Liquid chromatography-atomic fluorescence flow path analysis system

Abstract

The utility model provides a liquid chromatography-atomic fluorescence flow path analysis system, which relates to the technical field of chemical analysis, and comprises a mobile phase processing device, a sample online reaction device, a gas path device and a gas-liquid separation device, the sample online reaction device is used for carrying out separation, online ultraviolet digestion and hydride generation on a sample; according to the device, the mobile phase does not need to be degassed manually, an experimenter only needs to prepare the mobile phase and place a pipeline in a corresponding reagent bottle, and an instrument can perform online degassing on the mobile phase, so that the time required for preparing the mobile phase is saved, hydrogen is supplemented when a sample reacts with a reducing agent to generate gaseous hydride, the dosage of potassium borohydride is effectively reduced, and the production cost is reduced. While the physical health of experimenters is ensured and a friendly laboratory environment is provided, the influence of water vapor on a test result can be reduced, and the sensitivity and the stability of an instrument are improved.

Description

Technical Field

[0001] This utility model relates to the field of chemical analysis technology, and in particular to a liquid chromatography-atomic fluorescence flow path analysis system. Background Technology

[0002] Liquid chromatography-atomic fluorescence spectrometry (LC-AFS) is an analytical method that closely combines liquid chromatography (LC) and atomic fluorescence spectrometry (AFS). This method first uses the infusion pump of the LC to uniformly and stably inject the sample into the chromatographic column, separating elements of different forms and valence states. After appropriate reactions, these separated components are detected by atomic fluorescence. Due to its good separation performance, sensitivity and specificity, and the ability to accurately distinguish and determine elements of various forms and valence states, it is widely used in environmental monitoring, food analysis, biomedicine and other fields.

[0003] Currently, there are two main problems in the liquid chromatography-atomic fluorescence detection process. First, since LC-AFS uses liquid chromatography as the separation system, the mobile phase must be degassed before entering the high-pressure pump; otherwise, it will cause problems such as unstable baseline and increased detector noise. The commonly used degassed method is ultrasonic degassed, but excessive ultrasonic time may cause changes in the mobile phase temperature, affecting the peak effect and resolution. Moreover, when the temperature drops, it may also cause an increase in gas solubility, leading to the redissolved gas into the mobile phase. Second, after the sample is separated by the chromatographic column, it needs to react with a reducing agent under acidic conditions to generate hydrogen and gaseous hydrides for testing. The commonly used reducing agent is potassium borohydride, which has been listed in the list of easily explosive hazardous chemicals. In addition, its high concentration during use will generate a lot of water vapor, leading to unstable instrument test results. In severe cases, water vapor can clog the pipeline, resulting in significantly lower test results. Therefore, this utility model proposes a liquid chromatography-atomic fluorescence flow path analysis system to solve the problems existing in the prior art. Utility Model Content

[0004] To address the aforementioned problems, this invention proposes a liquid chromatography-atomic fluorescence flow path analysis system. This system eliminates the need for manual degassing of the mobile phase. Researchers only need to prepare the mobile phase and place the tubing in the corresponding reagent bottle; the instrument can then degas it online, saving time required for mobile phase preparation. Furthermore, hydrogen is added when the sample reacts with the reducing agent to generate gaseous hydrides, effectively reducing the amount of potassium borohydride used.

[0005] To achieve the purpose of this utility model, the utility model is implemented through the following technical solution: a liquid chromatography-atomic fluorescence flow path analysis system, including a mobile phase processing device, an online sample reaction device, a gas path device and a gas-liquid separation device, wherein the mobile phase processing device is used to degas the mobile phase online, and the online sample reaction device is used to separate the sample, perform online ultraviolet digestion and hydride generation;

[0006] The gas path device is used to provide carrier gas and supplement hydrogen, and the gas-liquid separation device is used to remove water vapor from the hydride.

