JP2011112603A - Multi-dimensional gas chromatography apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-dimensional gas chromatograph apparatus capable of accurately analyzing in a short time a sample passing through only a first column and a sample passing through both a first column and a second column using a mass spectrometer. Offer.
SOLUTION: A first column 5, a second column 6, a branch path 8, a mass spectrometer 7, and an outlet end of the first column 5 and an inlet end of the second column 6 are connected so as to circulate. Or the flow path changing connection mechanism 40 that can be switched so that the outlet end of the first column 5 and the inlet end of the branch path 8 are connected to flow, and the first oven 3. And a second dimensional gas chromatograph apparatus 1, wherein a main portion 6 b of the second column 6 is disposed inside the second oven 4, and is connected to the first column 5. 8 and the latter part of the second column 6 are arranged inside the first oven 3.
[Selection] Figure 1

Description

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

  In the fields of environmental analysis, petrochemical analysis, fragrance analysis, etc., it is necessary to separate each component in a sample having a complicated composition containing many kinds of trace components and perform quantitative analysis with high sensitivity. However, in a general gas chromatograph apparatus (hereinafter referred to as GC), a single column cannot be completely separated into a plurality of components, and sufficient quantitative analysis is often impossible. Therefore, in such a case, a multi-dimensional gas chromatograph apparatus (hereinafter referred to as multi-dimensional GC) in which a plurality of (for example, two) columns having different separation characteristics are combined is very useful.

Here, an example of a conventional multi-dimensional GC will be described (for example, see Patent Document 1). FIG. 5 is a schematic configuration diagram showing an example of a conventional multi-dimensional GC.
The multidimensional GC 101 includes a sample vaporizing chamber 2 into which a sample gas (for example, a sample containing an agrochemical component) and a carrier gas are introduced, a first column 5, a second column 106, a branch path 108, Flame ionization detector (FID) 50, MS detector (mass spectrometer) 7, flow path changing connection mechanism 40, first oven for controlling the temperature of first column 5 and the temperature of branch path 108 3, a second oven 4 that controls the temperature of the second column 106, a connecting portion 9 that connects the first oven 3 and the second oven 4, and a connection that connects the MS detector 7 and the second oven 4. Unit 15 and a computer (control unit) 110 that controls the entire multi-dimensional GC 101.

The first column 5 has a tubular shape with an inner diameter of 0.25 mm, for example, and has a length of 60 m. The first column 5 is coated with a stationary phase (for example, 5% by weight phenyldimethylpolysiloxane). When the sample gas passes through the first column 5, the distribution coefficient of each component Alternatively, each component moves at a speed corresponding to the solubility, and the components are sequentially discharged from the outlet end.
Further, the first column 5 is disposed in the first oven 3, and the temperature rise is controlled at an appropriate rate by the heater 3a of the first oven 3 during analysis. Also by this temperature increase control, when the sample gas passes through the first column 5, each component moves at a speed corresponding to the distribution coefficient or solubility of each component. For example, the computer 110 controls the temperature of the first column 5 to 50 ° C. (2 minutes) −20 ° C./minute−180° C.−5 ° C./minute−280° C. (30 minutes) by the heater 3a. Here, the time in parentheses is the time for holding at that temperature. (The same shall apply hereinafter)

The second column 106 is, for example, a tube having an inner diameter of 0.32 mm, and its length is 30 m. Then, a stationary phase (for example, trifluoropropylmethylpolysiloxane or the like) different from that of the first column 5 is applied inside the second column 6, and when the sample gas passes through the second column 106, Each component moves at a speed corresponding to the distribution coefficient or solubility of each component, and the components are sequentially discharged from the outlet end.
Further, the second column 106 is disposed in the second oven 4 and the temperature rise is controlled at an appropriate rate by the heater 4a of the second oven 4 during analysis. Even with this temperature increase control, when the sample gas passes through the second column 106, each component moves at a speed corresponding to the distribution coefficient or solubility of each component. For example, the computer 110 controls the temperature of the second column 106 to 40 ° C. (21 minutes) −5 ° C./minute−250° C. (5 minutes) by the heater 4a.

