JP2006226678A - Multi-dimensional gas chromatograph apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily perform the setting or confirmation of a switching program for automatically changing over the flow of a sample gas or the temperature program of a column oven. <P>SOLUTION: A chromatogram being the result of first monitoring analysis carried out only by a combination of a first column 4 and a first detector 8 is displayed on the screen of a display part 24 and, when an analyst sets the input of the switching program which shows a period wanting to carry out analysis more in detail by an input part 23 or the temperature program of column ovens 3 and 9 and a cooling trap 12, the set switching program and the set temperature program are displayed on the same time axis repeatedly. By this constitution, the propriety of input setting can be easily confirmed and work efficiency can be enhanced while a setting mistake can be also reduced. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a multi-dimensional gas chromatograph apparatus using a plurality of columns having different separation characteristics.

  In fields such as environmental analysis, petrochemical analysis, and fragrance analysis, it is necessary to separate each component in a sample with a complex composition containing many kinds of trace components and perform quantitative analysis with high sensitivity. In many cases, a tomographic (GC) apparatus cannot completely separate peaks of a plurality of components and cannot perform sufficient analysis. In such a case, a multi-dimensional gas chromatograph apparatus (hereinafter referred to as multi-dimensional GC) in which a plurality of columns having different separation characteristics are combined is very useful.

  For example, in the multi-dimensional GC described in Patent Document 1, the flow path after separating the sample components by flowing the sample gas vaporized in the sample vaporization chamber to the first column is the first detector side, the cooling trap, The sample gas branches into the second column and the second detector side, and usually the sample gas flowing out from the first column is introduced into the first detector to detect the sample component, and the first column cannot be sufficiently separated. The sample gas is selectively introduced into the second column through the cooling trap at the timing when the sample gas containing the target component passes, and after the separation characteristics are improved through the second column, the sample gas is introduced into the second detector. Perform detection.

  The cooling trap includes a cooling means and a heating means, and the components in the sample gas to be introduced are temporarily collected by cooling and condensing, and then rapidly heated to thereafter collect the components previously collected. Is vaporized in a short time and has a function of intensively feeding it to the second column. Therefore, by providing a cooling trap, it is possible to suppress the spread of the peak of the target component and increase the sensitivity.

  In order to switch the flow path of the sample gas in the multi-dimensional GC as described above, a flow path switching means having a structure called a Deans system is generally used as described in Patent Document 1.

  In the multi-dimensional GC as described above, a switching program for controlling the channel switching means as described above is created in advance in order to automatically switch channels during analysis. That is, first, as the first monitoring analysis of the sample to be analyzed, component separation is performed only in the first column, and a chromatogram is created based on the detection signal from the first detector. The analyst (operator) sees this chromatogram on the display screen, determines the portion where the peak of the target component to be analyzed in particular appears, and sets the sample injection time point to 0 so that the portion is included. A detailed analysis start point and end point are determined, and a numerical value is input from the keyboard to create a switching program for switching the flow path.

  On the other hand, the first and second columns are generally placed in different (sometimes the same) column ovens, and the column temperature is kept constant by the column oven during the analysis, or at an appropriate rate. The temperature is controlled at. When analyzing a sample containing a large number of components, a temperature rising analysis is generally performed. Thus, in order to determine the temperature change pattern of the column oven, the analyst also creates a temperature program prior to analysis. Furthermore, in the configuration including the cooling trap as described above, a temperature program for determining the temperature change pattern of the cooling trap is similarly created prior to the analysis.

  Therefore, when the second high-resolution analysis is performed after the first monitoring analysis is performed on the sample to be analyzed, a switching program that uses the time point of sample injection as a time reference, two (or one) column ovens It is necessary to set a temperature program for each and a temperature program for the cooling trap. Conventionally, these various programs are set by numerical input on the respective program creation screens. However, such a program needs to determine the timing in relation to each other, including the chromatogram that is the result of the monitoring analysis, which is troublesome for the analyst and often takes time to determine the conditions. In addition, misconfigurations due to analysts' misunderstandings and input errors tend to occur.

JP 11-248694 A

  The present invention has been made in view of these points. In the multi-dimensional GC, the setting operation of analysis conditions such as a switching program for switching channels and a temperature program for a column oven is simplified, and The main purpose is to reduce misconfiguration by making it easy to check.

