Intelligent online ion chromatograph with concentration prediction function and control method

Abstract

The present invention discloses an intelligent online ion chromatograph with a concentration pre-judgment function and a control method. The intelligent online ion chromatograph comprises: a chromatograph body, a concentration detection pre-dilution module and a secondary dilution module; the chromatograph body is provided with a multi-way valve, a second quantitative loop and an eluent drive pump, the concentration detection pre-dilution module comprises a six-way valve, a first quantitative loop, a first detector, a first mixer, a first mixing drive pump, a concentration detection drive pump and a first switching valve, and the secondary dilution module comprises a temporary storage container, a second switching valve, a second mixer, and a second mixing drive pump. The dilution multiple is automatically adjusted according to the sample concentration and the sample and the diluent are fully mixed to improve the detection accuracy of the intelligent online ion chromatograph with a concentration pre-judgment function.

Description

Technical Field

[0001] The present invention relates to the technical field of ion chromatography detection, and in particular to an intelligent online ion chromatograph with concentration prediction function and a control method. Background Art

[0002] Ion chromatography is mainly used for the analysis of environmental samples, including anions and cations in samples such as surface water, drinking water, rainwater, domestic sewage and industrial wastewater, acid precipitation and atmospheric particulate matter, and the analysis of trace impurities in water and reagents related to the microelectronics industry. During the use of the ion chromatograph, an automatic sampling device is generally used to realize the automatic sampling of samples. However, in actual use, there is a sample concentration that is too high and exceeds the detection range of the ion chromatograph. At this time, multiple samples need to be diluted. In order to automatically dilute the sample, Chinese patent publication number CN 108267356 A discloses a sample automatic dilution device, which uses a conductivity detector to check the concentration of the sample, and then dilutes the sample in the first quantitative loop as needed. In the process of diluting a specific multiple according to the detected concentration, the sample and the diluent rely on a long time diffusion to achieve mixing, and it is easy to cause the sample and the diluent to be mixed unevenly, resulting in inaccurate detection data and long-term mixing that does not meet the requirements of online ion chromatography instant analysis. In view of this, how to design a technology that automatically adjusts the dilution multiple according to the sample concentration and achieves sufficient mixing of the sample and the diluent to improve the detection accuracy is a technical problem to be solved by the present invention. Summary of the invention

[0003] The present invention provides an intelligent online ion chromatograph with a concentration prediction function and a control method, which can automatically adjust the dilution multiple according to the sample concentration and achieve full mixing of the sample and the diluent, so as to improve the detection accuracy of the intelligent online ion chromatograph with a concentration prediction function.

[0004] In order to achieve the above object, the present invention adopts the following technical scheme:

[0005] The present invention provides an intelligent online ion chromatograph with a concentration prediction function, comprising:

[0006] A chromatograph body, wherein the chromatograph body is provided with a multi-way valve, a second quantitative loop and an eluent driving pump, wherein the multi-way valve has a plurality of interfaces, and the liquid outlet of the eluent driving pump and the two ports of the second quantitative loop are respectively connected to the corresponding interfaces of the multi-way valve;

[0007] A concentration detection pre-dilution module, the concentration detection pre-dilution module comprising a six-way valve, a first quantitative loop, a first detector, a first mixer, a first mixing drive pump, a concentration detection drive pump and a first switching valve, the six-way valve having an inlet, a first diluent inlet, a first liquid outlet, a second liquid outlet and two connecting ports, the first quantitative loop is connected to the two connecting ports, the first liquid outlet is connected to the first detector and the concentration detection drive pump, the first switching valve is provided with a plurality of interfaces, the second liquid outlet, the first mixer and the first mixing drive pump are respectively connected to corresponding interfaces of the first switching valve;

[0008] A secondary dilution module, the secondary dilution module comprising a temporary storage container, a second switching valve, a second mixer, and a second mixing drive pump; the second switching valve is provided with a plurality of interfaces, a standard sample inlet, and a second diluent inlet, the temporary storage container, the second mixer, the second mixing drive pump, and the multi-way valve are respectively connected to corresponding interfaces of the second switching valve;

[0009] The six-way valve is configured to switch the first quantitative loop to connect the sample inlet with the first liquid outlet, and is also configured to switch the first quantitative loop to connect the first diluent inlet with the second liquid outlet;

[0010] The first switching valve is configured to switch the first mixing drive pump to connect to the second liquid outlet, the first mixer or the temporary storage container;

[0011] The second switching valve is configured to switch the second mixing drive pump to connect with the temporary storage container, the second mixer, the second diluent inlet, the standard sample inlet or the multi-way valve;

[0012] The multi-way valve is configured to switch the second sample loop to connect to the second mixing drive pump through the second switching valve, and is further configured to switch the second sample loop to connect to the eluent drive pump.

