JP2013195392A - Liquid chromatograph analyzer and temperature control method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid chromatograph analyzer capable of improving the peak shape of a chromatogram.SOLUTION: A thermography camera 13 detects a piping outer wall temperature of a preheating part 5 and an outer wall temperature of a separation column 6. A temperature setting part 16 presets a center part temperature and an inner wall surface part temperature of the separation column 6 respectively. A temperature control part 17 adjusts the temperature of the preheating part 5 by means of a first temperature control unit 12 in accordance with the difference between the center part preset temperature of the separation column 6 and the detected piping outer wall temperature of the preheating part 5. The temperature control part 17 controls the temperature of the separation column 6 by means of a second temperature control unit 11 in accordance with the difference between the inner wall surface part preset temperature of the separation column 6 and the detected outer wall temperature of the separation column 6.

Description

  The present invention relates to a liquid chromatograph, and more particularly to temperature control.

  An example of a conventional liquid chromatograph analyzer is shown in FIG. 17 (see FIG. 1 of Patent Document 1). In this conventional analyzer, the eluent in the reservoirs 51 and 52 is sent to the separation column 56 by the pump 53. In front of the separation column 56, there is an autosampler (injector) 54 as a sample introduction unit. The sample is injected into the eluent being sent and separated into each component in the column separation unit 56, and the detection unit 58, the separated sample is detected. Further, although the column separation unit 56 may be used in a room temperature environment, that is, in a state where it is exposed to an indoor space, there are sufficient cases, but temperature control is necessary to obtain highly reproducible data. In many cases, the mode of storing and using in the column oven 57 as a thermostat is the mainstream.

  As a temperature control method of the column oven 57 of the liquid chromatograph analyzer, there are an air circulation method, a liquid circulation method, a heat block method, and the like. Here, the air circulation method is a method of adjusting the temperature in the column oven 57 by stirring the air heated (or cooled) by a heat source such as a heater using a Peltier element or the like with a fan. The liquid circulation method uses a liquid such as water as a heat exchange medium instead of air in the air circulation method. Furthermore, in the heat block method, an object (separation column 56, piping, etc.) to be temperature-controlled is brought into close contact with a block formed of a metal having good thermal conductivity such as aluminum, and the metal block is heated with a heater or the like ( (Or cooling) and temperature control.

  Regardless of the type of temperature control method of the column oven 57, the current temperature of air, liquid, or heat block in the thermostat is detected by a temperature sensor, and the result is the amount of power supplied to a heating element such as a heater. Temperature control is also performed, such as feedback to.

  In the conventional example shown in FIG. 17, the preheating unit 55 is used as a means for heating the eluent sent from the pump 53 to the column oven 57 of the liquid chromatograph analyzer before introducing it into the separation column 56. I have. In addition, there exist patent document 2, patent document 3, etc. as what was equipped with such a preheating means, for example.

  The purpose of including the preheating unit 55 is to make the eluent before being introduced into the separation column 56 match the temperature of the separation column 56 as much as possible. Matching the temperature of the eluent and the separation column 56 in this manner provides good results for the reproducibility of the separation peak retention time. However, depending on the type of the separation column 56, the coincidence of the temperatures may adversely deteriorate the shape of the separation peak and impair the peak separation degree.

  Patent Document 1 also describes the following. In other words, if the peak shape of the chromatogram obtained by the analysis without preheating is leading (with a tail before the peak), preheating and raising the temperature will result in the peak shape of the resulting chromatogram. Can be observed in the direction of tailing (a state in which the tail is pulled after the peak). This phenomenon is due to a change in linear flow velocity due to a temperature difference between the center portion of the column and the wall surface portion and a column wall surface effect on the fluid. That is, when the “change in linear flow velocity” and the “column wall surface effect” cancel each other, the best peak shape is obtained.

Japanese Patent No. 4110142 Japanese Patent No. 3846013 JP 2000-111536 A

  By the way, it is the temperature of the eluent that most affects the temperature at the center of the separation column 56. Similarly, it is the outer wall temperature of the separation column 57 that is considered to most reflect the wall surface temperature of the separation column 56. Further, as described above, matching the temperature of the eluent (the central part of the separation column 56) with the temperature of the wall surface of the separation column 57 (the outer wall of the separation column 57) improves the reproducibility of the separation peak retention time. It gives good results. However, it has been found that depending on the type of the separation column 57, the coincidence of these temperatures adversely deteriorates the shape of the separation peak and may result in a loss of the peak separation degree.

  The present invention has been made in view of the circumstances as described above, and an object of the present invention is to provide a liquid chromatograph analyzer capable of improving the peak shape of a chromatogram and a temperature control method thereof.

  In order to solve the above problems, the present invention detects a separation column, a preheating unit that controls the temperature of the sample solution before flowing into the separation column, the temperature of the outer wall of the preheating unit, and the temperature of the outer wall of the separation column. A temperature detection means; a first temperature control means for controlling the temperature of the preheating portion based on the detection result of the temperature detection means; and a second temperature control for controlling the temperature of the separation column based on the detection result of the temperature detection means. And means.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid chromatograph analyzer which can aim at the improvement of the peak shape of a chromatogram, and its temperature control method are realizable.

1 is a configuration diagram of a liquid chromatograph analyzer according to a first embodiment of the present invention. FIG. It is a more specific block diagram inside the column oven of the first embodiment. It is a flowchart (temperature control of a preheating part) explaining the temperature control method of the liquid chromatograph analyzer of 1st Embodiment. It is a flowchart (temperature control of a separation column) explaining the temperature control method of the liquid chromatograph analyzer of 1st Embodiment. It is a more specific block diagram inside the column oven of the second embodiment. It is a flowchart (temperature control of a preheating part) explaining the temperature control method of the liquid chromatograph analyzer of 2nd Embodiment. It is a flowchart (temperature control of a separation column) explaining the temperature control method of the liquid chromatograph analyzer of 1st Embodiment. It is explanatory drawing which illustrates the setting screen via a GUI display part at the time of setting the temperature distribution in a separation column uniformly. It is explanatory drawing explaining the temperature distribution in the separation column obtained by the temperature control based on the setting of FIG. It is explanatory drawing which illustrates the setting screen via a GUI display part at the time of setting low center part temperature in a separation column. It is explanatory drawing explaining the temperature distribution in the separation column obtained by the temperature control based on the setting of FIG. It is explanatory drawing which illustrates the setting screen via a GUI display part at the time of setting high center part temperature in a separation column. It is explanatory drawing explaining the temperature distribution in the separation column obtained by the temperature control based on the setting of FIG. It is explanatory drawing which illustrates the setting screen via a GUI display part at the time of setting the partial temperature of the outer wall part of a separation column high. It is explanatory drawing explaining the temperature distribution in the separation column obtained by the temperature control based on the setting of FIG. It is explanatory drawing explaining the outer wall temperature detection of the separation column at the time of using a heat block system. It is a block diagram of the conventional liquid chromatograph analyzer.

