Automated chelate analysis apparatus and method for chelate analysis using the same

Abstract

The present invention relates to an automated chelate analysis device and a chelate analysis method using the same. More specifically, the apparatus comprises: a sample storage unit including a plurality of bottles in which a sample solution is stored; a switching valve connected to the sample storage unit to selectively connect one of the plurality of bottles to a flow path; a supply unit including a mobile phase storage unit in which a mobile phase solution is stored and a mobile phase pump for supplying the mobile phase solution of the mobile phase storage unit; an injector including a loop in which the sample solution of a bottle connected to the flow path is filled, and which injects the sample solution filled in the loop into the mobile phase solution supplied by the supply unit; a guard column for removing impurities from the mobile phase-sample solution transferred from the injector; an analysis column for separating chelates from the mobile phase-sample solution that has passed through the guard column; and a detection unit for measuring the conductivity value of the chelates separated after passing through the analysis column and detecting a signal. The apparatus includes a control unit that calculates the concentration of a chelate in a sample solution using the conductivity value, wherein the control unit is configured to calculate the concentration of a chelate in the sample solution by automatically performing sample solution selection, mobile phase solution supply, sample solution injection, chelate separation, and conductivity detection by controlling the switching valve, supply unit, injector, and detection unit according to a preset schedule.

Description

Technology Field

[0001] The present invention relates to an automated chelate analysis device and a chelate analysis method using the same.

[0002] More specifically, the invention relates to an automated chelate analysis device and a chelate analysis method using the same, wherein a plurality of bottles in which a sample solution is stored are automatically selected and injected into a mobile phase solution, thereby transferring the sample solution contained in the mobile phase solution to a guard column, an analysis column, and a detection unit so that precise and stable concentration measurement of the chelate is performed automatically. Background Technology

[0003] Ion chromatography (IC) is a technology that separates and detects inorganic and organic ions and chelates based on differences in time delay (retention time), using a pump, a separation analytical column, an eluent (mobile phase) suppressor, and a conductivity detector as its basic components.

[0004] With the emergence of commercial equipment in the mid-1970s, suppression-type conductivity detection became the standard for ion chromatography, and improvements in suppressor performance have evolved in direct correlation with IC performance.

[0005] Early filled bed suppressors required periodic regeneration, which was cumbersome to operate, but later, electrolytic regenerative suppressors such as self-regenerating suppressors (SRS) were introduced, enabling continuous operation and low noise.

[0006] These suppressors significantly improve the signal-to-noise ratio (S / N) of sample solution ions (or chelate species) by replacing the ionic components of the eluent with H+ / OH-, thereby lowering background conductivity.

[0007] Meanwhile, bubbles are a major obstacle to conductivity detection. A common solution to reduce this is the vacuum membrane degasser, which involves placing a gas-permeable tube in a vacuum chamber to remove dissolved gases from the solution. However, this method has the drawback of incurring maintenance burdens, such as the management of the vacuum pump and membrane.

[0008] In terms of sample injection, an autosampler / switching valve structure is common, which fills a precise volume into the sample loop of the injector and delivers it to the column as a mobile phase flow. Although various 6 / 7 / 10-port high-pressure valve configurations have been proposed, there was a problem in that integrated control, which encompasses schedule-based automatic switching and calibration of multiple sample solutions / standards based on long-term unattended continuous operation, had to rely on user-specific options or operating software.

[0009] Among the technologies related thereto, Korean Registered Patent Publication 10-1654776 discloses a chromatography-based automatic sample solution measuring device and measuring method, and a recording medium storing a program for implementing the same.

[0010] The above-described conventional chromatography-based automatic sample solution measuring device and measuring method, and a recording medium storing a program for implementing the same, are characterized by being able to automatically perform qualitative and quantitative analysis of a sample solution by measuring a standard substance with known components to set the detection time and the error range thereof, and by measuring the sample solution to be analyzed and comparing the detection time; in particular, by re-measuring the standard substance according to pre-set conditions or cycles and automatically updating the detection time serving as a comparison standard, the device is characterized by enabling accurate analysis at all times.

