JP2017211225A - Gas chromatograph device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reliably replace a residual gas in a column with a carrier gas at device activation even when a device configuration is complicated, and to raise the temperature of a column oven promptly to an analysis initial temperature after completion of the replacement and enable analysis to start.SOLUTION: When an indication for device activation is issued (S2), a control unit first calculates the average linear speed of a carrier gas by a prescribed calculation formula on the basis of information pertaining to the inside diameter and length of a column, column input pressure and output pressure, the type of carrier gas, etc., and a detected column oven temperature, for example, that are set as analysis conditions, and finds a required gas replacement time from the average linear speed and the column length. A start time ts is set from this time on (S3). When the start time ts elapses from a carrier gas supply start point of time (S4-S6), power to a heater is turned on and column oven temperature control is started (S7).SELECTED DRAWING: Figure 3

Description

  The present invention relates to a gas chromatograph apparatus. In addition, the gas chromatograph apparatus here contains the gas chromatograph mass spectrometer whose detector is a mass spectrometer naturally, regardless of the kind of detector.

  In a general gas chromatograph (hereinafter abbreviated as “GC”) device, a sample vaporized in a sample vaporization chamber provided at the inlet of the column is loaded onto a carrier gas and sent to the column, and various components contained in the sample pass through the column. In the process of separating. Then, the components that are separated and flow out sequentially are detected by a detector provided at the outlet of the column, and based on the detection signal, the time during which each component flows out of the column, that is, the retention time and the signal intensity corresponding to the component concentration Create a chromatogram showing the relationship.

  In the GC apparatus, a constant temperature analysis is usually performed in which the temperature of the column oven in which the column is built is maintained at a constant temperature higher than room temperature, or a temperature increase analysis is performed in which the temperature of the column oven is increased according to a predetermined temperature increase program. However, if the temperature of the column is raised while air is mixed in the column, the column may be deteriorated, for example, the liquid phase applied to the inner wall of the column is oxidized (see, for example, Patent Document 1). For this reason, in the conventional GC apparatus, the temperature of the column oven is not immediately increased even if an instruction to start the apparatus is issued from the apparatus stop state, but first the gas pressure control or the gas flow rate for feeding the carrier gas into the column. Start control only. Thereby, the gas in the column is replaced with a carrier gas such as helium or nitrogen. Then, temperature control of the column oven is started when a predetermined start-up waiting time (hereinafter referred to as “start time”) has elapsed from the start of carrier gas supply, and the inside of the column oven is brought to a predetermined temperature.

  On the other hand, the temperature control of the column oven and the sample vaporization chamber can be performed while maintaining the temperature of the detector at a high temperature so that the glass insert and septum, which are consumables of the sample vaporization chamber, can be replaced during operation (energization) of the GC apparatus A GC device having a function capable of stopping the pressure (or flow rate) control of the carrier gas (for example, an “INJ maintenance” function in a GC device manufactured by Shimadzu Corporation) is also known. In such an apparatus, it is necessary to restart the temperature control of the column oven and the sample vaporizing chamber and the pressure (or flow rate) control of the carrier gas after replacement of the consumables, and the atmosphere is mixed in the column at that time as well. Since there is a possibility, only the pressure (or flow rate) control of the carrier gas is restarted first, and the temperature control of the column oven is started after waiting for the start time from that point.

  In such a conventional GC apparatus, the start time is manually set by the user or a preset value such as 5 minutes or 10 minutes set in advance in the firmware of the apparatus is used. When the user sets the start time, the time required to replace the gas in the column from the gas flow rate value calculated based on the analysis conditions such as the type of carrier gas used at that time and the column inlet pressure In some cases, the start time is determined based on the estimated value, but in reality such calculation is quite complicated and troublesome. In addition, every time the analysis conditions are changed, it is necessary to recalculate the required time and change the start time setting.

  In particular, in a recent GC apparatus, a detector whose column outlet pressure is not an atmospheric pressure but a gas pressure corresponding to a set condition of the detector, such as a dielectric barrier discharge ionization detector (BID), is connected to the column outlet. (See Patent Document 2), a detector is connected to the column outlet via a backflush element (see Patent Document 3), and a plurality of analysis lines are provided in parallel (Patent Document 4). The system configuration is considerably complicated, for example, see Non-Patent Document 1). Therefore, in such a device, it is practically impossible for each user to set an appropriate start time according to the analysis conditions at that time, and the user does not have to calculate the time required to replace the gas in the column. Actually, a fairly long start time is set with a sufficient time margin.

  Therefore, although the column is actually filled with the carrier gas and the temperature of the column oven may be raised, the standby state is continued, which is a major cause of reducing the efficiency of GC analysis. In addition, since the carrier gas continues to flow even while waiting in vain, the amount of consumption of the carrier gas increases, which leads to an increase in the running cost of measurement.

JP 2013-44647 A Japanese Patent Laying-Open No. 2015-166699 JP 2010-20951 A JP 2007-3190 A

“Method Optimization System Triple Capillary Column GC”, [online], Shimadzu Corporation, [Search May 16, 2016], Internet <URL: http://www.an.shimadzu.co.jp/gc /tcc-gc.htm>

  The present invention has been made in view of the above problems, and the object of the present invention is to start the apparatus without burdening the user and waiting for a useless time even when the apparatus configuration is complicated. An object of the present invention is to provide a gas chromatograph capable of raising the temperature of a column oven after sufficiently replacing the residual gas in the column with a carrier gas.

