Mobile phase cyclic utilization type series-parallel two-dimensional liquid chromatographic analysis system

Abstract

A mobile phase recycling type series-parallel two-dimensional liquid chromatographic analysis system belongs to the technical field of liquid chromatographic analysis and comprises a first-dimensional liquid chromatographic column and a second-dimensional liquid chromatographic column which are sequentially connected in series, the first-dimensional liquid chromatographic column comprises a first liquid chromatographic column and a second liquid chromatographic column which are connected in parallel, and the second-dimensional liquid chromatographic column comprises a second liquid chromatographic column and a third liquid chromatographic column which are connected in parallel. The first-dimensional liquid chromatographic column is an independent first liquid chromatographic column, the second-dimensional liquid chromatographic column is an independent third liquid chromatographic column, the liquid inlet ends of the first liquid chromatographic column and the second liquid chromatographic column are connected with the liquid outlet end of the twelve-way valve, and the liquid outlet ends of the first liquid chromatographic column and the second liquid chromatographic column are connected with the first detector; a to-be-detected sample liquid outlet end of the first detector is connected with a liquid inlet end of the trapping column multi-way valve, a liquid outlet end of the trapping column multi-way valve is connected with a liquid inlet end of the third liquid chromatographic column, and a liquid outlet end of the third liquid chromatographic column is connected with the second detector. According to the invention, qualitative and quantitative analysis of two-dimensional liquid chromatography is realized, and cyclic utilization of the mobile phase is realized while the overall separation effect is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of liquid chromatography analysis, and particularly relates to a series-parallel two-dimensional liquid chromatography analysis system with recycled mobile phase. Background Art

[0002] The liquid chromatography analysis method is a method for separation and analysis based on the distribution difference of sample components between the mobile phase, i.e., the liquid phase, and the stationary phase, i.e., the chromatographic column packing. Since the birth of high-performance liquid chromatography, it has become the core tool for the analysis of complex samples in the fields of chemistry, biology, medicine, environment, etc.

[0003] Conventional liquid chromatography analysis systems generally have one separation unit, i.e., one-dimensional liquid chromatography. The separation mechanism of the chromatographic column is single, and for the analysis of some complex samples, the separation efficiency is low. In addition, when there are interfering substances with similar chemical properties and target substances in the sample, it is difficult to qualitatively analyze the chemical substances using a conventional liquid chromatography analysis system. Moreover, as the core tool of modern analytical chemistry and the pharmaceutical industry, the waste liquid generated during the operation of liquid chromatography usually contains a large amount of organic solvents. Traditional waste liquid treatment methods, such as entrusting a third party for treatment, not only have high costs but also cause waste of resources and environmental pollution.

[0004] To solve the above technical problems, the development of two-dimensional liquid chromatography has become an important direction. Currently, existing two-dimensional liquid chromatography is achieved by connecting independent chromatographic columns with different separation mechanisms in series. Due to the series arrangement of the chromatographic columns, the components to be measured need to enter the first-dimensional and second-dimensional liquid chromatography columns for adsorption and elution successively, improving the separation effect. The two-dimensional liquid chromatography analysis system includes off-line and on-line operation modes. During off-line operation, the components separated by the first-dimensional liquid chromatography column need to be manually collected and injected into the second-dimensional liquid chromatography column for analysis. Off-line operation mainly relies on manual operation, which is time-consuming and laborious, and the separation efficiency is low. On-line operation is achieved by using a multi-way valve switching method to collect the components of the first-dimensional liquid chromatography column and then enter the second-dimensional liquid chromatography column for a second separation. Compared with off-line operation, on-line operation can save manpower and improve the separation efficiency. However, existing two-dimensional liquid chromatography cannot achieve qualitative analysis of chemical substances, and has a large consumption of organic solvents. Waste liquid treatment mostly uses off-line distillation methods, with low efficiency. Summary of the Invention

[0005] In view of the above-mentioned shortcomings and deficiencies of the prior art, the present invention provides a series-parallel two-dimensional liquid chromatography analysis system with recycled mobile phase, which realizes qualitative and quantitative analysis of two-dimensional liquid chromatography, and realizes the recycling of the mobile phase while improving the overall separation effect.