[0007] A further improvement is made in that: the mobile phase processing device includes a first mobile phase bottle, a second mobile phase bottle, a degasser, a first liquid pump, a second liquid pump, a mobile phase tee, and an injection valve. The two inlets of the degasser are connected to the first mobile phase bottle and the second mobile phase bottle, respectively. The two outlets of the degasser are connected to the first liquid pump and the second liquid pump, respectively. The output ports of the first liquid pump and the second liquid pump are connected to the two side interfaces of the mobile phase tee, respectively. The output interface of the mobile phase tee is connected to the injection valve.

[0008] A further improvement is that the online sample reaction device includes a chromatographic column, a carrier or online digestion solution bottle, a carrier bottle, a reducing agent bottle, a peristaltic pump, a one-way valve, a chromatographic column tee, a carrier tee, a reducing agent tee, and an online ultraviolet digestion device; the carrier or online digestion solution bottle, the carrier bottle, and the reducing agent bottle are respectively connected to the inlet of the peristaltic pump's carrier or online digestion solution pump tube, the carrier pump tube, and the reducing agent pump tube, and the outlet of the carrier or online digestion solution pump tube, the carrier pump tube, and the reducing agent pump tube are respectively connected to the chromatographic column tee, the one-way valve, and the reducing agent tee, and the outlet of the one-way valve is connected to the carrier tee.

[0009] A further improvement is made in that: the lower end of the chromatographic column tee is connected to the outlet of the chromatographic column, and the inlet of the chromatographic column is connected to the outlet of the injection valve; one side of the chromatographic column tee is connected to the inlet of the online ultraviolet digestion device; one side of the flow carrier tee is connected to the outlet of the online ultraviolet digestion device; and the lower end of the reducing agent tee is connected to the upper end of the flow carrier tee.

[0010] A further improvement is that the gas path device includes an argon gas device, a hydrogen generator device, a gas path tee, and a gas path switch. The outlet of the argon gas device is connected to the lower interface of the gas path tee via a TPU gas tube, and the hydrogen generator device is connected to the inlet of the gas path switch. The upper interface of the gas path tee is connected to the outlet of the gas path switch via a TPU gas tube.

[0011] A further improvement is made in that: the gas-liquid separation device includes a primary gas-liquid separator, a secondary gas-liquid separator, a primary peristaltic pump, a secondary peristaltic pump, and a waste liquid tank; the liquid inlet of the primary gas-liquid separator is connected to one side of the reducing agent tee; the air inlet of the primary gas-liquid separator is connected to one side of the gas path tee; the liquid outlet of the primary gas-liquid separator is connected to the primary peristaltic pump; and the air outlet of the primary gas-liquid separator is connected to the air inlet of the secondary gas-liquid separator.

[0012] A further improvement is that: the outlet of the secondary gas-liquid separator is connected to the detection device, the drain outlet of the secondary gas-liquid separator is connected to the secondary peristaltic pump, the primary peristaltic pump is used to discharge the waste liquid in the primary gas-liquid separator into the waste liquid tank, and the secondary peristaltic pump is used to discharge the waste liquid in the secondary gas-liquid separator into the waste liquid tank.

[0013] The beneficial effects of this utility model are as follows:

[0014] 1. This invention eliminates the need for manual degassing of the mobile phase. Researchers only need to prepare the mobile phase and place the tubing in the corresponding reagent bottle; the instrument can then degas it online, saving time required for mobile phase preparation. Hydrogen is added when the sample reacts with the reducing agent to generate gaseous hydrides, effectively reducing the amount of potassium borohydride used. While ensuring the health of researchers and providing a friendly laboratory environment, it reduces the impact of moisture on test results, improves the sensitivity and stability of the instrument, and is environmentally friendly, safe, and easy to operate, making it highly valuable for widespread application.

[0015] 2. This utility model uses an online degasser to degas the mobile phase online, and can simultaneously control the flow of hydrogen through a gas circuit switch. This reduces instrument baseline drift while decreasing the concentration of reducing agent and water vapor, thus improving the accuracy of test data. During operation, two or more experimental procedures can be implemented. When switching between different experimental procedures, a one-way valve and a gas circuit switch can be used for control. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the structure of this utility model.

