Fully-automated in-line ion chromatography detection system and detection method

Abstract

A fully-automated in-line ion chromatography detection system, comprising an ultrapure water preparation module, a standard sample automated preparation module, a sample pretreatment module, a sample selection module and an ion chromatograph module. The ultrapure water preparation module can achieve in-line automated preparation of ultrapure water, so as to continuously provide ultrapure water having stable properties for the detection system, thus facilitating operations; the standard sample automated preparation module can achieve in-line continuous automated preparation of standard samples at different preset concentrations simply by using one standard sample stock solution bottle in cooperation with a selection valve and a metering pump, thereby reducing manual operations and saving time and effort, achieve consistency in the precision of prepared solutions of different concentrations, and further avoid concentration errors caused by the dead volume in tubes in the case of using preparation instruments, thus achieving higher precision in preparation; the sample selection module and the ion chromatograph module can efficiently and accurately complete determination and plotting of calibration curves and high-precision measurement of samples.

Description

Full-automatic online ion chromatography detection system and detection method TECHNICAL FIELD

[0001] The present application relates to the technical field of ion chromatography detection, and particularly relates to a full-automatic online ion chromatography detection system and a detection method. BACKGROUND

[0002] Ion chromatography is a kind of high performance liquid chromatography, and is a kind of liquid chromatography method for analyzing anions and cations. In the ion chromatography detection process, the calibration curve is used to establish the mathematical relationship between the target ion concentration in the sample and the response signal (such as peak area, peak height, etc.) generated in the chromatographic analysis, which is crucial for accurately determining the ion concentration in the sample. In the process of constructing the calibration curve, the first step is to prepare standard solutions. In the prior art, manual operation or cooperation with a preparation instrument is usually used to prepare multiple standard sample solutions, and after manual sampling, data recording and calibration curve drawing are performed through chromatographic analysis. However, this method has some problems: the work efficiency of manual preparation of standard samples is low, and the prepared concentration of standard samples is easy to be contaminated and has errors or inconsistent accuracy, which affects the accurate determination of ion chromatography. Or now, manual operation is used to cooperate with the preparation instrument to complete the preparation of the solution by taking liquid, mixing and other operations. The solution cannot be prepared online in real time, and needs to be prepared in advance and placed in the instrument for standby, but the concentration of some ions in the low-concentration standard solution changes with time, and cannot be stored for a long time. The concentration of the final standard solution is affected by the preparation in advance, and the dead volume of the existing preparation instrument will adversely affect the accuracy of the solution concentration. Therefore, based on the above problems, a full-automatic online ion chromatography detection system capable of preparing standard curves online in real time is provided, which is of great significance for accurate ion chromatography determination.

[0003] SUMMARY

[0004] The present application aims to provide a full-automatic online ion chromatography detection system and a detection method to solve the above technical problems in the background art.

[0005] To solve the above technical problems, the technical solution provided by the present application is:

[0006] In one aspect, the application provides a full-automatic online ion chromatography detection system, comprising an ultrapure water preparation module, a standard sample automatic preparation module, a sample pretreatment module, a sample selection module, and an ion chromatography module; the ultrapure water preparation module is used for online generation and supply of ultrapure water, and is connected with the standard sample automatic preparation module and the ion chromatography module through pipelines respectively; the standard sample automatic preparation module is connected with the ultrapure water preparation module at the front end and is connected with the sample selection module at the tail end, and is used for continuous preparation of standard sample solutions with different concentrations; the sample pretreatment module is connected with the sample selection module at the tail end, and is used for pretreatment of sample solutions to be detected; the sample selection module is connected with the ion chromatography module at the tail end, and is used for selection of standard sample solutions or sample solutions to be detected; and the ion chromatography module is used for quantitative detection of solutions flowing from the sample selection module.

[0007] On the basis of the above technical solution, the ultrapure water preparation module comprises an EDI device, a purification resin column, and an ultrapure water tank; desalted water is purified in sequence through the EDI device and the purification resin column, and the prepared ultrapure water is stored in the ultrapure water tank.

[0008] On the basis of the above technical solution, the standard sample automatic preparation module comprises at least one solution dilution assembly, the solution dilution assembly comprises a standard sample mother liquor bottle, a first selection valve, a metering pump, and a dilution container, the first selection valve is connected with the standard sample mother liquor bottle through a mother liquor pipeline and with the ultrapure water tank through an ultrapure water pipeline at the front end, and is connected with the metering pump at the tail end through a first pipeline, and the metering pump is connected with the dilution container through a second pipeline at the tail end.

[0009] On the basis of the above technical solution, the sample pretreatment module comprises a sample tank, a filter, and a degassing device, the filter is in communication with the sample tank through a sample pipeline at the front end and is in communication with the degassing device at the tail end, and the degassing device is connected with the sample selection module at the tail end.

[0010] On the basis of the above technical solution, the sample selection module comprises at least one sample injection selection valve, the sample injection selection valve is connected with the tail ends of the standard sample automatic preparation module and the sample pretreatment module at the front end respectively, and is connected with the front end of the ion chromatography module at the tail end.

[0011] On the basis of the above technical solution, the ion chromatography module comprises at least one ion chromatography detection assembly, the ion chromatography detection assembly comprises a first multi-way valve, an eluent generator, a chromatographic column, an suppressor, and a conductivity detector, the first multi-way valve is connected with the sample selection module and the eluent generator at the front end respectively, and is connected with the chromatographic column at the tail end, and the suppressor and the conductivity detector are arranged in sequence at the tail end of the chromatographic column; the eluent generator is connected with a solution pump through a pipeline, and the solution pump inlet is in communication with the ultrapure water tank.

