LIQUID CHROMATOGRAPHY AND METHOD FOR CONTROLLING LIQUID CHROMATOGRAPHY

Abstract

Provided is a liquid chromatograph that can deliver a mobile phase to a storage bottle without stopping analysis or delivery, and can suppress the entrance of air bubbles into a flow channel. A liquid chromatograph 100 comprises: a liquid delivery device 104 that delivers a mobile phase; a sample injection unit 105 that injects a sample into the mobile phase delivered from the liquid delivery device 104; a column 106 that separates the sample carried by the mobile phase delivered from the sample injection unit 105; and a detection device 108 that detects the sample separated by the separation column 106. The liquid chromatograph 100 further comprises: a storage bottle 102 that stores the mobile phase that the liquid delivery device 104 delivers; a mobile phase supply bottle 101 that supplies the mobile phase to the storage bottle 102; a mobile phase supply pump 103 that supplies the mobile phase stored in the mobile phase supply bottle 101 to the storage bottle 102; and a control unit 111 that controls the operation of the mobile phase supply pump 103 and sets the amount of mobile phase to be supplied to the storage bottle 102 from the mobile phase supply bottle 101.

Description

[Technical field]

[0001] The present invention relates to a liquid chromatograph and a method for controlling a liquid chromatograph. [Background technology]

[0002] Liquid chromatography (LC) is an analytical technique in which a liquid sample to be measured is introduced into a column that separates the liquid sample into each component contained in the liquid sample using a liquid mobile phase, and the separated components are detected by a detector connected downstream of the column. In order to detect each component of the liquid sample separated in the column, a detection unit such as an ultraviolet-visible spectrophotometer, a fluorometer, or a mass spectrometer is connected downstream of the column.

[0003] The separation performance of LC is mainly determined by the type of packing material packed in the column. As an example, in recent years, ultra-high performance liquid chromatographs (UHPLC) have been used, which realize high separation and high sensitivity analysis by packing small packing materials with a diameter of 2 μm or less in the column, and the throughput has been improved by performing continuous analysis of multiple samples.

[0004] In LC, the mobile phase delivered from the liquid delivery device not only transports the sample to be measured, but also separates the sample into its components based on differences in affinity with the stationary phase of the packing material packed in the column. LC uses a variety of mobile phases, including ultrapure water, organic solvents, and buffer solvents, and the operator selects the mobile phase to use with the LC system depending on the purpose of measurement and the type of liquid sample.

[0005] In this way, the mobile phase used in LC not only transports the measurement sample, but also has an impact on the measurement results. For example, air bubbles in the mobile phase may get mixed into the liquid delivery device or the flow path downstream of the liquid delivery device, causing a significant change in the measurement results. For this reason, operators who use LC monitor the remaining amount of mobile phase to prevent air bubbles from getting into the LC analysis flow path, and when it falls below a certain amount, they replace or supply mobile phase to continue the analysis.

[0006] In LC, while the analysis process is in progress, the solvent delivery device constantly delivers the mobile phase to the column and the detector. Therefore, when the remaining amount of mobile phase decreases, the operator must stop the LC once and replace the mobile phase, so the experiment must be performed while checking the volume of mobile phase consumed in the analysis and the remaining amount of solvent installed. Therefore, in order to avoid a situation where the solvent in the bottle runs out and air is sucked in, LCs are sometimes equipped with a function to prevent air bubbles from being mixed into the device by detecting the remaining amount of solvent using a liquid level detection sensor or weight detection sensor in the solvent supply bottle.

[0007] As a method for monitoring or managing the mobile phase used in LC, Patent Document 1 discloses a method in which an LC liquid delivery device calculates the consumed volume and remaining amount of the mobile phase from the discharge flow rate, time, mixing conditions of the mobile phase, and the like.

[0008] Furthermore, Patent Document 2 describes a system that monitors the remaining amount by providing a sensor in the installation section of the mobile phase used by LC to monitor the remaining amount, and notifies an operator when the remaining amount falls below a certain value.

[0009] Furthermore, Patent Document 3 discloses a system that monitors the consumption and remaining amount of each type of solvent from the output values ​​of sensors that monitor the mobile phase conditions and the remaining amount of mobile phase installed in multiple LCs connected on a network.

[0010] By installing such a monitoring system in the LC, the operator can recognize the remaining mobile phase before it becomes too low and affects the analysis, and can carry out the task of replacing or supplying the mobile phase.