[0017] The components include: 1. Mobile phase processing device; 2. Online sample reaction device; 3. Gas path device; 4. Gas-liquid separation device; 5. First mobile phase bottle; 6. Second mobile phase bottle; 7. Degasser; 8. First liquid phase pump; 9. Second liquid phase pump; 10. Mobile phase tee; 11. Injection valve; 12. Chromatographic column; 13. Carrier or online digestion solution bottle; 14. Carrier bottle; 15. Reducing agent bottle; 16. Peristaltic pump; 17. One-way valve; 18. Chromatographic column tee; 19. Carrier tee; 20. Reducing agent tee; 21. Online ultraviolet digestion device; 22. Argon device; 23. Hydrogen generator device; 24. Gas path tee; 25. Gas path switch; 26. First-stage gas-liquid separator; 27. Second-stage gas-liquid separator; 28. First-stage peristaltic pump; 29. ​​Second-stage peristaltic pump; 30. Waste liquid tank; 31. Detection device. Detailed Implementation

[0018] To deepen the understanding of this utility model, the following detailed description will be provided in conjunction with embodiments. These embodiments are only used to explain this utility model and do not constitute a limitation on the scope of protection of this utility model.

[0019] Example 1

[0020] according to Figure 1 As shown, this embodiment proposes a liquid chromatography-atomic fluorescence flow path analysis system, including a mobile phase processing device 1, an online sample reaction device 2, a gas path device 3, and a gas-liquid separation device 4. The mobile phase processing device 1 is used to degas the mobile phase online, and the online sample reaction device 2 is used to separate the sample, perform online ultraviolet digestion, and generate hydrides.

[0021] The gas path device 3 is used to provide carrier gas and supplement hydrogen, and the gas-liquid separation device 4 is used to remove water vapor from the hydride.

[0022] The mobile phase processing device 1 includes a first mobile phase bottle 5, a second mobile phase bottle 6, a degasser 7, a first liquid phase pump 8, a second liquid phase pump 9, a mobile phase tee 10, and a sample injection valve 11. The two inlets of the degasser 7 are connected to the first mobile phase bottle 5 and the second mobile phase bottle 6, respectively. The two outlets of the degasser 7 are connected to the first liquid phase pump 8 and the second liquid phase pump 9, respectively. The output ports of the first liquid phase pump 8 and the second liquid phase pump 9 are connected to the two side interfaces of the mobile phase tee 10, and the output interface of the mobile phase tee 10 is connected to the sample injection valve 11. The online degasser 7 performs online degassing of the mobile phase, and the hydrogen supply can be controlled via the gas path switch 25. This reduces instrument baseline drift while decreasing the concentration of reducing agent and water vapor, thus improving the accuracy of test data.

[0023] The online sample reaction device 2 includes a chromatographic column 12, a carrier or online digestion solution bottle 13, a carrier bottle 14, a reducing agent bottle 15, a peristaltic pump 16, a one-way valve 17, a column tee 18, a carrier tee 19, a reducing agent tee 20, and an online ultraviolet digestion device 21. The carrier or online digestion solution bottle 13, the carrier bottle 14, and the reducing agent bottle 15 are respectively connected to the inlet of the carrier or online digestion solution pump tube, the carrier pump tube, and the reducing agent pump tube of the peristaltic pump 16. The outlets of the carrier or online digestion solution pump tube, the carrier pump tube, and the reducing agent pump tube are respectively connected to the column tee 18, the one-way valve 17, and the reducing agent tee 20. The outlet of the one-way valve 17 is connected to the carrier tee 19. The one-way valve 17 ensures that the outlet of the carrier pump tube is open to the interface of the carrier tee 19.

[0024] The lower end of the column tee 18 is connected to the outlet of the column 12, and the inlet of the column 12 is connected to the outlet of the injection valve 11. One side of the column tee 18 is connected to the inlet of the online UV digestion device 21. One side of the flow carrier tee 19 is connected to the outlet of the online UV digestion device 21. The lower end of the reducing agent tee 20 is connected to the upper end of the flow carrier tee 19.