[0006] To achieve the above object, the main technical solutions adopted by the present invention include: A mobile phase recycling series-parallel two-dimensional liquid chromatography analysis system includes a first-dimensional liquid chromatography column and a second-dimensional liquid chromatography column connected in series in sequence. The first-dimensional liquid chromatography column includes two first liquid chromatography columns and a second liquid chromatography column connected in parallel. The second-dimensional liquid chromatography column is an independent third liquid chromatography column. The inlets of the first liquid chromatography column and the second liquid chromatography column are connected to the outlet of a twelve-port valve. The inlet of the twelve-port valve is connected to a sampler and a mobile phase inlet device of the first-dimensional liquid chromatography column through a first-dimensional pump. The outlets of the first liquid chromatography column and the second liquid chromatography column are connected to a first detector. The first-dimensional liquid chromatography column and the first detector are used for qualitative analysis of the component to be measured. The outlet of the first detector for the sample to be measured is connected to the inlet of a trapping column multi-port valve through a second-dimensional pump. The inlet of the trapping column multi-port valve is also connected to a mobile phase inlet device of the second-dimensional liquid chromatography column. The outlet of the trapping column multi-port valve is connected to the inlet of the third liquid chromatography column. The outlet of the third liquid chromatography column is connected to a second detector. The second-dimensional liquid chromatography column and the second detector are used for quantitative analysis of the component to be measured. The waste liquid outlets of the first detector, the second detector, the twelve-port valve, and the trapping column multi-port valve are connected to a waste liquid buffer tank, a thin film distillation device, a condensation device, a dehydration column device, an on-line detection device, and a solvent recovery tank in sequence.

[0007] Further, the twelve-way valve includes the first hole position of the twelve-way valve, the second hole position of the twelve-way valve, the third hole position of the twelve-way valve, the fourth hole position of the twelve-way valve, the fifth hole position of the twelve-way valve, the sixth hole position of the twelve-way valve, the seventh hole position of the twelve-way valve, the eighth hole position of the twelve-way valve, the ninth hole position of the twelve-way valve, the tenth hole position of the twelve-way valve, the eleventh hole position of the twelve-way valve, and the twelfth hole position of the twelve-way valve, which are arranged in sequence along the circumference. The first hole position of the twelve-way valve is connected to the fourth hole position of the twelve-way valve through the first quantitative ring, the seventh hole position of the twelve-way valve is connected to the tenth hole position of the twelve-way valve through the second quantitative ring, and the ninth hole position of the twelve-way valve is connected to the second hole position of the twelve-way valve through a pipeline. In the sample injection state, the first hole position of the twelve-way valve is communicated with the second hole position of the twelve-way valve, the third hole position of the twelve-way valve is communicated with the fourth hole position of the twelve-way valve, the fifth hole position of the twelve-way valve is communicated with the sixth hole position of the twelve-way valve, the seventh hole position of the twelve-way valve is communicated with the eighth hole position of the twelve-way valve, the ninth hole position of the twelve-way valve is communicated with the tenth hole position of the twelve-way valve, and the eleventh hole position of the twelve-way valve is communicated with the twelfth hole position of the twelve-way valve respectively through the flow guide grooves. The eighth hole position of the twelve-way valve is the sample injection end to be measured, the third hole position of the twelve-way valve is the sample waste liquid outlet end, the sixth hole position and the twelfth hole position of the twelve-way valve are the liquid inlet ends of the mobile phase of the first-dimensional liquid chromatography column, the fifth hole position and the eleventh hole position of the twelve-way valve are the liquid outlet ends of the mobile phase of the first-dimensional liquid chromatography column, and the liquid outlet ends of the fifth hole position and the eleventh hole position of the twelve-way valve are respectively connected to the liquid inlet ends of the first liquid chromatography column and the second liquid chromatography column; in the acquisition state, the first hole position of the twelve-way valve is communicated with the twelfth hole position of the twelve-way valve, the second hole position of the twelve-way valve is communicated with the third hole position of the twelve-way valve, the fourth hole position of the twelve-way valve is communicated with the fifth hole position of the twelve-way valve, the sixth hole position of the twelve-way valve is communicated with the seventh hole position of the twelve-way valve, the eighth hole position of the twelve-way valve is communicated with the ninth hole position of the twelve-way valve, and the tenth hole position of the twelve-way valve is communicated with the eleventh hole position of the twelve-way valve respectively through the flow guide grooves. The sample to be measured in the first quantitative ring and the second quantitative ring is brought into the first liquid chromatography column and the second liquid chromatography column by the mobile phase of the first-dimensional liquid chromatography column.