[0011] Here, we will briefly explain the solvent exchange process for the mobile phase installed in the LC. Generally, the mobile phase is filled in a glass or resin bottle and installed in the LC system. When the mobile phase in the bottle decreases, the LC analysis is stopped, the solvent delivery device is stopped, and the bottle is replaced with a new one filled with the mobile phase.

[0012] As mentioned above, if air bubbles get into the liquid delivery device, the mobile phase cannot be delivered stably, which can affect the analysis results. Therefore, when replacing the mobile phase bottle or adding mobile phase to the bottle, the operator using the LC must proceed with the work with extreme caution to prevent air bubbles from getting into the supply tube. However, it is difficult to completely eliminate the possibility of air bubbles getting into the tube. This is not simply due to the operator overlooking air bubbles or making operational mistakes, but also due to the influence of the operator's work experience, the installation environment of the device, and the type of solvent used.

[0013] For this reason, in most cases, as a preparatory operation, it is common practice to perform an air bubble evacuation process to remove air bubbles from within the piping after replacing the mobile phase bottle or after supplying additional mobile phase to the bottle, regardless of whether air bubbles are present or not. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] JP 2000-298122 A [Patent Document 2] Patent No. 4778748 [Patent Document 3] WO2020 / 183771A1 Summary of the Invention [Problem to be solved by the invention]

[0015] In recent years, many aspects of LC functionality have been automated, and systems for automatically monitoring the remaining amount of mobile phase and notifying the operator, such as the techniques described in Patent Documents 1 to 3, have been provided.

[0016] However, when actually replacing a mobile phase bottle or adding mobile phase to a bottle, the LC analysis and solvent delivery device must be stopped once, and the replacement work and preparation operations after the replacement must be performed by an operator.

[0017] Since this operation depends on the operator, the operator must be tied up for a certain amount of time after being notified of the low remaining amount of mobile phase to carry out preparatory operations, including bottle replacement and mobile phase supply operations.

[0018] Furthermore, there is a risk that other problems will occur, such as air bubbles being mixed into the flow path, due to the operator's work.In terms of analysis time, not only will throughput decrease because there will be times when the LC cannot be used, but if the operator does not recognize the notification that the remaining mobile phase is low, it may also occur that the analysis will be stopped for an even longer period of time.

[0019] An object of the present invention is to provide a liquid chromatograph and a method for controlling the liquid chromatograph that can supply a mobile phase to a storage bottle without stopping analysis and liquid transfer, and can suppress the introduction of air bubbles into the flow path. [Means for solving the problem]

[0020] In order to achieve the above object, the present invention is configured as follows.

[0021] A liquid chromatograph including a liquid delivery device that delivers a mobile phase, a sample injection section that injects a sample into the mobile phase, a column that separates the sample carried by the mobile phase, and a detection device that detects the separated sample, the liquid chromatograph further including: a storage bottle that stores the mobile phase delivered by the liquid delivery device; a mobile phase supply bottle that supplies the mobile phase to the storage bottle; a mobile phase supply pump that supplies the mobile phase stored in the mobile phase supply bottle to the storage bottle; and a control section that determines the amount of mobile phase to be supplied from the mobile phase supply bottle to the storage bottle. The control unit further includes a monitoring sensor for detecting a remaining amount of the mobile phase stored in the storage bottle, and when the remaining amount of the mobile phase in the storage bottle becomes equal to or less than a specified value based on a detection value of the monitoring sensor, the control unit drives the mobile phase supply pump to supply the mobile phase in the mobile phase supply bottle to the storage bottle, and when the control unit determines that the mobile phase in the storage bottle has reached a certain amount or more based on the remaining amount of the mobile phase detected by the monitoring sensor, the control unit stops the mobile phase supply pump, and further includes a control unit for controlling a relationship between the mobile phase supply bottle and the mobile phase supply pump. the mobile phase supply bottle being connected to an air vent; and a filter connected to an air vent of the mobile phase supply bottle. The control unit drives the mobile phase supply pump to supply the mobile phase in the mobile phase supply bottle to the storage bottle. When the air bubble detection sensor detects air bubbles in the piping, the control unit determines that the mobile phase supply bottle is empty and stops the mobile phase supply pump. A method for controlling a liquid chromatograph including a liquid delivery device that delivers a mobile phase, a sample injection section that injects a sample into the mobile phase, a column that separates the sample carried by the mobile phase, and a detection device that detects the separated sample, the method includes the steps of: storing the mobile phase delivered by the liquid delivery device in a storage bottle; storing the mobile phase in a mobile phase supply bottle that supplies the mobile phase to the storage bottle; determining an amount of mobile phase to be supplied from the mobile phase supply bottle to the storage bottle; and controlling the operation of a mobile phase supply pump to supply the mobile phase stored in the mobile phase supply bottle to the storage bottle. a monitoring sensor detects a remaining amount of the mobile phase stored in the storage bottle, and when the remaining amount of the mobile phase in the storage bottle becomes equal to or less than a specified value based on a detection value of the monitoring sensor, the mobile phase supply pump is driven to supply the mobile phase in the mobile phase bottle to the storage bottle, and based on the remaining amount of the mobile phase detected by the monitoring sensor, it is determined that the mobile phase in the storage bottle has reached a certain amount or more, and the mobile phase supply pump is stopped, and further, an air bubble detection sensor detects air bubbles in a pipe installed between the mobile phase supply bottle and the mobile phase supply pump, the storage bottle and the mobile phase supply bottle are connected by a gas conduit, the pressure in the storage bottle and the pressure in the mobile phase supply bottle are kept constant, the mobile phase supply pump is driven to supply the mobile phase in the mobile phase bottle to the storage bottle, and it is determined that the mobile phase supply bottle has become empty based on the air bubble detection sensor detecting air bubbles in the pipe, and the mobile phase supply pump is stopped. do.