The first aspect of the present invention made to solve the above problems includes a column, a column oven in which the column is built, a detector for detecting a component in the sample after passing through the column, A flow rate adjusting unit that adjusts the flow rate of the carrier gas supplied to the column, and a sample introduction unit that introduces the sample into the column by being placed on the flow of the carrier gas provided at the inlet of the column and adjusted by the flow rate adjusting unit A GC device comprising:
a) an information collecting unit for collecting at least information on column inlet pressure and outlet pressure, column length and inner diameter, carrier gas type, and column oven temperature;
b) Analyzing from the apparatus start-up operation, or at least the temperature adjustment by the column oven is stopped, or the column oven is maintained at a predetermined temperature and the supply of the carrier gas from the flow rate controller to the column is stopped. In the device return operation for returning to the steady standby state for the device, the column is based on the information collected by the information collection unit at any time before or before the start of the device start-up operation or the device return operation. A time calculation unit for calculating the time required for the gas in the column to be replaced by the carrier gas fed to
c) The time calculated by the time calculation unit or the time when a predetermined margin is expected from the time when the supply of the carrier gas from the flow rate adjustment unit to the column is started during the device start-up operation or device return operation. An analysis control unit that waits until elapse of time and permits temperature control with a temperature increase of the column oven,
It is characterized by having.

A second aspect of the present invention made to solve the above-described problems includes a column, a column oven in which the column is installed, and a detector that detects components in the sample after passing through the column. A flow rate adjusting unit that adjusts the flow rate of the carrier gas supplied to the column, and a sample introduction unit that introduces a sample into the column by being placed on the carrier gas flow provided at the inlet of the column and adjusted by the flow rate adjusting unit A GC device comprising:
a) an information collecting unit for collecting at least information on the outlet pressure of the column, the length and inner diameter of the column, the type of carrier gas, and the column oven temperature;
b) The analysis is started from the state where the apparatus is started or at least the temperature control by the column oven is stopped or the column oven is maintained at a predetermined temperature and the supply of the carrier gas from the flow rate controller to the column is stopped. In response to the device return operation for returning to the steady standby state, the information is collected in the column based on the information collected by the information collecting unit at the start time of the device start-up operation or the device return operation or any time before that. An inlet pressure calculation unit for calculating a column inlet pressure capable of realizing an average linear velocity of the carrier gas so that a time required for replacing the gas in the column with the carrier gas to be fed falls within the target value;
c) At the time of starting the apparatus or returning the apparatus, the target gas from the time when the supply of the carrier gas to the column from the flow rate adjusting unit is started under the setting of the column inlet pressure calculated by the inlet pressure calculating unit. An analysis control unit that waits until a time when a value or a predetermined allowance elapses and permits temperature control with a temperature increase of the column oven;
It is characterized by having.

Furthermore, in order to solve the above-mentioned problems, a third aspect of the present invention includes a column, a column oven in which the column is built, and a detector for detecting a component in the sample after passing through the column. A flow rate adjusting unit that adjusts the flow rate of the carrier gas supplied to the column, and a sample that is provided at the inlet of the column and that is introduced into the column by being placed on the carrier gas flow adjusted by the flow rate adjusting unit A GC device comprising: an introduction unit;
a) an information collecting unit that collects information on at least the inlet and outlet pressures of the column, the length and inner diameter of the column, and the type of carrier gas;
b) a temperature detector for detecting the temperature inside the column oven or the surrounding temperature;
c) Device start-up or device return operation for returning from a state where temperature control by at least the column oven is stopped and supply of carrier gas from the flow rate control unit to the column is stopped to a steady standby state for analysis execution In this case, after starting the supply of the carrier gas from the flow rate adjusting unit to the column, based on the information collected by the information collecting unit and the temperature repeatedly detected over time by the temperature detecting unit A replaced information calculation unit that calculates the length of the column that has already been replaced by the carrier gas by the carrier gas supplied to the column;
d) Determine whether the gas in the column has been sufficiently replaced based on the length of the column calculated by the replaced information calculation unit, and after determining that the gas has been sufficiently replaced, increase the temperature of the column oven An analysis control unit that permits temperature control with
It is characterized by having.

  In the present invention, the above-mentioned “at least temperature adjustment by the column oven is stopped or the column oven is maintained at a predetermined temperature and the supply of the carrier gas from the flow rate adjusting unit to the column is stopped. The “device return operation for returning to the steady standby state” is, for example, an operation in the “INJ maintenance” function or a function corresponding thereto.

  In general, the inner diameter and length of the column used, the inlet pressure and outlet pressure of the column, the type of carrier gas, the temperature of the column oven (constant temperature, temperature rising program, etc.), etc. are the analytical conditions prior to analysis. Set by the user and stored inside the device. Therefore, in the GC device according to the present invention, the information collection unit can extract necessary information from the information stored in this manner. However, the column outlet pressure depends on the type of detector used and the like, and may be atmospheric pressure depending on the detector. Further, when the detector is of a type in which other gas is supplied into the detection cell, such as the above-mentioned BID, the column outlet pressure is a set value for controlling the flow rate of the other gas in such a detector. Is obtained. Further, the column inlet pressure and the outlet pressure are not set values of analysis conditions, but may be measured values by a pressure sensor when gas is actually supplied based on the set values.