The branch path 108 is, for example, a tube having an inner diameter of 0.15 mm, and its length is 0.5 m. The stationary phase is not applied to the inside of the branch path 108, and when the sample gas passes through the branch path 108, each component moves in the order of entering from the inlet end, and the outlet end The components are discharged sequentially.
Since the branch path 108 is also arranged in the first oven 3 like the first column 5, the temperature is controlled at an appropriate rate by the heater 3 a of the first oven 3 during analysis. For example, the temperature of the branch path 108 is controlled to 50 ° C. (2 minutes) −20 ° C./minute−180° C.−5 ° C./minute−280° C. (30 minutes) by the heater 3a.

As the flow path changing connection mechanism 40, flow path switching means having a structure called a Deans system is generally used (see, for example, Patent Document 2).
An outlet end of the first column 5, an inlet end of the second column 106, and an inlet end of the branch path 108 are connected to the flow path changing connection mechanism 40. Then, the outlet end of the first column 5 and the inlet end of the second column 106 are connected so as to flow, or the outlet end of the first column 5 and the inlet end of the branch path 108 are connected. It is possible to switch to be either.

The flame ionization detector (FID) 50 detects ions generated by burning a compound in a hydrogen flame. Since it has sensitivity to a compound having a C—H bond, it has high sensitivity to a general organic substance, but it has a drawback that it cannot sense small molecular gases such as water and carbon dioxide.
When the MS detector 7 ionizes the compound in a vacuum with a high voltage applied, the ions fly in the MS detector 7 due to electrostatic force, and the flying ions are mass-charged by an electric / magnetic action or the like. By separating according to the ratio and then detecting each, a mass spectrum having the mass-to-charge ratio as the horizontal axis and the detection intensity as the vertical axis can be obtained. The mass spectrum contains various information, so it is an extremely powerful means for identifying known substances and determining the structure of unknown substances. However, since the MS detector 7 is large and expensive, there is a drawback that generally only one MS detector 7 can be arranged in one multidimensional GC 101.
The computer 110 includes a CPU 11, and a memory 12, a keyboard and a mouse that are input devices (not shown), and a display device (not shown) having a monitor screen and the like are connected.

  In such a multi-dimensional GC 101, hydrogen gas is ionized through the branch passage 108 after the sample gas vaporized in the sample vaporization chamber 2 flows into the first column 5 to separate the sample gas. The flow is branched into two flow paths: a flow path toward the detector 3 and a flow path toward the MS detector 7 via the second column 106. In general, the sample gas flowing out from the first column 5 is introduced into the flame ionization detector 3 via the branch path 108 to detect the sample component, and the target component that cannot be sufficiently separated by the first column 5 is included. The sample gas is selectively introduced into the second column 106 at the timing at which the sample gas passes, and the separation characteristics are improved through the second column 106 and then introduced into the MS detector 7 for detection.

However, the flame ionization detector 50 cannot perform analysis related to identification of a known substance or determination of the structure of an unknown substance, as compared with the MS detector 7. Therefore, it has been desired to detect the sample that has passed through only the first column 5 with the MS detector 7.
Therefore, a multi-dimensional GC using a double-hole Vespel ferrule has been developed in which a sample that has passed through only the first column 5 is also guided to the MS detector 7. FIG. 6 is a schematic configuration diagram illustrating another example of the multi-dimensional GC. In addition, the same code | symbol is attached | subjected about the thing similar to multidimensional GC101 mentioned above.
The multidimensional GC 151 includes a sample vaporizing chamber 2 into which a sample gas and a carrier gas are introduced, a first column 5, a second column 106, a branch path 158, an MS detector 7, and a flow path changing The connection mechanism 40, the first oven 3 that controls the temperature of the first column 5, the second oven 4 that controls the temperature of the second column 106 and the temperature of the branch 158, the first oven 3 and the second oven 4, a connecting unit 9 that connects the MS detector 7 and the second oven 4, and a computer (control unit) 160 that controls the entire multidimensional GC 151. The connecting portion 9 is a double hole Vespel ferrule, and can pass through the two channels of the second column 106 and the branch path 158.