[0013] In one embodiment, the concentration detection pre-dilution module is further provided with an injection valve, which is a two-position three-way valve, and has an inlet and two outlets, wherein the inlet of the injection valve is used to connect to a container for storing a sample, an outlet of the injection valve is connected to the liquid inlet of the six-way valve, and the other outlet of the injection valve is connected to the first switching valve;

[0014] The first switching valve is further configured to switch the first hybrid drive pump to communicate with the second liquid outlet of the six-way valve or the injection valve.

[0015] In one embodiment, the first switching valve includes a first switching sub-valve and a second switching sub-valve;

[0016] The first switching sub-valve is a two-position three-way valve, the first switching sub-valve has two inlets and one outlet, and the second switching sub-valve is provided with a plurality of interfaces;

[0017] One inlet of the first switching sub-valve is connected to the second liquid outlet of the six-way valve, and the other inlet of the first switching sub-valve is connected to the injection valve;

[0018] The outlet of the first switching sub-valve, the first mixer, the first mixing drive pump, and the temporary storage container are respectively connected to corresponding interfaces of the first switching valve.

[0019] In one embodiment, the first hybrid drive pump and the second hybrid drive pump are syringe pumps.

[0020] In one embodiment, a second detector is further provided between the first switching valve and the temporary storage container.

[0021] In one embodiment, the secondary dilution module further comprises a quantitative container, and the volume of the quantitative container is greater than the volume of the second quantitative loop;

[0022] The two ports of the quantitative container are respectively connected to the corresponding interfaces of the multi-way valve;

[0023] The multi-way valve is configured to switch the quantitative container to be connected to the second mixing drive pump through the second switching valve, and is also configured to switch the quantitative container to be connected to the eluent drive pump.

[0024] In one embodiment, two secondary dilution modules are included;

[0025] The first switching valve is configured to switch the first hybrid drive pump to communicate with the temporary storage container in one of the secondary dilution modules.

[0026] In one embodiment, a Na-type pretreatment column is further provided between the temporary storage container and the first switching valve in one of the secondary dilution modules.

[0027] In one embodiment, at least one of the secondary dilution modules further comprises a quantitative container, and the volume of the quantitative container is greater than the volume of the second quantitative loop;

[0028] The two ports of the quantitative container are respectively connected to the corresponding interfaces of the multi-way valve;

[0029] The multi-way valve is configured to switch the quantitative container to be connected to the second mixing drive pump through the second switching valve, and is also configured to switch the quantitative container to be connected to the eluent drive pump.

[0030] In one embodiment, the first detector is a conductivity detector or an ultraviolet detector.

[0031] Another embodiment of the present application further provides a control method for the above-mentioned intelligent online ion chromatograph with concentration prediction function, comprising:

[0032] Step 1: Concentration detection: The driving pump transports the sample in the sample storage tank to the first quantitative loop and the first detector in sequence, and the concentration of the sample is detected by the first detector;

[0033] Step 2: The first mixing drive pump delivers the diluent in the diluent storage tank to the first quantitative loop and delivers the sample in the first quantitative loop to the first mixer for pre-dilution of a set multiple to form a pre-mixed solution;

[0034] Step 3: The first mixing drive pump delivers the premixed liquid to a temporary storage container;

[0035] Step 4: According to the concentration of the sample detected by the first detector, the second mixing drive pump sucks a fixed amount of diluent from the diluent storage tank, and then extracts a fixed amount of premixed liquid from the temporary storage container, and the second mixing drive pump mixes the premixed liquid and the diluent to form a sample detection liquid;

[0036] Step 5: The second mixing drive pump delivers the mixed sample test liquid to the second quantitative loop, and then the eluent drive pump delivers the eluent in the eluent container to the second quantitative loop and outputs it into the separation column of the intelligent online ion chromatograph with concentration prediction function for chromatographic analysis.

[0037] In one embodiment, a second detector is further provided between the first switching valve and the temporary storage container;

[0038] Specifically, step 3 includes: in the process of the first mixing drive pump conveying the premixed liquid to the temporary storage container, the concentration of the premixed liquid is detected by the second detector;

[0039] Specifically, step 4 includes: according to the concentration of the sample detected by the second detector, the second mixing drive pump sucks a fixed amount of diluent from the diluent storage tank, and then extracts a fixed amount of premixed liquid from the temporary storage container, and the second mixing drive pump mixes the premixed liquid and the diluent to form a sample detection liquid.