[0008] Further, the multi-way valve of the trapping column is a six-way valve of the trapping column. The six-way valve of the trapping column includes a first hole position of the six-way valve of the trapping column, a second hole position of the six-way valve of the trapping column, a third hole position of the six-way valve of the trapping column, a fourth hole position of the six-way valve of the trapping column, a fifth hole position of the six-way valve of the trapping column, and a sixth hole position of the six-way valve of the trapping column, which are arranged in sequence along the circumference. The third hole position of the six-way valve of the trapping column is connected to the liquid outlet end of the first detector. The first hole position of the six-way valve of the trapping column is connected to one end of the trapping column. The fourth hole position of the six-way valve of the trapping column is connected to the other end of the trapping column. The second hole position of the six-way valve of the trapping column is the liquid outlet end of the sample waste liquid. The fifth hole position of the six-way valve of the trapping column is the liquid inlet end of the mobile phase of the second-dimensional liquid chromatography column. The sixth hole position of the six-way valve of the trapping column is the liquid outlet end of the mobile phase of the second-dimensional liquid chromatography column. The sixth hole position of the six-way valve of the trapping column is connected to the liquid inlet end of the third liquid chromatography column. In the trapping state, the first hole position of the six-way valve of the trapping column is communicated with the second hole position of the six-way valve of the trapping column, the third hole position of the six-way valve of the trapping column is communicated with the fourth hole position of the six-way valve of the trapping column, and the fifth hole position of the six-way valve of the trapping column is communicated with the sixth hole position of the six-way valve of the trapping column through the diversion groove. In the collection state, the second hole position of the six-way valve of the trapping column is communicated with the third hole position of the six-way valve of the trapping column, the fourth hole position of the six-way valve of the trapping column is communicated with the fifth hole position of the six-way valve of the trapping column, and the first hole position of the six-way valve of the trapping column is communicated with the sixth hole position of the six-way valve of the trapping column through the diversion groove. Further, the condensing device is a serpentine coil condenser tube, and the cooling method is circulating water condensation.

[0009] Further, the filler of the dehydration column device is a mixed filler of 3A molecular sieve and activated carbon powder.

[0010] Further, the on-line detection device is a near-infrared spectrometer.

[0011] Further, a PTFE filter membrane is provided in the solvent recovery tank.

[0012] Further, the pore diameter of the PTFE filter membrane is 0.22 um.

[0013] The beneficial effects of the present invention are as follows: The mobile phase recycling type series-parallel two-dimensional liquid chromatography analysis system of the present invention uses two parallel liquid chromatography columns as the first-dimensional liquid chromatography column to realize the qualitative analysis of the sample to be measured, and uses the second-dimensional liquid chromatography column in series to realize the quantitative analysis of the sample to be measured, improving the separation efficiency and separation effect, and improving the accuracy of qualitative analysis. The present invention also sets up a waste liquid recovery and treatment link to realize the recycling of the mobile phase, overcoming the problem of high loss of the mobile phase in the conventional two-dimensional liquid chromatography analysis system. Description of the Drawings

[0014] Figure 1 It is a schematic diagram of the flow path of the sample to be measured and the mobile phase of the first-dimensional liquid chromatography column in the injection state of the twelve-way valve; Figure 2Schematic diagram of the flow path of the sample to be tested and the mobile phase of the first - dimensional liquid chromatography column in the sampling state of the twelve - way valve; Figure 3 Schematic diagram of the flow path of the sample to be tested and the mobile phase of the second - dimensional liquid chromatography column in the trapping state of the six - way valve of the trapping column; Figure 4 Schematic diagram of the flow path of the sample to be tested and the mobile phase of the second - dimensional liquid chromatography column in the sampling state of the six - way valve of the trapping column.

[0015] In the figure: 1 is the first hole position of the twelve - way valve, 2 is the second hole position of the twelve - way valve, 3 is the third hole position of the twelve - way valve, 4 is the fourth hole position of the twelve - way valve, 5 is the fifth hole position of the twelve - way valve, 6 is the sixth hole position of the twelve - way valve, 7 is the seventh hole position of the twelve - way valve, 8 is the eighth hole position of the twelve - way valve, 9 is the ninth hole position of the twelve - way valve, 10 is the tenth hole position of the twelve - way valve, 11 is the eleventh hole position of the twelve - way valve, 12 is the twelfth hole position of the twelve - way valve, 13 is the first hole position of the six - way valve of the trapping column, 14 is the second hole position of the six - way valve of the trapping column, 15 is the third hole position of the six - way valve of the trapping column, 16 is the fourth hole position of the six - way valve of the trapping column, 17 is the fifth hole position of the six - way valve of the trapping column, 18 is the sixth hole position of the six - way valve of the trapping column. Detailed implementation mode

[0016] In order to better explain the present invention for easy understanding, the present invention will be described in detail below with reference to the accompanying drawings through specific implementation modes.