[0011] However, the aforementioned prior art has limitations in actual device implementation because it fails to clearly disclose specific flow path configurations and their mutual operation, and it is not suitable for performing automatic analysis for extended periods due to the absence of a function to automatically stop and restore the device's operation in error situations, such as abnormal conductivity values ​​or bubble generation. Prior art literature

[0012] Registered Patent Publication 10-1654776 (2016.08.31.) Registered Patent Publication 10-1359940 (2014.02.03.) The problem to be solved

[0013] The present invention has been devised to solve the above problems, and the problem to be solved by the present invention is to provide an automated chelate analysis device and a chelate analysis method using the same, wherein a plurality of bottles in which a sample solution is stored are automatically selected and injected into a mobile phase solution, thereby transferring the sample solution contained in the mobile phase solution to a guard column, an analysis column, and a detection unit so that precise and stable concentration measurement of the chelate is performed automatically. means of solving the problem

[0014] An automated chelate analysis device according to the present invention for solving the above problems comprises: a sample storage unit including a plurality of bottles in which a sample solution is stored; a switching valve connected to the sample storage unit and selectively connecting one of the plurality of bottles to a flow path; a supply unit including a mobile phase storage unit in which a mobile phase solution is stored and a mobile phase pump for supplying the mobile phase solution of the mobile phase storage unit; an injector including a loop in which the sample solution of a bottle connected to the flow path is filled and which injects the sample solution filled in the loop into the mobile phase solution supplied by the supply unit; a guard column for removing impurities from the mobile phase-sample solution transferred from the injector; an analysis column for separating chelates from the mobile phase-sample solution that has passed through the guard column; and a detection unit for measuring the conductivity value of the chelate separated after passing through the analysis column and detecting a signal. The apparatus includes a control unit that calculates the concentration of a chelate in a sample solution using the conductivity value, wherein the control unit is configured to calculate the concentration of a chelate in the sample solution by automatically performing sample solution selection, mobile phase solution supply, sample solution injection, chelate separation, and conductivity detection by controlling the switching valve, supply unit, injector, and detection unit according to a preset schedule.

[0015] In addition, the automated chelate analysis device according to the present invention is characterized by including a suppressor (SRS, Self-Regenerating Suppressor) installed between the analysis column and the detection unit and configured to suppress the detection of conductivity of the mobile phase solution contained in the chelate mixture separated from the mobile phase.

[0016] In addition, the automated chelate analysis device according to the present invention is characterized by including a degasser installed in a flow path connected to the detection unit to remove bubbles of the chelate mixture separated from the mobile phase by a gas stripping method using nitrogen gas.

[0017] In addition, the switching valve is characterized by having a plurality of channels to selectively switch one of the plurality of bottles of the sample storage unit to be connected to the flow path.

[0018] In addition, the control unit is characterized by including: an error detection module that detects when a conductivity value detected by the detection unit deviates from a preset allowable range or when an abnormal noise signal is detected; and a response module configured to stop the operation of the switching valve and the supply unit when an abnormal state is detected by the error detection module.

[0019] In addition, the control unit is characterized by including a recovery module configured to connect the loop of the injector to the discharge path to remove the residual sample solution and purge the path with nitrogen gas to switch to a state ready for reanalysis when an abnormal state is detected by the error detection module.

[0020] Meanwhile, a chelate analysis method using an automated chelate analysis device according to the present invention for solving the above problems comprises: a filling step in which a switching valve connects one of a plurality of bottles to a flow path so that a sample solution is filled into the loop of an injector; an injection step in which the sample solution in the loop is injected into a mobile phase solution supplied from a supply unit; a removal step in which the mobile phase-sample solution is transferred to a guard column to remove impurities; a separation step in which the mobile phase-sample solution from which impurities have been removed in the guard column is transferred to an analysis column to separate the chelate; a measurement step in which the chelate separated in the analysis column is transferred to a detection unit to measure a conductivity value; and a calculation step in which a chromatogram is created based on the conductivity value of the chelate and the concentration of the chelate in the sample solution is calculated using the same.

[0021] In addition, the chelate analysis method using the automated chelate analysis device according to the present invention is characterized by including a inhibition step after the separation step, wherein the chelate compound separated from the mobile phase that has passed through the analysis column passes through an inhibition section, and the components of the mobile phase solution contained in the chelate mixture separated from the mobile phase are converted so that conductivity is inhibited.