Hereinafter, embodiments of the liquid chromatograph analyzer of the present invention will be described in detail in the order of the first embodiment and the second embodiment with reference to the drawings.
[First Embodiment]

  FIG. 1 is a configuration diagram of a liquid chromatograph analyzer according to a first embodiment of the present invention. In the figure, the liquid chromatograph analyzer of the present embodiment has a configuration including reservoirs 1 and 2, a pump 3, an autosampler (injector) 4, a column oven 7, a detector 9, and a data processing unit 10. Further, the column oven 7 includes a preheating unit 5, a separation column 6 and a postcool unit 8. In the present embodiment, the separation column 6 has a long cylindrical shape in one direction.

  The sample solutions A and B in the reservoirs 1 and 2 are fed by the pump 3 while changing the mixed composition with time. Thereafter, a sample to be analyzed is added to the sample solution by an injector in the autosampler 4. The sample solution to which the sample has been added passes through the preheating unit 5 and is then introduced into the separation column 6 where it is separated for each component. Each component separated by the separation column 6 is detected by a detector 9. Based on the data detected by the detector 9, a chromatogram is created by the data processor 10 and stored in a memory or the like (not shown). The data processing unit 10 controls each unit in addition to the chromatogram creation process. A broken line in the figure is a control signal line for performing the control.

  As in the conventional example, in order to perform multi-component separation in the separation column 6 with good reproducibility, the separation column 6 is installed in a column oven 7 maintained at a constant temperature. The apparatus further has the following characteristic configuration. That is, the liquid chromatograph analyzer of this embodiment includes a thermography camera (temperature detection means) 13, a first temperature control unit 12, and a second temperature control unit 11, and the data processing unit 10 includes a temperature setting unit 16, An input / output unit 18 having a temperature control unit 17 and a GUI (Graphical User Interface) display unit 19 is provided. Here, the first temperature control means in the claims is realized by the first temperature control unit 12 and the temperature control unit 17, and the second temperature control means is realized by the second temperature control unit 11 and the temperature control unit 17. The

  The thermography camera 13 detects the temperature of the pipe outer wall of the preheating unit 5 and the outer wall temperature of the separation column 6. The first temperature control unit 12 adjusts the temperature of the preheating unit 5 based on the control instruction of the temperature control unit 17, and the second temperature control unit 11 controls the temperature of the separation column 6 based on the control instruction of the temperature control unit 17. Make adjustments.

  In the data processing unit 10, the temperature setting unit 16 determines the center temperature of the separation column 6 (the temperature of the preheating unit 5) based on the user setting input via the display screen of the GUI display unit 19 of the input / output unit 18. The inner wall surface temperature of the separation column 6 is set. The display screen of the GUI display unit 19 is configured on a display medium such as a liquid crystal display panel included in the input / output unit 18.

  Further, the temperature control unit 17 adjusts the temperature of the preheating unit 5 by the first temperature control unit 12 according to the difference between the center set temperature of the separation column 6 and the detected pipe outer wall temperature of the preheating unit 5. Furthermore, the temperature control unit 17 controls the temperature of the separation column 6 by the second temperature control unit 11 according to the difference between the inner wall surface set temperature of the separation column 6 and the detected outer wall temperature of the separation column 6. The temperature setting unit 16 and the temperature control unit 17 are functional groups of programs executed on a processor such as an MPU (Micro-Processing Unit) or DSP (Digital Signal Processor) included in the data processing unit 10. It is embodied as

  Here, the setting target in the temperature setting unit 16 and the detection target by the thermography camera 13 are different because it is difficult in terms of implementation to accurately detect the center temperature and the inner wall surface temperature of the separation column 6. In the embodiment, detection of the center temperature and the inner wall surface temperature of the separation column 6 is replaced by detection of the temperature of the outer wall of the pipe of the preheating unit 5 and the temperature of the outer wall of the separation column 6, respectively.

  Next, temperature control inside the column oven 7 having the above-described characteristic configuration will be described in detail with reference to a configuration diagram inside the column oven 7 shown in FIG. In the figure, a one-dot chain line represents a detection signal line input to the data processing unit 10 from various detection means, and a broken line represents a control signal line output from the data processing unit 10.

  First, the preheating unit 5 includes a heat block 5 a, a preheat pipe 21, a temperature sensor 14, and a first temperature control unit 12. One of the preheat pipes 21 is connected to a pipe from the autosampler 4 and the other is connected to a separation column 6. The preheat pipe 21 is made of a stainless steel pipe having good heat conduction. Moreover, what is necessary is just to use a Peltier device etc. for the 1st temperature control unit 12, for example.

  In addition, the preheat pipe 21 of the preheat unit 5 to which the sample solution that has passed through the autosampler 4 is sent is fitted into the heat block 5a. The first temperature control unit 12 for heating or cooling the heat block 5a is thermally coupled to the heat block 5a. The first temperature control unit 12 allows the preheat pipe 21, That is, the temperature of the sample solution before flowing into the separation column 6 is controlled.

  On the other hand, the temperature of the separation column 6 is adjusted by the second temperature control unit 11. FIG. 2 exemplifies a configuration of temperature adjustment by air circulation, and the second temperature control unit 11 includes a heater 11a and M fans 11b-1 to 11b-M. For example, a Peltier element or the like may be used as the heater 11a.

  The thermography camera 13 installed in the column oven 7 monitors the pipe outer wall of the preheating unit 5 and the outer wall of the separation column 6. The temperature data obtained by the thermography camera 13 is sent to the data processing unit 10, and after data processing, the pipe outer wall temperature of the preheating unit 5 and the outer wall temperature of the separation column 6 are specified as detection results. Here, the pipe outer wall of the preheating section 5 means the outer wall of the preheating pipe 21 in the section before the connection location with the separation column 6 after passing through the temperature control heat block 5 a of the preheating section 5.