[0017] The present invention provides a mobile - phase recycling series - parallel two - dimensional liquid chromatography analysis system, which includes a first - dimensional liquid chromatography column and a second - dimensional liquid chromatography column connected in series in sequence. The first - dimensional liquid chromatography column includes two parallel first liquid chromatography columns and second liquid chromatography columns. The second - dimensional liquid chromatography column is an independent third liquid chromatography column. The inlet ends of the first liquid chromatography column and the second liquid chromatography column are connected to the outlet end of the twelve - way valve. The inlet end of the twelve - way valve is connected to the injector and the mobile - phase inlet device of the first - dimensional liquid chromatography column through the first - dimensional pump. The outlet ends of the first liquid chromatography column and the second liquid chromatography column are connected to the first detector. The first - dimensional liquid chromatography column and the first detector are used for qualitative analysis of the components to be tested. The outlet end of the sample to be tested of the first detector is connected to the inlet end of the multi - way valve of the trapping column through the second - dimensional pump. The inlet end of the multi - way valve of the trapping column is also connected to the mobile - phase inlet device of the second - dimensional liquid chromatography column. The outlet end of the multi - way valve of the trapping column is connected to the inlet end of the third liquid chromatography column. The outlet end of the third liquid chromatography column is connected to the second detector. The second - dimensional liquid chromatography column and the second detector are used for quantitative analysis of the components to be tested. The waste - liquid outlet ends of the first detector, the second detector, the twelve - way valve, and the multi - way valve of the trapping column are connected to the waste - liquid buffer tank, the thin - film distillation device, the condensation device, the dehydration column device, the on - line detection device, and the solvent recovery tank in sequence.

[0018] Specifically, the mobile phase inlet device transports the mobile phase of the first - dimensional liquid chromatography column to the liquid inlet end of the twelve - way valve through the first - dimensional pump, and the injector transports the sample to be measured to the liquid inlet end of the twelve - way valve through the first - dimensional pump. In the acquisition state, the twelve - way valve transports the mobile phase of the first - dimensional liquid chromatography column and the sample to be measured to the first liquid chromatography column and the second liquid chromatography column. The types of the first liquid chromatography column and the second liquid chromatography column can be selected according to the chemical properties of the target component. For example, when the target component contains ionizable groups, a C18 bonded column and an ion - exchange column can be used in parallel; when the target component contains a benzene ring and may form π - π stacking interactions, a C18 bonded column, a phenyl column or a naphthyl column can be used in parallel; when the target component can form hydrogen bonds, a C18 bonded column, a cyano column or a pentafluorophenyl column can be used in parallel. Since the adsorption mechanisms of the first liquid chromatography column and the second liquid chromatography column for the target component are different, the elution mechanisms for the mixed mobile phase are also different, and there are differences in the retention times of the target component in the first liquid chromatography column and the second liquid chromatography column. The first detector will detect two target peaks, and by comparing the retention times of the two target peaks simultaneously, qualitative analysis of the target component in the sample is carried out. The sample to be measured then enters the multi - way valve of the trapping column and then enters the second detector for quantitative analysis. More specifically, the first detector and the second detector can be diode array detectors.

[0019] The waste liquids of the first detector, the second detector, the twelve - way valve, and the multi - way valve of the trapping column first enter the waste liquid buffer tank. The waste liquid buffer tank can specifically be a stainless - steel tank body with a volume of 10 L, and is internally monitored by a dual - monitoring of an ultrasonic liquid - level sensor and a float switch. Then the waste liquid enters the thin - film distillation device and the condensation device for preliminary distillation. Specifically, the thin - film distillation device is a prior art. Its evaporation cavity is a vertical Hastelloy cylinder with a nano - ceramic coating to prevent the adhesion of salt or sample residues, and is temperature - controlled by electric heating with an accuracy of ±0.5 °C. The condensation device can specifically be a serpentine coiled condenser made of quartz glass, and the cooling method is circulating - water condensation. After the waste liquid is preliminarily distilled by the thin - film distillation device and the condensation device, it enters the dehydration column device to remove moisture and impurities. Specifically, the packing of the dehydration column device is a mixed packing of 3A molecular sieve and activated carbon powder. More specifically, the 3A molecular sieve packing is made of alkali metal aluminosilicate, the particle size of the 3A molecular sieve packing is 0.5 mm, and the pore diameter of the packing is 0.3 nm. Finally, after the waste liquid is detected by the on - line detection device and the purity is qualified, it enters the solvent recovery tank for recycling. Specifically, the on - line detection device can be a near - infrared spectrometer, and a PTFE filter membrane with a pore diameter of 0.22 μm can be set in the solvent recovery tank to filter particulate matter in the solvent.