[0022] In a control method for a liquid chromatograph equipped with a liquid delivery device that delivers a mobile phase, a sample injection section that injects a sample into the mobile phase, a column that separates the sample carried by the mobile phase, and a detection device for detecting the separated sample, the mobile phase delivered by the liquid delivery device is stored in a storage bottle, the mobile phase is stored in a mobile phase supply bottle that supplies the mobile phase to the storage bottle, the amount of mobile phase supplied from the mobile phase supply bottle to the storage bottle is determined, and the operation of a mobile phase supply pump is controlled to supply the mobile phase stored in the mobile phase supply bottle to the storage bottle. Effect of the Invention

[0023] According to the present invention, it is possible to realize a liquid chromatograph and a method for controlling a liquid chromatograph that can supply a mobile phase to a storage bottle without stopping analysis and liquid transfer, and can suppress the introduction of air bubbles into the flow path. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 is a schematic diagram of a liquid chromatograph in Example 1. [Diagram 2] 4 is a flowchart of a process for supplying a mobile phase from a mobile phase supply bottle to a storage bottle in Example 1. [Diagram 3] FIG. 1 is a schematic diagram of a liquid chromatograph in Example 2. [Figure 4] 11 is a flowchart of a mobile phase supply process in Example 2. [Diagram 5] FIG. 11 is an explanatory diagram of the operation of the third embodiment. [Figure 6] FIG. 11 is a schematic diagram of a liquid chromatograph in Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings. The accompanying drawings show an embodiment based on the principle of the present invention, but are typical examples for understanding the principle of the present invention and are not intended to limit the present invention. EXAMPLES

[0026] Example 1 A first embodiment of the present invention will be described with reference to FIG.

[0027] FIG. 1 is a schematic diagram of a liquid chromatograph 100 according to a first embodiment of the present invention.

[0028] In FIG. 1, liquid chromatograph 100 comprises a liquid delivery device 104 that delivers a mobile phase, a sample injection section 105 that introduces a sample to be measured (also simply referred to as a sample) into an analysis flow path, a separation column 106 that separates the sample to be measured introduced into the analysis flow path and carried by the mobile phase delivered by liquid delivery device 104 into its components, and a detection device 108 that detects each component contained in the sample to be measured separated by separation column 106.

[0029] The liquid chromatograph 100 is also installed upstream of the liquid delivery device 104 and is equipped with a storage bottle 102 for storing the mobile phase, a monitoring sensor 109 for detecting the remaining amount of mobile phase in the storage bottle 102, a mobile phase supply bottle 101 for storing the mobile phase to supply it to the storage bottle 102, a mobile phase supply pump 103 for supplying the mobile phase from the mobile phase supply bottle 101 to the storage bottle 102, and a control unit 111 for monitoring and supplying the remaining amount of mobile phase.

