Automatic analysis system for large-volume sample injection on-line double-solid-phase extraction

Abstract

The invention discloses an automatic analysis system for large-volume sample injection and online dual-solid-phase extraction. The automatic analysis system is characterized by comprising large-volume sample injection-online dual-solid-phase extraction equipment and instrument analysis equipment, the large-volume sampling-online double-solid-phase extraction equipment and the instrument analysis equipment are respectively in communication connection with the cloud controller through a wireless communication module, the cloud controller is connected with a data storage server, and the data storage server is used for storing detection data of the large-volume sampling-online double-solid-phase extraction equipment and the instrument analysis equipment; the large-volume sampling-online double-solid-phase extraction equipment is connected with a detection sample intelligent identification system, and the detection sample intelligent identification system is connected with a storage analysis system; the method has good adaptability, the sample pretreatment time can be further saved, and the analysis and test efficiency is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of analysis systems, and in particular relates to an automatic analysis system for large-volume sample injection and online double-solid-phase extraction. Background Art

[0002] Liquid chromatography has been widely used in food safety, drug development, clinical diagnosis, toxicology and environmental monitoring. Due to the complexity of samples, sample pretreatment has become an indispensable part of liquid chromatography analysis. Sample pretreatment often requires operators to perform multiple manual steps to complete, which accounts for more than 80% of the overall analysis time. The commonly used method for sample pretreatment is solid phase extraction, which removes interfering substances in the sample and enriches trace components for easy detection and separation without damaging the chromatographic column. At present, the commonly used solid phase extraction is offline solid phase extraction.

[0003] For example, the existing Chinese patent with publication number CN118604215A discloses an online single-column solid-phase extraction system, which is characterized in that it includes a first six-way valve, a second six-way valve and a solid-phase extraction column; the first valve port of the first six-way valve is used for sample injection, the second valve port of the first six-way valve is used to connect to a first waste liquid pipe, a quantitative loop is connected between the third valve port of the first six-way valve and the sixth valve port of the first six-way valve, the fourth valve port of the first six-way valve is connected to the first valve port of the second six-way valve, and the fifth valve port of the first six-way valve is used to connect to a sample regeneration activation pump; the second valve port of the second six-way valve is used to connect to a second waste liquid pipe, the solid-phase extraction column is connected between the third valve port of the second six-way valve and the sixth valve port of the second six-way valve, the fourth valve port of the second six-way valve is used to connect to a liquid chromatography column, and the fifth valve port of the second six-way valve is used to connect to a liquid phase pump.

[0004] Another example is the existing Chinese patent with publication number CN208060458U, which discloses an online purification and solid phase extraction device for determining carbendazim in orange juice, characterized in that it includes an enrichment pump, an analysis pump, an automatic sampler, a ten-way valve, a column temperature box, an SPE column, an analysis column and a diode array detector; the analysis pump and the enrichment pump form a double pump, wherein the outlet of the enrichment pump is connected to the input end of the automatic sampler, and the analysis column is arranged in the column temperature box; when performing purification / solid phase extraction, the output end of the automatic sampler is connected to the input end of the SPE column through the ten-way valve, and the output end of the SPE column is connected to wastewater through the ten-way valve; the outlet of the analysis pump is connected to the input end of the analysis column through the ten-way valve, and the output end of the analysis column is connected to the input end of the diode array detector.

[0005] The above-mentioned patents and current technologies have some advantages respectively, but they still have the following disadvantages, such as: they cannot conveniently realize online detection, and are not easy to adapt to the needs of various detection scenarios, and need to be improved. Summary of the invention

[0006] The object of the present invention is to provide an automatic analysis system for large-volume sample injection and online double solid-phase extraction to solve the problems raised in the above-mentioned background technology.