[0022] In addition, the chelate analysis method using the automated chelate analysis device according to the present invention is characterized by including a bubble removal step after the separation step, wherein the chelate mixture separated from the mobile phase that has passed through the analysis column passes through a degasser to remove bubbles. Effects of the invention

[0023] According to the chelate analysis automation device and chelate analysis method using the same according to the present invention, a plurality of bottles in which a sample solution is stored are automatically selected and injected into a mobile phase solution, thereby transferring the sample solution contained in the mobile phase solution to a guard column, an analysis column, and a detection unit, so that precise and stable chelate concentration measurement is performed automatically. Brief explanation of the drawing

[0024] FIG. 1 is a diagram showing the flow path of an automated chelate analysis device according to the present invention. FIG. 2 is a drawing showing the control unit of an automated chelate analysis device according to the present invention. FIG. 3 is a diagram illustrating a chelate analysis method according to the present invention. FIG. 4 is a diagram showing the inhibition step of the chelate analysis method according to the present invention. FIG. 5 is a diagram showing the bubble removal step of the chelate analysis method according to the present invention. Specific details for implementing the invention

[0025] The present invention is capable of various modifications and may have various embodiments, and specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the invention to specific embodiments, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0026] When it is stated that one component is "connected" or "joined" to another component, it should be understood that while it may be directly connected or joined to that other component, there may also be other components in between.

[0027] On the other hand, when it is stated that one component is "directly connected" or "directly coupled" to another component, it should be understood that there are no other components in between.

[0028] The terms used in this specification are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as "comprising" or "having" are intended to indicate the existence of the features, numbers, processes, operations, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, processes, operations, components, parts, or combinations thereof.

[0029] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0030] The present invention will be described in more detail below with reference to the attached drawings. Prior to this, terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings. Based on the principle that the inventor can appropriately define the concepts of terms to best describe their invention, they should be interpreted in a meaning and concept consistent with the technical spirit of the present invention. Furthermore, unless otherwise defined, technical and scientific terms used shall have the meaning commonly understood by those skilled in the art to which this invention pertains. Descriptions of known functions and configurations that could unnecessarily obscure the essence of the present invention in the following description and attached drawings are omitted. The drawings presented below are provided as examples to ensure that the spirit of the present invention is sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms. Additionally, throughout the specification, the same reference numerals indicate the same components. It should be noted that the same components in the drawings are represented by the same reference numerals wherever possible.

[0031] The present invention relates to an automated chelate analysis device and a chelate analysis method using the same, wherein a plurality of bottles in which a sample solution is stored are automatically selected and injected into a mobile phase solution, thereby transferring the sample solution contained in the mobile phase solution to a guard column, an analysis column, and a detection unit so that precise and stable concentration measurement of the chelate is performed automatically.

[0032] The automated chelate analysis device and the chelate analysis method using the same according to the present invention will be described in detail below with reference to the attached drawings.

[0033] The chelate to be analyzed in the automated chelate analysis apparatus and the chelate analysis method using the same according to the present invention may include any one or a plurality of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), citric acid, hydroxyethyl ethylenediaminetriacetic acid (HEDTA), lauryl-substituted EDTA, polyaspartic acid, oxalic acid, glutamic acid, diacetic acid (GLDA), ethylenediamine-N,N'-dioxic acid (EDDS), gluconic acid, glucoheptonic acid, N,N'-ethylenebis-[2-(o-hydroxyphenyl)]-glycine (EHPG), and pyridine dicarboxylic acid (PCDA).

[0034] FIG. 1 is a diagram showing the flow path of an automated chelate analysis device according to the present invention, and FIG. 2 is a diagram showing the control unit of an automated chelate analysis device according to the present invention.

[0035] According to the attached FIGS. 1 and 2, the chelate analysis automation device of the present invention includes a sample storage unit (100), a switching valve (200), a supply unit (300), an injector (400), a guard column (510), an analysis column (520), a detection unit (600), and a control unit (700).

[0036] The chelate analysis automation device according to the present invention fills a sample solution selected from a plurality of sample solutions stored in the sample storage unit (100) into the injector (400), and then transfers it to the guard column (510), analysis column (520), and detection unit (600) to perform analysis of the chelate, thereby enabling easy automatic chelate analysis under the control of the control unit (700).

