Ion chromatography inhibition column regeneration system and regeneration method

Abstract

The invention discloses an ion chromatography suppression column regeneration system and method, the regeneration system comprises a rotary packed bed type suppressor system, the rotary packed bed type suppressor system is connected with a sample introduction flow path, a cleaning flow path, a regeneration flow path and three suppression columns, a mobile phase passes through a chromatographic column and the suppression columns in the sample introduction flow path and then enters a detector for detection, and the detection result is obtained. Methanesulfonic acid passes through an inhibition column located in the regeneration flow path in the regeneration flow path and then flows to a waste liquid bottle, in the cleaning flow path, a mobile phase passing through an inhibition column in the sample introduction flow path flows out of the detector, flows through an inhibition column located in the cleaning flow path, is electrolyzed by an electrodialysis mechanism arranged at an inlet of a solvent bottle and then enters the solvent bottle. According to the invention, the trouble of preparing a regeneration liquid by a conventional chemical column suppressor can be avoided, the functions of suppressing, regenerating, cleaning and the like can be realized only by one-way pump driving, the functions of continuous sample introduction and suppression are ensured, the link of artificially preparing the regeneration liquid is not needed, a regeneration liquid pump and a cleaning liquid pump are not needed, and the cost is lower.

Description

Technical Field

[0001] The present invention relates to an ion chromatography suppressor, and in particular to an ion chromatography suppressor column regeneration system and regeneration method. Background Art

[0002] Suppressors are components unique to ion chromatography. Their function is to neutralize and suppress the acid or base used in the mobile phase, significantly reducing the background conductivity and background noise level of the mobile phase. Simultaneously, the peak height of the chromatographic peak of the analyte is significantly increased, significantly improving the instrument's signal-to-noise ratio and detection limit (by approximately three orders of magnitude). The development of suppressors has gone through several stages. The earliest suppressors were resin-filled suppression columns, which could not be regenerated continuously and required downtime for regeneration, and also had a large dead volume. The second stage, the tubular fiber membrane suppressor commercialized in 1981, could operate continuously without downtime for regeneration, but had a lower suppression capacity and poor mechanical strength. The third stage was the flat micromembrane suppressor developed in 1985. Its greatest drawback was the need for regeneration with sulfuric acid.

[0003] The fourth stage suppressors currently used in the market are electrolytic self-regeneration suppressors and rotary packed column suppressors. Electrolytic self-regeneration suppressors generate H by electrolyzing water. + and OH - To provide the ions required in the suppression process and accelerate the migration of ions under the action of the electric field, thereby suppressing the acid or base in the analytical flow path, and can achieve continuous automatic regeneration and suppression without manual intervention. However, this electrolytic suppressor based on electrodialysis usually requires an ion exchange membrane for the migration of hydrogen ions or hydroxides and isolation of the flow path. The ion exchange membrane has limited tolerance to organic solvents, which reduces the life of the electrolytic regeneration suppressor in ion chromatography analysis of some complex matrices and cannot be widely used. Summary of the Invention

[0004] In order to address the deficiencies in the above-mentioned prior art, the purpose of the present invention is to provide an ion chromatography suppression column regeneration system and regeneration method. The present invention can eliminate the trouble of configuring regeneration liquid for conventional chemical column suppressors. Only one pump drive is required to achieve functions such as inhibition, regeneration and cleaning, ensuring continuous sampling and inhibition functions. There is no need to add an artificial configuration of regeneration liquid link, and there is no need to configure a regeneration liquid pump and a cleaning liquid pump, which is lower in cost.