In order to solve the above problems, a first invention includes a first column for separating components in an introduced sample, a second column having different separation characteristics from the first column, and the first column. A first detector for detecting the sample separated by the second column; a second detector for detecting the sample separated by the second column; and the sample passed through the first column for the first detector or the second A multi-dimensional gas comprising a flow path switching means for switching a flow path so as to selectively flow through one of the columns, and a common or independent column oven for controlling the temperature of the first and second columns. In the chromatograph device,
a) When a first analysis is performed on a predetermined sample in a state where the flow path is set so that the sample that has passed through the first column flows to the first detector by the flow path switching unit, the first analysis is performed. Chromatogram display means for displaying on the display screen a chromatogram created based on the detection signal obtained by the detector;
b) Prior to the second analysis of the predetermined sample, a flow path switching program for determining the switching control timing of the flow path switching means and a temperature program for determining the temperature change of the one or more column ovens are respectively operated by the operator. Operation means for setting,
c) Information associated with the passage of time based on the flow path switching program set by the operation means and one or more temperature programs is displayed in the same graph with the time axis aligned with the chromatogram displayed by the chromatogram display means. Display control means for displaying;
It is characterized by having.

Further, the second invention made to solve the above problems includes a first column for separating components in the introduced sample, a second column having different separation characteristics from the first column, and the first column. A first detector for detecting the sample separated by the column; a second detector for detecting the sample separated by the second column; and a flow to be cooled and heated provided in front of the second column. A cooling trap having a channel, channel switching means for switching the channel so that the sample that has passed through the first column flows selectively to either the first detector or the cooling trap, and the first and second In a multi-dimensional gas chromatograph apparatus comprising a common or independent column oven for temperature control of two columns,
a) When a first analysis is performed on a predetermined sample in a state where the flow path is set so that the sample that has passed through the first column flows to the first detector by the flow path switching unit, the first analysis is performed. Chromatogram display means for displaying on the display screen a chromatogram created based on the detection signal obtained by the detector;
b) a flow path switching program for determining the timing of switching control of the flow path switching means prior to the second analysis of the predetermined sample, a temperature program for determining a temperature change of the one or more column ovens, and Operating means for each operator to set a temperature program that determines the temperature change of the cooling trap,
c) Information with time passage based on the flow path switching program set by the operation means and a plurality of temperature programs is displayed in the same graph by aligning the time axis with the chromatogram displayed by the chromatogram display means. Display control means;
It is characterized by having.

  In the multi-dimensional GC according to the first and second inventions, the analyzer (operator) uses the operation means to change the flow path switching program or 1 to 2 prior to the second analysis (high resolution analysis) for a predetermined sample. When a plurality of temperature programs are set, the display control means is the same as the chromatogram acquired by the first analysis (monitoring analysis) with the passage switching program and information with the passage of time based on one to a plurality of temperature programs. Are displayed in the same graph with the time axis. Here, “information associated with the passage of time based on one or more temperature programs” is typically a line (graph) showing a pattern of temperature change accompanying time change. The “information with time passage based on the flow channel switching program” may be a line (graph) indicating a switching state with time change, but only indicates whether one of the two flow channels is selected. Therefore, for example, a display may be made to show only the time range in which one flow path is selected.

  As one aspect of the present invention, it is preferable that the information with the passage of time based on the flow path switching program and the temperature program, and the chromatogram are displayed with different display colors or different line types in an overlapping manner. Further, the same time axis may be displayed in a horizontal axis while being shifted so that the lines do not overlap in the vertical direction.

  By displaying on the display screen as described above, it becomes very easy to understand the mutual temporal relationship between the timing of channel switching by the channel switching means and the temperature change state of the column oven and the cooling trap. Therefore, the analyst can quickly determine whether or not the flow path switching program and the temperature program set by himself / herself are appropriate, and can make corrections if they are not appropriate. Thereby, setting of analysis conditions prior to the second high-resolution analysis can be performed efficiently. In addition, since it can be seen at a glance whether the set program is appropriate, it is possible to greatly reduce the probability of missing an incorrect setting due to misunderstanding of an analyst or an input error, and to perform a useless analysis due to an erroneous condition. Can be prevented.

  Hereinafter, an embodiment of a multi-dimensional GC according to the present invention will be described with reference to the drawings. FIG. 1 is an overall configuration diagram of a multi-dimensional GC according to this embodiment.