[0040] In one embodiment, if the sample does not need to be diluted;

[0041] The step 2 further comprises: a first hybrid drive pump directly sucks the sample in the sample storage tank;

[0042] The step 3 also includes: the first hybrid drive pump transports the sample to the temporary storage container and executes step 5;

[0043] The step 5 also includes: a second mixing drive pump transports the sample in the temporary storage container to the second quantitative loop, and then the eluent drive pump transports the eluent in the eluent container to the second quantitative loop and outputs it into the separation column of the intelligent online ion chromatograph with concentration prediction function for chromatographic analysis.

[0044] In one embodiment, a quantitative container is provided on the multi-way valve of the secondary dilution module;

[0045] If it is judged according to the value detected by the first detector that the concentration of the sample is lower than the set detection concentration range;

[0046] The step 2 further comprises: a first hybrid drive pump directly sucks the sample in the sample storage tank;

[0047] The step 3 also includes: the first hybrid drive pump transports the sample to the temporary storage container and executes step 5;

[0048] The step 5 also includes: the second mixing drive pump transports the sample in the temporary storage container to the quantitative container, and then the eluent drive pump transports the eluent in the eluent container to the quantitative container and outputs it into the separation column of the intelligent online ion chromatograph with concentration prediction function for chromatographic analysis.

[0049] The technical solution of the present invention has the following technical effects compared with the prior art: the sample is transported to the first detector through the concentration detection drive pump to detect whether the concentration of the sample needs to be diluted. When the sample needs to be diluted, the sample and the diluent can be sucked in by the first mixing drive pump for pre-dilution; the second mixing drive pump can transport the pre-mixed liquid to the temporary storage container of the secondary dilution module, and according to the information of the sample detection concentration, the secondary dilution module can be used to dilute the set multiple, so as to automatically adjust the dilution multiple according to the sample concentration and achieve full mixing of the sample and the diluent, so as to improve the detection accuracy of the intelligent online ion chromatograph with concentration prediction function. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is one of the structural principle diagrams of an embodiment of an intelligent online ion chromatograph with a concentration prediction function of the present invention;

[0051] Figure 2 This is the second structural principle diagram of an embodiment of the intelligent online ion chromatograph with concentration prediction function of the present invention;

[0052] Figure 3 This is the third structural principle diagram of an embodiment of the intelligent online ion chromatograph with concentration prediction function of the present invention.

[0053] Reference numerals:

[0054] 1. Concentration detection pre-dilution module; 11. Six-way valve; 12. First quantitative loop; 13. First detector; 14. First mixer; 15. First mixing drive pump; 16. Concentration detection drive pump; 17. First switching valve; 18. Injection valve;

[0055] 171, first switching sub-valve; 172, second switching sub-valve;

[0056] 2. Secondary dilution module; 21. Temporary storage container; 22. Second switching valve; 23. Second mixer; 24. Second mixing drive pump; 25. Na-type pretreatment column;

[0057] 3. Chromatograph body; 31. Separation column; 32. Suppressor; 33. Conductivity detector; 34. Multi-way valve; 35. Second quantitative loop; 36. Eluent drive pump; 37. Quantitative container;

[0058] 100, sample container; 200, diluent container; 300, eluent container; 400, standard sample container. DETAILED DESCRIPTION

[0059] Embodiment 1, as Figure 1-Figure 3 As shown, the present invention provides an intelligent online ion chromatograph with concentration pre-judgment function, comprising: an ion chromatograph sampling device and a chromatograph body 3. The ion chromatograph sampling device comprises a concentration detection pre-dilution module 1 and a secondary dilution module 2.

[0060] The chromatograph body 3 is provided with a multi-way valve 34, a second quantitative ring 35 and an eluent driving pump 36. The multi-way valve 34 has multiple interfaces. The liquid outlet of the eluent driving pump 36 and the two ports of the second quantitative ring 35 are respectively connected to the corresponding interfaces of the multi-way valve 34.

[0061] The concentration detection pre-dilution module 1 includes a six-way valve 11, a first quantitative ring 12, a first detector 13, a first mixer 14, a first mixing drive pump 15, a concentration detection drive pump 16 and a first switching valve 17. The six-way valve 11 has an inlet, a first diluent inlet, a first liquid outlet, a second liquid outlet and two connecting ports. The first quantitative ring 12 is connected to the two connecting ports. The first liquid outlet is connected to the first detector 13 and the concentration detection drive pump 16. The first switching valve 17 is provided with a plurality of interfaces. The second liquid outlet, the first mixer 14 and the first mixing drive pump 15 are respectively connected to the corresponding interfaces of the first switching valve 17.

[0062] The secondary dilution module 2 includes a temporary storage container 21, a second switching valve 22, a second mixer 23, and a second mixing drive pump 24; the second switching valve 22 is provided with a plurality of interfaces, a standard sample inlet and a second diluent inlet, and the temporary storage container 21, the second mixer 23, the second mixing drive pump 24, and the multi-way valve 34 are respectively connected to the corresponding interfaces of the second switching valve 22.