The branch path 158 is, for example, a tube having an inner diameter of 0.15 mm, and its length is 1 m. The stationary phase is not applied to the inside of the branch path 158, and when the sample gas passes through the branch path 158, each component moves in the order of entering from the inlet end, and the outlet end The components are discharged sequentially.
Since the branch path 158 is arranged in the second oven 4 similarly to the second column 106, the temperature rise is controlled at an appropriate rate by the heater 4a of the second oven 4 during analysis. For example, the temperature of the branch path 158 is controlled to be 40 ° C. (21 minutes) −5 ° C./minute−250° C. (5 minutes).

  In such multi-dimensional GC 151, the MS gas is detected in the flow path after separating the sample gas by flowing the sample gas vaporized in the sample vaporizing chamber 2 to the first column 5 without passing through the second column 6. Branching into two channels, a channel toward the detector 7 and a channel toward the MS detector 7 via the second column 6. Then, the sample gas that normally flows out from the first column 5 is introduced into the MS detector 7 via the branch path 158 to detect the sample component, and the sample gas contains the target component that cannot be sufficiently separated by the first column 5. The sample gas is selectively introduced into the second column 106 at the timing when the gas passes through, and the separation characteristics are improved through the second column 106 and then introduced into the MS detector 7 for detection.

JP 2006-226678 A JP 2006-064646 A

In such multi-dimensional GC 151, the sample gas introduced into the second column 106 is introduced into the MS detector 7 while passing through the second column 106, and the sample gas that has not been introduced into the second column 106. Is introduced into the MS detector 7 while passing through the branch path 158. At this time, it is necessary to prevent the sample gas passing through the second column 106 and the sample gas passing through the branch path 158 from being simultaneously introduced into the MS detector 7.
However, the temperature of the second column 106 is controlled at an appropriate rate by the heater 4a of the second oven 4 during the analysis, but the temperature of the branch path 158 is similarly controlled by the heater 4a. That is, the same temperature increase control is performed on the temperature of the second column 106 and the temperature of the branch path 158. Therefore, when the temperature of the second column 106 is controlled to 40 ° C. (21 minutes) −5 ° C./minute−250° C. (5 minutes), when the sample gas reaches the inlet end of the branch 158 Since the temperature of the branch path 158 is as low as 40 ° C., the sample components introduced from the first column 5 into the branch path 158 are aggregated inside the branch path 158, so that the sample detector can reach the MS detector 7 from the branch path 158. As a result, the sample components may not be analyzed. This agglomerated component is generally called a cold spot, and causes a reduction in analysis accuracy.

On the other hand, when the temperature of the branch path 158 is set high when the sample gas reaches the inlet end of the branch path 158, it is possible to prevent the occurrence of a cold spot inside the branch path 158. In this case, There are many restrictions on the separation conditions (initial temperature, etc.) in the second column 106, and as a result, it becomes difficult to improve the separation accuracy in the second column 106, or the analysis time for increasing the separation accuracy. Became longer.
Therefore, the present invention provides a multi-dimensional gauge that can accurately analyze in a short time a sample that has passed through only the first column and a sample that has passed through both the first column and the second column. An object of the present invention is to provide a scramograph apparatus.