[0020] More specifically, the twelve-way valve includes the first hole position 1 of the twelve-way valve, the second hole position 2 of the twelve-way valve, the third hole position 3 of the twelve-way valve, the fourth hole position 4 of the twelve-way valve, the fifth hole position 5 of the twelve-way valve, the sixth hole position 6 of the twelve-way valve, the seventh hole position 7 of the twelve-way valve, the eighth hole position 8 of the twelve-way valve, the ninth hole position 9 of the twelve-way valve, the tenth hole position 10 of the twelve-way valve, the eleventh hole position 11 of the twelve-way valve, and the twelfth hole position 12 of the twelve-way valve, which are arranged in sequence along the circumference. The first hole position 1 of the twelve-way valve is connected to the fourth hole position 4 of the twelve-way valve through a first quantitative ring, the seventh hole position 7 of the twelve-way valve is connected to the tenth hole position 10 of the twelve-way valve through a second quantitative ring, and the ninth hole position 9 of the twelve-way valve is connected to the second hole position 2 of the twelve-way valve through a pipeline. In the sample injection state, as Figure 1 shown, the first hole position 1 of the twelve-way valve is communicated with the second hole position 2 of the twelve-way valve, the third hole position 3 of the twelve-way valve is communicated with the fourth hole position 4 of the twelve-way valve, the fifth hole position 5 of the twelve-way valve is communicated with the sixth hole position 6 of the twelve-way valve, the seventh hole position 7 of the twelve-way valve is communicated with the eighth hole position 8 of the twelve-way valve, the ninth hole position 9 of the twelve-way valve is communicated with the tenth hole position 10 of the twelve-way valve, and the eleventh hole position 11 of the twelve-way valve is communicated with the twelfth hole position 12 of the twelve-way valve through diversion channels respectively. The eighth hole position 8 of the twelve-way valve is the sample injection end for the sample to be tested, the third hole position 3 of the twelve-way valve is the sample waste liquid outlet end, the sixth hole position 6 and the twelfth hole position 12 of the twelve-way valve are the liquid inlet ends for the mobile phase of the first-dimensional liquid chromatography column, the fifth hole position 5 and the eleventh hole position 11 of the twelve-way valve are the liquid outlet ends for the mobile phase of the first-dimensional liquid chromatography column, and the liquid outlet ends of the fifth hole position 5 and the eleventh hole position 11 of the twelve-way valve are respectively connected to the liquid inlet ends of the first liquid chromatography column and the second liquid chromatography column. The mobile phase of the first-dimensional liquid chromatography column enters the twelve-way valve from the sixth hole position 6 of the twelve-way valve and is output from the fifth hole position 5 of the twelve-way valve to the first liquid chromatography column; the other way enters the twelve-way valve from the twelfth hole position 12 of the twelve-way valve and is output from the eleventh hole position 11 of the twelve-way valve to the second liquid chromatography column. The sample to be tested enters the twelve-way valve from the eighth hole position 8 of the twelve-way valve, flows into the second quantitative ring along the diversion channel, then flows to the ninth hole position 9 of the twelve-way valve along the diversion channel, then flows to the second hole position 2 of the twelve-way valve along the pipeline, and then flows to the first hole position 1 of the twelve-way valve along the diversion channel and enters the first quantitative ring. The third hole position 3 of the twelve-way valve is the sample waste liquid outlet end, so that the sample to be tested is placed in the first quantitative ring and the second quantitative ring. After the first quantitative ring and the second quantitative ring are filled with the sample to be tested, switch the twelve-way valve to the acquisition state, as Figure 2As shown in the figure, in the sampling state, the first hole 1 of the twelve-way valve is communicated with the twelfth hole 12 of the twelve-way valve, the second hole 2 of the twelve-way valve is communicated with the third hole 3 of the twelve-way valve, the fourth hole 4 of the twelve-way valve is communicated with the fifth hole 5 of the twelve-way valve, the sixth hole 6 of the twelve-way valve is communicated with the seventh hole 7 of the twelve-way valve, the eighth hole 8 of the twelve-way valve is communicated with the ninth hole 9 of the twelve-way valve, and the tenth hole 10 of the twelve-way valve is communicated with the eleventh hole 11 of the twelve-way valve through the diversion channels respectively. The mobile phase of the first-dimensional liquid chromatography column enters the twelve-way valve from the twelfth hole 12 and the sixth hole 6 of the twelve-way valve respectively, and then drives the test samples in the first quantitative loop and the second quantitative loop to flow into the first liquid chromatography column and the second liquid chromatography column respectively.