  In the GC device according to the first aspect of the present invention, for example, when a device activation or device return operation is instructed by a user, the time calculation unit applies the information collected by the information collection unit to a predetermined calculation formula. The average linear velocity of the carrier gas fed to the column from the flow rate controller is calculated. Further, a gas replacement time required for replacing the gas in the column with the carrier gas under the average linear velocity is calculated. Here, it is assumed that the column oven temperature is constant, but the column oven is kept at a constant temperature (a temperature that does not cause deterioration of the liquid phase due to residual gas) until the gas in the column is replaced. The temperature may be adjusted, or the temperature may not be controlled at all (the heater is not energized). In the latter case, for example, the temperature detected by the temperature sensor that monitors the temperature inside the column oven or the temperature sensor that monitors the temperature inside the room in which the apparatus is installed may be regarded as the column oven temperature.

  The analysis control unit starts counting by a timer from the time when the supply of the carrier gas to the column from the flow rate adjusting unit is started, and whether or not the time has reached the time required for the gas replacement or the time for which a predetermined margin is expected. If the time reaches that time, temperature control with temperature rise of the column oven is permitted. As a result, until the residual gas in the column is completely replaced with the carrier gas, the temperature of the column oven is maintained at least at a temperature that does not cause deterioration of the liquid phase due to the residual gas, and the residual gas in the column becomes the carrier gas. The column oven temperature is set to the initial temperature for analysis without significant delay after complete replacement.

  In addition, when the time calculation unit calculates the gas replacement time using the analysis conditions set in advance by the user, it is not after an instruction to start or return the apparatus but at an appropriate time before that. The time required for gas replacement can also be calculated.

  In the first aspect of the GC apparatus according to the present invention, preferably, when at least a plurality of the columns are provided in parallel and the plurality of columns are used for analysis, the time calculation unit is configured to detect the gas in the column. It is preferable that the time required for replacing the column oven is calculated for each column, and the analysis control unit determines the timing for permitting temperature control of the column oven based on the longest time among the times for each column.

  When a plurality of columns arranged in parallel are used at the same time, the gas replacement time varies depending on the inner diameter and length of the column, the difference between the column inlet pressure and the outlet pressure, and the like. On the other hand, according to the above preferred configuration, even when a plurality of columns are used at the same time, the temperature of the column oven rises after the residual gas in the column having the longest gas replacement time is reliably replaced with the carrier gas. Therefore, deterioration of the liquid phase of the column can be reliably prevented.

In the first aspect of the GC device according to the present invention,
The apparatus further includes an input setting unit in which a user inputs and sets a waiting time from the carrier gas supply start time to the column oven temperature control start time,
The analysis control unit selects either the time calculated by the time calculation unit or a time allowing a predetermined margin and the standby time set by the input setting unit, and based on the selected time It is good also as a structure which determines the timing which permits the temperature control of the said column oven.

  In other words, according to this configuration, it is possible to switch between the automatically determined time and the time set by the user's own judgment to determine the timing for permitting the temperature control of the column oven. it can. Thereby, for example, not only to replace the residual gas in the column with the carrier gas, but also to clean the inside of the column (removal of contaminants) by keeping the carrier gas flowing for a certain period of time, The carrier gas can continue to flow for a considerably longer time than is automatically determined.

  In the GC apparatus according to the first aspect of the present invention, the gas inlet pressure is determined and the average linear velocity of the carrier gas is calculated by a predetermined calculation formula. However, in the GC apparatus according to the second aspect of the present invention, On the contrary, a target value is set for the time required for gas replacement, and the average linear velocity is adjusted so as to achieve the target value. Therefore, the inlet pressure calculation unit calculates, for example, a gas inlet pressure for obtaining an average linear velocity such that the required gas replacement time is within the target value by using an expression obtained by modifying the predetermined calculation expression. Then, the analysis control unit sets the gas inlet pressure to the value obtained by this calculation, waits for the target value of the required time for gas replacement or a predetermined allowance from the carrier gas supply start time, and waits for the column. Allow the oven temperature to rise. In the first aspect, for example, if the type of the carrier gas is changed, the gas replacement waiting time changes. However, according to the second aspect, even if the type of the carrier gas is changed or the column is replaced. The waiting time for gas replacement is always constant.

  In the GC apparatus according to the first aspect of the present invention, for example, the timing for permitting the temperature control of the column oven is determined based on the required gas replacement time determined at the time of starting the apparatus or before that time. In contrast, in the GC apparatus according to the third aspect of the present invention, the gas replacement time is not determined in advance, and the replaced information calculation unit calculates the average linear velocity of the carrier gas that is calculated every moment based on the actually measured temperature. From this, it is estimated which part of the total length of the column has been replaced with gas. Then, the analysis control unit permits the temperature control of the column oven after the time point when it is estimated that the residual gas is replaced with the carrier gas. Therefore, for example, even when the column oven temperature changes due to a large change in the ambient temperature, the temperature of the column oven can be increased after the residual gas in the column is reliably replaced with the carrier gas. it can. Further, the temperature of the column oven can be increased without delay from the time when the residual gas in the column is replaced with the carrier gas.