[0030] The mobile phase supply bottle 101 and the storage bottle 102 are provided with a vent 110 for equalizing the pressure inside the bottle with the atmospheric pressure. For this reason, one end of the vent 110 is disposed inside the storage bottle 102, and the other end of the vent 110 is open to the atmosphere.

[0031] The separation column 106 of the liquid chromatograph 100 is housed in a thermostatic device 107 in order to maintain the temperature around the column constant. However, the separation column 106 can also be used without being housed in the thermostatic device 107.

[0032] When the liquid chromatograph 100 is operating, the liquid delivery device 104 transports the sample to be measured introduced through the sample injection section 105 to the separation column 106, elutes it from the separation column 106, and delivers a mobile phase appropriate for the analysis for the purpose of transporting it to the detection section 108.

[0033] FIG. 2 is a flow chart of a process for supplying mobile phase from a mobile phase supply bottle 101 to a storage bottle 102 in response to a decrease in the mobile phase during operation of a liquid chromatograph 100.

[0034] As the liquid delivery device 104 aspirates the mobile phase from the storage bottle 102 and supplies the mobile phase into the LC analysis system, the amount of mobile phase remaining in the storage bottle 102 decreases, and when the amount of mobile phase remaining detected by the monitoring sensor 109 falls below a specified value, the control unit 111 determines that the amount of mobile phase remaining in the storage bottle 102 is low (step S201).

[0035] The monitoring sensor 109 for monitoring the remaining amount of the mobile phase may be a weight sensor, a floating sensor, an electrostatic sensor, an optical sensor, or the like.

[0036] When the monitoring sensor 109 detects that the remaining amount of the mobile phase is equal to or less than a specified value, the control unit 111 starts the mobile phase supply process (step S202) and starts supplying the mobile phase from the mobile phase supply bottle 101 to the storage bottle 102 by driving the mobile phase supply pump 103 (step S203).

[0037] When the mobile phase is supplied to the storage bottle 102 by the mobile phase supply pump 103, the control unit 111 determines whether the amount of mobile phase in the storage bottle 102 is equal to or greater than a certain amount based on the remaining amount of mobile phase detected by the monitoring sensor 109 (step S204). When the control unit 111 determines that the amount of mobile phase in the storage bottle 102 is equal to or greater than a certain amount, the control unit 111 stops the mobile phase supply pump 103 and stops the supply of the mobile phase from the mobile phase supply bottle 101 to the storage bottle 102 (step S205). Then, the mobile phase supply process is stopped (ended) (step S206).

[0038] As described above, according to the first embodiment of the present invention, the amount of mobile phase remaining in the mobile phase storage bottle 102 is monitored by the monitoring sensor 109, and when the amount of mobile phase remaining in the storage bottle 102 falls below a specified value, the control unit 111 is configured to drive the mobile phase supply pump 103 to supply the mobile phase from the mobile phase supply bottle 101 to the storage bottle 102. This eliminates the need for the operator to recognize the decrease in the amount of mobile phase remaining and to supply the mobile phase, and also makes it possible to prevent air bubbles from being mixed into the flow path due to the operator's work.

[0039] In other words, according to the first embodiment, it is possible to realize a liquid chromatograph and a method for controlling a liquid chromatograph that can supply the mobile phase to the storage bottle 102 without stopping the analysis and the liquid transfer, and can suppress the intrusion of air bubbles into the flow path.

[0040] In this embodiment 1, the timing to stop the mobile phase supply pump 103 is determined based on the remaining amount of mobile phase in the storage bottle 102 determined by the monitoring sensor 109. However, a similar mobile phase supply process can also be realized by, for example, calculating the drive time of the mobile phase supply pump 103 from the discharge flow rate of the mobile phase supply pump 103 and the volume of mobile phase to be supplied to the storage bottle 102, and operating and stopping the mobile phase supply pump 103 based on the calculated drive time.

[0041] Furthermore, the control unit 111 may calculate the remaining amount of mobile phase in the storage bottle 102 from the amount of liquid sent per hour and the operating time of the liquid sending device 104, determine that the amount has reached a specified value or less, and drive the mobile phase supply pump 103 to start supplying the mobile phase from the mobile phase supply bottle 101 to the storage bottle 109. In this case, as described above, the drive time of the mobile phase supply pump 103 is calculated from the discharge flow rate of the mobile phase supply pump 103 and the volume of mobile phase to be supplied to the storage bottle 102, and the mobile phase supply pump 103 is stopped based on the calculated drive time, thereby making it possible to omit the monitoring sensor 109.