  The multi-dimensional gas chromatograph apparatus of the present invention, which has been made to solve the above problems, is separated into each component contained in the sample by introducing the sample into the interior from the inlet end, The first column that sequentially discharges the components from the outlet end and the sample is introduced into the interior from the inlet end, so that the sample is separated into each component contained in the sample, and the components are sequentially discharged from the outlet end. , The second column consisting of the front part, the main part and the rear part from the inlet end to the outlet end, and the sample is introduced into the interior from the inlet end, whereby the components contained in the sample are sequentially discharged from the outlet end. The mass spectrometer connected to the branch path, the outlet end of the branch path and the outlet end of the second column, and the outlet end of the first column and the inlet end of the second column are circulated. A flow path changing connection mechanism that can be switched so as to be connected to each other or to be connected so as to circulate between the outlet end of the first column and the inlet end of the branch path, and the first oven And a second dimension oven, wherein the first column, the branch path, the flow path changing connection mechanism, and the front and rear portions of the second column are the first oven The main part of the second column is arranged inside the second oven.

Here, the “front part” of the second column refers to a part of the second column from the inlet end of the second column to an arbitrary distance. For example, the arbitrary distance is 1% of the entire second column. Above 10%. In the present invention, it is not necessary that all (100%) of the front part is disposed in the first oven. For example, 50% of the front part is disposed in the first oven, and 50% may be arranged between the first oven and the second oven (for example, the connecting portion).
The “main part” of the second column is a part sandwiched between the front part and the rear part.
The “rear part” of the second column is a part of the second column from the outlet end of the second column to an arbitrary distance. For example, the arbitrary distance is 1% to 10% of the entire second column. It becomes as follows. In the present invention, it is not necessary that all (100%) of the rear part is disposed in the first oven, and at least a part of the rear part may be disposed in the first oven, for example, 90% of the rear part. Is placed inside the first oven, 5% of the rear part is placed between the first oven and the second oven (for example, the connecting part), and 5% of the rear part is the first oven and mass spectrometry. You may arrange | position between gauges (for example, connection part).
The front part and / or the rear part may have a function of separating the sample into each component, or may not have a function of separating the sample into each component.

According to the multidimensional gas chromatograph apparatus of the present invention, the main part of the second column is arranged inside the second oven, but the branch path is not arranged inside the second oven. Thus, the temperature of the sample passing through the main part of the second column is controlled by the second oven at an appropriate rate. At this time, in the second oven, since the branch path is not arranged inside the second oven, it is not necessary to consider the occurrence of a cold spot inside the branch path.
On the other hand, the branch path and the rear stage portion of the second column are arranged inside the first oven. As a result, the sample passing through the branch passage is affected by the temperature of the first oven, but after passing through the first column, the temperature of the first oven is controlled to rise at an appropriate rate. Therefore, since the temperature of the first oven is already relatively high, it is possible to prevent the occurrence of a cold spot inside the branch path and, as a result, reach the mass spectrometer.
Therefore, in the multidimensional gas chromatograph apparatus of the present invention, the temperature of the main part of the second column is lowered while the sample passing through the branch path is introduced into the mass spectrometer. The sample reaching the column can be held inside the second column. Then, after the sample passing through the branch path is introduced into the mass spectrometer or just before it is introduced into the mass spectrometer, the main part of the second column is removed at an appropriate rate by the second oven. By controlling the temperature rise, the sample held in the second column can be separated and discharged. As a result, the sample passing through the second column and the sample passing through the branch path can be prevented from being simultaneously introduced into the mass spectrometer, and the second column can be separated to separate the sample. The temperature rise can be controlled by an oven at an appropriate rate.
Note that the sample that has passed through the former part and the main part of the second column is affected by the temperature of the first oven when passing through the latter part of the second column, but when passing through the first column, Since the temperature of the first oven is controlled after the temperature is controlled at an appropriate rate, the temperature of the first oven is already relatively high, so that a cold spot is prevented from occurring in the latter part of the second column. As a result, it reaches the mass spectrometer.