[0025] The gas path device 3 includes an argon gas device 22, a hydrogen generator device 23, a gas path tee 24, and a gas path switch 25. The outlet of the argon gas device 22 is connected to the lower interface of the gas path tee 24 via a TPU tubing. The hydrogen generator device 23 is connected to the inlet of the gas path switch 25. The upper interface of the gas path tee 24 is connected to the outlet of the gas path switch 25 via a TPU tubing. The gas path device 3 includes an argon gas device 22 for providing carrier gas, a hydrogen generator device 23 for supplementing hydrogen, a gas path tee 24 for mixing argon and hydrogen, and a gas path switch 25 for controlling the hydrogen flow. During operation, two or more experimental procedures can be implemented. Switching between different experimental procedures can be controlled using a one-way valve 17 and a gas path switch 25.

[0026] The gas-liquid separation device 4 includes a primary gas-liquid separator 26, a secondary gas-liquid separator 27, a primary peristaltic pump 28, a secondary peristaltic pump 29, and a waste liquid tank 30. The liquid inlet of the primary gas-liquid separator 26 is connected to one side interface of the reducing agent tee 20, the air inlet of the primary gas-liquid separator 26 is connected to one side interface of the gas passage tee 24, the liquid outlet of the primary gas-liquid separator 26 is connected to the primary peristaltic pump 28, and the air outlet of the primary gas-liquid separator 26 is connected to the air inlet of the secondary gas-liquid separator 27.

[0027] The outlet of the secondary gas-liquid separator 27 is connected to the detection device 31, and the drain outlet of the secondary gas-liquid separator 27 is connected to the secondary peristaltic pump 29. The primary peristaltic pump 28 is used to discharge the waste liquid in the primary gas-liquid separator 26 into the waste liquid tank 30, and the secondary peristaltic pump 29 is used to discharge the waste liquid in the secondary gas-liquid separator 27 into the waste liquid tank 30.

[0028] Example 2

[0029] according to Figure 1 As shown, this embodiment proposes a liquid chromatography-atomic fluorescence flow path analysis system, performing the first experimental procedure, which includes the following steps: isocratic elution, hydrogen replenishment, and digestion without UV light. The specific implementation is as follows: Turn on the hydrogen generator device 23 and the gas circuit switch 25; turn on the argon device 22; place the prepared mobile phase in the first mobile phase bottle 5, and turn on the degasser 7 and the first liquid phase pump 8; place the carrier liquid in the carrier or online digestion solution bottle 13, and connect the carrier or online digestion solution pump tube; place the reducing agent in the reducing agent bottle 15, and connect the reducing agent pump tube; turn on the peristaltic pump 16, and turn off the UV lamp of the online UV digestion device 21; ensure that the one-way valve 17 is not connected to the outlet of the carrier pump tube at the interface of the carrier tee 19; inject the sample into the injection valve 11 through a syringe pump or other injection device; under the push of the first liquid phase pump 8, the various components of the sample enter the chromatography system. The solution is separated in column 12 and then passes through column tee 18, where it mixes with the carrier solution in the carrier or online digestion bottle 13. The mixture then flows through the online UV digestion device 21 and carrier tee 19, where it mixes and reacts with the reducing agent solution in reducing agent bottle 15 in reducing agent tee 20. The mixture then enters the first-stage gas-liquid separator 26, where gaseous hydrides are generated. These gaseous hydrides are then introduced into the second-stage gas-liquid separator 27 for secondary gas-liquid separation under the action of argon-hydrogen gas mixed in gas path tee 24. The resulting product is then detected in the detection device 31. The waste liquid after the reaction is completed is discharged into the waste liquid tank 30 by the action of the first-stage peristaltic pump 28 and the second-stage peristaltic pump 29.