[0012] On the basis of the above technical scheme, further comprising a cleaning assembly, the cleaning assembly comprising a second waste liquid pipeline and a peristaltic pump, the second waste liquid pipeline being connected to the end of the standard sample automatic preparation module or the head of the ion chromatograph module, and the peristaltic pump being arranged on the second waste liquid pipeline.

[0013] In another aspect, the application also provides a full-automatic prior ion chromatography detection method, which adopts the full-automatic online ion chromatography detection system and comprises the following steps:

[0014] Preparation of ultrapure water; desalted water is introduced into the ultrapure water preparation module, ultrapure water is prepared in an online automatic generation mode, and the ultrapure water is stored in an ultrapure water tank for standby use;

[0015] Preparation of standard sample solution; according to a preset concentration of the standard sample solution, a standard sample automatic preparation module is adopted to automatically sample and online dilute the required volume of ultrapure water and stock solution, so as to obtain the standard sample solution with the preset concentration;

[0016] Determination of calibration curve; the standard sample solution obtained in the above step is introduced into the ion chromatograph module through the sample selection module for detection, so as to obtain the corresponding conductance detection value; the preparation and determination of the standard sample solution with different concentrations are repeated, so as to complete the value detection required for the calibration curve and draw the calibration curve;

[0017] Pre-treatment and detection of sample to be detected; the sample to be detected actually required to be detected is subjected to sample filtration and degassing operation through the sample pre-treatment module, and then is introduced into the ion chromatograph module through the sample selection module for detection, so as to obtain the corresponding conductivity detection value, form a chromatogram and perform subsequent quantitative calculation.

[0018] On the basis of the above technical scheme, the standard sample solution preparation method comprises the following steps:

[0019] Step one: rinse with standard sample stock solution; the pipeline is rinsed with the standard sample stock solution, so that the pipeline is filled with the standard sample stock solution after the rinsing is completed;

[0020] Step two: rinse with ultrapure water; the pipeline is rinsed with ultrapure water, so that the pipeline is filled with ultrapure water after the rinsing is completed;

[0021] Step three: add standard sample stock solution; the standard sample stock solution is introduced into the pipeline, and the required amount of standard sample stock solution is added to the dilution container;

[0022] Step four: add ultrapure water; ultrapure water is introduced into the pipeline, and the required amount of ultrapure water is added to the same dilution container as step three; after mixing, the standard sample solution with the required concentration can be prepared;

[0023] Step five: repeat the above steps three and four again to prepare the next standard sample solution of different concentration, so as to realize the online automatic preparation of standard sample solutions of different concentrations.

[0024] On the basis of the above technical solutions, the following steps are included:

[0025] Step one: flush the pipeline with the standard sample mother liquor, which is sequentially passed through the mother liquor pipeline, the first selection valve, the first pipeline, the metering pump and the second pipeline to complete the flushing; at this time, the mother liquor pipeline, the first pipeline and the second pipeline are filled with the standard sample mother liquor;

[0026] Step two: flush the pipeline with ultrapure water, which is sequentially passed through the ultrapure water pipeline, the first selection valve, the first pipeline, the metering pump and the second pipeline to complete the flushing; at this time, the ultrapure water pipeline, the first pipeline and the second pipeline are filled with ultrapure water; the initial state of the pipeline is set;

[0027] Step three: set the required amount of standard sample mother liquor to pass through the mother liquor pipeline, the first selection valve, the first pipeline, the metering pump and the second pipeline into the dilution container; at this time, the ultrapure water in the first pipeline and the second pipeline in step two is flushed into the dilution container; after the standard sample mother liquor is closed, there will be a dead volume of standard sample mother liquor remaining in the first pipeline and the second pipeline;

[0028] Step four: set the required amount of ultrapure water to pass through the ultrapure water pipeline, the first selection valve, the first pipeline, the metering pump and the second pipeline into the dilution container, and the ultrapure water flushes the remaining standard sample mother liquor in step three into the same dilution container; after the ultrapure water is closed, there is still ultrapure water remaining in the first pipeline and the second pipeline; at this time, the dilution container has taken the required amount of standard sample mother liquor and ultrapure water, completing the dilution process of the standard sample mother liquor and obtaining a standard sample solution of a preset concentration; at the same time, the pipeline also maintains the initial state in step two;

[0029] Step five: repeat the above steps three and four again to prepare the next standard sample solution of different concentration, so as to realize the online automatic preparation of standard sample solutions of different concentrations.

[0030] The technical solution provided by the present application has the following beneficial effects:

[0031] 1. This application incorporates an ultrapure water preparation module, enabling online automated preparation of ultrapure water. This provides a continuous and reliable supply of ultrapure water to the standard sample preparation module and the ion chromatography module, making operation more convenient. The standard sample preparation module requires only one standard sample stock solution bottle, along with a selection valve and a metering pump, to achieve online continuous automated preparation of standard sample solutions of different preset concentrations. This reduces manual operation, saves time and effort, and ensures good consistency in the accuracy of solutions prepared at different concentrations. It also effectively solves the concentration error caused by dead volume in the tubing when using preparation instruments, resulting in higher preparation accuracy. Combined with the sample selection module and the ion chromatography module, it can efficiently and accurately complete the determination and plotting of calibration curves. Furthermore, the detection system also includes a sample pretreatment module to pretreatment the sample before it enters the ion chromatography module for quantitative detection, resulting in higher accuracy of the detection results.