  Next, the temperature control method of the liquid chromatograph analyzer provided with the above components will be described with reference to FIGS. Here, FIG. 3 is a flowchart for explaining the temperature control procedure of the preheating section 5, and FIG. 4 is a flowchart for explaining the temperature control procedure of the separation column 6.

  In the analysis using the liquid chromatograph analyzer of the present embodiment, the user previously sets the center setting temperature and the wall surface setting temperature of the separation column 6 in the temperature setting unit 16 of the data processing unit 10, respectively. deep. And if the thermography camera 13 detects the pipe outer wall temperature of the preheating part 5 and the outer wall temperature of the separation column 6, the temperature control of the preheating part 5 and the temperature control of the separation column 6 will be independently processed in parallel.

  In the temperature control of the preheating unit 5 shown in FIG. 3, first, the temperature setting unit 16 acquires the center set temperature of the separation column 6 based on a user input via the GUI display unit 19 of the input / output unit 18 (step). S101). And the temperature control part 17 specifies the pipe outer wall temperature of the preheating part 5 from the temperature data obtained with the thermography camera 13, and acquires it as center part detection temperature of the separation column 6 (step S102).

  Next, the difference between the two, that is, “set temperature−detected temperature” is set as a difference ΔTP (step S103), and it is determined whether the difference ΔTP is a zero value, a positive value, or a negative value (step S104). ). Note that it is not necessary to strictly determine whether or not the difference ΔTP is a zero value, and it may be a determination that a temperature error tolerance (±) is provided and is regarded as a zero value when included in the tolerance. .

  When the difference ΔTP = 0, the current control by the first temperature control unit 12 is maintained (step S105), and the center temperature of the separation column 6 (the pipe outer wall temperature of the preheating unit 5) is currently equal to the center set temperature. Is displayed via the GUI display unit 19 of the input / output unit 18 to notify the user (step S108).

  If the difference ΔTP> 0, the temperature rise control is performed by the first temperature control unit 12 (step S106), and after time adjustment (step S109), the process returns to step 102 and a series of processes is repeated. Further, when the difference ΔTP <0, the temperature lowering control is performed by the first temperature control unit 12 (step S107), and after time adjustment (step S109), the process returns to step S102 to repeat the series of processes. By repeating such a series of processes, the pipe outer wall temperature of the preheating section 5, that is, the center temperature of the separation column 6 is adjusted to a temperature desired by the user.

  Here, the time adjustment in step S109 is to adjust the interval until the next temperature detection, and can be either a method of performing a series of processing at a constant cycle interval or a method of changing the execution interval. May be. In the case of the variable interval, for example, based on the difference between the current detected temperature and the set temperature, the structure of the preheating unit 5, and the control amount in the temperature increase or decrease control, the pipe outer wall temperature of the preheating unit 5 is set to the set temperature by the control. The time until reaching the time is estimated, and a time slightly shorter than the estimated time is set as an execution interval in consideration of the time delay (hysteresis) of heat exchange. Then, based on the progress determination by a timer or the like, the process of step S102 may be performed when the execution interval has elapsed.

  In the case of providing a temperature error tolerance (±), it is considered that the time delay of heat exchange is absorbed by the temperature error tolerance after the zero value of the difference ΔTP is determined. In setting the interval, the influence of the time delay of heat exchange may be reduced, and the estimated time may be set as it is.

  Next, in the temperature control of the separation column 6 shown in FIG. 4, first, the temperature setting unit 16 acquires the inner wall surface set temperature of the separation column 6 based on the user input via the GUI display unit 19 of the input / output unit 18. (Step S201). And the temperature control part 17 specifies the outer wall temperature of the separation column 6 from the temperature data obtained with the thermography camera 13, and acquires it as detection temperature (step S202).

  Next, the difference between the two, that is, “set temperature−detected temperature” is set as a difference ΔTC (step S203), and it is determined whether the difference ΔTC is a zero value, a positive value, or a negative value (step S204). ). The determination of the zero value of the difference ΔTC is the same as the determination of the zero value of the difference ΔTP.

  When the difference ΔTC = 0, the current control by the second temperature control unit 11 is maintained (step S205), and the inner wall surface temperature (outer wall temperature) of the separation column 6 is currently set to the inner wall surface temperature setting. The message is displayed via the GUI display unit 19 of the input / output unit 18 to notify the user (step S208).

  Further, when the difference ΔTC> 0, the temperature rise control is performed by the second temperature control unit 11 (step S206), and after time adjustment (step S209), the process returns to step S202 to repeat the series of processes. Further, when the difference ΔTC <0, the temperature lowering control is performed by the second temperature control unit 11 (step S207), and after time adjustment (step S209), the process returns to step 202 to repeat a series of processes. By repeating such a series of processes, the inner wall surface temperature of the separation column 6 is adjusted to the desired inner wall surface temperature set by the user. Here, the time adjustment in step S209 is the same as the temperature control of the preheating unit 5 (see FIG. 3).

  Further, the configuration on the outlet side of the separation column 6 will be described. It is known that the solution temperature after passing through the separation column 6 affects the detection result. That is, when the solution that has come out of the column oven 7 enters the detector 9 with a liquid temperature that is too high, the noise and drift of the detector 9 increase, leading to a decrease in detection sensitivity. Therefore, before the solution exiting from the column oven 7 reaches the detector 9, it is necessary to perform a so-called post-cooling in which the temperature of the solution is returned to room temperature or the temperature in the detector 9.

  In general, there is known a method for dealing with a long channel (tube) connecting the separation column 6 and the detector 9. However, in this method, since the band spread due to the laminar flow in the tube results in the loss of the separation degree of the separation column 6, a configuration in which a post-cooling mechanism is inserted between the separation column 6 and the detector 9 is proposed. ing. In the present embodiment, such a postcool section 8 is provided, the postcool pipe 22 is disposed after passing through the separation column 6, and the postcool pipe 22 is fitted into the heat block 8a to adjust the temperature.

  As described above, the liquid chromatograph analyzer and the temperature control method thereof according to this embodiment include the separation column 6 and the preheating unit 5 that controls the temperature of the sample solution before flowing into the separation column 6. In the liquid chromatograph analyzer, the thermography camera (temperature detection means) 13 detects the temperature of the outer wall of the pipe of the preheating unit 5 and the temperature of the outer wall of the separation column 6 (temperature detection step), and the first temperature control unit 12 and the temperature control unit. 17 (first temperature control means) controls the temperature of the preheating unit 5 based on the detection result of the thermographic camera 13 (first temperature control step), and the second temperature control unit 11 and the temperature control unit 17 (second temperature control). Means) to control the temperature of the separation column 6 based on the detection result of the thermographic camera 13 (second temperature control system). -Up).