  According to the GC device of the present invention, even if the user himself / herself does not perform complicated calculations, or even when the device configuration is complicated and the calculation by the user is substantially impossible, the device activation When the apparatus is restored, the residual temperature in the column is sufficiently replaced with the carrier gas, and the temperature of the column oven can be raised to the initial analysis temperature without significant delay. Thereby, it is possible to reliably prevent deterioration of the column due to raising the temperature of the column in a state where air or the like remains in the column. At the same time, it is possible to reduce the time loss caused by waiting without increasing the temperature of the column despite the replacement of the residual gas in the column with the carrier gas, thereby improving the efficiency of analysis. At the same time, it is possible to prevent the carrier gas from being wasted.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic block diagram of GC apparatus which is 1st Example of this invention. The figure which shows the time change of the carrier gas average linear velocity at the time of apparatus starting in the GC apparatus of 1st Example. The control flowchart at the time of apparatus starting in the GC apparatus of 1st Example. The schematic block diagram of GC apparatus which is 2nd Example of this invention. The control flowchart at the time of apparatus starting in the GC apparatus of 2nd Example. The schematic block diagram of GC apparatus which is 3rd Example of this invention. The figure which shows an example of the time change of the carrier gas average linear velocity at the time of apparatus starting in the GC apparatus of 3rd Example. The control flowchart at the time of apparatus starting in the GC apparatus of 3rd Example. The figure which shows the structural example of GC apparatus in case a sample vaporization chamber is common and there are multiple columns and detectors. The figure which shows the structural example of GC apparatus in case a detector is common and there are multiple sample vaporization chambers and columns.

[First embodiment]
A GC apparatus according to a first embodiment of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a schematic configuration diagram of the GC apparatus according to the first embodiment.
This GC apparatus includes a column 7 accommodated in a column oven 5, a sample vaporization chamber 1 provided at the inlet end of the column 7, a detector 8 provided at the outlet end of the column 7, and the sample vaporization chamber 1. A carrier gas flow path 2 provided with a flow controller (FC) 3 in the middle of supplying carrier gas, an injector 4 for injecting a sample into the sample vaporizing chamber 1, and a heater 6 provided in the column oven 5 A flow control unit 13 for controlling the flow controller 3, a temperature control unit 14 for controlling the temperature adjustment by the heater 6, a control unit 10 for controlling these units, and an input unit 11 for the user to input analysis conditions and the like And a display unit 12 for confirming information input by the user and displaying an analysis result. In FIG. 1, some components that are not related to the characteristic operation of the GC device according to the present embodiment, such as a signal processing unit that processes a signal detected by the detector 8, are omitted.

  The type of the detector 8 is not particularly limited, and various detectors commonly used as detectors for GC devices, such as a flame ionization detector, a flame photometric detector, a flame thermonic detector, An electron capture detector, a thermal conductivity detector, a dielectric barrier discharge ionization detector, a mass spectrometer, or the like can be selectively used. Further, as a sample introduction part for introducing a sample into the column 7, a head space sampler or the like may be used instead of the sample vaporizing chamber 1.

  In addition, as is the case with many recent GC devices, at least a part of the control unit 10 realizes its function by executing dedicated control software installed in a personal computer in advance on the computer. Can be.

  A characteristic control operation at the time of starting the apparatus in the GC apparatus of this embodiment will be described with reference to FIGS. FIG. 3 is a control flowchart at the time of starting the apparatus, and FIG. 2 is a diagram showing a change with time in the average linear velocity of the carrier gas at the time of starting the apparatus. Here, the state before “device activation” means that the main power supply of the device itself is on and the control unit 10 can perform operations such as setting conditions for analysis described later, while the analysis unit main body Is a state where the operation has stopped.

First, the user sets various analysis conditions from the input unit 11 (step S1). That is, the analysis condition setting processing unit 101 displays a predetermined analysis condition setting screen on the screen of the display unit 12, and the user performs various selection conditions and numerical values by the input unit 11, so that various analysis conditions can be set. Set. The analysis conditions here include the inner diameter and length of the column 7 to be used, the type of carrier gas to be used, the column inlet pressure, the column outlet pressure, and the column oven temperature condition (constant temperature / temperature increase selection and temperature program). The inner diameter of the column 7 is desirably an actual inner diameter obtained by subtracting the film thickness of the liquid phase applied to the inner wall of the column 7 from the inner diameter of the column 7 itself. The analysis condition setting processing unit 101 stores the input analysis conditions in the analysis condition storage unit 102.
When using analysis conditions already stored in the analysis condition storage unit 102, it is only necessary to give an instruction to that effect.

  Further, the column outlet pressure depends on the type of the detector 8 to be used. For example, in some detectors, the column outlet pressure becomes atmospheric pressure, and in some cases, the gas supplied to the detection cell of the detector (for example, Some are determined by the supply pressure of makeup gas or plasma gas. Therefore, the type of the detector 8 is set instead of the column outlet pressure as the analysis condition, and the column outlet pressure is automatically set to the atmospheric pressure or the column pressure is automatically set according to the set type of the detector 8. The outlet pressure may be set to the gas supply pressure to the detection cell of the detector. Further, when the detector 8 is a mass spectrometer, the outlet end of the column 7 is in a vacuum atmosphere, so the column outlet pressure is set to a gas pressure in a predetermined vacuum atmosphere, or a vacuum atmosphere as described later. It may be set to an actual measurement value of a pressure sensor that detects the gas pressure inside.

Next, when the user instructs to start the apparatus from the input unit 11 (step S2), the start time calculation unit 103 receives the instruction and calculates the start time ts as follows (step S3).
In general, the average linear velocity U of the carrier gas flowing through the column in the GC apparatus can be calculated by the following equation (1).
U = 0.234375 × (K / μ) × [{(Pin + Patm) ² − (Pout + Patm) ² } ² / {(Pin + Patm) ³ − (Pout + Patm) ³ }] (1)
Here, U: average linear velocity [cm / s], K: (D × 100) ² / L, D: column inner diameter [mm], L: column length [m], μ: carrier gas viscosity Coefficient [10 ⁻⁶ Pa · s], Pin: Column inlet pressure [kPa], Pout: Column outlet pressure [kPa], Patm: Atmospheric pressure [kPa]. The viscosity coefficient μ of the carrier gas is determined by the type and temperature (column oven temperature) of the carrier gas.