[0063] Among them, the six-way valve 11 is configured to switch the first quantitative ring 12 to connect the sample inlet and the first liquid outlet, and is also configured to switch the first quantitative ring 12 to connect the first diluent inlet and the second liquid outlet; the first switching valve 17 is configured to switch the first mixing drive pump 15 to connect the second liquid outlet, the first mixer 14 or the temporary storage container 21; the second switching valve 22 is configured to switch the second mixing drive pump 24 to connect the temporary storage container 21, the first mixer 14, the second diluent inlet, the standard sample inlet or the multi-way valve 34; the multi-way valve 34 is configured to switch the second quantitative ring 35 to connect the second mixing drive pump 24 through the second switching valve 22, and is also configured to switch the second quantitative ring 35 to connect the eluent drive pump 36.

[0064] In addition, the chromatograph body 3 generally includes a separation column 31 , a suppressor 32 , and a conductivity detector 33 which are connected in sequence, and the separation column 31 is connected to a multi-way valve 34 .

[0065] Specifically, in actual use, the injection port is used to connect the sample container 100, and the first diluent inlet and the second diluent inlet are used to connect the diluent container 200. After the ion chromatographic injection device is started, the concentration detection drive pump 16 is powered on and started first. At this time, the six-way valve 11 switches the first quantitative loop 12 to connect between the sample container 100 and the first detector 13. Driven by the concentration detection drive pump 16, the sample in the sample container 100 flows through the first quantitative loop 12 and enters the first detector 13 for detection. After the concentration of the sample is detected by the first detector 13, the dilution multiple of the sample can be determined.

[0066] Then, the six-way valve 11 switches the first quantitative ring 12 to connect between the diluent container 200 and the first switching valve 17. At this time, the first switching valve 17 switches the first mixing drive pump 15 to be connected to the six-way valve 11. Under the action of the first mixing drive pump 15, the sample in the first quantitative ring 12 and the quantitative diluent are sucked in. Then, the first switching valve 17 switches the first mixing drive pump 15 to be connected to the first mixer 14. The first mixing drive pump 15 allows the sample and the diluent to be evenly mixed in the first mixer 14 to form a premixed liquid. Finally, the first switching valve 17 switches the first mixing drive pump 15 to be connected to the temporary storage container 21, and the first mixing drive pump 15 transports the premixed liquid to the temporary storage container 21.

[0067] The second switching valve 22 can switch the second mixing drive pump 24 to be connected to the diluent container 200 and the temporary storage container 21 respectively. According to the final dilution multiple of the sample, a quantitative premix and diluent are sucked in through the second mixing drive pump 24. Then, the second switching valve 22 switches the second mixing drive pump 24 to be connected to the second mixer 23. The second mixing drive pump 24 enables the premix and diluent to be evenly mixed in the second mixer 23 to form a sample detection liquid; finally, the second switching valve 22 switches the second mixing drive pump 24 to be connected to the multi-way valve 34 to transport the sample detection liquid to the second quantitative ring 35.

[0068] In this way, the multi-way valve 34 can switch the second quantitative loop 35 to connect the eluent driving pump 36 and the separation column 31, so that the eluent in the eluent container 300 is transported to the second quantitative loop 35 through the eluent driving pump 36 to enter the separation column 31 for chromatographic analysis. For the specific detection process of the chromatograph body 3, reference can be made to conventional chromatographic analysis equipment, which will not be limited or elaborated here.

[0069] In actual use, in order to calculate the concentration of unknown samples, standard substances are usually used for calculation, and different samples correspond to different standard samples. To detect a certain unknown sample, 5-10 points of standard solutions of different concentrations of the standard sample of the sample are generally configured. The specific operation is as follows: the concentrated standard sample 400 is sucked into the injection tube of the second mixing drive pump 24 through the second switching valve 22, the second switching valve is switched to the diluent (pure water) 200, the pure water is sucked into the injection tube of the second mixing drive pump 24, the second switching valve 22 is switched to the mixer 23, and the dilution solution of the standard sample is pushed and pulled back and forth in the injection tube 24 to the mixer 23 to mix, and then accurately diluted to the concentration of one point of the standard sample, and the peak height and peak area of ​​one standard sample point of this concentration are obtained through chromatographic analysis. By analogy, the concentrated standard sample can be automatically diluted with different amounts of pure water to 5-10 points of standard samples of different concentrations, and the peak height and peak area of ​​5-10 points are obtained after chromatographic analysis, and a standard curve can be obtained. Substituting the peak height and peak area of ​​the unknown sample concentration into the curve, the concentration of the unknown sample can be obtained.