[0042] Example 2 Next, a second embodiment of the present invention will be described with reference to FIG.

[0043] 3, the sample introduction section 105, the thermostat 107, and the detector 108 downstream of the liquid delivery device 104 are omitted from the illustration. The liquid chromatograph 100A is installed upstream of the liquid delivery device 104, and includes a storage bottle 102 for storing a mobile phase, a monitoring sensor 109 for detecting the remaining amount of the mobile phase in the storage bottle 102, a mobile phase supply bottle 101 for supplying the mobile phase to the storage bottle 102, an information storage section 301 provided in the mobile phase supply bottle 101, an information reading section 302 for reading information recorded in the information storage section 301, a mobile phase supply pump 103 for supplying the mobile phase from the mobile phase supply bottle 101 to the storage bottle 102, an air bubble detection sensor 303 for detecting air bubbles in a pipe provided between the mobile phase supply pump 103 and the mobile phase supply bottle 101, a display section 306, and a control section 111 for monitoring and supplying the remaining amount of the mobile phase.

[0044] The inside of the mobile phase supply bottle 101 and the inside of the storage bottle 102 are connected by a gas conduit 304 provided to equalize the pressure inside the bottles. That is, the gas conduit 304 connects the storage bottle 102 and the mobile phase supply bottle 101 to each other, and keeps the pressure inside the storage bottle 102 and the pressure inside the mobile phase supply bottle 101 constant. Also, one end of an air vent 110 for equalizing the pressure inside the mobile phase supply bottle 101 with atmospheric pressure is disposed inside the mobile phase supply bottle 101. The other end of the air vent 110 located on the outside side of the mobile phase supply bottle 101 is connected to a filter 305 for preventing the mobile phase inside the supply bottle 101 from diffusing to the outside and for preventing dust around the mobile phase supply bottle 101 from entering the mobile phase supply bottle 101.

[0045] The information storage unit 301 of the mobile phase supply bottle 101 stores information regarding the mobile phase, such as the type of mobile phase contained in the mobile phase supply bottle 101 and the manufacturing date, and the control unit 111 determines whether the mobile phase supply bottle 101 is properly installed based on the information contained in the information storage unit 301 read by the information reading unit 302, whether the mobile phase supply bottle 101 is installed, whether it is installed incorrectly, the expiration date, etc.

[0046] The information storage unit 301 may be a barcode or an RFID tag.

[0047] FIG. 4 is a flow chart of a mobile phase supply process in the second embodiment of the present invention.

[0048] When the remaining amount of mobile phase determined from the detection value of the monitoring sensor 109 falls below a specified value, the control unit 111 determines that the remaining amount of mobile phase in the storage bottle 102 is low (step S401), and starts the mobile phase supply process (step S402).

[0049] After starting the mobile phase supply process in step S402, the control unit 111 reads the information stored in the information storage unit 301 provided in the mobile phase supply bottle 101 via the information reading unit 302, and confirms that the mobile phase supply bottle 101 is properly installed (step S403). At this time, if the mobile phase supply bottle 101 to which mobile phase has already been supplied is installed, or if it is determined that the remaining amount of mobile phase in the mobile phase supply bottle 101 is low, an instruction to install or replace the mobile phase supply bottle 101 is displayed on the display unit 306 (step S404).

[0050] If the control unit 111 determines that the mobile phase supply bottle 101 is in an appropriate state, the control unit 111 drives the mobile phase supply pump 103 to start supplying the mobile phase from the mobile phase supply bottle 101 to the storage bottle 102 (step S405).

[0051] If the air bubble sensor 303 detects air bubbles in the piping connecting the mobile phase supply pump 103 and the mobile phase supply bottle 101 while the mobile phase supply pump 103 is discharging the mobile phase (step S406), the control unit 111 causes all of the mobile phase in the mobile phase supply bottle 101 to be supplied to the storage bottle 102, determines that the mobile phase supply bottle 101 is empty, and stops the mobile phase supply pump 103 (step S408).

[0052] Following step S408, the control unit 111 displays an instruction to replace the mobile phase supplying bottle 101 on the display unit 306 (step S410), and ends the mobile phase supplying process (step S412).