[0032] 2. The standard sample solution preparation method provided in this application enables online automatic preparation of standard sample solutions, reducing manual operation and improving work efficiency and preparation accuracy. The design of each step and its operational sequence effectively solves the problem of the influence of dead volume in the instrument and tubing on the final concentration accuracy of the prepared solution in existing technologies. It is unaffected by dead volume, resulting in high concentration accuracy. Furthermore, it eliminates the need to consider the concentration influence between two preparations of standard sample solutions with different concentrations. The tubing is automatically flushed during the preparation process, thus setting the initial state of the tubing and eliminating the need for repeated tubing cleaning. This enables continuous automatic preparation of standard sample solutions with different required concentrations, resulting in high work efficiency, greater convenience, and strong practicality. Attached Figure Description

[0033] Figure 1 is a schematic diagram of the overall structure of the present invention;

[0034] Figure 2 is a schematic diagram of the pure water preparation module in this invention;

[0035] Figure 3 is a schematic diagram of the automatic standard sample preparation module in this invention;

[0036] Figure 4 is a schematic diagram of the ion chromatograph module in this invention;

[0037] Figure 5 is a logic block diagram of step one in the standard sample solution preparation method of the present invention;

[0038] Figure 6 is a logic block diagram of step two in the standard sample solution preparation method of the present invention;

[0039] Figure 7 is a logic block diagram of step three in the standard sample solution preparation method of the present invention;

[0040] Figure 8 is a logic block diagram of step four in the standard sample solution preparation method of the present invention. DETAILED DESCRIPTION

[0041] The application will be further described below in connection with the drawings and examples:

[0042] In the present application, unless otherwise explicitly specified and limited, the terms "mounting", "connecting", "connecting", "fixing" and the like should be understood in a broad sense, for example, it can be fixedly connected, or it can be detachably connected, or it can be integrated; it can be directly connected, or it can be indirectly connected through an intermediate medium; it can be the internal communication of two elements or the interaction relationship of two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0043] In the description of the present application, it should be understood that the terms "left", "right", "front", "back", "top", "bottom", etc. indicate the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application.

[0044] As shown in FIGS. 1-8, the present application provides a full-automatic online ion chromatography detection system, comprising an ultrapure water preparation module 1, a standard sample automatic preparation module 2, a sample pretreatment module 3, a sample selection module 4, and an ion chromatography module 5; the ultrapure water preparation module 1 is used for online generation and supply of ultrapure water, and is connected with the standard sample automatic preparation module 2 and the ion chromatography module 5 through pipelines respectively; the standard sample automatic preparation module 2 is connected with the ultrapure water preparation module 1 at the front end and is connected with the sample selection module 4 at the tail end, and is used for continuous preparation of standard sample solutions of different concentrations; the sample pretreatment module 3 is connected with the sample selection module 4 at the tail end, and is used for pretreatment of sample solutions to be measured; the sample selection module 4 is connected with the ion chromatography module 5 at the tail end, and is used for selecting standard sample solutions or sample solutions to be measured; the ion chromatography module 5 is used for quantitative detection of solutions flowing from the sample selection module 4.

[0045] In the application, the on-line automatic preparation of ultrapure water is realized by the ultrapure water preparation module 1, which provides continuous and reliable ultrapure water for the standard sample automatic preparation module 2 and the ion chromatograph module 5, and the operation is more convenient. In the standard sample automatic preparation module 2, only one standard sample mother liquor bottle is needed to cooperate with a selection valve and a metering pump to realize the on-line continuous automatic preparation of standard sample solutions with different preset concentrations. The preparation, storage and use of standard samples by manual operation or manual preparation instrument in the prior art are avoided, the manual operation pollution and preparation error are reduced, time and labor are saved, the preparation efficiency is higher, the measurement deviation caused by the concentration change of low-concentration standard samples during long-time storage is reduced, the adverse effects of the dead volume of the existing preparation instrument on the solution concentration accuracy are avoided by the new pipeline connection mode and preparation process of the on-line preparation device, the operation is more convenient, the concentration preparation accuracy of standard sample solutions with different concentrations is high and the consistency is good, and the subsequent high detection accuracy is ensured. The sample selection module 4 and the ion chromatograph module 5 can realize the determination and drawing of the calibration curve with high efficiency and high precision. The sample pretreatment module 3 is further included in the detection system to pretreat the sample to be measured, and then the sample selection module 4 is used to enter the ion chromatograph module 5 to quantitatively detect the sample to be measured, so that the accuracy of the detection result is higher.

[0046] On the basis of the above technical scheme, as shown in Figure 2, the ultrapure water preparation module 1 includes an EDI device 11, a purification resin column 12 and an ultrapure water tank 13. The desalted water is sequentially purified by the EDI device 11 and the purification resin column 12, and the prepared ultrapure water is stored in the ultrapure water tank 13.

[0047] In the application, the ultrapure water can be automatically generated on-line and used in the detection system, the operation is more convenient, the cleanliness of the ultrapure water can be ensured, and the accuracy of the ion chromatograph detection data is ensured. Specifically, in the embodiment, since the purity of the ultrapure water required in the system is higher than that of pure water, the desalted water which has been preliminarily purified is introduced into the ultrapure water preparation module, or untreated water can be introduced according to the requirements, and the ultrapure water meeting the use requirements is obtained after multiple purifications. The EDI device 11 can further purify the desalted water introduced into the system, and then pass through the purification resin column 12 to remove ions again, so that the ion residual level is extremely low, and the requirement of ultrapure water is met, that is, the electrical resistivity needs to reach 18.25 MΩ*cm, which lays a foundation for subsequent accurate detection.

[0048] It should be noted that the EDI (Electrodeionization) device in the present application can be obtained from the prior art, and the main purpose is to obtain ultrapure water, and the basic principle is to use electric field force to drive the ions in the water to pass through the ion exchange membrane to realize the directional migration and separation of the ions, and continuously remove the ion pollutants in the water by cooperating with the regeneration process of the ion exchange resin; The core components of the common EDI device include an ion exchange membrane stack, a direct current power supply, a concentrated water circulating pump, and related control and monitoring equipment.