[0070] In order to meet the requirements of switching injection of multiple samples, multiple sample containers 100 are connected to the sample switching valve 102, and different sample injections are switched through the sample switching valve 102. At the same time, a sample pre-treatment device 101 can be provided between the sample container 100 and the sample switching valve 102, and the sample pre-treatment device 101 is configured to filter and / or remove organic matter from the sample flowing through. At the same time, the sample output from the sample switching valve 102 can be processed by the sample pre-treatment device 101 again.

[0071] Specifically, the sample may be pre-treated by a sample pre-treatment device, and the pre-treatment method may include at least filtering and / or removing organic matter. As for the specific entity of the sample pre-treatment device, the sample pre-treatment device 101 used in the ion chromatography analysis process in the prior art may be adopted, and the specific entity of the sample pre-treatment device is not limited here.

[0072] In addition, a plurality of dilution containers may be provided and switched for use by the dilution switching valve 201 .

[0073] The sample is transported to the first detector 13 through the concentration detection drive pump 16 to detect whether the concentration of the sample needs to be diluted. When the sample needs to be diluted, the sample and the diluent can be sucked in for pre-dilution through the first mixing drive pump 15; the second mixing drive pump 24 can transport the pre-mixed liquid to the temporary storage container 21 of the secondary dilution module 2. According to the information of the sample detection concentration, the secondary dilution module 2 can be used to dilute the set multiple, so as to automatically adjust the dilution multiple according to the sample concentration and achieve full mixing of the sample and the diluent, so as to improve the detection accuracy of the intelligent online ion chromatograph with concentration prediction function.

[0074] In one embodiment, the concentration detection pre-dilution module 1 is further provided with an injection valve 18, which is a two-position three-way valve, and has an inlet and two outlets. The inlet of the injection valve 18 is used to connect to a container for storing samples, one outlet of the injection valve 18 is connected to the liquid inlet of the six-way valve 11, and the other outlet of the injection valve 18 is connected to the first switching valve 17;

[0075] The first switching valve 17 is further configured to switch the first hybrid drive pump 15 to communicate with the second liquid outlet of the six-way valve 11 or the injection valve 18 .

[0076] Specifically, in actual use, for different samples, there are cases where the concentration of the sample does not need to be diluted for detection. To this end, an injection valve 18 is added to connect the sample container 100. The sample in the sample container 100 can selectively enter the six-way valve 11 through the injection valve 18 for concentration detection and dilution. The sample can also enter the six-way valve 11 for concentration detection to confirm that no dilution is required.

[0077] When the sample does not need to be diluted, the sample is directly delivered to the first switching valve 17 through the injection valve 18, and then the first mixing drive pump 15 delivers the sample to the temporary storage container 21. Similarly, the first mixing drive pump 15 delivers the sample directly to the second quantitative ring 35 without dilution.

[0078] Furthermore, the first switching valve 17 includes a first switching sub-valve 171 and a second switching sub-valve 172;

[0079] The first switching sub-valve 171 is a two-position three-way valve, the first switching sub-valve 171 has two inlets and one outlet, and the second switching sub-valve 172 is provided with a plurality of interfaces;

[0080] One inlet of the first switching sub-valve 171 is connected to the second liquid outlet of the six-way valve 11, and the other inlet of the first switching sub-valve 171 is connected to the injection valve 18;

[0081] The outlet of the first switching sub-valve 171 , the first mixer 14 , the first mixing drive pump 15 , and the temporary storage container 21 are respectively connected to corresponding interfaces of the first switching valve 17 .

[0082] Specifically, the first switching valve 17 may adopt a split structure, and the first switching sub-valve 171 and the second switching sub-valve 172 cooperate to realize the first hybrid drive pump 15 being connected to the injection valve 18 and the six-way valve 11 respectively.

[0083] Preferably, in order to improve the uniformity of mixing, the first mixing drive pump 15 and the second mixing drive pump 24 are syringe pumps.

[0084] Specifically, the syringe pump can directly extract a certain amount of solution on the one hand, and on the other hand, when mixing, the syringe pump can be pushed and pulled repeatedly to make the sample and the diluent fully mixed.

[0085] In some embodiments, a second detector (not shown) is further disposed between the first switching valve 17 and the temporary storage container 21 .

[0086] Specifically, the concentration of the premixed solution can be further detected by the second detector to confirm whether the predilution reaches the set predilution multiple. At the same time, the secondary dilution module 2 will finally determine the final dilution multiple based on the concentration of the premixed solution detected by the second detector, thereby more effectively improving the accuracy of the dilution.

[0087] Wherein, for the first detector and the second detector, a conductivity detector or an ultraviolet detector may be used depending on the sample to be detected.