[0053] In step S406, if the air bubble sensor 303 does not detect any air bubbles in the piping, the process proceeds to step S407. In step S407, the monitoring sensor 109 detects that the mobile phase supply pump 103 is supplying the mobile phase to the storage bottle 102. To serve During the supply, overflow monitoring is performed so that the mobile phase in the storage bottle 102 does not exceed the storage limit capacity of the storage bottle 102. If the monitoring sensor 109 does not detect an overflow, the process returns to step S406.

[0054] In step S407, if the output value of the monitoring sensor 109 indicates that the mobile phase is equal to or greater than a specified value, the control unit 111 determines that there is a high risk of an overflow, detects an overflow, and stops the mobile phase supply pump 103 to terminate the supply of the mobile phase (step S409). If the pump is stopped due to an overflow detection, the control unit 111 calculates the remaining amount of mobile phase in the mobile phase supply bottle 101 from the drive time and flow rate of the mobile phase supply pump 103, and updates and records the remaining amount (step P S 411), and the mobile phase supply process is terminated (S412).

[0055] According to the second embodiment of the present invention, in addition to the same effects as those of the first embodiment, the following effects can be obtained.

[0056] In the second embodiment, the movement phase Since the inside of the supply bottle 101 and the inside of the storage bottle 102 are connected by a gas conduit 304, the internal pressures of the mobile phase supply bottle 101 and the storage bottle 102 are equalized, which prevents errors in detecting the remaining amount of mobile phase in the storage bottle 102 due to a pressure difference, thereby enabling more accurate detection of the remaining amount.

[0057] In the second embodiment, the mobile phase supply bottle 101 is provided with an information storage unit 301 in which information such as the type of mobile phase in the mobile phase supply bottle 101 and the manufacturing date is recorded, and the information recorded in the information storage unit 301 is read by an information reading unit 302, and the control unit 111 performs a determination of whether the mobile phase supply bottle 101 is installed, whether it is installed incorrectly, and whether the expiration date has passed, thereby confirming that the mobile phase supply bottle 101 is installed appropriately. This makes it possible to recognize whether the appropriate mobile phase supply bottle 101 is installed before the operation of the mobile phase in the liquid chromatograph 100.

[0058] Furthermore, in Example 2, a filter 305 is connected to the ventilation hole 110 of the mobile phase supply bottle 101, thereby preventing the mobile phase in the mobile phase supply bottle 101 from diffusing to the outside and preventing dust and the like around the mobile phase supply bottle 101 from entering the mobile phase supply bottle 101.

[0059] In addition, a monitoring sensor (similar to monitoring sensor 109) can be provided to detect the remaining amount of mobile phase in mobile phase supply bottle 101, and control unit 111 can recognize the remaining amount of mobile phase in mobile phase supply bottle 101 and display it on display unit 306.

[0060] Example 3 Next, a third embodiment of the present invention will be described.

[0061] In the examples shown in Examples 1 and 2, the monitoring sensor 109 detects a decrease in the amount of mobile phase remaining in the storage bottle 102 and prompts the mobile phase supply bottle 101 to be prepared for operation and installed as a preliminary step to driving the mobile phase supply pump 103, as will be described with reference to FIG. 5.

[0062] The configuration of the liquid chromatograph in the third embodiment is the same as that in the first or second embodiment, and therefore illustration and detailed description thereof will be omitted. However, it is assumed that the first embodiment has a display unit 306 similar to that in the second embodiment added thereto.

[0063] FIG. 5 is an explanatory diagram of the operation of the third embodiment, showing an example of the transition of the remaining amount of mobile phase in the storage bottle 102 calculated from the output value of the monitoring sensor 109, with the vertical axis indicating the remaining amount of mobile phase and the horizontal axis indicating the number of days elapsed.

[0064] 5, immediately after the mobile phase is supplied from the mobile phase supply bottle 101 to the storage bottle 102, the storage bottle 102 is in a state 501 filled with the mobile phase, and when the mobile phase is consumed by the analysis operation of the liquid chromatograph 100 or 100A, the amount of mobile phase remaining in the storage bottle 102 decreases. At this time, the mobile phase remaining amount V in preparation for operation is set to V before the mobile phase remaining amount state 503 is reached, at which the control unit 111 operates the mobile phase supply pump 103. A Set.

[0065] The control unit 111 detects the bottleneck amount calculated from the detection value of the monitoring sensor 109. 102 The remaining mobile phase in the preparation for operation is V A When the mobile phase supply bottle 101 reaches this state (state 502), the display unit 306 is caused to display that the mobile phase supply bottle 101 is ready for operation.