[0021] More specifically, the multi-way valve of the trapping column is a six-way valve of the trapping column. The six-way valve of the trapping column includes the first hole 13, the second hole 14, the third hole 15, the fourth hole 16, the fifth hole 17, and the sixth hole 18 of the six-way valve of the trapping column arranged in sequence along the circumference. The third hole 15 of the six-way valve of the trapping column is connected to the liquid outlet end of the first detector. The first hole 13 of the six-way valve of the trapping column is connected to one end of the trapping column. The fourth hole 16 of the six-way valve of the trapping column is connected to the other end of the trapping column. The second hole 14 of the six-way valve of the trapping column is the liquid outlet end of the sample waste liquid. The fifth hole 17 of the six-way valve of the trapping column is the liquid inlet end of the mobile phase of the second-dimensional liquid chromatography column. The sixth hole 18 of the six-way valve of the trapping column is the liquid outlet end of the mobile phase of the second-dimensional liquid chromatography column. The sixth hole 18 of the six-way valve of the trapping column is connected to the liquid inlet end of the third liquid chromatography column. The six-way valve of the trapping column samples the test samples within two minutes before and after the peak time of the first detector to the trapping column. In the trapping state, as Figure 3 shown in the figure, the first hole 13 of the six-way valve of the trapping column is communicated with the second hole 14 of the six-way valve of the trapping column, the third hole 15 of the six-way valve of the trapping column is communicated with the fourth hole 16 of the six-way valve of the trapping column, and the fifth hole 17 of the six-way valve of the trapping column is communicated with the sixth hole 18 of the six-way valve of the trapping column through the diversion channels. The test sample enters the six-way valve of the trapping column from the third hole 15 of the six-way valve of the trapping column, flows along the diversion channel to the fourth hole 16 of the six-way valve of the trapping column and enters the trapping column, and then the test sample flows out from the first hole 13 of the six-way valve of the trapping column and flows along the diversion channel to the second hole 14 of the six-way valve of the trapping column. The mobile phase of the second-dimensional liquid chromatography column enters the six-way valve of the trapping column from the fifth hole 17 of the six-way valve of the trapping column, and flows to the third liquid chromatography column after flowing out from the sixth hole 18 of the six-way valve of the trapping column. After the trapping column is filled with the test sample, the six-way valve of the trapping column is switched to the sampling state. As Figure 4As shown in the figure, in the collection state, the second hole position 14 of the trap column six-way valve is communicated with the third hole position 15 of the trap column six-way valve, the fourth hole position 16 of the trap column six-way valve is communicated with the fifth hole position 17 of the trap column six-way valve, and the first hole position 13 of the trap column six-way valve is communicated with the sixth hole position 18 of the trap column six-way valve through the diversion groove. The mobile phase of the second-dimensional liquid chromatography column drives the sample to be measured in the trap column to flow to the third liquid chromatography column.

[0022] Example 1 The sample to be measured is a methanol solution containing cyanazine. Using the series-parallel two-dimensional liquid chromatography analysis system of the present invention, the mobile phases of the first-dimensional liquid chromatography column and the second-dimensional liquid chromatography column are both acetonitrile-water mixed mobile phases, with a dosage of acetonitrile: water volume ratio of 2:8. The flow rates of the mobile phases of the first-dimensional liquid chromatography column and the second-dimensional liquid chromatography column are both 1.5 mL / min, the injection volume is 20 μL, the detector is a diode array detector, the detection wavelength is 222 nm, and about 5 L of waste liquid is generated.

[0023] The sample to be measured enters the parallel first liquid chromatography column and second liquid chromatography column through a twelve-way valve. The first liquid chromatography column is a C18 chromatography column, and the second liquid chromatography column is a phenyl chromatography column. The first detector is used to perform qualitative analysis on the sample to be measured. The trap column six-way valve collects the sample to be measured within two minutes before and after the peak time of the first detector and sends it to the trap column. The trap column six-way valve is first switched to the trapping state, and the sample to be measured enters the trap column. After the sample to be measured fills the trap column six-way valve, it is then switched to the collection state, and the sample to be measured enters the third liquid chromatography column for further quantitative analysis. The third liquid chromatography column is a C18 chromatography column.

[0024] The waste liquid generated in the system enters the thin-film distillation device, with an evaporation temperature of 82 °C, a condensate water flow rate of 3 L / min, an acetonitrile recovery rate ≥ 91%, and a recovery purity ≥ 99.3%.

[0025] Example 2 The sample to be measured is a methanol solution containing cyanazine and metribuzin. Cyanazine is the target component, and metribuzin is the interfering substance. Using the series-parallel two-dimensional liquid chromatography analysis system of the present invention, the mobile phases of the first-dimensional liquid chromatography column and the second-dimensional liquid chromatography column are both methanol-water mixed mobile phases, with a dosage of methanol: water volume ratio of 3:7. The flow rates of the mobile phases of the first-dimensional liquid chromatography column and the second-dimensional liquid chromatography column are both 0.75 mL / min, the injection volume is 20 μL, the detector is a diode array detector, and the detection wavelength is 222 nm.