  Specifically, the temperature setting unit 16 (temperature setting means) sets the center temperature and the inner wall surface temperature of the separation column 6 (temperature setting step), respectively, and the first temperature control unit 12 and the temperature control unit 17 (first control unit). 1 temperature control means) controls the temperature of the preheating unit 5 in accordance with the difference between the center set temperature of the separation column 6 and the pipe outer wall temperature of the preheating unit 5 detected by the thermography camera 13 (first temperature control). Step), and in the second temperature control unit 11 and the temperature control unit 17 (second temperature control means), the difference between the set inner wall surface temperature of the separation column 6 and the outer wall temperature of the separation column 6 detected by the thermography camera 13 is calculated. Accordingly, the temperature of the separation column 6 is controlled (second temperature control step).

  As described above, independent feedback control is performed in parallel for each of the center temperature and the inner wall surface temperature of the separation column 6, so that the center portion of the separation column 6 in the short axis direction from the center portion to the wall surface portion. The temperature distribution can be arbitrarily set to a uniform distribution having a temperature gradient. Here, the long axis is an axis in the direction in which the solution flows from the inlet to the outlet of the separation column 6, and the short axis is an axis that intersects the long axis perpendicularly and passes through the central portion and the outer wall of the separation column 6.

  Therefore, the method of grasping and managing the temperature gradient in the short axis direction according to the present embodiment is the one-dimensionally grasping and managing the temperature gradient in the long axis direction of the separation column 6 from the inlet to the outlet of the separation column 6. By combining the methods, the temperature gradient of the separation column 6 can be grasped and managed two-dimensionally.

  In addition, as described above, depending on the type of the separation column 6, there is a situation in which the uniform temperature distribution in the minor axis direction may deteriorate the shape of the separation peak and impair the peak separation degree. Under such circumstances, the one-dimensional temperature gradient in the short axis direction of the separation column 6 can be grasped and managed, or the two-dimensional temperature gradient in the short and long axes of the separation column 6 can be grasped and managed. By performing the management, not only the reproducibility of the chromatogram but also the peak shape can be improved with respect to the degree of symmetry and the like.

  More specifically, for example, when the diameter of the separation column 6 is relatively small, the temperature distribution in the minor axis direction is made uniform, and when the diameter is relatively large, the center of the separation column 6 is It has been experimentally confirmed that the peak shape can be improved with respect to the reproducibility and symmetry of the chromatogram if the temperature gradient is such that the temperature is high and the temperature near the inner wall is low. .

Therefore, for each type such as the diameter of the separation column 6, the center temperature and the inner wall surface temperature of the separation column 6 from which a better peak shape can be obtained are obtained by preliminary experiments or the like conducted in advance by the manufacturer or the user. In the analysis using the graph analyzer, the reproducibility and symmetry of the chromatogram can be obtained by presetting the center temperature and the inner wall surface temperature of the separation column 6 via the temperature setting unit 16 of the data processing unit 10. Etc., the peak shape can be improved.
[Second Embodiment]

  Next, a liquid chromatograph analyzer and a temperature control method thereof according to a second embodiment of the present invention will be described. The liquid chromatograph analyzer according to this embodiment is configured so that the second temperature control unit 11 according to the first embodiment is arranged in the first to Nth temperature control blocks (N is an integer of 2 or more) along the long axis direction of the separation column 6. And the temperature of the separation column 6 is controlled by dividing it into first to Nth temperature control zones along the long axis direction of the separation column 6. This is equivalent to the embodiment (FIG. 1). That is, in the present embodiment, the temperature distribution in the major axis direction of the separation column 6 can be arbitrarily set in the configuration of the first embodiment in which the temperature distribution in the minor axis direction of the separation column 6 can be arbitrarily set. Is added.

  FIG. 5 shows a more specific configuration diagram inside the column oven 37 in the present embodiment. In the figure, the same components as those in the first embodiment (FIGS. 1 and 2) are denoted by the same reference numerals, and detailed description thereof is omitted. Similarly to FIG. 2, the alternate long and short dash line in the figure represents a detection signal line input from the various detection means to the data processing unit 20, and the broken line represents a control signal line output from the data processing unit 20.

  As a characteristic configuration of the liquid chromatograph analyzer of the present embodiment, similarly to the first embodiment, a thermographic camera (temperature detection means) 13, a first temperature control unit 12, and a second temperature control unit 23 are provided. The data processing unit 20 includes an input / output unit 28 having a temperature setting unit 26, a temperature control unit 27, and a GUI display unit 29. Here, the first temperature control means described in the claims is realized by the first temperature control unit 12 and the temperature control unit 27, and the second temperature control means is realized by the second temperature control unit 23 and the temperature control unit 27. The

  The first temperature control unit 12 adjusts the temperature of the preheating unit 5 based on the control instruction of the temperature control unit 27, and the second temperature control unit 23 adjusts the temperature of the separation column 6 based on the control instruction of the temperature control unit 27. Do. Further, unlike the first embodiment, the second temperature control unit 11 includes N temperature control blocks, that is, first temperature control blocks 11a-1 to 11th, along the long axis direction of the separation column 6. A temperature control block 11a-N and M fans 11b-1 to 11b-M are provided. Here, N and M are integers, and N> M in FIG. For example, a Peltier element or the like may be used for the first temperature control unit 12 and the first temperature control block 11a-1 to the Nth temperature control block 11a-N.

  In addition, the thermography camera 13 has the pipe outer wall temperature of the preheating unit 5 and the first position to the Nth position of the outer wall of the separation column 6 facing the first to Nth temperature control blocks 11a-1 to 11a-N. Each temperature is detected.

  In the data processing unit 20, the temperature setting unit 26 is based on the setting input via the display screen of the GUI display unit 29 of the input / output unit 28, and the center temperature of the separation column 6 (the temperature of the preheating unit 5), First to Nth temperatures of the inner wall surface of the separation column 6 facing the first to Nth temperature control blocks 11a-1 to 11a-N are set, respectively.