[0066] In the case where the liquid chromatograph in the third embodiment has the same configuration as that in the second embodiment, the control unit 111 reads information in the information storage unit 301 provided in the mobile phase supply bottle 101 by the information reading unit 302, and thereby, the mobile phase supply pump 103 is operated before the state 503 is reached. A When this state is reached (state 502), the presence or absence of a mobile phase supply bottle 101 and the remaining amount of mobile phase in the mobile phase supply bottle 101 are recognized, and if there is not enough mobile phase to supply to the storage bottle 102, an instruction to install or replace the mobile phase supply bottle 101 is output to the display unit 306.

[0067] According to the third embodiment, in addition to being able to obtain the same effects as those of the first and second embodiments, the operation readiness of the mobile phase supply bottle 101 can be displayed before the control unit 111 reaches the operation readiness mobile phase remaining state 503 in which the mobile phase supply pump 103 is operated. Therefore, preparation for replacement of the mobile phase supply bottle 101 can be performed before the remaining amount of mobile phase in the mobile phase supply bottle 101 reaches the amount required for supply to the storage bottle 102.

[0068] Example 4 Next, a fourth embodiment of the present invention will be described with reference to FIG.

[0069] In the liquid chromatograph 100B according to the fourth embodiment, the storage bottle 102 in the example described in the second embodiment is housed in a highly light-shielding case 601, and a deuterium lamp 602 is installed in the case 601.

[0070] The control unit 111 turns on the deuterium lamp 602 to sterilize the inside of the storage bottle 102. At this time, it is desirable to keep the deuterium lamp 602 on all the time, but since the ultraviolet light emitted by the deuterium lamp 602 not only has a sterilizing effect but can also cause material deterioration, it is also possible to use a control algorithm that irradiates the lamp for a certain period of time every certain period, for example every 24 hours.

[0071] In addition, in this Example 4, a form in which ultraviolet light is irradiated from the deuterium lamp 602 from the outside of the storage bottle 102 is described, but the same effect can be expected by, for example, connecting a small deuterium lamp to the cap portion of the storage bottle 102 and directly irradiating ultraviolet light to the inside of the storage bottle 102.

[0072] In addition, in this embodiment 4, a sterilization function using a deuterium lamp 602 is proposed for the storage bottle 102 in which the mobile phase is likely to be stored for a long period of time, but a similar function may be provided by disposing a deuterium lamp that irradiates ultraviolet light on the mobile phase supply bottle 101.

[0073] According to the fourth embodiment, in addition to being able to obtain the same effects as those of the second embodiment, the mobile phase in the storage bottle 102 can be kept in a sterilized state for a long period of time. [Explanation of symbols]

[0074] 100, 100A, 100B... liquid chromatograph, 101... mobile phase supply bottle, 102... storage bottle, 103... mobile phase supply pump, 104... liquid delivery device, 105... sample injection section, 106... separation column, 107... thermostatic device, 108... detection device, 109... monitoring sensor, 110... vent, 111... control section, 301... information storage section, 302... information reading section, 303... air bubble detection sensor, 304... gas guide pipe, 305... filter, 306... display section, 601... light-shielding case, 602... deuterium lamp

Claims

1. A liquid chromatograph comprising: a liquid delivery device that delivers a mobile phase; a sample injection section that injects a sample into the mobile phase delivered from the liquid delivery device; a separation column that separates the sample carried by the mobile phase delivered from the sample injection section; and a detection device that detects the sample separated by the separation column, a storage bottle for storing the mobile phase to be delivered by the liquid delivery device; a mobile phase supply bottle for supplying the mobile phase to the storage bottle; a mobile phase supply pump that supplies the mobile phase stored in the mobile phase supply bottle to the storage bottle; a control unit that controls an operation of the mobile phase supply pump and determines an amount of the mobile phase to be supplied from the mobile phase supply bottle to the storage bottle; Equipped with Furthermore, a monitoring sensor for detecting a remaining amount of the mobile phase stored in the storage bottle; the control unit, when the remaining amount of the mobile phase in the storage bottle becomes equal to or less than a specified value based on the detection value of the monitoring sensor, drives the mobile phase supply pump to supply the mobile phase in the mobile phase supply bottle to the storage bottle, and when it determines that the mobile phase in the storage bottle has become equal to or more than a certain amount based on the remaining amount of the mobile phase detected by the monitoring sensor, stops the mobile phase supply pump; Furthermore, an air bubble detection sensor that detects air bubbles in a pipe installed between the mobile phase supply bottle and the mobile phase supply pump; a gas conduit connecting the storage bottle and the mobile phase supply bottle and maintaining a constant pressure in the storage bottle and a constant pressure in the mobile phase supply bottle; a filter connected to a vent of the mobile phase supply bottle; Equipped with the control unit drives the mobile phase supply pump to supply the mobile phase in the mobile phase supply bottle to the storage bottle, and determines that the mobile phase supply bottle is empty by the air bubble detection sensor detecting air bubbles in the piping, and stops the mobile phase supply pump.