[0005] The technical solution adopted by the present invention to solve its technical problem is: an ion chromatography suppression column regeneration system includes a rotor and a stator, the rotor and the stator are rotatably connected, the stator is connected to an injection flow path, a cleaning flow path and a regeneration flow path, the rotor is connected to a first suppression column, a second suppression column and a third suppression column, and the first suppression column, the second suppression column and the third suppression column are respectively connected to the injection flow path, the cleaning flow path and the regeneration flow path in turn through the rotor;

[0006] The injection flow path is provided with a chromatographic column and a detector, and the mobile phase passes through the chromatographic column and the suppression column located in the injection flow path in the injection flow path and then enters the detector for detection;

[0007] The regeneration flow path is provided with a solvent bottle loaded with methanesulfonic acid, and the methanesulfonic acid in the solvent bottle passes through the suppression column located in the regeneration flow path and then flows to the waste liquid bottle;

[0008] The inlet of the cleaning flow path is connected to the outlet of the detector, and the outlet of the cleaning flow path is connected to the inlet of the solvent bottle. In the cleaning flow path, the mobile phase after passing through the suppression column in the injection flow path flows out of the detector, flows through the suppression column located in the cleaning flow path, and then enters the solvent bottle after electrolysis by the electrodialysis mechanism provided at the inlet of the solvent bottle.

[0009] Optionally, the rotor is the rotor part of a rotating packed bed type suppressor, and the stator is the stator part of a rotating packed bed type suppressor.

[0010] Optionally, the first inhibition column, the second inhibition column, and the third inhibition column are three equivalent inhibition columns.

[0011] Based on the above technical solution, the present invention also provides a method for regenerating an ion chromatography suppression column, which comprises the following steps:

[0012] S1, the system switches to the first state, so that the first inhibition column is located in the injection flow path, the second inhibition column is located in the regeneration flow path, and the third inhibition column is located in the cleaning flow path, wherein,

[0013] S 11 In the injection flow path, the mobile phase enters the first suppressor column after passing through the chromatographic column, and the ion exchange reaction is completed in the first suppressor column, so that the conductivity of the mobile phase is suppressed;

[0014] S 12 In the regeneration flow path, methanesulfonic acid loaded in the solvent bottle enters the second suppression column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the second suppression column, so that the second suppression column regains the ability to suppress the conductivity of the mobile phase;

[0015] S 13 In the cleaning flow path, the mobile phase flowing out of the detector is used as a cleaning liquid, flows through the third suppression column, and cleans the third suppression column. The cleaned mobile phase enters the electrodialysis mechanism;

[0016] S2, the system switches to the second state, so that the first inhibition column is located in the regeneration flow path, the second inhibition column is located in the cleaning flow path, and the third inhibition column is located in the injection flow path, wherein,

[0017] S 21In the injection flow path, the mobile phase enters the third suppressor column after passing through the chromatographic column, and the ion exchange reaction is completed in the third suppressor column, so that the conductivity of the mobile phase is suppressed;

[0018] S 22 In the regeneration flow path, methanesulfonic acid loaded in the solvent bottle enters the first suppression column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the first suppression column, so that the first suppression column regains the ability to suppress the conductivity of the mobile phase;

[0019] S 23 In the cleaning flow path, the mobile phase flowing out of the detector is used as a cleaning liquid, flows through the second suppression column, and cleans the second suppression column. The cleaned mobile phase enters the electrodialysis mechanism;

[0020] S3, the system switches to the third state, so that the first inhibition column is located in the cleaning flow path, the second inhibition column is located in the injection flow path, and the third inhibition column is located in the regeneration flow path, wherein,

[0021] S 31 In the injection flow path, the mobile phase enters the second suppressor column after passing through the chromatographic column, and the ion exchange reaction is completed in the second suppressor column, so that the conductivity of the mobile phase is suppressed;

[0022] S 32 In the regeneration flow path, methanesulfonic acid loaded in the solvent bottle enters the third suppressor column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the third suppressor column, so that the third suppressor column regains the ability to suppress the conductivity of the mobile phase;

[0023] S 33 In the cleaning flow path, the mobile phase flowing out of the detector is used as a cleaning liquid, flows through the first suppression column, and cleans the first suppression column. The cleaned mobile phase enters the electrodialysis mechanism.