  In the multi-dimensional GC of the present embodiment, a first column (monitor column) 4 disposed in a first column oven 3 is provided in a sample vaporizing chamber 1 for vaporizing a liquid sample injected by an injector 2. Inlet end is connected. The outlet end of the first column 4 is connected to the flow path switching unit 5, and is branched into the first branch pipe 6 and the second branch pipe 7 by the flow path switching unit 5. The end of the first branch pipe 6 is connected to the first detector 8, and the end of the second branch pipe 7 is a second column (main column) 10 disposed in the second column oven 9 via the cooling trap 12. Connected to the inlet end of the. The outlet end of the second column 10 is connected to the second detector 11. The channel switching unit 5 is, for example, a Deans type channel switching unit, and the sample gas that has passed through the first column 4 is changed by switching the channel of the makeup gas in accordance with an instruction from the analysis control unit 21 described later. It flows alternatively to the first branch pipe 6 and the second branch pipe 7. At this time, the same makeup gas as the carrier gas flows through the other branch pipe. In addition, the thing of the structure which this applicant proposes in Japanese Patent Application No. 2004-250341 can also be utilized as the flow-path switching part 5. FIG.

  The first and second column ovens 3 and 9 include heaters 3a and 9a for controlling the temperature, respectively. The cooling trap 12 includes a cooling unit 12a that introduces liquid nitrogen and a heater 12b that rapidly heats the channel in order to cool the channel through which the sample gas flows to an extremely low temperature.

  Detection signals from the first detector 8 and the second detector 11 are both sent to the data processing unit 20, where a chromatogram is created by the data processing unit 20 and predetermined quantitative analysis and qualitative analysis processing are executed. The operation of the injector 2 and the flow path switching unit 5, the heating operation of the heaters 3a, 9a and 12b, and the cooling operation of the cooling unit 12a are controlled by the analysis control unit 21 under the general instruction of the central control unit 22. . The central control unit 22 also controls the data processing unit 20 and receives processing results such as chromatograms from the data processing unit 20 and displays them on the display unit 24. Connected to the central control unit 22 are an input unit 23 for performing various input settings including analysis conditions and a display unit 24 for displaying analysis conditions, analysis results, and the like. The entities of the central control unit 22 and the data processing unit 20 are general-purpose personal computers, and control / processing as described later is achieved by operating predetermined control / processing programs installed in the computer.

  An example of an operation during characteristic analysis in the multi-dimensional GC will be described with reference to FIGS. 2 to 6 are examples of displays output on the screen of the display unit 24 in the analysis execution process. For a sample to be analyzed, a chromatogram is first acquired by performing monitoring analysis by a combination of the first column 4 and the first detector 8 as the first analysis. That is, under the control of the analysis control unit 21, the carrier gas that has passed through the first column 4 is introduced into the first detector 8, and makeup gas is caused to flow through the second column 10. In this state, when a small amount of liquid sample is injected into the sample vaporizing chamber 1 by the injector 2, the vaporized sample rides on the carrier gas and is introduced into the first column 4, depending on its component while passing through the first column 4. The first detector 8 is reached in a time-separated state with a time difference. The data processing unit 20 creates a chromatogram based on the detection signal from the first detector 8.

  After the monitoring analysis is completed, when the operator performs a predetermined operation with the input unit 23 to instruct the setting of conditions for the high-resolution analysis that is the second analysis, the central control unit 22 that has received this instruction displays on the display unit 24 a diagram. A program setting screen 30 as shown in FIG. On the program setting screen 30, a chromatogram display unit 31 for displaying the chromatogram acquired in the previous monitoring analysis is arranged on the upper stage, and a temperature program display unit 32 for displaying the temperature program in a tabular form on the lower left side. However, a switching program display unit 33 for displaying a switching program for switching the flow path in a tabular form is arranged on the lower right side. 3 and 6 are examples of display on the chromatogram display unit 31, FIG. 4 is an example of display on the temperature program display unit 32, and FIG. 5 is a diagram showing an example of display on the switching program display unit 33. In the state where the program setting screen 30 is opened, the columns of the tables of the switching program and the temperature program are all blank, that is, no program is set, and what is displayed on the chromatogram display unit 31 is shown in FIG. It is a graph like this.

  The analyst finds the peak of the target component to be analyzed in detail by looking at the chromatogram as shown in FIG. 3 displayed on the chromatogram display unit 31, and switches the flow path suitable for analyzing the target component in detail. The numerical value of the switching program is input and set in the table of the switching program display unit 33. In addition, for each temperature program of the cooling trap 12, the first column oven (monitor GC oven in FIG. 4) 3, and the second column oven (main GC oven in FIG. 4) 9, the target components are analyzed in detail. An appropriate numerical value is input and set in each table of the temperature program display unit 32.