[0037] The sample storage unit (100) includes a plurality of bottles (110) in which a sample solution is stored.

[0038] Each of the above bottles (110) may be configured to store a sample solution to be analyzed, a standard solution, a blank solution, etc. separately, and the sample storage unit (100) may be configured to stably store various sample solutions stored in the bottles (110) for a long period of time.

[0039] The above sample storage unit (100) may include a gas supply module (120) configured to prevent the sample solution from deteriorating by spraying nitrogen gas into the bottle (110) when the sample solution is stored for a long period of time.

[0040] The above gas supply module (120) can be configured to spray nitrogen gas into the bottle (110) so that the sample solution stored in the bottle (110) maintains a low temperature state, thereby stably protecting the sample solution from the external environment.

[0041] The switching valve (200) is connected to the sample storage unit (100) and configured to selectively connect one of the plurality of bottles (110) to the flow path.

[0042] The switching valve (200) is configured with a plurality of channel structures, and each channel can be installed to correspond 1:1 with specific bottles among the plurality of bottles (110).

[0043] The above-mentioned switching valve (200) is rotated according to a signal from the control unit (700) described later, or is opened and closed electronically so that the selected bottle (110) is connected to the flow path, thereby allowing the sample solution to be transported.

[0044] The switching valve (200) above may be structured so that no leakage occurs even under high pressure conditions, and may be made of a material with pressure resistance and chemical resistance such as PEEK (Polyether ether ketone) and ceramic.

[0045] The above supply unit (300) includes a mobile phase storage unit in which a mobile phase solution is stored and a mobile phase pump that supplies the mobile phase solution of the mobile phase storage unit.

[0046] At this time, the mobile phase pump of the supply unit (300) may be configured as a high-precision pump, for example, a piston pump or a dual piston pump including a pulse suppression function.

[0047] The mobile phase solution supplied by the above supply unit (300) may be composed of a composition suitable for the separation of chelates, and may be configured to stably transport the injected sample solution by supplying it at a constant flow rate and pressure according to the control of the above control unit (700).

[0048] The above-mentioned injector (400) includes a loop (410) into which a sample solution of a bottle (110) connected to the above-mentioned flow path is filled, and the sample solution filled in the loop (410) is injected into a mobile phase solution supplied by the above-mentioned supply unit (300).

[0049] At this time, the loop (410) may be configured to have a fixed capacity (e.g., 20 μL, 50 μL, 100 μL, etc.) so that the injection amount can be selected according to the user's needs.

[0050] The sample solution can be configured to be transferred to the guard column (510) by the flow of the mobile solution after being filled into the loop (410), and in this process, the sample solution can be configured to be injected at an accurate flow rate in a certain volume according to the capacity of the loop (410).

[0051] The above-mentioned injector (400) may include a cleaning channel to prevent cross-contamination caused by residual sample solution.

[0052] The guard column (510) above pre-treats the mobile phase-sample solution transferred from the injector (400) by removing impurities before it reaches the analysis column (520) described later.

[0053] The above guard column (510) is configured to extend the life of the analysis column (520) by removing relatively large particles, impurities, and matrix components that may be contained in the mobile phase-sample solution, and may be configured to adsorb and remove impurities and allow the analysis component (chelate) to pass through by including a packing material identical or similar to that of the analysis column (520) described later.

[0054] The above guard column (510) can be configured to be easily replaced and used by being exchanged at regular intervals.

[0055] The above analysis column (520) separates chelates from the mobile phase-sample solution that has passed through the above guard column (510).

[0056] The above analysis column (520) may be filled with an ion exchange resin or a special filler having metal-ligand selectivity, and may be configured to separate the chelate from the mobile phase-sample solution using the difference in retention time of the chelate.

[0057] The above analysis column (520) can be configured to increase the stability of the chelate separation environment by maintaining it at a constant temperature.

[0058] Meanwhile, the chelate analysis automation device of the present invention may include a suppressor (SRS, Self-Regenerating Suppressor) (800) installed between the analysis column (520) and the detection unit (600) and configured to suppress the detection of conductivity of the mobile phase solution contained in the chelate mixture separated from the mobile phase.

[0059] More specifically, the suppressor (800) replaces the ions (e.g., carbonate ions, sodium ions, etc.) contained in the mobile phase solution used for analysis with hydrogen ions or hydroxide ions so that the mobile phase solution has properties similar to water.