[0030] Example 3

[0031] according to Figure 1As shown, this embodiment proposes a liquid chromatography-atomic fluorescence flow path analysis system to perform a second experimental procedure, which includes the following steps: gradient elution, no hydrogen gas added, and UV digestion. The specific implementation method is as follows: Close the gas circuit switch 25; turn on the argon gas device 22; place the prepared mobile phase A in the first mobile phase bottle 5 and the prepared mobile phase B in the second mobile phase bottle 6; turn on the degasser 7, the first liquid phase pump 8, and the second liquid phase pump 9; place the online digestion solution in the carrier or online digestion solution bottle 13 and install the carrier or online digestion solution pump tubing; place the carrier in the carrier bottle 14 and install the carrier pump tubing; place the reducing agent in the reducing agent bottle 15 and install the reducing agent pump tubing; turn on the peristaltic pump 16 and turn on the UV lamp of the online UV digestion device 16; ensure that the one-way valve 17 is open from the outlet of the carrier pump tubing to the interface of the carrier tee 19; inject the sample into the injection valve 11 through the syringe pump or other injection device, and inject the sample into the injection valve 11 via the first liquid phase pump 8 / second liquid phase pump. Driven by 9, the various components of the sample enter the chromatographic column 12 and are separated. Then, they pass through the chromatographic column tee 18 and mix with the online digestion solution in the carrier or online digestion solution bottle 13. They then flow together through the online ultraviolet digestion device 16, mix with the carrier solution in the carrier tee 19, and mix and react with the reducing agent solution in the reducing agent bottle 15 in the reducing agent tee 20. They then enter the first-stage gas-liquid separator 26, where gaseous hydrides are generated. Under the action of argon gas in the gas path tee 24, the gaseous hydrides enter the second-stage gas-liquid separator 27 for secondary gas-liquid separation. The products generated then enter the detection device 31 for detection. The waste liquid after the reaction is completed is discharged into the waste liquid tank 30 by the action of the first-stage peristaltic pump 28 and the second-stage peristaltic pump 29.

[0032] After the experiment, the pipeline was cleaned with pure water. The carrier or online digestion pump tubing, the carrier pump tubing, and the reducing agent pump tubing were placed in pure water. The peristaltic pump 16 was turned on, and the pipeline was cleaned with pure water. After cleaning, the pump clamp was released. The corresponding cleaning solutions were placed in the first mobile phase bottle 5 and the second mobile phase bottle 6. The first liquid phase pump 8 and the second liquid phase pump 9 were turned on to clean the liquid phase pumps and the chromatographic column 12. After cleaning, the liquid phase pumps were turned off. In the above experimental procedure, the flow rate of the solutions in the first mobile phase bottle 5 and the second mobile phase bottle 6 was controlled by the liquid phase pumps, and the hydrogen flow was controlled by the gas circuit switch 25.

[0033] This liquid chromatography-atomic fluorescence flow path analysis system eliminates the need for manual degassing of the mobile phase. Operators only need to prepare the mobile phase and place the tubing in the corresponding reagent bottle; the instrument then performs online degassing, saving time previously required for mobile phase preparation. Hydrogen is added when the sample reacts with the reducing agent to generate gaseous hydrides, effectively reducing the amount of potassium borohydride used. This ensures the health of researchers, provides a friendly laboratory environment, reduces the impact of moisture on test results, and improves the sensitivity and stability of the instrument. It is environmentally friendly, safe, and easy to operate, making it highly valuable for widespread adoption. Furthermore, this product uses an online degasser 7 to degas the mobile phase online, and the hydrogen supply can be controlled via a gas path switch 25. This reduces baseline drift while minimizing the concentration of the reducing agent and moisture, improving the accuracy of test data. During operation, two or more experimental procedures can be implemented, and switching between different procedures can be controlled using a one-way valve 17 and a gas path switch 25.

[0034] The foregoing has shown and described the basic principles, main features, and advantages of this utility model. Those skilled in the art should understand that this utility model is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of this utility model. Various changes and modifications can be made to this utility model without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed utility model. The scope of protection of this utility model is defined by the appended claims and their equivalents.

Claims

1. A liquid chromatography-atomic fluorescence flow analysis system, comprising a mobile phase processing device (1), a sample online reaction device (2), a gas path device (3) and a gas-liquid separation device (4), characterized in that: The mobile phase processing device (1) is used to degas the mobile phase online, and the sample online reaction device (2) is used to separate the sample, perform online ultraviolet digestion, and generate hydrides. The gas path device (3) is used to provide carrier gas and supplement hydrogen, and the gas-liquid separation device (4) is used to remove water vapor from the hydride.