[0026] The sample to be tested enters the parallel first liquid chromatography column and second liquid chromatography column through a twelve-way valve. The first liquid chromatography column is a C18 chromatography column, and the second liquid chromatography column is a phenyl chromatography column. The first detector is used to perform qualitative analysis on the sample to be tested. The six-way valve of the trapping column collects the sample to be tested within two minutes before and after the peak emergence time detected by the first detector into the trapping column. The six-way valve of the trapping column is first switched to the trapping state, and the sample to be tested enters the trapping column. After the sample to be tested fills the six-way valve of the trapping column, it is then switched to the collection state, and the sample to be tested enters the third liquid chromatography column for further quantitative analysis. The third liquid chromatography column is a C18 chromatography column.

[0027] The waste liquid generated in the system enters the thin-film distillation device, with an evaporation temperature of 65 °C, a condensate water flow rate of 3 L / min, a methanol recovery rate ≥ 94%, and a recovery purity ≥ 99.6%.

[0028] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Modifications, alterations, substitutions, and variations made by those of ordinary skill in the art to the above embodiments all fall within the scope of the present invention.

Claims

1. A mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system, characterized in that: The invention comprises a first-dimensional liquid chromatography column and a second-dimensional liquid chromatography column connected in series in sequence, wherein the first-dimensional liquid chromatography column comprises two first liquid chromatography columns and a second liquid chromatography column connected in parallel, and the second-dimensional liquid chromatography column is an independent third liquid chromatography column, the liquid inlet ends of the first liquid chromatography column and the second liquid chromatography column are connected to the liquid outlet end of a twelve-way valve, the liquid inlet end of the twelve-way valve is connected to an injector and a mobile phase liquid inlet device of the first-dimensional liquid chromatography column through a first-dimensional pump, the liquid outlet ends of the first liquid chromatography column and the second liquid chromatography column are connected to a first detector, the first-dimensional liquid chromatography column and the first detector are used for qualitative analysis of components to be measured, and the first The liquid outlet end of the detector for the sample to be tested is connected to the liquid inlet end of the multi-way valve of the capture column through a second-dimensional pump. The liquid inlet end of the multi-way valve of the capture column is also connected to the mobile phase liquid inlet device of the second-dimensional liquid chromatography column. The liquid outlet end of the multi-way valve of the capture column is connected to the liquid inlet end of the third liquid chromatography column. The liquid outlet end of the third liquid chromatography column is connected to the second detector. The second-dimensional liquid chromatography column and the second detector are used for quantitative analysis of the components to be tested. The waste liquid outlet ends of the first detector, the second detector, the twelve-way valve and the multi-way valve of the capture column are connected to the waste liquid buffer tank, the thin film distillation device, the condensation device, the dehydration column device, the online detection device and the solvent recovery tank in sequence.