[0007] To achieve the above object, the present invention provides the following technical solutions: an automatic analysis system for large volume injection online double solid phase extraction, comprising a large volume injection-online double solid phase extraction device and an instrumental analysis device;

[0008] The large volume injection-online dual solid phase extraction device and the instrument analysis device are respectively connected to the cloud controller through a wireless communication module, and the cloud controller is connected to a data storage server, and the data storage server is used to store the detection data of the large volume injection-online dual solid phase extraction device and the instrument analysis device;

[0009] The large volume injection-online dual solid phase extraction device is connected to a detection sample intelligent identification system, and the detection sample intelligent identification system is connected to a storage and analysis system, and the storage and analysis system analyzes and stores relevant data information of the detection data according to the analysis results of the instrument analysis device and the identification results of the detection sample intelligent identification system;

[0010] The cloud controller is also connected to an intelligent unmanned supervision system, and the cloud controller is also connected to a sample pre-processing information automatic identification system and a sample test automatic labeling system;

[0011] The large volume injection-online dual solid phase extraction equipment includes a liquid chromatography pump for pushing samples and solvents required for solid phase extraction, an automatic sample injector for loading and collecting samples, a high pressure six-way valve and a high pressure ten-way valve for flow path switching, and two solid phase extraction columns for enriching target substances and removing impurities;

[0012] The instrumental analysis equipment includes but is not limited to liquid chromatograph, gas chromatograph, liquid-mass spectrometer, gas-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer and other chromatography, mass spectrometry and spectral analysis instruments.

[0013] Preferably, the intelligent unmanned supervision system includes a data result extraction module, a reaction parameter information acquisition module, a sample processing data management module, and a real-time monitoring module. The data result extraction module, the reaction parameter information acquisition module, and the sample processing data management module are respectively connected to the cloud controller to upload the respectively acquired data to the data storage server. The real-time monitoring module detection includes a visual camera, and the visual camera performs external real-time observation of the large-volume injection-online dual solid-phase extraction equipment and the instrument analysis equipment. The large-volume injection-online dual solid-phase extraction equipment and the instrument analysis equipment are respectively connected to the cloud controller.

[0014] Preferably, the sample testing automatic labeling system includes a data acquisition module, a data upload and processing module, a data transmission and sharing module, a dynamic management and control module and an automatic labeling module. The data acquisition module collects sample test information, and the data upload and processing module uploads the sample test information collected by the data acquisition module to the cloud controller through the data transmission and sharing module. The cloud controller assigns labeling information to each group of tested samples through the dynamic management and control module, and the automatic labeling module automatically adds labels according to the assigned labeling information.

[0015] Preferably, the automatic sampler includes a sample tray, the sample tray is provided with a plurality of placement positions for placing sample bottles, the placement positions are respectively marked with position numbers, and when collecting samples, quantitative samples are collected by a liquid chromatography pump or infrared light sensing technology, and internal standards and / or substitutes are added online by the automatic sampler; a pressure sensor is provided in the placement position, the pressure sensor is electrically connected to the control input end of the PLC controller, and the control output end of the PLC controller is connected to a position number management system, and the position number management system includes a position number generation submodule and a position number storage submodule.

[0016] Preferably, the liquid chromatography pump has a built-in low-pressure gradient proportional valve, and the low-pressure gradient proportional valve is used to selectively push four different solvents.

[0017] Preferably, the sample tray is placed on a multi-directional motion device, on which are placed a liquid injection needle for sampling and labeling, a sample bottle for placing standard liquid and waste liquid, and a nitrogen blowing device for controlling the nitrogen gas flow path. The multi-directional motion device is electrically connected to the control output terminal of the PLC controller.

[0018] Preferably, the high-pressure six-way valve and the high-pressure ten-way valve are used in series to achieve alternate extraction of samples by two solid phase extraction columns and nitrogen drying of the solid phase extraction columns.

[0019] Preferably, the high-pressure six-way valve is equipped with a quantitative loop ranging from a few microliters to tens of milliliters, and the high-pressure ten-way valve is used to carry two parallel solid phase extraction columns.