[0088] In one embodiment of the present application, the secondary dilution module 2 further includes a quantitative container 37, and the volume of the quantitative container 37 is greater than the volume of the second quantitative ring 35;

[0089] The two ports of the quantitative container 37 are respectively connected to the corresponding ports of the multi-way valve 34;

[0090] The multi-way valve 34 is configured to switch the quantitative container 37 to connect to the second mixing drive pump 24 through the second switching valve 22 , and is also configured to switch the quantitative container 37 to connect to the eluent drive pump 36 .

[0091] Specifically, in actual use, there is a situation where the sample concentration is too low and exceeds the sample concentration detection range. Since the sample concentration is too low to be concentrated, in order to meet the detection requirements of samples with too low concentration, a larger quantitative container 37 (such as a longer quantitative ring or concentration column, etc.) can be configured on the multi-way valve 34.

[0092] In this way, when the concentration of the sample detected by the concentration detection pre-dilution module 1 is lower than the detection range of the set concentration, the multi-way valve 34 switches the quantitative container 37 to participate in the work, which is similar to the process where the sample does not need to be diluted.

[0093] Since the volume of the quantitative container 37 is larger, a sufficient amount of sample can be obtained, so that the total amount of sample that finally enters the separation column 31 is increased. When a large amount of sample is output from the multi-way valve 34 for ion chromatography analysis under the action of the eluent driving pump 36, although the concentration of the sample is low, the sufficient amount of sample makes the total amount of the detected substance meet the detection requirements, and then the detection requirements of the sample with too low concentration can be met, which more effectively broadens the application scope of the intelligent online ion chromatograph with concentration prediction function, and the degree of intelligence is higher.

[0094] In another embodiment of the present application, the ion chromatography sampling device may include two secondary dilution modules 2;

[0095] The first switching valve 17 is configured to switch the first hybrid drive pump 15 to communicate with the temporary storage container 21 in one of the secondary dilution modules 2 .

[0096] Specifically, in order to reduce the investment cost of the equipment, when it is necessary to meet the requirements of both cation and anion detection, two secondary dilution modules 2 are configured, one of which is used for diluting cation samples, and the other is used for diluting anion samples, wherein the inlet of the temporary storage container 21 of the secondary dilution module 2 for diluting anion samples is also provided with a Na-type pretreatment column 25. Each secondary dilution module 2 is connected to a corresponding chromatograph body 3.

[0097] The first switching valve 17 is used to switch the liquid outlet of the first hybrid drive pump 15 to be connected with the liquid inlet of the temporary storage container 21 of one of the secondary dilution modules 2 .

[0098] Similarly, in order to meet the detection requirements of low-concentration samples, at least one of the secondary dilution modules 2 also includes a quantitative container 37, the volume of which is greater than the volume of the second quantitative ring 35; the two ports of the quantitative container 37 are respectively connected to the corresponding interfaces of the multi-way valve 34; wherein the multi-way valve 34 is configured to switch the quantitative container 37 to connect to the second mixing drive pump 24 through the second switching valve 22, and is also configured to switch the quantitative container 37 to connect to the eluent drive pump 36.

[0099] The first switching valve 17 , the injection valve 18 , and the second switching valve 22 are all multi-turn one valves.

[0100] Embodiment 2, the present invention further provides a control method of an intelligent online ion chromatograph with a concentration prediction function according to the above embodiment, comprising:

[0101] Step 1: Concentration detection The driving pump transports the sample in the sample storage tank to the first quantitative loop and the first detector in sequence, and the concentration of the sample is detected by the first detector. Specifically, the concentration of the sample to be detected is first detected by the first detector.

[0102] Step 2, the first mixing drive pump transports the diluent in the diluent storage tank to the first quantitative loop and transports the sample in the first quantitative loop to the first mixer for pre-dilution of a set multiple to form a premixed liquid. Specifically, the first mixing drive pump can be a syringe pump, and the first mixing drive pump pushes and pulls reciprocatingly so that the sample and the diluent flow back and forth between the first mixer and the first mixing drive pump to mix to form a premixed liquid.

[0103] Step 3: The first mixing drive pump delivers the premixed liquid to a temporary storage container.

[0104] Step 4: According to the concentration of the sample detected by the first detector, the second mixing drive pump sucks a fixed amount of diluent from the diluent storage tank, and then extracts a fixed amount of premixed liquid from the temporary storage container, and the second mixing drive pump mixes the premixed liquid and the diluent to form a sample detection liquid. Specifically, the second mixing drive pump can be a syringe pump, and the second mixing drive pump pushes and pulls back and forth so that the premixed liquid and the diluent flow back and forth between the second mixer and the second mixing drive pump to mix and form a sample detection liquid.