[0024] By adopting the above technical solution, the present invention can avoid the trouble of configuring regeneration liquid for conventional chemical column suppressors. Only one pump drive is needed to realize the functions of inhibition, regeneration and cleaning, ensuring continuous sampling and inhibition functions. There is no need to add an artificial configuration of regeneration liquid link, and there is no need to configure a regeneration liquid pump and a cleaning liquid pump, which is lower in cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the system structure of the present invention. DETAILED DESCRIPTION

[0026] The present application will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely for the purpose of explaining the relevant invention and are not intended to limit the invention. It should also be noted that, for ease of description, only portions relevant to the invention are shown in the accompanying drawings.

[0027] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0028] like Figure 1 As shown, the present invention discloses an ion chromatography suppression column regeneration system. As is well known, the suppressor is a core component in ion chromatography technology, which is used to neutralize and suppress the acid or alkali of the mobile phase, so that the background conductivity value and background noise level of the mobile phase are greatly reduced, and the peak height of the chromatographic peak of the ion to be measured is greatly increased. The regeneration system of the present invention includes a rotor and a stator, the rotor is rotatably connected to the stator, and the stator is connected to an injection flow path 100, a cleaning flow path 200 and a regeneration flow path 300, and the rotor is connected to a first suppression column, a second suppression column and a third suppression column. The first suppression column, the second suppression column and the third suppression column are three equivalent suppression columns. The first suppression column, the second suppression column and the third suppression column are respectively connected to the injection flow path 100, the cleaning flow path 200 and the regeneration flow path 300 through the rotor, so that each suppression column undergoes the three processes of injection, regeneration and cleaning in sequence.

[0029] In the present invention, a chromatographic column 110 and a detector 120 are provided in the inlet flow path 100. The mobile phase passes through the chromatographic column and suppressor column in the inlet flow path before entering the detector 120 for detection. A solvent bottle 310 containing methanesulfonic acid is provided in the regeneration flow path 300. The methanesulfonic acid in the solvent bottle 310 passes through the suppressor column in the regeneration flow path and flows to a waste liquid bottle 320. The inlet of the cleaning flow path 200 is connected to the outlet of the detector 120, and the outlet of the cleaning flow path 200 is connected to the inlet of the solvent bottle 310. In the cleaning flow path 300, the mobile phase flows from the detector 120, passes through the suppressor column, is electrolyzed by an electrodialysis mechanism 330 provided at the inlet of the solvent bottle 310, and then enters the solvent bottle 310.

[0030] In one embodiment of the present invention, the suppressor may be a rotating packed bed suppressor. Then the rotor in the present invention is the rotor part of the rotating packed bed suppressor, and the stator is the stator part of the rotating packed bed suppressor.

[0031] The regeneration system according to the present invention is implemented by the following steps when circulating the eluent:

[0032] S1, the system switches to the first state, so that the first inhibition column is located in the injection flow path 100, the second inhibition column is located in the regeneration flow path 300, and the third inhibition column is located in the cleaning flow path 200.

[0033] S 11 In the injection flow path 100, the mobile phase enters the first suppression column after passing through the chromatographic column 110, and completes the ion exchange reaction in the first suppression column, so that the conductivity of the mobile phase is suppressed;

[0034] S 12 In the regeneration flow path 300, the methanesulfonic acid loaded in the solvent bottle 310 enters the second suppression column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the second suppression column, so that the second suppression column regains the ability to suppress the conductivity of the mobile phase;

[0035] S 13 In the cleaning flow path 200, the mobile phase flowing out of the detector 120 is used as a cleaning liquid, flows through the third suppression column, and cleans the third suppression column. The cleaned mobile phase enters the electrodialysis mechanism;

[0036] S2, the system switches to the second state, so that the first inhibition column is located in the regeneration flow path 300, the second inhibition column is located in the cleaning flow path 200, and the third inhibition column is located in the injection flow path 100.