[0020] Preferably, the control input end of the PLC controller is connected to a plurality of visual cameras, and the plurality of visual cameras are respectively arranged at the automatic sample injector and the liquid chromatography pump, and the control output end of the PLC controller is electrically connected to an alarm module.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] This system can realize intelligent-unsupervision. This system has strong applicability. Different solid phase extraction columns can be used to connect chromatographic and spectral equipment for quantitative analysis. This system adopts dual-path solid phase extraction to save waiting time. This system can realize automatic identification of sample pretreatment information and automatic addition of sample test. The online SPE equipment and instrument analysis equipment share a sample tray to realize the combination of the two devices, thereby realizing online detection. The six-way valve used in the present invention can carry a few milliliters to tens of milliliters of quantitative bads. Two parallel processed solid phase extraction columns can be overlapped for pretreatment, which greatly reduces the time occupied by a single sample in the entire batch sample. In addition, this system can be freely matched with different analytical instruments to meet the needs of various detection scenarios. By adding a liquid chromatography pump, the present invention can realize the connection of the ten-way valve with the sample injection pipeline of analytical instruments such as liquid chromatograph, liquid-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer, etc., so that it can flexibly and efficiently switch to the mode in which the eluent is fully used for sample injection analysis, further improving the analysis sensitivity. In addition, this system has a remote communication control function. By applying wireless communication modules, cloud controllers and PLC controllers, remote intelligent wireless control can be achieved to improve the intelligence of this system. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 One of the system block diagrams of the present invention;

[0024] Figure 2 This is the second system block diagram of the present invention;

[0025] Figure 3 This is the third system block diagram of the present invention;

[0026] Figure 4 It is a schematic diagram of the eluent collection mode of the present invention. DETAILED DESCRIPTION

[0027] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] Example 1

[0029] See also Figure 1-Figure 4The present invention provides a technical solution: an automatic analysis system for large-volume sampling online double solid-phase extraction, comprising a large-volume sampling online double solid-phase extraction device and an instrument analysis device; the large-volume sampling online double solid-phase extraction device and the instrument analysis device are respectively connected to a cloud controller through a wireless communication module, the cloud controller is connected to a data storage server, and the data storage server is used to store the detection data of the large-volume sampling online double solid-phase extraction device and the instrument analysis device; the large-volume sampling online double solid-phase extraction device is connected to a detection sample intelligent recognition system, and the detection sample intelligent recognition system is connected to a storage analysis system The storage and analysis system analyzes and stores the relevant data of the test data according to the analysis results of the instrument analysis equipment and the identification results of the test sample intelligent identification system; the cloud controller is also connected to the intelligent unmanned supervision system, the cloud controller is also connected to the sample pre-treatment information automatic identification system and the sample test automatic spike addition system; the large volume injection-online dual solid phase extraction equipment includes a liquid chromatography pump for pushing samples and solvents required for solid phase extraction, an automatic sampler for loading and collecting samples, a high-pressure six-way valve and a high-pressure ten-way valve for flow switching, and two solid phase extraction columns for enriching the target and removing impurities;

[0030] Instrumental analysis equipment includes, but is not limited to, liquid chromatograph, gas chromatograph, liquid-mass spectrometer, gas-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer and other chromatography, mass spectrometry and spectral analysis instruments.

[0031] Among them, the intelligent unmanned supervision system includes a data result extraction module, a reaction parameter information acquisition module, a sample processing data management module, and a real-time monitoring module. The data result extraction module, the reaction parameter information acquisition module, and the sample processing data management module are respectively connected to the cloud controller, and the respectively acquired data are uploaded to the data storage server. The real-time monitoring module detection includes a visual camera, and the visual camera performs external real-time observation of the large-volume injection-online dual solid-phase extraction equipment and the instrument analysis equipment. The large-volume injection-online dual solid-phase extraction equipment and the instrument analysis equipment are respectively connected to the cloud controller.