[0105] Step 5: The second mixing drive pump delivers the mixed sample test liquid to the second quantitative loop, and then the eluent drive pump delivers the eluent in the eluent container to the second quantitative loop and outputs it into the separation column of the intelligent online ion chromatograph with concentration prediction function for chromatographic analysis.

[0106] Furthermore, a second detector is provided between the first switching valve and the temporary storage container;

[0107] Specifically, step 3 includes detecting the concentration of the premixed liquid by the second detector during the process of the first mixing drive pump delivering the premixed liquid to the temporary storage container.

[0108] Specifically, step 4 includes: according to the concentration of the sample detected by the second detector, the second mixing drive pump sucks a fixed amount of diluent from the diluent storage tank, and then extracts a fixed amount of premixed liquid from the temporary storage container, and the second mixing drive pump mixes the premixed liquid and the diluent to form a sample detection liquid.

[0109] Based on the above embodiment, optionally, the concentration of the sample is detected in step 1, such as when the sample does not need to be diluted.

[0110] The step 2 further comprises: a first hybrid drive pump directly sucks the sample in the sample storage tank;

[0111] The step 3 also includes: the first hybrid drive pump transports the sample to the temporary storage container and executes step 5;

[0112] The step 5 also includes: a second mixing drive pump transports the sample in the temporary storage container to the second quantitative loop, and then the eluent drive pump transports the eluent in the eluent container to the second quantitative loop and outputs it into the separation column of the intelligent online ion chromatograph with concentration prediction function for chromatographic analysis.

[0113] Specifically, after detection by the first detector, if the sample concentration meets the detection range of the ion chromatograph, the sample can be directly delivered to the second quantitative loop without additional dilution.

[0114] Furthermore, a quantitative container is provided on the multi-way valve of the secondary dilution module; if it is judged that the concentration of the sample is lower than the set detection concentration range according to the value detected by the first detector;

[0115] The step 2 further comprises: a first hybrid drive pump directly sucks the sample in the sample storage tank;

[0116] The step 3 also includes: the first hybrid drive pump transports the sample to the temporary storage container and executes step 5;

[0117] The step 5 also includes: the second mixing drive pump transports the sample in the temporary storage container to the quantitative container, and then the eluent drive pump transports the eluent in the eluent container to the quantitative container and outputs it into the separation column of the intelligent online ion chromatograph with concentration prediction function for chromatographic analysis.

[0118] Specifically, when the concentration of the sample is too low and exceeds the sample concentration detection range, and the sample cannot be concentrated due to its low concentration, in order to meet the detection requirements of samples with too low concentration, a second quantitative device 330 with a larger capacity (such as a longer concentration column, etc.) can be configured on the injection valve 310.

[0119] In this way, when the concentration of the sample is lower than the set concentration detection range, the multi-way valve switches the quantitative container to participate in the work, so as to obtain a sufficient amount of sample through the quantitative container. Due to the large total amount of the sample, when a large amount of sample is transported to the ion chromatography analysis under the action of the eluent driving pump, although the sample concentration is low, the sufficient amount of sample makes the total amount of the detected substance meet the detection requirements, and thus can meet the detection requirements of the sample with too low concentration, which more effectively broadens the application scope of the intelligent chromatograph and has a higher degree of intelligence.

[0120] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. An intelligent online ion chromatograph with concentration prediction function, characterized in that: include: A chromatograph body, wherein the chromatograph body is provided with a multi-way valve, a second quantitative loop and an eluent driving pump, wherein the multi-way valve has a plurality of interfaces, and the liquid outlet of the eluent driving pump and the two ports of the second quantitative loop are respectively connected to the corresponding interfaces of the multi-way valve; A concentration detection pre-dilution module, the concentration detection pre-dilution module comprising a six-way valve, a first quantitative loop, a first detector, a first mixer, a first mixing drive pump, a concentration detection drive pump and a first switching valve, the six-way valve having an inlet, a first diluent inlet, a first liquid outlet, a second liquid outlet and two connecting ports, the first quantitative loop is connected to the two connecting ports, the first liquid outlet is connected to the first detector and the concentration detection drive pump, the first switching valve is provided with a plurality of interfaces, the second liquid outlet, the first mixer and the first mixing drive pump are respectively connected to corresponding interfaces of the first switching valve; A secondary dilution module, the secondary dilution module comprising a temporary storage container, a second switching valve, a second mixer, and a second mixing drive pump; the second switching valve is provided with a plurality of interfaces, a standard sample inlet, and a second diluent inlet, the temporary storage container, the second mixer, the second mixing drive pump, and the multi-way valve are respectively connected to corresponding interfaces of the second switching valve; The six-way valve is configured to switch the first quantitative loop to connect the sample inlet with the first liquid outlet, and is also configured to switch the first quantitative loop to connect the first diluent inlet with the second liquid outlet; The first switching valve is configured to switch the first mixing drive pump to connect to the second liquid outlet, the first mixer or the temporary storage container; The second switching valve is configured to switch the second mixing drive pump to connect with the temporary storage container, the second mixer, the second diluent inlet, the standard sample inlet or the multi-way valve; The multi-way valve is configured to switch the second sample loop to connect to the second mixing drive pump through the second switching valve, and is further configured to switch the second sample loop to connect to the eluent drive pump.