  In this example, the temperature program of the cooling trap 12 is held at a temperature of −150 ° C. for 3.7 minutes, and then raised to 250 ° C. at a rate of 500 ° C./min. Further, the temperature program of the first column oven 3 is held at a temperature of 40 ° C. for 0.5 minutes, and then raised to 200 ° C. at a rate of 50 ° C./min. Further, the temperature program of the second column oven 9 is held at a temperature of 50 ° C. for 4.5 minutes, and then raised to 180 ° C. at a rate of 30 ° C./min. Furthermore, the switching program is set so that the sample gas is allowed to flow to the second branch pipe 7 only during the time range of 3.2 minutes to 3.45 minutes, and the sample gas is allowed to flow to the first branch pipe 6 during other periods. It is what has been.

  When the analyst inputs a numerical value for each of these temperature programs and switching programs, the central control unit 22, as shown in FIG. 6, shows three broken lines indicating temperature changes according to the three types of temperature programs. Are superimposed on the chromatogram displayed on the chromatogram display unit 31 and displayed in different colors. Further, the time range in which the second branch pipe 7 (that is, the main column side) is selected by the switching program is displayed in the chromatogram graph as a hatched area. In FIG. 6, since colors cannot be expressed, they are indicated by different line types. Actually, the broken lines corresponding to the three temperature programs are red, orange, and green (or other colors may be used). The time range in which the main column side is selected is a blue diagonal line, and the chromatogram curve is black. Of course, when such different colors cannot be displayed, it may be displayed with different line types as in the above embodiment.

  The temperature program and the switching program set as described above are stored in a memory included in the central control unit 22. When the high resolution analysis is started on the sample to be analyzed in accordance with an instruction from the operator, the central control unit 22 determines the heaters 3a, 9a, 12b, the cooling unit 12a, and the cooling program according to the switching program and the temperature program stored in the memory. A command is issued to the analysis control unit 21 to operate the flow path switching unit 5, and under the control of the analysis control unit 21, the heaters 3a, 9a, 12b and the cooling unit 12a are heated or cooled as time passes. The flow path switching unit 5 switches the flow path as time elapses.

  That is, when the temperature program and the switching program are set as shown in FIGS. 4 and 5, first, the flow path switching unit 5 moves the carrier gas that has passed through the first column 4 to the first branch pipe 6 side. The makeup gas is allowed to flow to the second branch pipe 7 side. In this state, when a small amount of liquid sample is injected into the sample vaporizing chamber 1 by the injector 2, the vaporized sample rides on the carrier gas and is introduced into the first column 4, depending on its components while passing through the first column 4. The first detector 8 is reached in a time-separated state with a time difference.

  Initially, the temperature of the first column oven 3 is maintained at 40 ° C., but the temperature starts to rise at a rate of 50 ° C./min after 0.5 minutes have elapsed since the sample injection. When 3.2 minutes have passed since the sample injection, the flow path switching unit 5 causes the sample gas that has passed through the first column 4 to flow to the second branch pipe 7 side according to the switching program, and to the first branch pipe 6 side. Switch the flow path to allow makeup gas to flow. As a result, the sample gas containing the component separated in the first column 4 reaches the cooling trap 12. At this time, the cooling trap 12 is cooled to −150 ° C. by the cooling unit 12 a, so the component in the sample gas is Only the carrier gas that condenses and remains in the cooling trap 12 and maintains a gaseous state at this temperature is fed into the second column 10.

  Further, when 3.45 minutes have elapsed from the time of sample injection, the flow path switching unit 5 causes the sample gas that has passed through the first column 4 to flow again to the first branch pipe 6 side, and make-up to the second branch pipe 7 side. The flow path is returned to the original state so that the upgas flows. Accordingly, only the components in the sample gas that have reached the flow path switching unit 5 in the period of 0.25 minutes from 3.2 minutes to 3.45 minutes from the sample injection time are collected in the cooling trap 12. Thereafter, the cooling trap 12 is rapidly heated by the heater 12b from the point of 3.7 minutes, and the temperature rises to 250 ° C. in 0.8 minutes. The components collected in the cooling trap 12 are rapidly vaporized by this heating, and are concentrated into a second column 10 in a short time. The temperature of the second column oven 9 starts to rise at a rate of 30 ° C./minute after 4.5 minutes from the time of sample injection, and the sample introduced while passing through the second column 10 heated by this. The components are separated and detected by the second detector 11.