  As described above, the analysis condition information storage unit 102 stores the inner diameter D and length L of the column 7, the column inlet pressure Pin, the column outlet pressure Pout, and the type of carrier gas as analysis conditions. Further, the atmospheric pressure Patm is usually the standard atmospheric pressure 101.325 [kPa], but an actual measured value of the atmospheric pressure detected by the attached atmospheric pressure sensor may be used. When the heater 6 is not energized and the temperature is not controlled, the column oven temperature is generally standard at least within a time range (a few minutes to a few tens of minutes at least) enough to fill the column 7 with a carrier gas. It can be regarded as constant at a typical room temperature (for example, about 20 to 25 ° C.) or an initial detection temperature of a temperature sensor (not shown) attached to the heater 6. Therefore, the start time calculation unit 103 reads necessary information from the analysis condition information storage unit 102, collects necessary information from an attached sensor such as a temperature sensor as necessary, and applies them to the equation (1). The average linear velocity U is calculated. In this case, since it is assumed that the analysis conditions including the column oven temperature do not change, the average linear velocity is also constant as shown in FIG.

  The start time calculation unit 103 calculates a required gas replacement time t1 required to replace all residual gases existing in the column 7 with the carrier gas from the average linear velocity U and the column length L. The gas replacement time t1 may be used as it is as the start time ts. However, it is preferable to allow for an appropriate margin in consideration of calculation errors, variations in parameter values of analysis conditions, and the like. For example, a start time ts may be set to 1.05 × ta with a margin of 5%.

  In parallel with the calculation of the start time ts, the analysis control unit 104 controls the carrier gas flow rate in the flow controller 3 via the flow rate control unit 13 so that the gas inlet pressure becomes a set target value, and a constant flow rate is obtained. Thus, the supply of the carrier gas is started (step S4). And the analysis control part 104 starts the time measurement by an internal timer with the start of supply of carrier gas (step S5). Thereafter, it is repeatedly determined whether or not the internal timer has reached the start time ts (step S6).

  The gas remaining in the column 7 is pushed out by the carrier gas sent to the column 7 through the sample vaporizing chamber 1, and the gas in the column 7 is gradually replaced with the carrier gas. Since the average linear velocity of the carrier gas is kept constant as shown in FIG. 2, the rate at which the residual gas is replaced with the carrier gas is also constant. When the time measured by the internal timer reaches the start time ts, the analysis control unit 104 supplies a heating current to the heater 6 via the temperature control unit 14 and the temperature of the column oven 5 according to the set constant temperature or temperature rise conditions. Control is started (step S7).

When the internal timer reaches the start time ts, the gas in the column 7 is completely replaced with the carrier gas. Therefore, even if the temperature of the column oven 5 is rapidly increased in step S7, it is possible to prevent deterioration of the liquid phase of the column 7 due to oxygen remaining in the column 7. When the temperature of the column oven 5 reaches, for example, a predetermined initial temperature, the analysis control unit 104 determines that preparation for analysis is complete (Yes in step S8), and enters a standby state for receiving an actual analysis start instruction. Transition is made (step S9). Alternatively, when the automatic GC analysis start is designated, the GC analysis is started immediately.
As described above, in the GC apparatus of this embodiment, the temperature of the column oven 5 can be raised to the initial analysis temperature without delay after the residual gas in the column 7 is replaced with the carrier gas.

  In the above embodiment, the heater 6 is not energized until the residual gas in the column 7 is replaced with the carrier gas, but the liquid phase is not oxidized by the atmosphere (oxygen) remaining in the column 7. If the temperature is low, the temperature of the column oven 5 may be adjusted during this period. For example, the column oven 5 may be adjusted to a constant temperature of 50 ° C. simultaneously with the start of the apparatus, and the start time ts may be calculated assuming that the column oven temperature is 50 ° C. By adjusting the temperature of the column oven 5 in this manner, the actual average linear velocity of the carrier gas becomes substantially constant, so that the error between the start time calculated by calculation and the actually required start time is reduced.

  Further, although the description of the above embodiment is the control at the time of starting the apparatus, the carrier gas is supplied to the column 7 and the sample, for example, the temperature of the detector 8 is adjusted as in the “INJ maintenance” function described above. Other than the state in which the temperature control of the vaporization chamber 1 and the column oven 5 is stopped, the other components can also be used for control when the apparatus returns from the operating state to the state where analysis is possible. .

In the above embodiment, the column inlet pressure and the outlet pressure for calculating the average linear velocity are basically the values set as one of the analysis conditions, but are actually measured by the attached pressure sensor. The pressure value may be used for the calculation.
In addition, the detector 8 may not be directly connected to the outlet end of the column 7 but may be connected via the backflush element. In this case, the column outlet pressure is connected to the backflush element. The control pressure of the flow controller may be used. In the configuration shown in FIG. 1, there is only one analysis line including the sample vaporizing chamber 1, the column 7, and the detector 8, but there is a GC apparatus in which a plurality of analysis lines are arranged in parallel. How to determine the start time ts in that case will be described later.

  In the above embodiment, the timing at which the temperature control of the column oven 5 is started is automatically determined based on the start time ts. However, in some cases, after the carrier gas continues to flow through the column 7 for a longer time, the column Sometimes it is desired to start the temperature control of the oven 5. For example, it is a case where it is desired to remove dirt adhering to the inside of the column 7 by flowing a carrier gas. Therefore, in the GC apparatus of the above embodiment, it is possible to select which one of the start time input in advance by the user and the start time automatically calculated as described above is used, and the start of whichever is selected is selected. You may make it determine the timing which starts the temperature control of the column oven 5 using time.