[0037] S 21 In the injection flow path 100, the mobile phase enters the third suppression column after passing through the chromatographic column 110, and completes the ion exchange reaction in the third suppression column, so that the conductivity of the mobile phase is suppressed;

[0038] S 22 In the regeneration flow path 300, the methanesulfonic acid loaded in the solvent bottle 310 enters the first suppression column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the first suppression column, so that the first suppression column regains the ability to suppress the conductivity of the mobile phase;

[0039] S 23 In the cleaning flow path 200 , the mobile phase flowing out of the detector 120 is used as a cleaning liquid, flows through the second suppression column, and cleans the second suppression column. The cleaned mobile phase enters the electrodialysis mechanism 330 ;

[0040] S3, the system switches to the third state, so that the first inhibition column is located in the cleaning flow path 200, the second inhibition column is located in the injection flow path 100, and the third inhibition column is located in the regeneration flow path 300.

[0041] S 31In the injection flow path 100, the mobile phase enters the second suppression column after passing through the chromatographic column 110, and completes the ion exchange reaction in the second suppression column, so that the conductivity of the mobile phase is suppressed;

[0042] S 32 In the regeneration flow path 300, the methanesulfonic acid loaded in the solvent bottle 310 enters the third suppression column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the third suppression column, so that the third suppression column regains the ability to suppress the conductivity of the mobile phase;

[0043] S 33 In the cleaning flow path 200 , the mobile phase flowing out of the detector 120 is used as a cleaning liquid, flows through the first suppression column, and cleans the first suppression column. The cleaned mobile phase enters the electrodialysis mechanism.

[0044] The above steps are repeated in this way to achieve continuous operation of the three suppression columns.

[0045] The following describes the regeneration process of this system using Na2CO3 solution as the eluent.

[0046] In the injection flow path 100, the suppression column is a suppression column that has been eluted with methanesulfonic acid, and its resin contains H + When the Na2CO3 solution flows through the suppression column, the Na + With H in the resin + An exchange reaction occurs, producing NaHCO₃ and H₂O. The reaction process is: R-SO₃H + Na₂CO₃ → R-SO₃Na + NaHCO₃ + H₂O, where R represents the functional group of the cation exchange resin. Both NaHCO₃ and H₂O have very low conductivity, thus suppressing the conductivity of the mobile phase.

[0047] In the regeneration flow path 300, the methanesulfonic acid solution contacts and reacts with the cation exchange resin after being eluted with Na2CO3, and the Na + With H in methanesulfonic acid + Make the swap and reload H + to the resin. This reaction can be represented as: R-SO3Na+CH3SO3→R-SO3H+CH3SO3Na.

[0048] In the cleaning flow path 200, a low-conductance mobile phase is used to load H + The inhibitor column is cleaned, and then the mobile phase enters the electrodialysis mechanism 330 as an electrolyte for electrolysis to generate H + methanesulfonic acid as the eluent.

[0049] The above description is merely a preferred embodiment of the present application and an illustration of the technical principles employed. Those skilled in the art should understand that the scope of the invention herein is not limited to the technical solutions formed by the specific combination of the above-mentioned technical features, but also encompasses other technical solutions formed by any combination of the above-mentioned technical features or their equivalents without departing from the inventive concept. For example, a technical solution formed by replacing the above-mentioned features with (but not limited to) technical features having similar functions disclosed in this application.

[0050] Except for the technical features described in the specification, the remaining technical features are known technologies to those skilled in the art. In order to highlight the innovative features of the present invention, the remaining technical features will not be described here in detail.