  Further, the temperature control unit 27 is configured so that the temperature of the preheating unit 5 is controlled by the first temperature control unit 12 according to the difference between the center set temperature of the separation column 6 and the pipe outer wall temperature of the preheating unit 5 detected by the thermography camera 13. Make adjustments. Further, when k = 1 to N, the temperature control unit 27 responds to the difference between the kth set temperature of the inner wall surface of the separation column 6 and the kth temperature of the outer wall of the separation column 6 detected by the thermography camera 13. Thus, the temperature of the separation column 6 is controlled by the kth temperature control block.

  Next, the temperature control method of the liquid chromatograph analyzer provided with the above components will be described with reference to FIGS. Here, FIG. 6 is a flowchart for explaining the temperature control procedure of the preheating unit 5, and FIG. 7 is a flowchart for explaining the temperature control procedure of the separation column 6.

  In the analysis using the liquid chromatograph analyzer of the present embodiment, the user preliminarily separates the center temperature of the separation column 6 and the first to Nth temperature control blocks 11a-1 to 11a-N. 6 are set in the temperature setting unit 26 of the data processing unit 20, respectively. At this time, a temperature error allowable range is also set for each setting item. In addition, from the relative numerical relationship of all set values (including the temperature error tolerance), it is judged whether the user setting is feasible in light of the temperature control characteristics of the liquid chromatograph analyzer. It is desirable to adopt a configuration in which the user is notified of this by an identification display of the corresponding part, a guidance message, or the like.

  Then, the thermography camera 13 causes the pipe outer wall temperature of the preheating unit 5 and the temperatures of the first position to the Nth position of the outer wall of the separation column 6 facing the first to Nth temperature control blocks 11a-1 to 11a-N. Is detected, the temperature control of the preheating section 5 and the temperature control of the separation column 6 are independently performed in parallel.

  In the temperature control of the preheating unit 5 in FIG. 6, the temperature setting unit 26 first sets the center set temperature of the separation column 6 (setting of the preheating unit 5) based on a user input via the GUI display unit 29 of the input / output unit 28. Temperature) is acquired (step S301). And the temperature control part 17 specifies the pipe outer wall temperature of the preheating part 5 from the temperature data obtained with the thermography camera 13, and acquires it as center part detection temperature of the separation column 6 (step S302).

  Next, the difference between the two, that is, “set temperature−detected temperature” is set as a difference ΔTP (step S303), and the absolute value of the difference ΔTP is equal to or less than the temperature error allowable range ΔTer for the set temperature of the preheating unit 5. Whether or not (step S304).

  When the absolute value of the difference ΔTP is equal to or less than the temperature error allowable range ΔTer, the center temperature of the separation column 6 (pipe outer wall temperature of the preheating unit 5) is almost the set temperature, so the first temperature control unit 12 The current control by is maintained (step S306). Then, a message indicating that the temperature at the center of the separation column 6 is almost the set temperature is displayed via the GUI display unit 29 of the input / output unit 28 to notify the user (step S309).

  On the other hand, if the absolute value of the difference ΔTP exceeds the temperature error allowable range ΔTer, the process proceeds to step S305 to determine whether the difference ΔTP is a positive value or a negative value. When the difference ΔTP> 0, the temperature rise control is performed by the first temperature control unit 12 (step S307), and after the time adjustment (step S310), the process returns to step S302 to repeat the series of processes.

  When the difference ΔTP <0, the temperature lowering control is performed by the first temperature control unit 12 (step S308), and after time adjustment (step S310), the process returns to step 302 to repeat a series of processes. By repeating such a series of processes, the pipe outer wall temperature of the preheating section 5, that is, the center temperature of the separation column 6 is adjusted to a temperature desired by the user. Here, the time adjustment in step S310 is the same as in the first embodiment (step S109 in FIG. 3).

  Next, in the temperature control of the separation column 6 in FIG. 7, the k-th temperature control area of the separation column 6 performed by the k-th temperature control block 11 a-k (k = 1 to N) of the second temperature control unit 23. The temperature control is as follows. The temperature control by the first to Nth temperature control blocks 11a-1 to 11a-N of the second temperature control unit 23 is performed independently.

  First, the temperature setting unit 26 acquires the k-th set temperature on the inner wall surface of the separation column 6 facing the k-th temperature control block 11a-k based on a user input via the GUI display unit 29 of the input / output unit 28. (Step S401). Then, the temperature control unit 27 specifies the temperature of the kth position of the outer wall of the separation column 6 facing the kth temperature control block 11a-k from the temperature data obtained by the thermography camera 13, and the kth position Obtained as the detected temperature (step S402).

  Next, the difference between the two, that is, “the kth set temperature−the detected temperature at the kth position” is set as a difference ΔTCk (step S403), and the absolute value of the difference ΔTCk is an allowable temperature error for the kth set temperature. It is determined whether or not it is within the range ΔTker (step S404). If it is not within the temperature error allowable range ΔTker, it is determined whether the difference ΔTCk is a positive value or a negative value (step S405).

  When the absolute value of the difference ΔTCk is within the temperature error allowable range ΔTker for the kth set temperature, the current control by the kth temperature control block 11a-k of the second temperature control unit 23 is maintained (step S406). Currently, a message that the k-th position temperature of the outer wall of the separation column 6 is almost the k-th set temperature is displayed via the GUI display unit 29 of the input / output unit 28 to notify the user (step S409). ).

  When the difference ΔTCk> 0, the temperature increase control is performed by the kth temperature control block 11a-k of the second temperature control unit 11 (step S407), and after the time adjustment (step S410), the process proceeds to step 402. Go back and repeat the process. Further, when the difference ΔTCk <0, the temperature decrease control is performed by the kth temperature control block 11a-k of the second temperature control unit 11 (step S408), and after time adjustment (step S410), the process returns to step S402. Repeat the series of processes. By repeating such a series of processes, the k-th position temperature of the outer wall of the separation column 6 is adjusted to a temperature desired by the user. Here, the time adjustment in step S410 is equivalent to the first embodiment (step S209 in FIG. 4).

  Next, input setting to the temperature setting unit 26 via the display screen of the GUI display unit 29 of the input / output unit 28 will be described with reference to specific examples shown in FIGS. In the following description, the second temperature control unit 11 is configured by first to fourth temperature control blocks 11a-1 to 11a-4, and the first to fourth temperature control units 11a-1 to 11a-4 are arranged along the long axis direction of the separation column 6. It is assumed that temperature control is performed by dividing into temperature control zones.