[0049] More preferably, the ultrapure water tank 13 is provided with a liquid level sensor. By providing a liquid level sensor, the ultrapure water in the ultrapure water tank 13 can be prepared and supplemented in time to meet the demand for ultrapure water in the system.

[0050] On the basis of the above technical scheme, as shown in FIG. 3, the standard sample automatic preparation module 2 includes at least one solution dilution assembly, which includes a standard sample mother liquor bottle 21, a first selection valve 22, a metering pump 23, and a dilution container 24. The first end of the first selection valve 22 is connected to the standard sample mother liquor bottle 21 through a mother liquor pipeline 25, connected to the ultrapure water tank 13 through an ultrapure water pipeline 26, and connected to the first end of the metering pump 23 through a first pipeline 27. The end of the metering pump 23 is connected to the dilution container 24 through a second pipeline 28.

[0051] In the present application, by providing a standard sample automatic preparation module 2, in cooperation with the ultrapure water preparation module 1, the online automatic preparation of standard sample solutions used in the calibration curve can be realized. The preparation and storage of standard samples in the prior art are not required, and the use of manual operation or manual preparation instrument is avoided. The working efficiency is high and the storage steps are reduced. At the same time, the concentration preparation precision of the standard sample solution is high and the consistency is good, which avoids the adverse effects of the dead volume of the preparation instrument on the solution concentration precision, and ensures the subsequent high detection precision. Specifically, the ultrapure water from the ultrapure water tank 13 and the mother liquor from the standard sample mother liquor bottle 21 flow through the first selection valve 22, the first pipeline 27, the metering pump 23, and the second pipeline 28 respectively through the ultrapure water pipeline 26 and the mother liquor pipeline 25, and then enter the dilution container 24. The metering pump is provided to accurately measure and deliver the preset delivery amount of ultrapure water and mother liquor, i.e. by adding a predetermined volume of ultrapure water and mother liquor in the dilution container to mix uniformly, a standard sample solution with a corresponding concentration is obtained by dilution; The preparation of standard sample solutions with different concentrations can be prepared by delivering the required ultrapure water volume and mother liquor volume according to the preset concentration to the dilution container. After the online preparation of standard sample solutions with different concentrations, the samples are respectively injected for detection to realize the determination of the calibration curve, which is simple and convenient, and has high precision.

[0052] In the preferred embodiment, the standard sample automatic preparation module 2 comprises a cation solution dilution assembly 201 and an anion solution dilution assembly 202, which are structurally identical and arranged in parallel and connected to the sample selection module 4.

[0053] Preferably, the standard sample automatic preparation module 2 in the embodiment comprises two sets of solution dilution assemblies, which are arranged in parallel to prepare and feed the cation and anion solutions, thereby improving the preparation efficiency and preventing cross contamination and ensuring the accuracy of the solution concentration.

[0054] In the preferred embodiment, the second pipeline 28 is provided with a second selection valve 29, and the first waste liquid pipeline 210 is connected to the second selection valve 29.

[0055] Preferably, the second selection valve 29 is provided to clean the pipeline before the dilution container 24, that is, the ultrapure water in the ultrapure water tank 13 is sequentially passed through the ultrapure water pipeline 26, the first selection valve 22, the first pipeline 27, and the metering pump 23, and then flows out through the first waste liquid pipeline 210 connected to the second selection valve 29, thereby completing the cleaning of the pipeline and part of the device.

[0056] Based on the above technical solution, the sample pretreatment module 3 comprises a sample tank, a filter 31, and a degassing device 32. The filter 31 is connected to the sample tank through a sample pipeline 33 at the first end and connected to the degassing device 32 at the second end. The degassing device 32 is connected to the sample selection module 4.

[0057] In the present application, the sample pretreatment module 3 is provided before sample detection to pretreat the sample to be detected, which can effectively prevent pollution, reduce the influence of impurities that may exist in the sample on the detection result, and protect the subsequent ion chromatograph module 5 to maintain the analysis performance. Specifically, the prepared sample solution to be detected is stored in the sample tank. When detection is required, the sample to be detected enters the filter 31 through the sample pipeline 33 to remove the particulate matter, suspended matter, and other impurities that may interfere with the analysis result or damage the chromatographic system, thereby ensuring the purity of the sample and improving the accuracy and sensitivity of the analysis. The sample solution to be detected that flows out of the filter 31 enters the degassing device 32 to remove the dissolved gas contained in the sample solution to be detected, eliminate the interference of bubbles, maintain a stable flow rate and pressure during transportation, and ensure the accuracy of ion chromatographic analysis and the normal operation of the instrument.

[0058] It should be noted that the filter and degassing device in the embodiment can be obtained from the prior art; wherein the filter is a common needle sample filter, a microporous filter membrane or a pretreatment column, etc.

[0059] On the basis of the above technical solutions, the sample selection module 4 at least includes one sample selection valve 41, the first end of the sample selection valve 41 is connected with the standard sample automatic preparation module 2 and the sample pretreatment module 3 respectively, and the last end is connected with the first end of the ion chromatograph module 5.

[0060] By setting the sample selection module 4, mainly including the sample selection valve 41, each sample selection valve 41 contains at least two channels, that is, it can be selected to enter the standard sample solution for the determination of the calibration curve or to enter the sample solution to be measured for the quantitative detection of the actual sample, realizing automatic sample selection and more convenient operation; more preferably, two sample selection valves 41 are arranged in the sample selection module 4 in the embodiment, one of which corresponds to the sample inlet of the anion standard sample solution and the sample solution to be measured, and the other of which corresponds to the sample inlet of the cation standard sample solution and the sample solution to be measured, that is, the sample inlets of the anion and cation solutions are separated, avoiding cross contamination, and the detection result is more accurate and has higher precision.