  As described above, according to the multidimensional gas chromatograph apparatus of the present invention, a sample that has passed through only the first column and a sample that has passed through both the first column and the second column are shortened by a mass spectrometer. It can be analyzed accurately in time.

It is a schematic block diagram which shows an example of the multidimensional GC which concerns on embodiment. It is an example of the total ion chromatogram when all the samples pass only the 1st column. It is an example of the total ion chromatogram of the sample which passed only the 1st column. It is an example of the total ion chromatogram of the sample which passed both the 1st column and the 2nd column. It is a schematic block diagram which shows an example of the conventional multidimensional GC. It is a schematic block diagram which shows another example of the conventional multidimensional GC.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments described below, and it goes without saying that various aspects are included without departing from the spirit of the present invention.

FIG. 1 is a schematic configuration diagram illustrating an example of a multi-dimensional GC according to the embodiment. In addition, the same code | symbol is attached | subjected about the thing similar to multidimensional GC151 mentioned above.
The multidimensional GC1 has a sample vaporizing chamber 2 into which a sample gas and a carrier gas are introduced, a first column 5, a second column 6 including a front portion 6a, a main portion 6b, and a rear portion 6c, and a branch. The first oven 3 for controlling the temperatures of the path 8, the MS detector 7, the flow path changing connection mechanism 40, the first column 5, the branch path 8, and the front part 6a and the rear part 6c of the second column 6. A second oven 4 for controlling the temperature of the main portion 6b of the second column 6, a connecting portion 9 for connecting the first oven 3 and the second oven 4, an MS detector 7 and the first oven 4 A connecting unit 14 to be connected and a computer (control unit) 10 for controlling the entire multi-dimensional GC1 are provided.

The connecting portion 9 has a cylindrical shape (for example, an inner diameter of 7 mm and a height of 250 mm) having a heat retaining mechanism, and the inside penetrates from one end to the other end. Thereby, it is possible to pass through the two flow paths of the front part 6 a of the second column 6 and the rear part 6 c of the second column 6.
The connecting portion 14 has a cylindrical shape (for example, an inner diameter of 1 mm and a height of 150 mm) having a heat retaining mechanism, and the inside penetrates from one end to the other end. Thereby, the two flow paths of the branch path 8 and the rear stage portion 6c of the second column 6 can be penetrated.

The branch path 8 is, for example, a tube having an inner diameter of 0.15 mm, and its length is 0.5 m. The stationary phase is not applied to the inside of the branch path 8, and when the sample gas passes through the branch path 8, each component moves in the order in which it enters from the inlet end, and the outlet end The components are discharged sequentially.
At this time, the first half portion of the branch path 8 (for example, 0.45 m which is 90%) is arranged inside the first oven 3. Thereby, the sample gas passing through the branch path 8 is affected by the temperature of the first oven 3, but when the sample gas passes through the first column 5, the heater 3 a of the first oven 3 is appropriately set. Since the temperature rise is controlled at the rate, the temperature of the first oven 3 is relatively high, so that it is possible to prevent the occurrence of a cold spot inside the branch path 8.
In addition, the latter half part (for example, 0.05m which is 10%) of the branch path 8 is arrange | positioned inside the connection part 14. FIG.

The second column 6 is, for example, a tube having an inner diameter of 0.32 mm, and its length is 30 m. Then, a stationary phase (for example, trifluoropropylmethylpolysiloxane or the like) different from that of the first column 5 is applied inside the second column 6, and when the sample gas passes through the second column 6, Each component moves at a speed corresponding to the distribution coefficient or solubility of each component, and the components are sequentially discharged from the outlet end.
At this time, the main part (for example, 29 m, etc.) 6b of the second column 6 is disposed in the second oven 4, and the temperature rise is controlled at an appropriate rate by the heater 4a of the second oven 4 during analysis. Even with this temperature increase control, when the sample gas passes through the second column 6, each component moves at a speed corresponding to the distribution coefficient or solubility of each component.
In addition, the first half portion (for example, 0.05 m which is 50%) of the front stage portion 6a (for example, 0.1 m) of the second column 6 is disposed inside the first oven 3, and The latter half portion (for example, 0.05 m which is 50%) of the front stage portion 6a is disposed inside the connecting portion 9.
In addition, the first half portion (for example, 0.05 m, which is 5%) of the rear stage portion 6c (for example, 0.9 m) of the second column 6 is disposed inside the connecting portion 9, and the rear portion 6c of the second column 6 is disposed. The central part (for example, 0.8 m which is 90%) is arranged inside the first oven 3 and the latter half part (for example, 0.05 m which is 5%) of the rear stage part 6c of the second column 6 Is arranged inside the connecting portion 14.