  8, 10, 12, and 14 exemplify the display screen 101 of the GUI display unit 29 of the input / output unit 28 in different cases. The display screen 101 includes a column temperature setting area 102 for setting the temperature of the separation column 6 and an in-column temperature distribution area 105 for displaying the estimated temperature distribution in the separation column 6.

  Further, the column temperature setting area 102 includes a column center temperature setting area 103 for setting the center temperature of the separation column 6 (preheating temperature in the figure), and first to fourth temperature control blocks 11a-1 to 11a. 4 is provided with a column wall surface temperature setting region 104 for setting the first temperature to the fourth temperature (in the figure, the column wall surface first temperature to the column wall surface fourth temperature) of the inner wall surface of the separation column 6 facing -4. Moreover, a temperature error allowable range can be set for each temperature setting of the central portion and the inner wall surface portion of the separation column 6.

  In the temperature setting unit 26, the preheating unit temperature and the column wall surface first temperature to the column wall surface fourth temperature are set by user settings in the column temperature setting region 102, and the major axis direction of the separation column 6 is based on these set temperatures. And a temperature distribution in a two-dimensional plane of the short axis direction orthogonal to the long axis direction are estimated. The temperature distribution is estimated by, for example, simulation or table reference. When estimating by simulation, a simulator having an equivalent thermal model of the separation column 6 is prepared separately, and a set temperature is input to the simulator to obtain a simulation experiment result. For estimation by table reference, a table in which a temperature distribution corresponding to a combination of a set temperature and a temperature error allowable range is registered in advance in a storage unit (not shown) of the data processing unit 20 is prepared. The method of referring to is adopted. The temperature distribution in the separation column 6 estimated in this way is displayed in the column temperature distribution area 105.

  First, a case where the temperature distribution in the two-dimensional plane in the major axis direction and the minor axis direction in the separation column 6 is set uniformly will be described with reference to FIGS. When the temperature distribution is set uniformly, the same temperature is set as the preheating portion temperature and the column wall surface first temperature to the column wall surface fourth temperature. In the example of FIG. 8, each set temperature is 50 ° C. and the temperature error allowable range is ± 2 ° C.

  As shown in FIG. 9A, the major axis direction of the separation column 6 is x, and the first position to the fourth position of the separation column 6 facing the first to fourth temperature control blocks 11a-1 to 11a-4. Are defined as y1 to y4, respectively. In this case, the temperature distribution in the major axis x direction of the separation column 6 is constant as shown in FIG. 9B, and the temperature distribution in the minor axis y1 to y4 direction of the separation column 6 is shown in FIG. 9C. It is constant as shown in (c-1) to (c-4). As a result, the two-dimensional temperature distribution in the separation column 6 is estimated to be uniform as shown in FIG. 9D, and the uniform distribution is also displayed in the column temperature distribution region 105 in FIG. It will be.

  Next, a case where the center temperature in the separation column 6 is set lower than the inner wall surface temperature will be described with reference to FIGS. 10 and 11. In the example of FIG. 10, the setting of the preheating part temperature is 50 ° C., each setting of the column wall surface first temperature to the column wall surface fourth temperature is 60 ° C., and the temperature error allowable range for each setting is ± 2 ° C.

  If each axis is defined in the same way as FIG. 9A as shown in FIG. 11A, the temperature distribution in the major axis x direction of the separation column 6 is approximately 50 ° C. on the inlet side as shown in FIG. 11B. However, as it goes to the outlet side, it has a temperature gradient that approaches 60 ° C. due to the influence of the inner wall surface of the separation column 6. Further, the temperature distributions in the minor axis y1 to y4 directions at the first position to the fourth position of the separation column 6 are respectively shown from (c-1) to (c-4) in FIG. The temperature gradient increases toward the inner wall surfaces on both sides, and the temperature gradient gradually decreases from the first position toward the fourth position. As a result, the two-dimensional temperature distribution in the separation column 6 has a temperature gradient that rises from the center toward both inner wall surfaces in the minor axis direction, as shown in FIG. It is estimated that the distribution becomes gentle from the inlet side to the outlet side in the long axis direction, and a similar distribution is displayed in the in-column temperature distribution region 105 of FIG.

  Next, a case where the center temperature in the separation column 6 is set higher than the inner wall surface temperature will be described with reference to FIGS. In the example of FIG. 12, the setting of the preheating part temperature is 60 ° C., each setting of the column wall surface first temperature to the column wall surface fourth temperature is 50 ° C., and the temperature error allowable range for each setting is ± 2 ° C.

  If each axis is defined as shown in FIG. 9A as shown in FIG. 13A, the temperature distribution in the major axis x direction of the separation column 6 is approximately 60 ° C. on the inlet side as shown in FIG. 13B. However, as it goes to the outlet side, it has a temperature gradient that approaches 50 ° C. due to the influence of the inner wall surface of the separation column 6. Further, the temperature distributions in the minor axis y1 to y4 directions at the first position to the fourth position of the separation column 6 are respectively shown from (c-1) to (c-4) in FIG. There is a temperature gradient in which the temperature decreases toward both inner wall surfaces, and the temperature gradient gradually decreases from the first position toward the fourth position. As a result of these, the two-dimensional temperature distribution in the separation column 6 has a temperature gradient that falls from the center toward both inner wall surfaces in the minor axis direction, as shown in FIG. It is estimated that the distribution becomes gentle from the inlet side to the outlet side in the long axis direction, and a similar distribution is displayed in the in-column temperature distribution region 105 of FIG.

  Next, a case in which the partial temperature of the outer wall portion of the separation column 6 is set higher than the other portion temperature and the central portion temperature of the outer wall portion will be described with reference to FIGS. In the example of FIG. 14, the setting of the preheating part temperature and the column wall surface second temperature is 60 ° C., the setting of the other column wall surface first temperature, the column wall surface third temperature, and the column wall surface fourth temperature is 50 ° C., The allowable temperature error range for the setting is ± 2 ° C.