[0032] Among them, the sample testing automatic labeling system includes a data acquisition module, a data upload and processing module, a data transmission and sharing module, a dynamic management and control module and an automatic labeling module. The data acquisition module collects sample test information, and the data upload and processing module uploads the sample test information collected by the data acquisition module to the cloud controller through the data transmission and sharing module. The cloud controller assigns labeling information to each group of tested samples through the dynamic management and control module, and the automatic labeling module automatically adds labels according to the assigned labeling information.

[0033] Among them, the automatic sampler includes a sample tray, which is provided with a plurality of placement positions for placing sample bottles, and the placement positions are respectively marked with position numbers. When collecting samples, quantitative samples are collected through a liquid chromatography pump or infrared light sensing technology, and internal standards and / or substitutes are added online through the automatic sampler; a pressure sensor is arranged in the placement position, and the pressure sensor is electrically connected to the control input end of the PLC controller, and the control output end of the PLC controller is connected to a position number management system, which includes a position number generation submodule and a position number storage submodule.

[0034] Among them, the liquid chromatography pump has a built-in low-pressure gradient proportional valve, which is used to selectively push four different solvents.

[0035] Among them, the sample tray is placed on a multi-directional motion device, on which are placed liquid sampling needles for sampling and labeling, sample bottles for placing standard liquid and waste liquid, and a nitrogen blowing device for controlling the nitrogen flow path. The multi-directional motion device is electrically connected to the control output end of the PLC controller.

[0036] Among them, the high-pressure six-way valve and the high-pressure ten-way valve are used in series to realize the alternate extraction of samples by two solid phase extraction columns and the nitrogen blowing drying of the solid phase extraction columns.

[0037] Among them, the high-pressure six-way valve is equipped with a quantitative loop ranging from a few microliters to tens of milliliters, and the high-pressure ten-way valve is used to carry two parallel solid-phase extraction columns.

[0038] Among them, the control input end of the PLC controller is connected to a plurality of visual cameras, and the plurality of visual cameras are respectively arranged at the automatic sample injector and the liquid chromatography pump. The control output end of the PLC controller is electrically connected to an alarm module.

[0039] Among them, the online SPE equipment and instrument analysis equipment of this system share a sample tray to realize the combination of the two devices, thereby realizing online detection. The six-way valve used in the present invention can carry a few milliliters to tens of milliliters of quantitative bad, and the two parallel processed solid phase extraction columns can be overlapped for pre-treatment, which greatly reduces the time occupied by a single sample in the entire batch sample. In addition, the system can be freely matched with different analytical instruments to meet the needs of various detection scenarios. By adding a liquid chromatography pump, the present invention can realize the connection of the ten-way valve with the sample injection pipeline of analytical instruments such as liquid chromatograph, liquid-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer, etc., so that it can be flexibly and efficiently switched to the mode in which the eluent is fully applied to the sample injection analysis, further improving the analysis sensitivity. In addition, the system has a remote communication control function. By applying a wireless communication module, a cloud controller and a PLC controller, remote intelligent wireless control can be realized to improve the intelligence of the system.

[0040] Example 2

[0041] refer to Figure 1-Figure 4 This embodiment discloses an automatic water sample analysis system, which includes a large-volume water sample injection-online dual solid phase extraction device and an instrumental analysis device. The large-volume injection-online dual solid phase extraction device includes a high-pressure six-way valve, a high-pressure ten-way valve, a liquid chromatography pump, an automatic sampler, and two solid phase extraction columns. The instrumental analysis device includes but is not limited to liquid chromatographs, gas chromatographs, liquid-mass spectrometers, gas chromatographs, inductively coupled plasma mass spectrometers, atomic fluorescence spectrometers and other chromatography, mass spectrometry, and spectral analysis instruments. The online SPE device and the instrumental analysis device share a sample tray to realize the combination of the two devices, thereby realizing online detection. The six-way valve can carry a few milliliters to tens of milliliters of quantitative bads, and the two parallel-processed solid phase extraction columns can perform overlapping pre-treatments, which greatly reduces the time occupied by a single sample in the entire batch sample. The system can be freely matched with different analytical instruments to meet the needs of various detection scenarios.