Further, instead of selecting the start time in advance, for example, after the start time ts is calculated in step S3, the value is displayed on the screen of the display unit 12, and the user who has confirmed this is actually used for control. The start time to be newly entered may be re-inputted, or the displayed start time may be appropriately corrected.
Further, the remaining time until the temperature control of the column oven 5 is started is displayed on the screen of the display unit 12, and the user performs a predetermined operation before it becomes zero, so that the remaining time is appropriately set. You may make it extend only time (for example, 1 minute, 3 minutes, etc.).

[Second Embodiment]
Next, a GC apparatus according to a second embodiment of the present invention will be described with reference to the accompanying drawings. FIG. 4 is a schematic configuration diagram of the GC apparatus according to the second embodiment, and FIG. 5 is a control flowchart when the apparatus is activated. In FIG. 4, the same components as those in FIG. Further, in FIG. 5, steps S11, S12, S18, and S19 are steps for performing exactly the same processing as steps S1, S2, S8, and S9 in FIG.

As shown in FIG. 4, the GC device of this embodiment includes a standby column inlet pressure calculation unit 105 instead of the start time calculation unit 103 provided in the GC device of the first embodiment.
A characteristic control operation at the time of starting the apparatus in the GC apparatus of this embodiment will be described with reference to FIG. When the apparatus is instructed to start the apparatus, the standby column inlet pressure calculation unit 105 starts the start time (the time required for gas replacement or the time obtained by adding a margin to the start time calculated from the average linear velocity of the carrier gas obtained by the equation (1). ) Is a column inlet pressure for realizing an average linear velocity that falls within a preset target value ta (the column inlet pressure obtained here is different from the column inlet pressure set by the user. (Referred to as "inlet pressure") (step S13). It is clear that this is a reverse calculation of the start time ts in the GC apparatus of the first embodiment.

  When the standby column inlet pressure is obtained, the analysis control unit 104 uses the flow controller 3 via the flow rate control unit 13 so that the actual column inlet pressure is not the column inlet pressure set by the user but the standby column inlet pressure. The carrier gas flow rate is controlled, and the supply of the carrier gas is started at a constant flow rate (step S14). Then, the time measurement by the internal timer is started, and it is repeatedly determined whether or not the time measurement by the internal timer has reached the target value ta of the start time (step S16). If the time has reached the target value ta, the analysis control unit 104 changes the target value so that the actual column inlet pressure becomes the column inlet pressure set by the user, and the flow controller via the flow rate control unit 13. 3 is controlled, and a heating current is supplied to the heater 6 via the temperature control unit 14, and temperature control of the column oven 5 is started according to the set constant temperature or temperature rising conditions (step S17).

  In the GC apparatus of the second embodiment, the start time is constant even if the analysis conditions other than the column inlet pressure, such as the type of carrier gas, change. For this reason, it is convenient for the user in that the waiting time until the start of temperature control is always the same.

[Third embodiment]
Next, a GC apparatus according to a third embodiment of the present invention will be described with reference to the accompanying drawings. FIG. 6 is a schematic configuration diagram of the GC device according to the third embodiment, FIG. 7 is a diagram showing an example of the time change of the carrier gas average linear velocity when the device is started, and FIG. 8 is a control flowchart when the device is started. In FIG. 6, the same components as those in FIG. Further, in FIG. 8, steps S21, S22, S23, S29, and S30 are steps for performing exactly the same processing as steps S1, S2, S4, S8, and S9 in FIG.

  In the GC apparatus of the third embodiment, it is assumed that the temperature is not adjusted in the column oven 5 until the gas in the column 7 is replaced with the carrier gas (of course, the temperature adjustment is performed in the column oven 5). However, if the temperature is controlled, it is less necessary to adopt the configuration of the GC device of the third embodiment). When temperature adjustment is not performed in the column oven 5, the temperature in the column oven 5 is affected by the environmental temperature (room temperature) in which the GC device is installed. Therefore, when the environmental temperature varies, the temperature in the column oven 5 may vary. Since the average linear velocity of the carrier gas changes when the temperature in the column oven 5 varies while the carrier gas is being fed to replace the gas in the column 7, the average linear velocity of the carrier gas is assumed to be constant. If the start time ts is calculated, a deviation may occur.

  Normally, it is unlikely that the environmental temperature will fluctuate so much in about 10 minutes, so in practice the deviation of the above start time ts is not so great, but it is ensured that the wasteful waiting time is eliminated as much as possible. In the case where it is desired to replace the gas in 7, the configuration of the third embodiment is preferable. As shown in FIG. 6, in the GC apparatus of the third embodiment, instead of the start time calculation section 103 in the GC apparatus of the first embodiment, an average linear velocity calculation section 106, a replaced column length calculation section 107, and a replacement An end determination unit 108 is provided.

A characteristic control operation at the time of starting the apparatus in the GC apparatus of this embodiment will be described with reference to FIGS.
When the user gives an instruction to start the apparatus, the analysis control unit 104 controls the carrier gas flow rate in the flow controller 3 through the flow rate control unit 13 so that the gas inlet pressure becomes the set target value, and a constant flow rate is obtained. Thus, the supply of the carrier gas is started (step S23). Next, the average linear velocity calculation unit 106 detects the latest temperature by a temperature sensor (not shown) for detecting the temperature in the column oven 5 (step S24), and stores it in the temperature and analysis condition information storage unit 102. Using the information other than the column oven temperature, that is, the column inlet pressure, the outlet pressure, the inner diameter and length of the column 7 and the type of carrier gas, the latest value of the average linear velocity U is calculated based on the equation (1). Calculate (step S25). When the column oven temperature is different, the average linear velocity U changes because the viscosity count μ in the equation (1) is different.