[0061] On the basis of the above technical solutions, as shown in Figure 4, the ion chromatograph module 5 at least includes a set of ion chromatograph detection components, the ion chromatograph detection components include a first multi-way valve 51, an eluent generator 52, a chromatographic column 53, a suppressor 54 and a conductivity detector 55, the first end of the first multi-way valve 51 is connected with the sample selection module 4 and the eluent generator 52 respectively, and the last end is connected with the chromatographic column 53, the suppressor 54 and the conductivity detector 55 are sequentially arranged at the last end of the chromatographic column 53; the eluent generator 52 is connected with the infusion pump 56 through a pipeline, and the infusion pump inlet is communicated with the ultrapure water tank 13.

[0062] The foregoing prepared standard sample solution or sample solution to be tested enters the ion chromatograph module 2 through the sample selection module, the eluent is automatically prepared on-line by the eluent generator 52 to provide a continuous supply for the detection system; the sample and the eluent enter the subsequent chromatographic column 53, the suppressor 54 through different channels of the first multi-way valve 51, and finally enter the conductivity detector 55 for detection; the chromatographic column 53 is a key component in ion chromatographic analysis, and a cation chromatographic column or an anion chromatographic column is set according to the analysis requirement to realize effective separation of each component in the mixture according to different physical and chemical properties of the substances to be separated; the suppressor 54 is used to remove the strong electrolyte background conductivity in the eluent to improve the detection sensitivity; the conductivity detector 55 is used to measure the conductivity change of the effluent to obtain ion concentration information; finally, the data processing system receives the electrical signals output by the conductivity detector to form a calibration curve or a chromatogram, etc., and performs peak identification and quantitative calculation, etc.

[0063] It should be noted that the ion chromatograph module in the present application can use the existing ion chromatograph equipment of the present company to complete the quantitative detection of ion concentration; the chromatographic column, the suppressor and the conductivity detector can be obtained from the prior art as long as the ion chromatographic detection is realized.

[0064] In the preferred embodiment, the ion chromatograph module 5 includes a cation chromatographic detection assembly 501 and an anion chromatographic detection assembly 502, and is correspondingly provided with a cation solution dilution assembly 201 and an anion solution dilution assembly 202, and the cation chromatographic detection assembly 501 and the anion chromatographic detection assembly 502 have the same structure assembly and are arranged in parallel.

[0065] In the present embodiment, the cation chromatographic detection assembly 501 and the anion chromatographic detection assembly 502 are provided corresponding to the cation solution dilution assembly 201 and the anion solution dilution assembly 202, respectively diluting, sampling and detecting the cation standard sample mother liquor and the anion standard sample mother liquor, independent of each other and not affecting each other, avoiding cross contamination between the cation solution and the anion solution, more convenient operation and realizing high-precision detection. The types of the corresponding eluent and the types of the chromatographic column and the suppressor in the cation chromatographic detection assembly and the anion chromatographic detection assembly are adaptively adjusted according to the cation or anion detection.

[0066] On the basis of the above technical solution, a cleaning assembly 6 is further included, the cleaning assembly 6 includes a second waste liquid pipeline 61 and a peristaltic pump 62, the second waste liquid pipeline 61 is connected at the end of the standard sample automatic preparation module 2 or the first end of the ion chromatograph module 5, and the peristaltic pump 62 is arranged on the second waste liquid pipeline 61.

[0067] By setting the cleaning assembly 6 at the end of the standard sample automatic preparation module 2 and the head of the ion chromatograph module 5, independent cleaning operation can be facilitated for each section of pipeline in each module, the cleanliness of the overall detection system is improved, meanwhile, the collection of waste liquid is facilitated, the residual or mutual influence between different concentrations of solution in the pipeline after long-time use is avoided, and the detection accuracy in the subsequent detection is affected.

[0068] In the preferred embodiment, the third selection valve 7 is arranged between the end of the dilution container 24 and the sample selection module 4. That is, one channel of the third selection valve 7 is connected with the sample injection selection valve 41 of the sample selection module 4, so that the prepared standard sample solution is transported to the subsequent ion chromatograph module 5 for determination of the calibration curve; the other channel is connected with the cleaning assembly 6, that is, the ultrapure water flows out from the second waste liquid pipeline 61 after passing through the first selection valve 22, the metering pump 23, the second selection valve 29, the dilution container 24, the third selection valve 7 and the peristaltic pump 62 in sequence, so that the pipeline in the standard sample automatic preparation module 2 is cleaned in time, and the operation is more convenient.

[0069] In the preferred embodiment, one outlet channel of the first multi-way valve 51 is connected with the cleaning assembly 6. By arranging the cleaning assembly 6 on one outlet channel of the first multi-way valve 51, the pipeline in the standard sample automatic preparation module 2 and the sample selection module 4 can be cleaned.

[0070] In the preferred embodiment, the waste liquid collection module 8 is further included, the waste liquid collection module 8 includes a waste liquid collector 81, a waste liquid pump 82 and a waste liquid tank 83, a plurality of waste liquid pipelines are connected to the waste liquid collector 81, the waste liquid tank 83 is connected with the waste liquid collector 81 through a discharge pipeline 84, and the waste liquid pump 82 is arranged on the discharge pipeline 84.