[0060] This action lowers the background conductivity of the mobile solution, thereby enabling the detection of the conductivity signal of the sample solution component more clearly in the detection unit (600) described later.

[0061] In other words, the signal-to-noise ratio of the mobile phase solution is improved to increase the peak detection sensitivity of the chelate.

[0062] In addition, the above-mentioned suppression unit (800) can be implemented in an electrochemical manner or an ion exchange membrane manner, and can be configured to enable continuous use for a long period of time by including a structure that automatically regenerates without an external solution supply.

[0063] In addition, the chelate analysis automation device of the present invention may include a degasser (900) installed in a flow path connected to the detection unit (600) to remove bubbles of the chelate mixture separated from the mobile phase by a gas stripping method using nitrogen gas.

[0064] That is, the degasser (900) may be configured to allow the chelate mixture separated from the mobile phase within the flow path to flow through a microporous membrane or contact chamber, and to remove bubbles or gas by contacting it with nitrogen gas supplied from the outside.

[0065] The above degasser (900) can be configured to prevent noise generation due to signal instability and improve analysis reliability when removing bubbles from the chelate mixture separated from the mobile phase.

[0066] The above detection unit (600) includes a conductivity cell (610) that measures the conductivity value of the chelate separated by passing through the analysis column (520), and detects a signal using the conductivity value measured by the conductivity cell (610).

[0067] The conductivity cell (610) above can be configured to convert changes in the ion concentration of the incoming solution into an electrical signal, and the electrical signal can be transmitted to a control unit (700) described later to be used for creating a chromatogram and calculating the concentration.

[0068] The above detection unit (600) may include a high-sensitivity sensor and a signal amplification circuit and may be configured to minimize noise by being made of a shielding structure.

[0069] The control unit (700) is configured to perform peak detection and integration on the conductivity signal input from the detection unit (600), and to convert the conductivity response of each peak into a corresponding chelate concentration and output it according to a pre-prepared standard calibration curve.

[0070] That is, the control unit (700) is configured to integrally control the entire automated chelate analysis device according to the present invention, and can be configured to automatically control the switching valve (200), supply unit (300), injector (400), and detection unit (600) according to a preset schedule to automatically perform sample solution selection, mobile phase solution supply, chelate separation, and conductivity detection, thereby calculating the concentration of the chelate in the sample solution.

[0071] For example, the control unit (700) may be configured to repeat the process of automatically selecting and injecting samples according to a preset schedule. More specifically, the control unit (700) may connect the switching valve (200) to the corresponding bottle to sequentially select each sample bottle (110) registered in the schedule, and may fill the loop (410) by operating a syringe pump or a separate injector drive unit; upon receiving a signal that the filling is complete, the supply unit (300) may be controlled to maintain a preset flow rate and the injector (400) may be switched to an injection mode so that the sample in the loop is transferred to the guard column (510) and the analysis column (520) by the mobile phase solution; and after injecting each sample, the loop and injection path may be cleaned using a designated cleaning solution (e.g., mobile phase solution or cleaning solvent) and the same operation may be repeated for the next sample.

[0072] The control unit (700) may include a collection module (740) that collects and stores signals detected by the detection unit (600), and the control unit (700) may be configured to create a chromatogram based on the signals collected by the collection module (740).

[0073] Additionally, the control unit (700) may include a database (750) in which calibration information (calibration curve, reference retention time, and conductivity response value) obtained under the analysis conditions is stored based on the signal detected from the detection unit (600) and the analysis conditions used for the analysis (mobile phase solution composition, flow rate, identification information of the analysis column, and inhibition state).

[0074] The control unit (700) may be configured to determine the type and concentration of the chelate contained in the sample solution by referring to information stored in the database (750) and matching it with the retention time and conductivity response of the signal detected by the detection unit (600).

[0075] In addition, the control unit (700) may be configured to improve analysis accuracy by dynamically correcting the supply flow rate and supply pressure of the supply unit (300) in real time when the concentration of the sample solution or the detection signal is unstable during the analysis of the chelate, thereby maintaining the retention time deviation within an allowable range.