  The replaced column length calculation unit 107 calculates the column that has been replaced with the carrier gas in the entire length L of the column 7 from the latest value of the calculated average linear velocity U and the elapsed time from the start of carrier gas delivery. The length La is calculated (step S26). The replacement end determination unit 108 determines whether or not the replacement of the gas in the column 7 has ended by determining whether or not the calculated column length La exceeds the total length of the column 7 (step S27). If it is determined that the gas replacement has not yet been completed, the process returns from step S27 to S24, and the processes of steps S24 to S27 are repeated.

  When the temperature in the column oven 5 changes with time, for example, the average linear velocity of the carrier gas changes as shown in FIG. Since the column length La replaced with the carrier gas corresponds to the area of the region surrounded by the oblique lines in FIG. 7, the calculation in step S26 is substantially the calculation of this area value. When it is determined in step S27 that the replacement of the gas in the column 7 has been completed, the analysis control unit 104 supplies a heating current to the heater 6 via the temperature control unit 14, and according to the set constant temperature or temperature increase conditions. The temperature control of the column oven 5 is started (step S28). As in the above embodiment, in step S27, it is assumed that the replacement is completed when a predetermined margin has elapsed from the time when it is determined that the calculated column length La exceeds the total length of the column 7. You may judge. Alternatively, the result is the same even if the total length of the column 7 to be compared with the replaced column length La is made longer with a margin in mind.

  In the GC apparatus of the third embodiment, while monitoring the actual temperature of the column oven 5, the length of the portion of the column 7 that is actually replaced with the carrier gas is obtained by calculation based on the temperature. The temperature of the column oven 5 is allowed to rise when the actual length of the column 7 is exceeded or a little later than that. Therefore, the start time is not determined at the time of starting the apparatus or starting the apparatus return operation, and there is some inconvenience in that it is unclear when the start time ends, but the temperature of the column oven 5 is not adjusted. In addition, there is an advantage that the temperature of the column oven 5 can be raised with almost no wasteful time after the gas in the column 7 is surely replaced with the carrier gas.

In the GC apparatus of the above embodiment, there is only one combination of the analysis line, that is, the sample vaporizing chamber 1, the column 7, and the detector 8. However, depending on the configuration of the apparatus, a plurality of analysis lines are provided in parallel. There is.
FIG. 9 shows an example of a configuration when the sample vaporizing chamber 1 is common and there are a plurality of combinations of the columns 7a to 7b and the detectors 8a to 8c (see Non-Patent Document 1). In this case, since the carrier gas supplied to the sample vaporizing chamber 1 branches and flows to the three columns 7a to 7c, the average linear velocity of the carrier gas flowing to each of the columns 7a to 7c and the respective columns 7a to 7c The start time varies depending on the length. Therefore, when the GC apparatus of the first embodiment has the apparatus configuration shown in FIG. 9, the start time is calculated for each of the columns 7 a to 7 c, and the longest start time among them is adopted to adopt the column oven 5. The timing for starting the temperature control may be determined.

  Further, even if the column inlet pressure changes, the magnitude relationship of the start times in the plurality of columns does not change. Therefore, when the GC apparatus of the second embodiment has the apparatus configuration shown in FIG. 9, first, the start time is temporarily calculated for each of the plurality of columns 7a to 7c to find the column with the longest start time. The standby column inlet pressure may be determined so that the start time for the column falls below the target value ta. Also in the GC apparatus of the third embodiment having the apparatus configuration shown in FIG. 9, first, a start time is temporarily calculated for each of the plurality of columns 7a to 7c to find a column having the longest start time. In addition, it is only necessary to determine the end timing of the gas replacement with the procedure described with reference to FIG. 8 only for that column.

  In the configuration shown in FIG. 9, the sample vaporization chamber is common to a plurality of columns. However, even when the sample vaporization chamber is provided independently for each column, the sample vaporization chamber, the column, and the detector to be used simultaneously. If the combinations are known, the start time can be calculated for each combination. Therefore, the user specifies the combination of sample vaporization chamber, column, and detector to be used simultaneously as one of the analysis conditions, and when multiple combinations are specified, find the longest start time in the same way as above, Based on this, the timing for starting the temperature control of the column oven 5 may be determined.

  FIG. 10 shows an example of a configuration in the case where the detector 80 which is a mass spectrometer, for example, is common and there are a plurality of combinations of the sample vaporization chambers 1a to 1b (also flow controllers 3a to 3b) and the columns 7a to 7b. (See Patent Document 4). In this case, since the flow controllers 3a to 3b are provided independently for the columns 7a to 7b, the two columns 7a to 7b may be used at the same time, or only one of them may be selectively used. Sometimes used. Therefore, which column 7a to 7b is used is set in advance as one of the analysis conditions, and when only one column 7a to 7b is used according to the setting, the column 7a to 7 to be used is used. What is necessary is just to calculate the start time corresponding to 7b. When two (or more) columns 7a-7b are used at the same time, the start time for each of the columns 7a-7b is calculated and the longest start time is adopted. The timing for starting the temperature control 5 may be determined.

  Moreover, since the said Example is an example of this invention, even if it corrects, changes, and adds suitably in the range of the meaning of this invention, it is clear that it is included by the claim of this application.