2. A mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system according to claim 1, characterized in that: The twelve-way valve comprises a first hole position (1) of the twelve-way valve, a second hole position (2) of the twelve-way valve, a third hole position (3) of the twelve-way valve, a fourth hole position (4) of the twelve-way valve, a fifth hole position (5) of the twelve-way valve, a sixth hole position (6) of the twelve-way valve, a seventh hole position (7) of the twelve-way valve, an eighth hole position (8) of the twelve-way valve, a ninth hole position (9) of the twelve-way valve, a tenth hole position (10) of the twelve-way valve, an eleventh hole position (11) of the twelve-way valve, and a twelfth hole position (12) of the twelve-way valve, the first hole position (1) of the twelve-way valve being connected to the fourth hole position (4) of the twelve-way valve via a first quantitative ring, and the twelve-way valve The seventh hole position (7) of the twelve-way valve is connected to the tenth hole position (10) of the twelve-way valve through a second quantitative loop, the ninth hole position (9) of the twelve-way valve is connected to the second hole position (2) of the twelve-way valve through a pipeline, and in the injection state, the first hole position (1) of the twelve-way valve is connected to the second hole position (2) of the twelve-way valve, the third hole position (3) of the twelve-way valve is connected to the fourth hole position (4) of the twelve-way valve, the fifth hole position (5) of the twelve-way valve is connected to the sixth hole position (6) of the twelve-way valve, the seventh hole position (7) of the twelve-way valve is connected to the eighth hole position (8) of the twelve-way valve, the ninth hole position (9) of the twelve-way valve is connected to the tenth hole position (10) of the twelve-way valve, and the eleventh hole position (11) of the twelve-way valve is connected to the eleventh hole position (12) of the twelve-way valve. The twelfth hole position (12) of the two-way valve is connected through the guide groove, the eighth hole position (8) of the twelve-way valve is the injection end of the sample to be tested, the third hole position (3) of the twelve-way valve is the outlet end of the sample waste liquid, the sixth hole position (6) of the twelve-way valve and the twelfth hole position (12) of the twelve-way valve are the inlet end of the mobile phase of the first dimension liquid chromatography column, the fifth hole position (5) of the twelve-way valve and the eleventh hole position (11) of the twelve-way valve are the outlet end of the mobile phase of the first dimension liquid chromatography column, and the outlet ends of the fifth hole position (5) of the twelve-way valve and the eleventh hole position (11) of the twelve-way valve are connected to the inlet ends of the first liquid chromatography column and the second liquid chromatography column respectively; in the collection state, the ten holes (6) and the twelfth hole position (12) of the twelve-way valve are the inlet ends of the mobile phase of the first dimension liquid chromatography column, and the fifth hole position (5) of the twelve-way valve and the eleventh hole position (11) of the twelve-way valve are connected to the inlet ends of the first liquid chromatography column and the second liquid chromatography column respectively. The first hole position (1) of the two-way valve and the twelfth hole position (12) of the twelve-way valve, the second hole position (2) of the twelve-way valve and the third hole position (3) of the twelve-way valve, the fourth hole position (4) of the twelve-way valve and the fifth hole position (5) of the twelve-way valve, the sixth hole position (6) of the twelve-way valve and the seventh hole position (7) of the twelve-way valve, the eighth hole position (8) of the twelve-way valve and the ninth hole position (9) of the twelve-way valve, and the tenth hole position (10) of the twelve-way valve and the eleventh hole position (11) of the twelve-way valve are respectively connected through the guide groove, and the samples to be tested in the first quantitative loop and the second quantitative loop are brought into the first liquid chromatography column and the second liquid chromatography column through the mobile phase of the first-dimensional liquid chromatography column.

3. A mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system according to claim 1, characterized in that: The trapping column multi-way valve is a trapping column six-way valve, which comprises a first hole position (13) of the trapping column six-way valve, a second hole position (14) of the trapping column six-way valve, a third hole position (15) of the trapping column six-way valve, a fourth hole position (16) of the trapping column six-way valve, a fifth hole position (17) of the trapping column six-way valve, and a sixth hole position (18) of the trapping column six-way valve, which are sequentially arranged along the circumference. The third hole position (15) of the trapping column six-way valve is connected to the liquid outlet of the first detector, the first hole position (13) of the trapping column six-way valve is connected to one end of the trapping column, the fourth hole position (16) of the trapping column six-way valve is connected to the other end of the trapping column, the second hole position (14) of the trapping column six-way valve is the sample waste liquid outlet, the fifth hole position (17) of the trapping column six-way valve is the liquid inlet of the mobile phase of the second-dimensional liquid chromatography column, and the sixth hole position (18) of the trapping column six-way valve is connected to the liquid outlet of the first detector. The position (18) is the liquid outlet end of the mobile phase of the second-dimensional liquid chromatography column, and the sixth hole position (18) of the six-way valve of the capture column is connected to the liquid inlet end of the third liquid chromatography column; in the capture state, the first hole position (13) of the six-way valve of the capture column and the second hole position (14) of the six-way valve of the capture column, the third hole position (15) of the six-way valve of the capture column and the fourth hole position (16) of the six-way valve of the capture column, and the fifth hole position (17) of the six-way valve of the capture column and the sixth hole position (18) of the six-way valve of the capture column are connected through the guide groove; in the collection state, the second hole position (14) of the six-way valve of the capture column and the third hole position (15) of the six-way valve of the capture column, the fourth hole position (16) of the six-way valve of the capture column and the fifth hole position (17) of the six-way valve of the capture column, and the first hole position (13) of the six-way valve of the capture column and the sixth hole position (18) of the six-way valve of the capture column are connected through the guide groove.

4. A mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system according to claim 1, characterized in that: The condensing device is a serpentine coil type condensing tube, and the cooling method is circulating water condensation.

5. The mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system according to claim 1, characterized in that: The filler of the dehydration column device is a mixed filler of 3A molecular sieve and activated carbon powder.

6. A mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system according to claim 1, characterized in that: The online detection device is a near infrared spectrometer.

7. The mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system according to claim 1, characterized in that: A PTFE filter membrane is arranged in the solvent recovery tank.

8. The mobile phase recycling serial-parallel two-dimensional liquid chromatography analysis system according to claim 7, characterized in that: The pore size of the PTFE filter membrane is 0.22 um.

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