[0042] By adding a liquid chromatography pump, the present invention can realize the connection of the ten-way valve with the sampling pipeline of analytical instruments such as liquid chromatograph, liquid-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer, etc., so as to flexibly and efficiently switch to a mode in which all eluents are used for sampling analysis, thereby further improving the analysis sensitivity.

[0043] A large volume injection-online dual solid phase extraction automatic analysis system of this embodiment includes a large volume injection-online dual solid phase extraction device and an instrument analysis device;

[0044] Large volume injection - online dual solid phase extraction equipment includes a liquid chromatography pump for pushing samples and solvents required for solid phase extraction, an automatic sampler for loading and collecting samples, a high-pressure six-port valve and a high-pressure ten-port valve for flow path switching, and two solid phase extraction columns for enriching the target and removing impurities;

[0045] Instrumental analysis equipment includes, but is not limited to, liquid chromatograph, gas chromatograph, liquid-mass spectrometer, gas-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer and other chromatography, mass spectrometry and spectral analysis instruments.

[0046] The online dual solid phase extraction device and the instrumental analysis device share an automatic sampler and a sample tray, thereby realizing large volume injection-online dual solid phase extraction device and the instrumental analysis device in combination.

[0047] Among them, the sample tray is provided with multiple placement positions for placing sample bottles, and the placement positions are marked with position numbers. When collecting samples, quantitative sample collection can be achieved through liquid chromatography pump or infrared light sensing technology, and internal standards and / or substitutes can be added online through an automatic sampler.

[0048] Among them, the liquid chromatography pump has a built-in low-pressure gradient proportional valve that can selectively push four different solvents.

[0049] The sample tray is placed on a multi-directional motion device, on which are placed a liquid injection needle for sampling and adding a standard, a sample bottle for placing a standard liquid and a waste liquid, and a nitrogen blowing device for controlling a nitrogen gas flow path.

[0050] Among them, by adding a liquid chromatography pump and directly connecting the ten-way valve to the sampling pipeline of analytical instruments such as liquid chromatograph, liquid-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer, etc., it is convenient to switch to a mode in which the eluent is entirely used for sampling analysis.

[0051] Among them, the high-pressure six-way valve and the high-pressure ten-way valve are used in series, which can realize the alternate extraction of samples by two solid phase extraction columns and realize the nitrogen blowing drying function of the solid phase extraction column.

[0052] Among them, the high-pressure six-way valve can carry a quantitative loop ranging from a few microliters to tens of milliliters, and the high-pressure ten-way valve can carry two parallel solid-phase extraction columns.

[0053] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An automatic analysis system for large volume injection online double solid phase extraction, characterized in that: Including large volume injection-online dual solid phase extraction equipment and instrumental analysis equipment; The large volume injection-online dual solid phase extraction device and the instrument analysis device are respectively connected to the cloud controller through a wireless communication module, and the cloud controller is connected to a data storage server, and the data storage server is used to store the detection data of the large volume injection-online dual solid phase extraction device and the instrument analysis device; The large volume injection-online dual solid phase extraction device is connected to a detection sample intelligent identification system, and the detection sample intelligent identification system is connected to a storage and analysis system, and the storage and analysis system analyzes and stores relevant data information of the detection data according to the analysis results of the instrument analysis device and the identification results of the detection sample intelligent identification system; The cloud controller is also connected to an intelligent unmanned supervision system, and the cloud controller is also connected to a sample pre-processing information automatic identification system and a sample test automatic labeling system; The large volume injection-online dual solid phase extraction equipment includes a liquid chromatography pump for pushing samples and solvents required for solid phase extraction, an automatic sample injector for loading and collecting samples, a high pressure six-way valve and a high pressure ten-way valve for flow path switching, and two solid phase extraction columns for enriching target substances and removing impurities; The instrumental analysis equipment includes but is not limited to liquid chromatograph, gas chromatograph, liquid-mass spectrometer, gas-mass spectrometer, inductively coupled plasma mass spectrometer, atomic fluorescence spectrometer and other chromatography, mass spectrometry and spectral analysis instruments.

