 66 is switched so that the second waste liquid inlet 663 is connected to the first waste liquid outlet 662. After passing through the waste discharge device 65, it is discharged to the outside in real time through the three-way pipe.

[0110] like Figure 12 and Figure 13 As shown, the atomic fluorescence test is for arsenic and mercury, and the emission spectrometer is for testing the peak spectra of copper, cadmium, zinc, lead, nickel and other elements. The carrier 1 used in the acquisition stage is 2%-5% hydrochloric acid carrier, and the sample 3 matrix liquid used in the emission spectrometer is 1%-2% nitric acid and 5%-10% formic acid.

[0111] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. An atomic fluorescence and microplasma emission spectrometry integrated detection system, characterized by: It includes a sample injection system (4), a data processing system (5), a hydride reaction system (6), an atomization system (7) and a micro plasma excitation device (9); The atomization system (7) is connected to the sample injection system (4) through the hydride reaction system (6); the reducing agent (2) and the sample (3) enter the hydride reaction system (6) simultaneously through the sample injection system (4); the atomization of the element to be measured is completed in the atomization system (7); and finally, the fluorescence spectrum is detected by the atomic fluorescence detection system (8). The atomic fluorescence detection system (8) is data-connected to the data processing system (5); The microplasma excitation device (9) is connected to the sample injection system (4); the sample (3) enters the microplasma excitation device (9) through the sample injection system (4), participates in a discharge reaction in the microplasma excitation device (9), generates microplasma, and the emission spectrum detection system (11) completes the acquisition of emission spectrum signals of relevant elements; the emission spectrum detection system (11) is data-connected to the data processing system (5).

2. The atomic fluorescence and microplasma emission spectrometry integrated detection system according to claim 1, characterized in that: The micro plasma excitation device (9) comprises a discharge reaction chamber (90), wherein a metal electrode (91) is provided at the upper portion of the discharge reaction chamber (90), and a graphite electrode tube (92) is provided at the lower portion of the discharge reaction chamber (90), wherein the metal electrode (91) and the graphite electrode tube (92) are respectively connected to the anode and cathode of the micro plasma excitation power supply (10), wherein a ceramic tube (93) is provided in the graphite electrode tube (92), and the upper end of the ceramic tube (93) extends into the cavity of the discharge reaction chamber (90), and the lower end of the ceramic tube (93) is connected to the injection system (4) via an injection capillary (94), and a lens positioning window (901) is provided on the side wall of the discharge reaction chamber (90), and the emission spectrum detection system (11) is provided on one side of the lens positioning window (901); A waste liquid receiving tank (95) is provided at the bottom end of the discharge reaction chamber (90); The sample injection system (4) includes a peristaltic pump (41) and a liquid inlet switching valve (42); The peristaltic pump (41) is provided with two pump tubes, the reducing agent (2) is connected to the hydride reaction system (6) through the first pump tube, and the sample (3) is connected to the liquid inlet switching valve (42) through the second pump tube; The liquid inlet switching valve (42) is provided with a liquid inlet end (422), a first liquid outlet end (421) and a second liquid outlet end (423), the liquid inlet end (422) is connected to the second pump tube of the peristaltic pump (41), the first liquid outlet end (421) is connected to the hydride reaction system (6), and the second liquid outlet end (423) is connected to the sampling capillary (94).

3. The integrated atomic fluorescence and microplasma emission spectrometry detection system according to claim 2, characterized in that: The hydride reaction system (6) includes a four-way mixer (62), and the four-way mixer (62) is provided with a first inlet (621), a second inlet (622), a third inlet (623) and an outlet (624); The first inlet (621) is connected to a first pump tube of the peristaltic pump (41); The second inlet (622) is connected to the first liquid outlet (421); The third inlet (623) is connected to the first air outlet (613) of the air source three-way switching valve (61), and the air source three-way switching valve (61) is also provided with an air source inlet (612) connected to an external air source; The outlet (624) is connected to the gas-liquid separation device (69), and the exhaust end of the gas-liquid separation device (69) is connected to the atomization system (7).

4. The integrated atomic fluorescence and microplasma emission spectrometry detection system according to claim 3, characterized in that: The gas source three-way switching valve (61) is further provided with a second gas outlet (611), a through vent hole is provided in the metal electrode (91), and the second gas outlet (611) is connected to the vent hole of the metal electrode (91).

5. The integrated atomic fluorescence and microplasma emission spectrometry detection system according to claim 3, characterized in that: The gas-liquid separation device (69) includes a primary gas-liquid separator (63) and a secondary gas-liquid separator (64); The first-stage gas-liquid separator (63) is provided with a first feed port (631), a first gas separation port (632), and a first liquid separation port (633); the second-stage gas-liquid separator (64) is provided with a second feed port (641), a second gas separation port (642), and a second liquid separation port (643); The first feed port (631) is connected to the outlet (624), the first gas separation port (632) is connected to the second feed port (641), and the first liquid separation port (633) is connected to a waste discharge system (68); The second gas separation port (642) is connected to the atomization system (7), and the second liquid separation port (643) is connected to the waste discharge system (68).