[0071] By arranging the waste liquid collection module 8, the waste liquid generated in the overall automatic online ion chromatograph detection system can be collected, discharged and post-treated in time, which is convenient, time-saving and labor-saving; specifically, the plurality of modules in the ion chromatograph detection system of the application are involved in multiple cleaning during use, so that waste liquid is often generated, the waste liquid in the system is collected into the waste liquid collector through different waste liquid pipelines by the power provided by the waste liquid pump, and then discharged into the waste liquid tank, which is convenient for subsequent recycling and treatment. Specifically, the first waste liquid pipeline 210, the second waste liquid pipeline 61 provided with the cleaning assembly in the plurality of modules and the waste liquid pipeline connected to the end of the ion chromatograph module 5 can be connected to the waste liquid collector 81, so that the waste liquid in the overall detection system can be collected.

[0072] The application further provides an automatic online ion chromatograph detection method, which adopts the automatic online ion chromatograph detection system and includes the following steps:

[0073] ultra-pure water preparation; the desalted water is introduced into the ultra-pure water preparation module 1, and the ultra-pure water is prepared in an online automatic generation mode, and is stored in the ultra-pure water tank 13 for standby;

[0074] standard sample solution preparation; according to a preset concentration of the standard sample solution, the required volume of the ultra-pure water and the stock solution are automatically sampled and online diluted by the standard sample automatic preparation module 2 to obtain the standard sample solution with the preset concentration;

[0075] determination of a calibration curve; the standard sample solution obtained in the above step is introduced into the ion chromatograph module 5 through the sample selection module 4 for detection to obtain corresponding conductive detection values; the preparation and determination of the standard sample solution with different concentrations are repeated to complete the value detection required for the calibration curve and draw the calibration curve;

[0076] pretreatment and detection of a sample to be tested; the sample to be tested actually required to be detected is subjected to sample filtration and degassing operation by the sample pretreatment module 3, and then is introduced into the ion chromatograph module 5 through the sample selection module 4 for detection to obtain corresponding conductivity detection values, form a chromatogram and perform subsequent quantitative calculation.

[0077] On the basis of the above technical scheme, the standard sample solution preparation method comprises the following steps:

[0078] Step one: rinse the sample mother liquor; the sample mother liquor is used to flush the pipeline, and the flushing is completed after the pipeline is filled with the sample mother liquor;

[0079] Step two: flush with ultra-pure water; the pipeline is flushed with ultra-pure water, and the flushing is completed after the pipeline is filled with ultra-pure water;

[0080] Step three: add the sample mother liquor; the sample mother liquor is introduced into the pipeline, and the required amount of sample mother liquor is added to the dilution container;

[0081] Step four: add ultra-pure water; the ultra-pure water is introduced into the pipeline, and the required amount of ultra-pure water is added to the same dilution container as step three; after mixing, the standard sample solution with the required concentration can be prepared;

[0082] Step five: repeat steps three and four above to prepare the next standard sample solution with a different concentration, and realize online automatic preparation of the standard sample solution with different concentrations.

[0083] On the basis of the above technical scheme, the following steps are included:

[0084] Step one: the sample mother liquor is used to flush the pipeline, and the sample mother liquor is flushed from the sample mother liquor bottle 21 through the mother liquor pipeline 25, the first selection valve 22, the first pipeline 27, the metering pump 23, and the second pipeline 28 in sequence; at this time, the mother liquor pipeline 25, the first pipeline 27, and the second pipeline 28 are filled with the sample mother liquor;

[0085] Step two: the ultrapure water is used to flush the pipeline, and the ultrapure water is flushed through the ultrapure water pipeline 26, the first selection valve 22, the first pipeline 27, the metering pump 23, and the second pipeline 28 in sequence; at this time, the ultrapure water pipeline 26, the first pipeline 27, and the second pipeline 28 are filled with the ultrapure water; the initial state of the pipeline is set;

[0086] Step three: the required amount of sample mother liquor is set to pass through the mother liquor pipeline 25, the first selection valve 22, the first pipeline 27, the metering pump 23, and the second pipeline 28 in sequence and then enter the dilution container 24; at this time, the ultrapure water in the first pipeline 27 and the second pipeline 28 in step two is flushed into the dilution container 24; after the sample mother liquor is closed, there is a dead volume of sample mother liquor remaining in the first pipeline 27 and the second pipeline 28;

[0087] Step four: the required amount of ultrapure water is set to pass through the ultrapure water pipeline 26, the first selection valve 22, the first pipeline 27, the metering pump 23, and the second pipeline 28 in sequence and then enter the dilution container 24, and the ultrapure water flushes the remaining sample mother liquor in step three into the same dilution container 24; after the ultrapure water is closed, there is still ultrapure water remaining in the first pipeline 27 and the second pipeline 28; at this time, the dilution container 24 has obtained the required amount of sample mother liquor and ultrapure water, a dilution process of the sample mother liquor is completed, and a standard sample solution with a preset concentration is obtained; at the same time, the pipeline also maintains the initial state in step two;

[0088] Step five: steps three and four are repeated again to prepare a standard sample solution with a different concentration, and online automatic preparation of standard sample solutions with different concentrations is realized.

[0089] Specifically, the initial state of the pipeline in step two is that the mother liquor pipeline 25 is filled with the mother liquor, and the ultrapure water pipeline 26, the first pipeline 27, and the second pipeline 28 are filled with the ultrapure water.

[0090] The preparation method of the standard sample solution provided in the application realizes online automatic preparation of the standard sample solution, reduces manual operation, improves work efficiency and preparation accuracy; wherein the design of each step and the operation sequence effectively solves the influence of the instrument and the dead volume in the pipeline on the concentration accuracy of the final prepared solution in the prior art, is not affected by the dead volume, and has high concentration accuracy; at the same time, the concentration influence between the preparation of two standard sample solutions with different concentrations is not considered, the pipeline is automatically flushed during the preparation process, that is, the initial state of the pipeline is set, and repeated cleaning of the pipeline is not required, realizing continuous automatic preparation of standard sample solutions with different required concentrations, high work efficiency, more convenient to use, and strong practicality.