Claims

1. An ion chromatography suppression column regeneration system, characterized in that: The invention comprises a rotor and a stator, wherein the rotor is rotatably connected to the stator, the stator is connected to an injection flow path, a cleaning flow path and a regeneration flow path, the rotor is connected to a first inhibition column, a second inhibition column and a third inhibition column, and the first inhibition column, the second inhibition column and the third inhibition column are respectively connected to the injection flow path, the cleaning flow path and the regeneration flow path in turn through the rotor; The injection flow path is provided with a chromatographic column and a detector, and the mobile phase passes through the chromatographic column and the suppression column located in the injection flow path in the injection flow path and then enters the detector for detection; The regeneration flow path is provided with a solvent bottle loaded with methanesulfonic acid, and the methanesulfonic acid in the solvent bottle passes through the suppression column located in the regeneration flow path and then flows to the waste liquid bottle; The inlet of the cleaning flow path is connected to the outlet of the detector, and the outlet of the cleaning flow path is connected to the inlet of the solvent bottle. In the cleaning flow path, the mobile phase after passing through the suppression column in the injection flow path flows out of the detector, flows through the suppression column located in the cleaning flow path, and then enters the solvent bottle after electrolysis by the electrodialysis mechanism provided at the inlet of the solvent bottle.

2. The ion chromatography suppression column regeneration system according to claim 1, characterized in that: The rotor is the rotor part of the rotating packed bed type suppressor, and the stator is the stator part of the rotating packed bed type suppressor.

3. The ion chromatography suppression column regeneration system according to claim 2, characterized in that: The first inhibition column, the second inhibition column, and the third inhibition column are three equivalent inhibition columns.

4. A regeneration method for the ion chromatography suppression column regeneration system according to any one of claims 1 to 3, characterized in that: The following steps are included: S1, the system switches to the first state, so that the first inhibition column is located in the injection flow path, the second inhibition column is located in the regeneration flow path, and the third inhibition column is located in the cleaning flow path, wherein, S 11 In the injection flow path, the mobile phase enters the first suppressor column after passing through the chromatographic column, and the ion exchange reaction is completed in the first suppressor column, so that the conductivity of the mobile phase is suppressed; S 12 In the regeneration flow path, methanesulfonic acid loaded in the solvent bottle enters the second suppression column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the second suppression column, so that the second suppression column regains the ability to suppress the conductivity of the mobile phase; S 13 In the cleaning flow path, the mobile phase flowing out of the detector is used as a cleaning liquid, flows through the third suppression column, and cleans the third suppression column. The cleaned mobile phase enters the electrodialysis mechanism; S2, the system switches to the second state, so that the first inhibition column is located in the regeneration flow path, the second inhibition column is located in the cleaning flow path, and the third inhibition column is located in the injection flow path, wherein, S 21 In the injection flow path, the mobile phase enters the third suppressor column after passing through the chromatographic column, and the ion exchange reaction is completed in the third suppressor column, so that the conductivity of the mobile phase is suppressed; S 22 In the regeneration flow path, methanesulfonic acid loaded in the solvent bottle enters the first suppression column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the first suppression column, so that the first suppression column regains the ability to suppress the conductivity of the mobile phase; S 23 In the cleaning flow path, the mobile phase flowing out of the detector is used as a cleaning liquid, flows through the second suppression column, and cleans the second suppression column. The cleaned mobile phase enters the electrodialysis mechanism; S3, the system switches to the third state, so that the first inhibition column is located in the cleaning flow path, the second inhibition column is located in the injection flow path, and the third inhibition column is located in the regeneration flow path, wherein, S 31 In the injection flow path, the mobile phase enters the second suppressor column after passing through the chromatographic column, and the ion exchange reaction is completed in the second suppressor column, so that the conductivity of the mobile phase is suppressed; S 32 In the regeneration flow path, methanesulfonic acid loaded in the solvent bottle enters the third suppressor column through the pump, so that the methanesulfonic acid completes the ion exchange reaction in the third suppressor column, so that the third suppressor column regains the ability to suppress the conductivity of the mobile phase; S 33 In the cleaning flow path, the mobile phase flowing out of the detector is used as a cleaning liquid, flows through the first suppression column, and cleans the first suppression column. The cleaned mobile phase enters the electrodialysis mechanism.

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