[0076] In addition, the control unit (700) can be configured to control the switching valve (200) so that the plurality of sample solutions are automatically selected and injected according to a preset schedule, thereby updating the automatic calibration curve by weighted regression and automatically reflecting the calibration data before and after the analysis of the sample solutions.

[0077] In addition, the control unit (700) may include a judgment module that learns conductivity signal patterns through deep learning and determines whether to detect outliers and automatically re-inject, thereby correcting the reliability of the analysis without user intervention.

[0078] Additionally, the control unit (700) may include an error detection module (710) that detects when a conductivity value detected by the detection unit (600) deviates from a preset allowable range or when an abnormal noise signal is detected, and a response module (720) configured to stop the operation of the switching valve (200) and the supply unit (300) when an abnormal state is detected by the error detection module (710).

[0079] That is, the error detection module (710) may be configured to monitor in real time device malfunctions, sample solution contamination, and bubble problems during analysis, and the response module (720) is configured to prevent the continuous accumulation of defective data and to minimize equipment damage or analysis errors when an abnormal state is detected by the error detection module (710).

[0080] Additionally, the control unit (700) may include a recovery module (730) configured to connect the loop (410) of the injector (400) to the discharge path to remove the remaining sample solution and to purge the path with nitrogen gas to switch to a state ready for reanalysis when an abnormal state is detected by the error detection module (710).

[0081] The recovery process by the above recovery module (730) is configured to be performed automatically by the above control unit (700), so that it can be configured to quickly return from an error state to a normal state without user intervention.

[0082] In addition, the chelate analysis automation device according to the present invention may include a syringe pump configured to inject and drain a cleaning solution through the injector (400) and loop (410) to prevent cross-contamination (carry-over), a pressure sensor configured to detect pressure inside the flow path to detect bubble generation, blockage, leakage, etc. at an early stage, and a nitrogen regulator configured to maintain a constant pressure of nitrogen gas supplied to the degasser (900) so that bubble removal can be performed efficiently inside the degasser (900).

[0083] FIG. 3 is a diagram showing a chelate analysis method according to the present invention, FIG. 4 is a diagram showing a suppression step of a chelate analysis method according to the present invention, and FIG. 5 is a diagram showing a bubble removal step of a chelate analysis method according to the present invention.

[0084] According to the attached FIGS. 3 to 5, the chelate analysis method of the present invention includes a connecting step (S10), a filling step (S20), a removal step (S30), a separation step (S40), a measurement step (S50), and a calculation step (S60).

[0085] The chelate analysis method according to the present invention utilizes an automated chelate analysis device comprising a sample storage unit (100), a switching valve (200), a supply unit (300), an injector (400), a guard column (510), an analysis column (520), a detection unit (600), and a control unit (700).

[0086] 1. Filling step (S10)

[0087] The filling step (S10) is a step in which, under the control of the control unit (700), the switching valve (200) connects one of the plurality of bottles (110) to a flow path so that the sample solution is filled into the loop (410) of the injector (400).

[0088] At this time, the sample solution filled into the loop (410) of the injector (400) may be configured to be overfilled into the loop (410) by having a flow rate greater than the volume of the loop (410).

[0089] Additionally, if it is determined that the viscosity of the sample solution filled into the loop (410) of the injector (400) exceeds a preset range, it may be configured to be filled after being filtered using a pretreatment filter (0.2 to 0.45 μm).

[0090] Additionally, the switching valve (200) may be configured to have a plurality of channels and be individually connected to each of the plurality of bottles (110), and by selecting one of the plurality of channels according to the control of the control unit (700) and connecting it to the flow path, the sample solution of the bottle (110) may be transferred through the flow path.

[0091] 2. Injection step (S20)

[0092] The filling step (S20) is a step of injecting the sample solution of the loop (410) into the mobile phase solution supplied from the supply unit (300).

[0093] The mobile phase pump of the supply unit (300) may be configured to supply the mobile phase solution by being composed of a dynamic pressure pump and a metering pump structure.

[0094] 3. Removal step (S30)

[0095] The removal step (S30) is a step in which the mobile phase-sample solution is transferred to a guard column (510) to remove impurities.

[0096] The above removal step (S30) is intended to prevent the analysis column (520) from being damaged by relatively large particles of impurities or a matrix, and the guard column (510) configured to filter out impurities in the above removal step (S30) may be configured to use an ion exchange filler of the same series as the analysis column (520).