[0091] The preparation method of the standard sample solution is shown in the logic block diagram of FIGS. 5 to 8, wherein the thick arrows in the figure represent the liquid added in the step and the flow direction thereof, and it should be noted that the state diagram after two liquids are added in the dilution container in FIG. 8 does not represent the stratification phenomenon in the dilution container.

[0092] Specifically, first, in the process of pipeline flushing: in step one, mother liquor is used to rinse the pipeline, the main purpose is to fill the mother liquor concentrate in the mother liquor pipeline 25, in step two, ultrapure water is used to flush the pipeline, that is, in addition to the mother liquor pipeline 25, the ultrapure water pipeline 26, the first pipeline 27 and the second pipeline 28 are filled with ultrapure water; secondly, in the process of continuous preparation: the first selection valve 22 and the metering pump 23 work together, first add the required amount of mother liquor, at this time the residual ultrapure water in the pipeline, that is, the ultrapure water in the first pipeline 27 and the second pipeline 28, is added to the dilution container 24, and a part of the dead volume of mother liquor will be left in the corresponding pipeline; then add the required amount of ultrapure water, the ultrapure water will add the residual mother liquor in the pipeline, that is, the mother liquor in the first pipeline 27 and the second pipeline 28, to the dilution container 24, and the corresponding pipeline will be cleaned to ultrapure water; since the residual ultrapure water in the pipeline at this time is equal in volume to the residual ultrapure water in the pipeline in step two, the error caused by the dead volume of the ultrapure water pipeline is eliminated, and the dead volume of the mother liquor pipeline is also excluded for the same reason; at the same time, the pipeline is in the initial state of the pipeline, and when the standard sample solution of the previous concentration is completed, the preparation of the standard sample solution of the next concentration is carried out, that is, the process of adding mother liquor and ultrapure water in steps three and four is repeated to complete the preparation of the standard sample solution of the next concentration. Therefore, by using the continuous preparation method of the standard sample solution in the present application, the continuous automatic preparation of standard sample solutions of different concentrations can be realized, and repeated cleaning of the pipeline is not required, and the operation is more convenient, wherein the setting of each step and the sequence between the steps in the preparation method of the present application plays a crucial role and is one of the important points of the present application, that is, if the flushing or liquid adding sequence of the mother liquor and the ultrapure water is changed, not only the error caused by the dead volume cannot be solved, but also a larger preparation error will be caused.

[0093] The selector devices mentioned in the present application, such as the first selection valve, the second selection valve, the third selection valve, the sample selection valve and the multi-way valve, can all use the multi-channel selection valve in the prior art, which is mainly used for the selection and sampling of different liquid samples, and the metering pump can be obtained from the prior art, and the present application does not involve the improvement of the specific structure of the selection valve or the metering pump. At the same time, the above-mentioned first end and the last end are defined according to the direction of liquid flow, which is only for the convenience of understanding the technical solution and does not constitute a limitation on the present application.

[0094] The basic principles and main features of the present application are shown and described above, and it is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, therefore the embodiments should be regarded as exemplary and non-limiting, the scope of the present application is defined by the appended claims rather than the above description, therefore all changes falling within the meaning and scope of the essential elements of the claims are intended to be included in the present application.

[0095] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes every feature or implementation described herein. The specification can include implicit combinations of explicitly mentioned features and / or implicit combinations of implicitly mentioned features. Such combinations are also expressly included within the scope of the specification and an embodiment.

Claims

1. A fully automated online ion chromatography detection system, characterized in that, The system includes an ultrapure water preparation module (1), an automatic standard sample preparation module (2), a sample pretreatment module (3), a sample selection module (4), and an ion chromatograph module (5). The ultrapure water preparation module (1) is used for the online generation and supply of ultrapure water and is connected to the automatic standard sample preparation module (2) and the ion chromatograph module (5) through pipelines. The automatic standard sample preparation module (2) is connected at one end to the ultrapure water preparation module (1) and at the other end to the sample selection module (4) for the continuous preparation of standard sample solutions of different concentrations. The sample pretreatment module (3) is connected at the other end to the sample selection module (4) for the pretreatment of the sample solution to be tested. The sample selection module (4) is connected to the ion chromatograph module (5) at its end and is used to select a standard sample solution or a sample solution to be tested. The ion chromatograph module (5) is used to perform quantitative detection on the solution flowing in from the sample selection module (4).

2. The fully automated online ion chromatography detection system according to claim 1, characterized in that, The ultrapure water preparation module (1) includes an EDI device (11), a purification resin column (12), and an ultrapure water tank (13); the demineralized water is purified by passing through the EDI device (11) and the purification resin column (12) in sequence, and the prepared ultrapure water is stored in the ultrapure water tank (13).

3. The fully automated online ion chromatography detection system according to claim 2, characterized in that, The standard sample automatic preparation module (2) includes at least one solution dilution assembly, which includes a standard sample mother liquor bottle (21), a first selection valve (22), a metering pump (23), and a dilution container (24). The first selection valve (22) is connected to the standard sample mother liquor bottle (21) through a mother liquor pipeline (25) and to an ultrapure water tank (13) through an ultrapure water pipeline (26). The end of the valve is connected to the first end of the metering pump (23) through a first pipeline (27). The end of the metering pump (23) is connected to the dilution container (24) through a second pipeline (28).

4. The fully automated online ion chromatography detection system according to claim 1, characterized in that, The sample pretreatment module (3) includes a sample container, a filter (31) and a degassing device (32). The first end of the filter (31) is connected to the sample container through a sample pipeline (33), and the last end is connected to the first end of the degassing device (2). The last end of the degassing device (32) is connected to the sample selection module (4).