2. 2. The liquid chromatograph according to claim 1, the mobile phase supply bottle has an information storage unit that stores information about the mobile phase contained in the mobile phase supply bottle, an information reading unit that reads the information stored in the information storage unit, A liquid chromatograph characterized in that the control unit determines whether the mobile phase supply bottle is properly installed based on the information read by the information reading unit and stored in the information storage unit.

3. 2. The liquid chromatograph according to claim 1, A display unit is provided, The liquid chromatograph is characterized in that, when the remaining amount of mobile phase in the storage bottle reaches the amount of mobile phase remaining in preparation for operation before the mobile phase supply pump is driven, the control unit displays on the display unit that the mobile phase supply bottle is ready for operation.

4. 2. The liquid chromatograph according to claim 1, A liquid chromatograph comprising a deuterium lamp for irradiating the storage bottle or the mobile phase supply bottle with ultraviolet light.

5. A method for controlling a liquid chromatograph comprising: a liquid delivery device that delivers a mobile phase; a sample injection unit that injects a sample into the mobile phase delivered from the liquid delivery device; a separation column that separates the sample carried by the mobile phase delivered from the sample injection unit; and a detection device that detects the sample separated by the separation column, comprising: The mobile phase delivered by the liquid delivery device is stored in a storage bottle; storing the mobile phase in a mobile phase supply bottle which supplies the mobile phase to the storage bottle; determining an amount of the mobile phase to be dispensed from the mobile phase supply bottle to the storage bottle; Controlling the operation of a mobile phase supply pump to supply the mobile phase stored in the mobile phase supply bottle to the storage bottle; Furthermore, Detecting the remaining amount of the mobile phase stored in the storage bottle by a monitoring sensor; when the remaining amount of the mobile phase in the storage bottle becomes equal to or less than a specified value based on the detection value of the monitoring sensor, the mobile phase supply pump is driven to supply the mobile phase in the mobile phase supply bottle to the storage bottle; determining whether the amount of the mobile phase in the storage bottle has reached a certain level or more based on the remaining amount of the mobile phase detected by the monitoring sensor; Stopping the mobile phase supply pump; Furthermore, detecting air bubbles in a pipe installed between the mobile phase supply bottle and the mobile phase supply pump by an air bubble detection sensor; a gas conduit is provided between the storage bottle and the mobile phase supply bottle, and the pressure in the storage bottle and the pressure in the mobile phase supply bottle are kept constant; a mobile phase supplying pump for supplying the mobile phase in the mobile phase supplying bottle to the storage bottle, and a bubble detection sensor for detecting air bubbles in the piping to determine that the mobile phase supplying bottle is empty, and the mobile phase supplying pump is stopped.

6. 6. The method for controlling a liquid chromatograph according to claim 5, the mobile phase supply bottle has an information storage unit that stores information about the mobile phase contained in the mobile phase supply bottle, A method for controlling a liquid chromatograph, characterized in that it is determined whether the mobile phase supply bottle is properly installed from the information stored in the information storage unit read by an information reading unit that reads the information stored in the information storage unit.

7. 6. The method for controlling a liquid chromatograph according to claim 5, A method for controlling a liquid chromatograph, characterized in that when the remaining amount of mobile phase in the storage bottle reaches an operational preparation mobile phase remaining amount before the mobile phase supply pump is driven, a display unit displays that the mobile phase supply bottle is ready for operation.

8. 6. The method for controlling a liquid chromatograph according to claim 5, A method for controlling a liquid chromatograph, comprising irradiating the storage bottle or the mobile phase supply bottle with ultraviolet light from a deuterium lamp.

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