  If each axis is defined as shown in FIG. 9A as shown in FIG. 15A, the temperature distribution in the major axis x direction of the separation column 6 is approximately 60 ° C. on the inlet side as shown in FIG. 15B. However, as it goes to the outlet side, it has a temperature gradient that approaches 50 ° C. due to the influence of the column wall near the outlet. In addition, the temperature distribution in the minor axis y1 to y4 direction at the first position to the fourth position of the separation column 6 is as shown in (c-1) to (c-4) of FIG. The temperature distribution in the minor axis y1, y3, y4 direction at the first position, the third position, and the fourth position has a temperature gradient in which the temperature drops from the center toward both inner wall surfaces, from the inlet side to the outlet side. However, the temperature distribution in the direction of the minor axis y2 at the second position has a temperature gradient in which the temperature once decreases from the center toward both inner wall surfaces and then increases again. .

  As a result of these, the two-dimensional temperature distribution in the separation column 6 generally has a temperature gradient that falls from the center toward both inner wall surfaces in the minor axis direction, as shown in FIG. 15 (d). The temperature gradient has a gentle distribution from the inlet side to the outlet side in the long axis direction, but it is estimated that the vicinity of the second position has a locally different distribution. In addition, a similar distribution is displayed in the in-column temperature distribution region 105 of FIG.

  As described above, in the liquid chromatograph analysis apparatus and the temperature control method thereof according to this embodiment, the second temperature control unit 23 and the temperature control unit 27 (second temperature control means) are arranged in the major axis direction of the separation column 6. The temperature of the separation column 6 is controlled by dividing it into first to Nth temperature control zones (N is an integer of 2 or more), and the center of the separation column 6 is controlled by the temperature setting unit 26 (temperature setting means). And the inner wall surface portion kth temperature of the separation column 6 in the kth temperature control zone (k = 1 to N) are set (temperature setting step). Further, in the first temperature control unit 12 and the temperature control unit 27 (first temperature control means), according to the difference between the center set temperature of the separation column 6 and the temperature of the outer wall of the preheating unit 5 detected by the thermography camera 13. Then, the temperature of the preheating section 5 is controlled (first temperature control step), and the second temperature control unit 23 and the temperature control section 27 (second temperature control means) are used for the inner wall surface section kth set temperature and thermography of the separation column 6. The temperature of the kth temperature control zone is controlled according to the difference from the kth position temperature of the outer wall of the separation column 6 detected by the camera 13 (second temperature control step).

  As described above, independent feedback control is performed in parallel for each of the center temperature and the inner wall surface temperature of the separation column 6, and the inner wall surface temperature of the separation column 6 is divided into first to Nth temperature control zones. Since the independent feedback control is performed in parallel, the temperature distribution from the central portion of the separation column 6 to the inner wall surface in the short axis direction of the separation column 6 is uniform or has a temperature gradient. The temperature distribution from the inlet side to the outlet side of the separation column 6 in the major axis direction of the separation column 6 can be arbitrarily set to a uniform or distribution having a temperature gradient. As a result, the temperature gradient of the separation column 6 can be grasped and managed in two dimensions in the major axis direction and the minor axis direction of the separation column 6 from the inlet to the outlet of the separation column 6, and also in the first embodiment. As mentioned, the peak shape can be improved with respect to the reproducibility and symmetry of the chromatogram. Further, according to the liquid chromatograph analyzer of the present embodiment and the temperature control method thereof, the temperature can be individually controlled by dividing into N temperature control zones along the long axis direction of the separation column 6. The temperature distribution can be locally controlled, and the temperature distribution can be set more finely than in the first embodiment.

  In the second embodiment described above, the second temperature control unit 11 includes first to Nth temperature control blocks 11a-1 to 11a-N and M fans 11b-1 to 11b-M. However, the present invention is not limited to this configuration, and any other device may be used as long as the temperature of the separation column 6 is individually controlled by dividing it into a plurality of temperature control zones along the long axis direction of the separation column 6. The configuration / method may be used.

  For example, in the configuration equivalent to the first embodiment, a method of individually adjusting the rotational speeds of the fans 11b-1 to 11b-M arranged in the long axis direction of the separation column 6 is conceivable. However, in this method, the rotational speed of the fans 11b-1 to 11b-M can be adjusted stepwise to give a gentle temperature gradient in the major axis direction of the separation column 6, but as in the second embodiment. It is difficult to arbitrarily set a temperature distribution having local changes.

  As another configuration, a configuration in which the temperature control block and the fan are set as a set and a plurality of the sets are arranged in the major axis direction of the separation column 6 is also conceivable. That is, by adjusting the temperature (heat generation amount) of the kth (k = 1 to N) temperature control block and adjusting the rotation speed of the kth fan, the local change is further made than in the second embodiment. It is possible to arbitrarily set a temperature distribution having

(Modification)
The first embodiment and the second embodiment have been described in detail with reference to the drawings. However, the present invention is not limited to these embodiments, and there are design changes and the like that do not depart from the gist of the present invention. Is included in the present invention. Below, the modification of this invention is demonstrated.

  In the above-described embodiment, the air circulation type second temperature control unit 11 or 23 provided with a heater and a fan is used. However, other liquid circulation methods or heat block methods may be used. Moreover, it is not limited to such a well-known technique, The thing of the system which is not used for the conventional column oven, such as what used a far-infrared lamp, may be used.

  Further, when the heat block method is used instead of the air circulation method, when the outer wall temperature of the separation column 6 is detected in a non-contact manner like the thermographic camera 13, a structural device is required to improve the detection accuracy. It becomes. FIG. 16 is an explanatory diagram for explaining the detection of the outer wall temperature of the separation column 6 when the heat block method is used. As shown in the figure, in the heat block method, the outer periphery of the separation column 6 is covered with the heat block 31, but an open section is partially formed in the heat block 31, and the separation column 6 is formed by the thermography camera 13. It is desirable to detect the temperature of the outer wall.

  In the above-described embodiment, the thermography camera 13 is used as the temperature detection means as the non-contact type sensor. However, a contact type may be used, and a temperature sensor such as a thermocouple may be used. . In this case, a temperature sensor is installed in close contact with the outer wall surface of the preheat pipe 21 to constitute the first temperature detection means, and the temperature of the pipe outer wall of the preheat unit 5 is detected. Further, a temperature sensor is installed in close contact with the outer wall surface of the separation column 6 to constitute a second temperature detection means, and the outer wall temperature of the separation column 6 is detected.