DESCRIPTION OF SYMBOLS 1, 1a, 1b ... Sample vaporization chamber 2, 2a, 2b ... Carrier gas flow path 3, 3a, 3b ... Flow controller 4 ... Injector 5 ... Column oven 6 ... Heater 7, 7a, 7b, 7c ... Column 8, 8a, 8b, 8c, 80 ... detector 10 ... control unit 101 ... analysis condition setting processing unit 102 ... analysis condition information storage unit 103 ... start time calculation unit 104 ... analysis control unit 105 ... standby column inlet pressure calculation unit 106 ... average line Speed calculation unit 107 ... Replaced column length calculation unit 108 ... Replacement end determination unit 11 ... Input unit 12 ... Display unit 13 ... Flow rate control unit 14 ... Temperature control unit

Claims (5)

A column, a column oven in which the column is built, a detector for detecting a component in the sample after passing through the column, a flow rate adjusting unit for adjusting the flow rate of the carrier gas supplied to the column, A sample introduction unit for introducing a sample into the column by being placed on a carrier gas flow adjusted at the flow rate adjustment unit provided at an inlet of the column,
a) an information collecting unit for collecting at least information on column inlet pressure and outlet pressure, column length and inner diameter, carrier gas type, and column oven temperature;
b) Analyzing from the apparatus start-up operation, or at least the temperature adjustment by the column oven is stopped, or the column oven is maintained at a predetermined temperature and the supply of the carrier gas from the flow rate controller to the column is stopped. In the device return operation for returning to the steady standby state for the device, the column is based on the information collected by the information collection unit at any time before or before the start of the device start-up operation or the device return operation. A time calculation unit for calculating the time required for the gas in the column to be replaced by the carrier gas fed to
c) The time calculated by the time calculation unit or the time when a predetermined margin is expected from the time when the supply of the carrier gas from the flow rate adjustment unit to the column is started during the device start-up operation or device return operation. An analysis control unit that waits until elapse of time and permits temperature control with a temperature increase of the column oven,
A gas chromatograph apparatus comprising: The gas chromatograph apparatus according to claim 1,
When at least a plurality of the columns are provided in parallel and the plurality of columns are used for analysis, the time calculation unit calculates the time required for replacing the gas in the column for each column, and the analysis control The unit determines a timing for permitting temperature control of the column oven based on the longest time among the times for each column. A gas chromatograph apparatus according to claim 1 or 2,
The apparatus further includes an input setting unit in which a user inputs and sets a waiting time from the carrier gas supply start time to the column oven temperature control start time,
The analysis control unit selects either the time calculated by the time calculation unit or a time allowing a predetermined margin and the standby time set by the input setting unit, and based on the selected time A gas chromatograph apparatus for determining a timing for permitting temperature control of the column oven. A column, a column oven in which the column is built, a detector for detecting a component in the sample after passing through the column, a flow rate adjusting unit for adjusting the flow rate of the carrier gas supplied to the column, A sample introduction unit for introducing a sample into the column by being placed on a carrier gas flow adjusted at the flow rate adjustment unit provided at an inlet of the column,
a) an information collecting unit for collecting at least information on the outlet pressure of the column, the length and inner diameter of the column, the type of carrier gas, and the column oven temperature;
b) The analysis is started from the state where the apparatus is started or at least the temperature control by the column oven is stopped or the column oven is maintained at a predetermined temperature and the supply of the carrier gas from the flow rate controller to the column is stopped. In response to the device return operation for returning to the steady standby state, the information is collected in the column based on the information collected by the information collecting unit at the start time of the device start-up operation or the device return operation or any time before that. An inlet pressure calculation unit for calculating a column inlet pressure capable of realizing an average linear velocity of the carrier gas so that a time required for replacing the gas in the column with the carrier gas to be fed falls within the target value;
c) At the time of starting the apparatus or returning the apparatus, the target gas from the time when the supply of the carrier gas to the column from the flow rate adjusting unit is started under the setting of the column inlet pressure calculated by the inlet pressure calculating unit. An analysis control unit that waits until a time when a value or a predetermined allowance elapses and permits temperature control with a temperature increase of the column oven;
A gas chromatograph apparatus comprising: A column, a column oven in which the column is built, a detector for detecting a component in the sample after passing through the column, a flow rate adjusting unit for adjusting the flow rate of the carrier gas supplied to the column, A sample introduction unit configured to introduce a sample into the column by being placed on a carrier gas flow adjusted at the flow rate adjustment unit provided at an inlet of the column,
a) an information collecting unit that collects information on at least the inlet and outlet pressures of the column, the length and inner diameter of the column, and the type of carrier gas;
b) a temperature detector for detecting the temperature inside the column oven or the surrounding temperature;
c) Device start-up or device return operation for returning from a state where temperature control by at least the column oven is stopped and supply of carrier gas from the flow rate control unit to the column is stopped to a steady standby state for analysis execution In this case, after starting the supply of the carrier gas from the flow rate adjusting unit to the column, based on the information collected by the information collecting unit and the temperature repeatedly detected over time by the temperature detecting unit A replaced information calculation unit that calculates the length of the column that has already been replaced by the carrier gas by the carrier gas supplied to the column;
d) Determine whether the gas in the column has been sufficiently replaced based on the length of the column calculated by the replaced information calculation unit, and after determining that the gas has been sufficiently replaced, increase the temperature of the column oven An analysis control unit that permits temperature control with
A gas chromatograph apparatus comprising:

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