6. The atomic fluorescence and microplasma emission spectrometry integrated detection system according to claim 5, characterized in that: The bottom of the waste liquid receiving tank (95) is provided with a waste liquid outlet (952); The waste discharge system (68) includes a waste discharge solenoid valve (66), which is provided with a first waste liquid inlet (661), a second waste liquid inlet (663) and a first waste liquid outlet (662), wherein the first waste liquid inlet (661) is connected to the first liquid separation port (633), the first waste liquid outlet (662) is connected to the feed port of the first waste discharge device (65), and the second waste liquid inlet (663) is connected to the waste liquid outlet (952); The waste discharge system (68) further includes a second waste discharge device (67), and the second liquid separation port (643) is connected to the feed port of the second waste discharge device (67); The discharge ports of the first waste discharge device (65) and the second waste discharge device (67) are connected to the outside world through three-way pipes.

7. The integrated atomic fluorescence and microplasma emission spectrometry detection system according to claim 2, characterized in that: The discharge reaction chamber (90) is a structure with an open side wall, and a discharge reaction cavity (908) is provided in the discharge reaction chamber (90); The metal electrode (91), the graphite electrode tube (92), and the ceramic tube (93) are arranged vertically coaxially. The metal electrode (91) and the graphite electrode tube (92) are close to each other with a certain gap between them. The upper end of the ceramic tube (93) passes through the graphite electrode tube (92) and is located between the metal electrode (91) and the graphite electrode tube (92). The metal electrode (91) is fixedly connected to the top wall of the discharge reaction chamber (90) via a first locking device (903), and the graphite electrode tube (92) is fixedly connected to the bottom wall of the discharge reaction chamber (90) via a second locking device (904); The discharge reaction chamber (90) is connected to the emission spectrum detection system (11) via a fixing plate (110); The bottom wall of the discharge reaction chamber (90) is provided with a through waste liquid channel (905), and the waste liquid channel (905) connects the waste liquid receiving tank (95) and the discharge reaction chamber (908); A capillary fixing hole (951) is provided on the side wall of the waste liquid receiving tank (95), and the sampling capillary (94) passes through the capillary fixing hole (951) and is connected to the ceramic tube (93).

8. The integrated atomic fluorescence and microplasma emission spectrometry detection system according to claim 7, characterized in that: An electrode positioning device (902) is provided in the discharge reaction chamber (908); a connection end (902-1) is provided at the lower end of the electrode positioning device (902); the connection end (902-1) is provided on the inner bottom wall of the discharge reaction chamber (908); a rotatable swing rod (902-2) is provided at the waist of the electrode positioning device (902); the top surface of the swing rod (902-2) contacts and cooperates with the bottom end of the metal electrode (91); and the bottom surface of the swing rod (902-2) contacts and cooperates with the top end of the graphite electrode tube (92); The gap area between the metal electrode (91) and the graphite electrode tube (92) corresponds to the lens positioning window (901).

9. The integrated atomic fluorescence and microplasma emission spectrometry detection system according to claim 7, characterized in that: The metal electrode (91) is connected to a first electrode conductive block (906); the first electrode conductive block (906) passes through the discharge reaction chamber (90) and is connected to the anode of the micro plasma excitation power supply (10); The graphite electrode tube (92) is connected to a second electrode conductive block (907), and the second electrode conductive block (907) passes through the discharge reaction chamber (90) and is connected to the cathode of the micro plasma excitation power supply (10).

10. The atomic fluorescence and microplasma emission spectrometry integrated detection system according to claim 7, characterized in that: The first locking device (903) comprises a first locking nut (903-1) and a first locking sleeve (903-2), and the top wall of the discharge reaction chamber (90) is provided with a first screw hole (903-3); The first locking sleeve (903-2) and the first locking nut (903-1) are sequentially sleeved on the outer wall of the metal electrode (91), and the outer wall of the first locking nut (903-1) is threadedly connected in the first screw hole (903-3); The first locking sleeve (903-2) is funnel-shaped, and a small-diameter side wall of the first locking sleeve (903-2) is provided with a plurality of spaced-apart notches. The small-diameter end of the first locking sleeve (903-2) is inserted into the interior of the first locking nut (903-1), and the large-diameter side of the first locking sleeve (903-2) abuts against the inner bottom wall of the first screw hole (903-3); The second locking device (904) comprises a second locking sleeve (904-1), a second locking nut (904-2), and a docking nut (904-3); and the bottom wall of the discharge reaction chamber (90) is provided with a second screw hole (904-4); The second locking sleeve (904-1) has the same structure as the first locking sleeve (903-2), and the second locking nut (904-2) has the same structure as the first locking nut (903-1); The connection relationship among the graphite electrode tube (92), the second locking sleeve (904-1), the second locking nut (904-2), and the second screw hole (904-4) is the same as the connection relationship among the metal electrode (91), the first locking sleeve (903-2), the first locking nut (903-1), and the first screw hole (903-3); The inner wall of the lower end of the second locking nut (904-2) is provided with a thread, the outer wall of the upper end of the docking nut (904-3) is threadedly connected to the second locking nut (904-2), and the injection capillary (94) is connected to the ceramic tube (93) through the docking nut (904-3).

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