  In addition, although the temperature sensor 14 is installed in the preheating part 5 in order to perform the temperature control by the first temperature control unit 12, this is treated as the second temperature detecting means, and the temperature sensor 14 is detected. The center temperature of the separation column 6 may be estimated by performing a predetermined correction on the value. That is, the outer wall temperature of the preheat pipe 21 at the connection point with the separation column 6 is obtained by a predetermined correction, and the center temperature of the separation column 6 is estimated from the outer wall temperature. According to this modification, although the accuracy of temperature detection is slightly lowered, the number of parts can be reduced and the device cost can be reduced.

  In the above-described embodiment, the preheating unit 5 is installed in the column oven 7 or 37. However, the present invention is not limited to this, and the preheating unit 5 may be installed in the autosampler 4. The column oven 7 or 37 and the autosampler 4 may be configured as separate units.

  Further, the post-cool unit 8 is similarly installed in the column oven 7 or 37. However, the post-cool unit 8 may be installed in the detector 9 without being limited thereto. The column oven 7 or 37 and the detector 9 may be configured as separate units.

DESCRIPTION OF SYMBOLS 1, 2 Reservoir 3 Pump 4 Autosampler 5 Preheating part 5a, 8a, 31 Heat block 6 Separation column 7, 37 Column oven 8 Postcool part 9 Detector 10, 20 Data processing part 11 2nd temperature control unit (2nd temperature) Control means)
11a heater 11a-1 to 11a-N temperature control block 11b-1 to 11b-n fan 12 first temperature control unit (first temperature control means)
13 Thermography camera (temperature detection means)
14, 15 Temperature sensor 16, 26 Temperature setting section (temperature setting means)
17, 27 Temperature controller (control means)
18, 28 Input / output section (input / output means)
19, 29 GUI display 21 Preheat tube 22 Postcool tube

Claims (10)

A separation column;
A preheating section for controlling the temperature of the sample solution before flowing into the separation column;
Temperature detecting means for detecting the temperature of the outer wall of the preheating unit and the temperature of the outer wall of the separation column;
First temperature control means for controlling the temperature of the preheating part based on the detection result of the temperature detection means;
Second temperature control means for controlling the temperature of the separation column based on the detection result of the temperature detection means;
A liquid chromatograph analyzer characterized by comprising: Temperature setting means for setting a center temperature and an inner wall temperature of the separation column,
The first temperature control means controls the temperature of the preheating part according to the difference between the center set temperature of the separation column and the temperature of the outer wall of the preheating part detected by the temperature detection means,
The second temperature control means controls the temperature of the separation column according to the difference between the set temperature of the inner wall surface of the separation column and the temperature of the outer wall of the separation column detected by the temperature detection means. The liquid chromatograph analyzer according to claim 1.   2. The temperature detecting means includes first temperature detecting means for detecting the temperature of the outer wall of the preheating section, and second temperature detecting means for detecting the temperature of the outer wall of the separation column. Or the liquid chromatograph analyzer of Claim 2.   The liquid chromatography according to any one of claims 1 to 3, wherein the temperature detection means, the first temperature detection means, and / or the second temperature detection means are non-contact sensors. Graph analyzer. The second temperature control means is divided into first to Nth temperature control blocks (N is an integer of 2 or more) along the long axis direction of the separation column,
The temperature detecting means or the second temperature detecting means detects the temperature at the k-th position of the outer wall of the separation column facing the k-th temperature control block (k = 1 to N),
The temperature setting means respectively sets the kth temperature of the inner wall surface portion of the separation column facing the kth temperature control block;
The second temperature control unit is configured to perform the k-th temperature control block according to the difference between the k-th set temperature of the inner wall surface of the separation column and the temperature at the k-th position of the outer wall of the separation column detected by the temperature detection unit. The liquid chromatograph analyzer according to any one of claims 2 to 4, wherein the temperature of the separation column is controlled. Having input / output means;
The temperature setting means sets the center temperature of the separation column and the inner wall surface temperature or the inner wall surface k-th temperature of the separation column via the input / output means, and sets the center temperature of the separation column and the separation temperature. Estimating a temperature distribution in two dimensions of the major axis direction of the separation column and the minor axis direction orthogonal to the major axis direction based on the inner wall surface set temperature of the column or the inner wall surface k-th set temperature, and the input / output means 6. The liquid chromatograph analyzer according to claim 2, wherein the temperature distribution estimated through the output is output. A temperature control method for a liquid chromatograph analyzer having a separation column and a preheating unit for controlling the temperature of the sample solution before flowing into the separation column,
A temperature detecting step for detecting the temperature of the outer wall of the preheating unit and the temperature of the outer wall of the separation column;
A first temperature control step for controlling the temperature of the preheating unit based on the detection result of the temperature detection step;
A second temperature control step for controlling the temperature of the separation column based on the detection result of the temperature detection step;
A temperature control method for a liquid chromatograph analyzer, comprising: A temperature setting step for setting the center temperature and the inner wall surface temperature of the separation column,
The first temperature control step controls the temperature of the preheating part according to the difference between the center set temperature of the separation column and the temperature of the outer wall of the preheating part detected in the temperature detection step,
In the second temperature control step, the temperature of the separation column is controlled in accordance with a difference between an inner wall surface set temperature of the separation column and a temperature of the outer wall of the separation column detected in the temperature detection step. The temperature control method of the liquid chromatograph analyzer of Claim 7. In the second temperature control step, the temperature of the separation column is controlled by dividing it into first to Nth temperature control zones (N is an integer of 2 or more) along the long axis direction of the separation column;
The temperature detecting step detects the k-th position temperature of the outer wall of the separation column in the k-th temperature control zone (k = 1 to N),
The temperature setting step sets the kth temperature of the inner wall surface of the separation column in the kth temperature control zone,
In the second temperature control step, according to a difference between the k-th set temperature of the inner wall surface of the separation column and the k-th position temperature of the outer wall of the separation column detected in the temperature detection step, The temperature control method for a liquid chromatograph analyzer according to claim 7 or 8, wherein the temperature is controlled. The liquid chromatograph analyzer has input / output means,
In the temperature setting step, a setting step of setting a central portion temperature of the separation column and an inner wall surface temperature or an inner wall surface portion kth temperature of the separation column through the input / output means;
Based on the set temperature at the center of the separation column and the set temperature at the inner wall surface of the separation column or the set temperature at the inner wall surface of the separation column, the major axis direction of the separation column and the minor axis direction orthogonal to the major axis direction An estimation step for estimating a temperature distribution;
The temperature control method for a liquid chromatograph analyzer according to claim 8 or 9, further comprising an output step of outputting a temperature distribution estimated via the input / output means.

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