[0097] At this time, the control unit (700) can track ΔP through pressure information collected via pressure sensors installed at the front and rear ends of the guard column (510) and, if it is determined that the threshold of the guard column (510) has been exceeded, notify the user with sound or display, etc., so that it can be replaced.

[0098] 4. Separation step (S40)

[0099] The separation step (S40) is a step in which the mobile phase-sample solution from which impurities have been removed in the guard column (510) is transferred to the analysis column (520) and the chelate is separated.

[0100] At this time, the analysis column (520) may be made of an anion / cation exchange resin and may be configured to maintain the column temperature at 25 to 35 degrees Celsius.

[0101] 5. Measurement step (S50)

[0102] The measurement step (S50) is a step in which the chelate separated from the analysis column (520) is transferred to the detection unit (600) and the conductivity value of the chelate is measured.

[0103] The chelate separated by passing through the analysis column (520) is transferred to the detection unit (600), and the detection unit (600) is configured to measure the conductivity value of the sample solution using a conductivity cell (610).

[0104] The above detection unit (600) may include a conductivity cell (610) that typically includes two electrodes and a temperature correction sensor (620), and may be configured to correct the temperature dependence of the conductivity and measure the conductivity value more stably.

[0105] In the measurement step (S50) above, the measured conductivity value of the chelate can be transmitted to the control unit (700) and configured to be used to calculate the concentration of the chelate in the sample solution in the calculation step (S60) described later.

[0106] 6. Output stage (S60)

[0107] The calculation step (S60) is a step of creating a chromatogram based on the conductivity value of the chelate and using it to calculate the concentration of the chelate in the sample solution.

[0108] The conductivity values ​​collected from the detection unit (600) can be converted into a chromatogram form by the control unit (700), and can be configured so that peaks corresponding to each component are analyzed.

[0109] The control unit (700) may be configured to calculate the concentration of the chelate in the sample solution according to the peak area or peak height by applying a preset calibration curve, and the result calculated in the calculation step (S60) may be stored in a separate database or output in the form of a report and displayed to the user.

[0110] 7. Inhibition phase (S43)

[0111] Meanwhile, the chelate analysis method of the present invention may include a suppression step (S43) after the separation step (S40), in which the mobile phase solution and sample solution that have passed through the analysis column (520) pass through a suppression unit (800), thereby converting the components of the mobile phase solution and suppressing the conductivity.

[0112] At this time, the suppression unit (800) may be configured to suppress conductivity by converting the ionic components of the mobile solution into components similar to water.

[0113] The above suppression step (S43) minimizes the background conductivity of the mobile solution itself so that the conductivity value of the chelate in the sample solution can be detected more clearly with high sensitivity, and can be configured to be performed in an electrochemical manner without supplying a separate regeneration solution so as to maintain stable performance even during long-term continuous operation.

[0114] 8. Bubble removal step (S45)

[0115] In addition, the chelate analysis method of the present invention may include a bubble removal step (S45) after the separation step (S40), in which the mobile phase solution and sample solution that have passed through the analysis column (520) pass through a degassing unit (900) to remove bubbles.

[0116] If bubbles are present in the mobile phase solution and sample solution, problems such as noise, baseline instability, or peak distortion may occur during conductivity detection.

[0117] According to the present invention, by automatically selecting a plurality of bottles in which a sample solution is stored and injecting them into a mobile phase solution, the sample solution contained in the mobile phase solution is transferred to a guard column, an analysis column, and a detection unit, thereby enabling the precise and stable measurement of the chelate concentration to be performed automatically.

[0118] Although various embodiments of the present invention have been presented and described in the above description, the present invention is not necessarily limited thereto, and those skilled in the art will understand that various substitutions, modifications, and changes are possible within the scope of the technical concept of the present invention. Explanation of the symbols

[0119] 100 : Sample storage unit 110 : Bottle 120 : Gas supply module 200 : Switching valve 300 : Supply unit 400 : Injector 410 : Loop 510 : Guard Column 520 : Analysis Column 600 : Detector 610: Conductivity cell 620: Temperature compensation sensor 700 : Control unit 710: Error detection module 720: Response module 730 : Recovery Module 740 : Collection Module 750 : Database 800 : Inhibitory zone 900 : Digestive