2. The liquid chromatography-atomic fluorescence flow analysis system according to claim 1, characterized in that: The mobile phase processing device (1) includes a first mobile phase bottle (5), a second mobile phase bottle (6), a degasser (7), a first liquid pump (8), a second liquid pump (9), a mobile phase tee (10), and a sample injection valve (11). The two inlets of the degasser (7) are connected to the first mobile phase bottle (5) and the second mobile phase bottle (6) respectively. The two outlets of the degasser (7) are connected to the first liquid pump (8) and the second liquid pump (9) respectively. The output ports of the first liquid pump (8) and the second liquid pump (9) are connected to the two side interfaces of the mobile phase tee (10) respectively, and the output interface of the mobile phase tee (10) is connected to the sample injection valve (11).

3. The liquid chromatography-atomic fluorescence flow analysis system according to claim 2, characterized in that: The online sample reaction device (2) includes a chromatographic column (12), a carrier or online digestion solution bottle (13), a carrier bottle (14), a reducing agent bottle (15), a peristaltic pump (16), a one-way valve (17), a chromatographic column tee (18), a carrier tee (19), a reducing agent tee (20), and an online ultraviolet digestion device (21). The carrier or online digestion solution bottle (13), the carrier bottle (14), and the reducing agent bottle (15) are respectively connected to the inlet of the carrier or online digestion solution pump tube, the carrier pump tube, and the reducing agent pump tube of the peristaltic pump (16), and the outlet of the carrier or online digestion solution pump tube, the carrier pump tube, and the reducing agent pump tube are respectively connected to the chromatographic column tee (18), the one-way valve (17), and the reducing agent tee (20), and the outlet of the one-way valve (17) is connected to the carrier tee (19).

4. The liquid chromatography-atomic fluorescence flow analysis system according to claim 3, characterized in that: The lower end of the column tee (18) is connected to the outlet of the column (12), and the inlet of the column (12) is connected to the outlet of the injection valve (11). One side of the column tee (18) is connected to the inlet of the online ultraviolet digestion device (21). One side of the flow carrier tee (19) is connected to the outlet of the online ultraviolet digestion device (21). The lower end of the reducing agent tee (20) is connected to the upper end of the flow carrier tee (19).

5. The liquid chromatography-atomic fluorescence flow analysis system according to claim 4, characterized in that: The gas circuit device (3) includes an argon gas device (22), a hydrogen generator device (23), a gas circuit tee (24), and a gas circuit switch (25). The outlet of the argon gas device (22) is connected to the lower interface of the gas circuit tee (24) through a TPU gas tube. The hydrogen generator device (23) is connected to the inlet of the gas circuit switch (25). The upper interface of the gas circuit tee (24) is connected to the outlet of the gas circuit switch (25) through a TPU gas tube.

6. The liquid chromatography-atomic fluorescence flow analysis system according to claim 5, characterized in that: The gas-liquid separation device (4) includes a primary gas-liquid separator (26), a secondary gas-liquid separator (27), a primary peristaltic pump (28), a secondary peristaltic pump (29), and a waste liquid tank (30). The inlet of the primary gas-liquid separator (26) is connected to one side of the reducing agent tee (20). The air inlet of the primary gas-liquid separator (26) is connected to one side of the gas path tee (24). The outlet of the primary gas-liquid separator (26) is connected to the primary peristaltic pump (28). The outlet of the primary gas-liquid separator (26) is connected to the inlet of the secondary gas-liquid separator (27).

7. The liquid chromatography-atomic fluorescence flow path analysis system according to claim 6, characterized in that: The outlet of the secondary gas-liquid separator (27) is connected to the detection device (31), and the drain outlet of the secondary gas-liquid separator (27) is connected to the secondary peristaltic pump (29). The primary peristaltic pump (28) is used to discharge the waste liquid in the primary gas-liquid separator (26) into the waste liquid tank (30), and the secondary peristaltic pump (29) is used to discharge the waste liquid in the secondary gas-liquid separator (27) into the waste liquid tank (30).

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