  The data processing unit 20 creates a chromatogram based on the detection signal from the second detector 11, and the central control unit 22 displays the chromatogram on the screen of the display unit 24. In this chromatogram, overlapping peaks that have not been sufficiently separated in the monitoring analysis are sufficiently separated in the second column 10, so that qualitative analysis and quantitative analysis of each component are possible.

  In the above embodiment, the three temperature programs and the switching program are displayed so as to be completely superimposed on the chromatogram. However, the lines may be displayed so as not to overlap each other on the same time axis. Further, the arrangement of the display units in the program setting screen 30 shown in FIG. 2 is not limited to this, and can be modified as appropriate.

  Moreover, the said Example is an example and it is clear that a change and correction can be made suitably in the range of the meaning of this invention.

1 is an overall configuration diagram of a multi-dimensional GC according to an embodiment of the present invention. The figure which shows an example of the display output on the screen of a display part in the multidimensional GC of a present Example. The figure which shows an example of the chromatogram display part (before program setting) which comprises a part of display in FIG. The figure which shows an example of the temperature program display part which comprises a part of display in FIG. The figure which shows an example of the switching program display part which comprises a part of display in FIG. The figure which shows an example of the chromatogram display part (after program setting) which comprises a part of display in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Sample vaporization chamber 2 ... Injector 3 ... 1st column oven 4 ... 1st column 5 ... Flow path switching part 6 ... 1st branch pipe 7 ... 2nd branch pipe 8 ... 1st detector 9 ... 2nd column oven 10 Second column 11 Second detector 12 Cooling trap 20 Data processing unit 21 Analysis control unit 22 Central control unit 23 Input unit 24 Display unit 30 Program setting screen 31 Chromatogram display unit 32 Temperature program display unit 33... Switching program display unit

Claims (3)

A first column that separates components in the introduced sample; a second column that has different separation characteristics from the first column; a first detector that detects the sample separated by the first column; A second detector for detecting a sample separated by the second column, and a flow path to selectively flow the sample that has passed through the first column to either the first detector or the second column. In a multidimensional gas chromatograph apparatus comprising a flow path switching means and a common or independent column oven for controlling the temperature of the first and second columns,
a) When a first analysis is performed on a predetermined sample in a state where the flow path is set so that the sample that has passed through the first column flows to the first detector by the flow path switching unit, the first analysis is performed. Chromatogram display means for displaying on the display screen a chromatogram created based on the detection signal obtained by the detector;
b) Prior to the second analysis of the predetermined sample, a flow path switching program for determining the switching control timing of the flow path switching means and a temperature program for determining the temperature change of the one or more column ovens are respectively operated by the operator. Operation means for setting,
c) Information associated with the passage of time based on the flow path switching program set by the operation means and one or more temperature programs is displayed in the same graph by combining the chromatogram displayed by the chromatogram display means and the time axis. Display control means for displaying;
A multi-dimensional gas chromatograph apparatus comprising: A first column that separates components in the introduced sample; a second column that has different separation characteristics from the first column; a first detector that detects the sample separated by the first column; A second detector for detecting a sample separated by the second column; a cooling trap provided in front of the second column and having a channel to be cooled and heated; and a sample that has passed through the first column. A flow path switching means for switching a flow path so as to selectively flow to either the first detector or the cooling trap, and a common or independent column oven for controlling the temperature of the first and second columns, In a multi-dimensional gas chromatograph apparatus comprising:
a) When a first analysis is performed on a predetermined sample in a state where the flow path is set so that the sample that has passed through the first column flows to the first detector by the flow path switching unit, the first analysis is performed. Chromatogram display means for displaying on the display screen a chromatogram created based on the detection signal obtained by the detector;
b) a flow path switching program for determining the timing of switching control of the flow path switching means, a temperature program for determining temperature changes of the one or more column ovens, prior to the second analysis of the predetermined sample; Operating means for each operator to set a temperature program that determines the temperature change of the cooling trap,
c) Information with time passage based on the flow path switching program set by the operation means and a plurality of temperature programs is displayed in the same graph by aligning the time axis with the chromatogram displayed by the chromatogram display means. Display control means;
A multi-dimensional gas chromatograph apparatus comprising: The information according to the passage of time based on the flow path switching program and the temperature program, and the chromatogram are displayed with different display colors or different line types, respectively, and are superimposed on each other. Multi-dimensional gas chromatograph equipment.

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