2. The automatic analysis system for large volume injection online double solid phase extraction according to claim 1, characterized in that: The intelligent unmanned supervision system includes a data result extraction module, a reaction parameter information acquisition module, a sample processing data management module, and a real-time monitoring module. The data result extraction module, the reaction parameter information acquisition module, and the sample processing data management module are respectively connected to the cloud controller, and the respectively acquired data are uploaded to the data storage server. The real-time monitoring module detection includes a visual camera, and the visual camera performs external real-time observation of the large-volume injection-online dual solid-phase extraction equipment and the instrument analysis equipment. The large-volume injection-online dual solid-phase extraction equipment and the instrument analysis equipment are respectively connected to the cloud controller.

3. The automatic analysis system for large volume injection online double solid phase extraction according to claim 2, characterized in that: The sample testing automatic labeling system includes a data acquisition module, a data upload and processing module, a data transmission and sharing module, a dynamic management and control module and an automatic labeling module. The data acquisition module acquires sample testing information. The data upload and processing module uploads the sample testing information acquired by the data acquisition module to the cloud controller through the data transmission and sharing module. The cloud controller assigns labeling information to each group of tested samples through the dynamic management and control module. The automatic labeling module automatically adds labels according to the assigned labeling information.

4. The automatic analysis system for large volume injection online double solid phase extraction according to claim 2, characterized in that: The automatic sampler includes a sample tray, which is provided with a plurality of placement positions for placing sample bottles, and the placement positions are respectively marked with position numbers. When collecting samples, quantitative samples are collected by a liquid chromatography pump or infrared light sensing technology, and internal standards and / or substitutes are added online by the automatic sampler; a pressure sensor is provided in the placement position, and the pressure sensor is electrically connected to the control input end of the PLC controller. The control output end of the PLC controller is connected to a position number management system, and the position number management system includes a position number generation submodule and a position number storage submodule.

5. The automatic analysis system for large volume injection online double solid phase extraction according to claim 1, characterized in that: The liquid chromatography pump is internally provided with a low-pressure gradient proportional valve, and the low-pressure gradient proportional valve is used for selectively pushing four different solvents.

6. The automatic analysis system for large volume injection online double solid phase extraction according to claim 4, characterized in that: The sample tray is placed on a multi-directional motion device, on which are placed a liquid injection needle for sampling and labeling, a sample bottle for placing standard liquid and waste liquid, and a nitrogen blowing device for controlling the nitrogen gas flow path. The multi-directional motion device is electrically connected to the control output end of the PLC controller.

7. The automatic analysis system for large volume injection online double solid phase extraction according to claim 1, characterized in that: The high-pressure six-way valve and the high-pressure ten-way valve are used in series to realize the alternate extraction of samples by two solid phase extraction columns and the nitrogen blowing drying of the solid phase extraction columns.

8. The automatic analysis system for large volume injection online double solid phase extraction according to claim 1, characterized in that: The high-pressure six-way valve is equipped with a quantitative loop ranging from a few microliters to tens of milliliters, and the high-pressure ten-way valve is used to carry two parallel solid phase extraction columns.

9. The automatic analysis system for large volume injection online double solid phase extraction according to claim 1, characterized in that: The control input end of the PLC controller is connected to a plurality of visual cameras, which are respectively arranged at the automatic sample injector and the liquid chromatography pump. The control output end of the PLC controller is electrically connected to an alarm module.

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