2. The intelligent online ion chromatograph with concentration prediction function according to claim 1, characterized in that: The concentration detection pre-dilution module is also provided with an injection valve, which is a two-position three-way valve, and has an inlet and two outlets. The inlet of the injection valve is used to connect to a container for storing samples, one outlet of the injection valve is connected to the liquid inlet of the six-way valve, and the other outlet of the injection valve is connected to the first switching valve; The first switching valve is further configured to switch the first hybrid drive pump to communicate with the second liquid outlet of the six-way valve or the injection valve.

3. The intelligent online ion chromatograph with concentration prediction function according to claim 2, characterized in that: The first switching valve includes a first switching sub-valve and a second switching sub-valve; The first switching sub-valve is a two-position three-way valve, the first switching sub-valve has two inlets and one outlet, and the second switching sub-valve is provided with a plurality of interfaces; One inlet of the first switching sub-valve is connected to the second liquid outlet of the six-way valve, and the other inlet of the first switching sub-valve is connected to the injection valve; The outlet of the first switching sub-valve, the first mixer, the first mixing drive pump, and the temporary storage container are respectively connected to corresponding interfaces of the first switching valve.

4. The intelligent online ion chromatograph with concentration prediction function according to claim 1, characterized in that: The first hybrid drive pump and the second hybrid drive pump are syringe pumps.

5. The intelligent online ion chromatograph with concentration prediction function according to any one of claims 1 to 4, characterized in that: The secondary dilution module further comprises a quantitative container, the volume of which is greater than the volume of the second quantitative loop; The two ports of the quantitative container are respectively connected to the corresponding interfaces of the multi-way valve; The multi-way valve is configured to switch the quantitative container to be connected to the second mixing drive pump through the second switching valve, and is also configured to switch the quantitative container to be connected to the eluent drive pump.

6. The intelligent online ion chromatograph with concentration prediction function according to any one of claims 1 to 4, characterized in that: It comprises two secondary dilution modules, and the multi-way valve of each secondary dilution module is connected to the corresponding chromatograph body; The first switching valve is configured to switch the first hybrid drive pump to communicate with the temporary storage container in one of the secondary dilution modules.

7. The intelligent online ion chromatograph with concentration prediction function according to claim 6, characterized in that: A Na-type pretreatment column is further provided between the temporary storage container and the first switching valve in one of the secondary dilution modules.

8. The intelligent online ion chromatograph with concentration prediction function according to claim 6, characterized in that: At least one of the secondary dilution modules further comprises a quantitative container, the volume of the quantitative container being greater than the volume of the second quantitative loop; The two ports of the quantitative container are respectively connected to the corresponding interfaces of the multi-way valve; The multi-way valve is configured to switch the quantitative container to be connected to the second mixing drive pump through the second switching valve, and is also configured to switch the quantitative container to be connected to the eluent drive pump.

9. The intelligent online ion chromatograph with concentration prediction function according to claim 1, characterized in that: The first detector is a conductivity detector or an ultraviolet detector.

10. A control method for an intelligent online ion chromatograph with a concentration prediction function as claimed in any one of claims 1 to 9, characterized in that: include: Step 1: Concentration detection: The driving pump transports the sample in the sample storage tank to the first quantitative loop and the first detector in sequence, and the concentration of the sample is detected by the first detector; Step 2: The first mixing drive pump delivers the diluent in the diluent storage tank to the first quantitative loop and delivers the sample in the first quantitative loop to the first mixer for pre-dilution of a set multiple to form a pre-mixed solution; Step 3: The first mixing drive pump delivers the premixed liquid to a temporary storage container; Step 4: According to the concentration of the sample detected by the first detector, the second mixing drive pump sucks a fixed amount of diluent from the diluent storage tank, and then extracts a fixed amount of premixed liquid from the temporary storage container, and the second mixing drive pump mixes the premixed liquid and the diluent to form a sample detection liquid; Step 5: The second mixing drive pump delivers the mixed sample test liquid to the second quantitative loop, and then the eluent drive pump delivers the eluent in the eluent container to the second quantitative loop and outputs it into the separation column of the intelligent online ion chromatograph with concentration prediction function for chromatographic analysis.

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