5. The fully automated online ion chromatography detection system according to claim 1, characterized in that, The sample selection module (4) includes at least one injection selection valve (41). The first end of the injection selection valve (41) is connected to the end of the standard sample automatic preparation module (2) and the sample pretreatment module (3), respectively, and the end is connected to the first end of the ion chromatograph module (5).

6. The fully automated online ion chromatography detection system according to claim 1, characterized in that, The ion chromatograph module (5) includes at least one set of ion chromatography detection components. The ion chromatography detection components include a first multi-way valve (51), an eluent generator (52), a chromatographic column (53), a suppressor (54), and a conductivity detector (55). The first multi-way valve (51) is connected to the sample selection module (4) and the eluent generator (52) at its head and to the chromatographic column (53) at its tail. The suppressor (54) and the conductivity detector (55) are arranged sequentially at the tail of the chromatographic column (53). The eluent generator (52) is connected to the infusion pump (56) through a pipeline. The inlet of the infusion pump is connected to the ultrapure water tank (13).

7. A fully automated online ion chromatography detection system according to any one of claims 1 to 6, characterized in that, It also includes a cleaning assembly (6), which includes a second waste liquid line (61) and a peristaltic pump (62). The second waste liquid line (61) is connected to the end of the standard sample automatic preparation module (2) or the beginning of the ion chromatograph module (5). The peristaltic pump (62) is installed on the second waste liquid line (61).

8. A fully automated online ion chromatography detection method, employing the fully automated online ion chromatography detection system according to any one of claims 1 to 7, characterized in that, Includes the following steps: Ultrapure water preparation: Demineralized water is introduced into the ultrapure water preparation module (1) and ultrapure water is prepared by online automatic generation. The ultrapure water is then stored in the ultrapure water tank (13) for later use. Preparation of standard sample solution: According to the preset concentration of standard sample solution, the required volume of ultrapure water and mother liquor is automatically injected and diluted online using the standard sample automatic preparation module (2) to obtain a standard sample solution of preset concentration. Determination of calibration curves; The standard sample solution obtained in the previous step is entered into the ion chromatograph module (5) through the sample selection module (4) for detection to obtain the corresponding conductivity detection value; the preparation and determination of standard sample solutions of different concentrations are repeated to complete the numerical detection required for the calibration curve and the plotting of the calibration curve; Sample pretreatment and detection: The sample to be tested is filtered and degassed through the sample pretreatment module (3), and then enters the ion chromatograph module (5) through the sample selection module (4) for detection, so as to obtain the corresponding conductivity detection value, form a chromatogram and perform subsequent quantitative calculation.

9. The fully automated online ion chromatography detection method according to claim 8, characterized in that, The preparation of the standard sample solution includes the following steps: Step 1: Rinse with standard stock solution; Rinse the pipeline with standard stock solution until the pipeline is completely filled with standard stock solution to complete the rinsing; Step 2: Ultrapure water rinsing; Rinse the pipeline with ultrapure water until the pipeline is completely filled with ultrapure water to complete the rinsing process; Step 3: Add standard stock solution; introduce standard stock solution into the pipeline, and add the required amount of standard stock solution to the dilution container; Step 4: Add ultrapure water; introduce ultrapure water into the pipeline, and add the required amount of ultrapure water to the same dilution container as in Step 3; after mixing, the standard sample solution of the required concentration can be prepared. Step 5: Repeat steps 3 and 4 above to prepare standard sample solutions of different concentrations, thereby achieving online automatic preparation of standard sample solutions of different concentrations.

10. The fully automated online ion chromatography detection method according to claim 8, characterized in that, The preparation of the standard sample solution includes the following steps: Step 1: The pipeline is flushed with standard mother liquor. The standard mother liquor is flushed from the standard mother liquor bottle (21) through the mother liquor pipeline (25), the first selection valve (22), the first pipeline (27), the metering pump (23), and the second pipeline (28) in sequence. At this time, the mother liquor pipeline (25), the first pipeline (27), and the second pipeline (28) are all filled with standard mother liquor. Step 2: The pipeline is flushed with ultrapure water. The ultrapure water passes through the ultrapure water pipeline (26), the first selector valve (22), the first pipeline (27), the metering pump (23), and the second pipeline (28) in sequence to complete the flushing. At this time, the ultrapure water pipeline (26), the first pipeline (27), and the second pipeline (28) are all filled with ultrapure water. The initial state of the pipeline is set. Step 3: The required amount of standard sample mother liquor is sequentially passed through the mother liquor pipeline (25), the first selection valve (22), the first pipeline (27), the metering pump (23), and the second pipeline (28) before entering the dilution container (24); at this time, the ultrapure water in the first pipeline (27) and the second pipeline (28) in Step 2 is flushed into the dilution container (24); after the standard sample mother liquor is closed, there will be a dead volume of standard sample mother liquor remaining in the first pipeline (27) and the second pipeline (28); Step 4: The required amount of ultrapure water is sequentially passed through ultrapure water pipeline (26), first selection valve (22), first pipeline (27), metering pump (23), and second pipeline (28) into dilution container (24). The ultrapure water flushes the residual standard mother liquor from step 3 into the same dilution container (24). After the ultrapure water is turned off, ultrapure water still remains in the first pipeline (27) and the second pipeline (28). At this time, the required amount of standard mother liquor and ultrapure water are collected in the dilution container (24), completing one dilution process of the standard mother liquor and obtaining a standard sample solution of the preset concentration. At the same time, the pipeline also maintains the initial state in step 2. Step 5: Repeat steps 3 and 4 above to prepare the next standard sample with different concentrations. Solution preparation enables the online automatic preparation of standard sample solutions of different concentrations.

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