Claims

Claim 1 A sample storage unit (100) comprising a plurality of bottles (110) in which a sample solution is stored; a switching valve (200) connected to the sample storage unit (100) and selectively connecting one of the plurality of bottles (110) to a flow path; a supply unit (300) comprising a mobile phase storage unit in which a mobile phase solution is stored and a mobile phase pump that supplies the mobile phase solution of the mobile phase storage unit; an injector (400) comprising a loop (410) in which the sample solution of the bottle (110) connected to the flow path is filled, and injecting the sample solution filled in the loop (410) into the mobile phase solution supplied by the supply unit (300); a guard column (510) for removing impurities from the mobile phase-sample solution transferred from the injector (400); an analysis column (520) for separating chelates from the mobile phase-sample solution that has passed through the guard column (510); and the separated chelates that have passed through the analysis column (520). The apparatus includes a detection unit (600) that measures the conductivity value of the chelate and detects a signal; and a control unit (700) that calculates the concentration of the chelate in the sample solution using the conductivity value. The control unit (700) is configured to calculate the concentration of the chelate in the sample solution by automatically performing sample solution selection, mobile phase solution supply, sample solution injection, chelate separation, and conductivity detection by controlling the switching valve (200), supply unit (300), injector (400), and detection unit (600) according to a preset schedule. The control unit (700) includes an error detection module (710) that detects when the conductivity value detected by the detection unit (600) deviates from a preset allowable range or when an abnormal noise signal is detected; and a response module (720) configured to stop the operation of the switching valve (200) and the supply unit (300) when an abnormal state is detected by the error detection module (710).A chelate analysis automation device characterized by including, wherein the control unit (700) includes a recovery module (730) configured to connect the loop (410) of the injector (400) to the discharge path to remove residual sample solution and purge the path with nitrogen gas to switch to a state ready for re-analysis when an abnormal state is detected by the error detection module (710). Claim 2 An automated chelate analysis device according to claim 1, characterized by including a suppressor (SRS, Self-Regenerating Suppressor) (800) installed between the analysis column (520) and the detection unit (600) and configured to suppress the detection of conductivity of the mobile phase solution contained in the chelate mixture separated from the mobile phase. Claim 3 An automated chelate analysis device according to claim 1, characterized by including a degasser (900) installed in a channel connected to the detection unit (600) and removing bubbles of the chelate mixture separated from the mobile phase by a gas stripping method using nitrogen gas. Claim 4 The chelate analysis automation device according to claim 1, wherein the switching valve (200) is provided with a plurality of channels to selectively switch one of the plurality of bottles (110) of the sample storage unit (100) to be connected to a flow path. Claim 5 delete Claim 6 delete Claim 7 A chelate analysis method using an automated chelate analysis device described in any one of claims 1 to 4, comprising: a filling step (S10) in which a switching valve (200) is connected to one of a plurality of bottles (110) by a flow path according to the control of a control unit (700) so that a sample solution is filled into a loop (410) of an injector (400); an injection step (S20) in which the sample solution of the loop (410) is injected into a mobile phase solution supplied from a supply unit (300); a removal step (S30) in which the mobile phase-sample solution is transferred to a guard column (510) to remove impurities; a separation step (S40) in which the mobile phase-sample solution from which impurities have been removed in the guard column (510) is transferred to an analysis column (520) to separate the chelate; and a measurement step (S50) in which the chelate separated in the analysis column (520) is transferred to a detection unit (600) to measure a conductivity value. A chelate analysis method characterized by including a calculation step (S60) of creating a chromatogram based on the conductivity value of the chelate and calculating the concentration of the chelate in the sample solution using the chromatogram. Claim 8 A chelate analysis method characterized by including, in claim 7, a suppression step (S43) in which, after the separation step (S40), the chelate compound separated from the mobile phase passing through the analysis column (520) passes through a suppression section (800), thereby converting the components of the mobile phase solution contained in the chelate mixture separated from the mobile phase so as to suppress conductivity. Claim 9 A chelate analysis method characterized by including, in claim 7, a bubble removal step (S45) in which the chelate mixture separated from the mobile phase that has passed through the analysis column (520) passes through a degassing machine (900) after the separation step (S40), thereby removing bubbles.

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