Based on the temperature control program, the computer 10 is arranged in the first oven, the first column 5 and the first half part of the branch path 8, the first half part of the front part 6a of the second column 6 and the central part of the rear part 6c. Is controlled by the heater 3a to, for example, 50 ° C. (2 minutes) −20 ° C./minute−180° C.−5 ° C./minute−280° C. (30 minutes). Further, the temperature of the main portion 6b of the second column 6 is controlled to 40 ° C. (21 minutes) −5 ° C./minute−250° C. (5 minutes) by the heater 4a, for example. As described above, the temperature control program allows the sample passing through only the first column 5 to pass through the first column 5 and the branch path 8 and be introduced into the MS detector 7. The temperature of the main portion 6b is maintained at a low temperature such as 40 ° C. Thereby, the sample gas that has passed through the first column 5 and reached the main portion 6 b of the second column 6 can be held near the inlet of the main portion 6 b of the second column 6. After the sample passing through the first column 5 and the branch path 8 is introduced into the MS detector 7, the temperature of the heater 4a is controlled at an appropriate rate. Thereby, the sample held near the inlet of the main portion 6 b of the second column 6 can be passed through the second column 6 and introduced into the MS detector 7.
The central portion of the rear stage portion 6c of the second column 6 is disposed in the first oven 4, but when the sample gas passes through the first column 5, the heater 3a of the first oven 3 is at an appropriate rate. Since the temperature rise is controlled, the temperature of the first oven 3 is as high as 280 ° C., so that the sample gas that passes through the rear portion 6 c of the second column 6 reaches the MS detector 7. .

The computer 10 includes a CPU (control unit) 11, and further includes a memory (storage unit) 12, a keyboard and mouse that are input devices (not shown), and a display device (not shown) having a monitor screen and the like. It is connected.
The function processed by the CPU 11 will be described in block form. The CPU 11 includes a connection mechanism control unit 21 that controls the flow path changing connection mechanism 40, an MS detector control unit 23 that controls the MS detector 7, and a measurement unit 24. .

The connection mechanism control unit 21 controls the flow path changing connection mechanism 40, the heater 3a, and the heater 4a based on the flow path changing program and the temperature program.
Here, the case where each pesticide component in the pesticide mixed sample is quantitatively analyzed will be described. FIG. 2 is an example of a total ion chromatogram when all the samples have passed only through the first column. 3 is an example of a total ion chromatogram of a sample that has passed only through the first column, and FIG. 4 is an example of a total ion chromatogram of a sample that has passed through both the first column and the second column. is there. 2 to 4, the vertical axis represents ion intensity, and the horizontal axis represents detection time (minutes) from the start of measurement.
The temperature control program adopts the control program described above, and for the first oven, 50 ° C. (2 minutes) —20 ° C./minute—180° C.—5 ° C./minute—280° C. (30 minutes), for the second oven It was controlled at 40 ° C. (21 minutes) −5 ° C./minute−250° C. (5 minutes).
For example, first, at the measurement start time T1 (0.0 minutes), the outlet end of the first column 5 and the inlet end of the branch path 8 are connected so as to flow. That is, the sample gas passes through the first column 5 and the branch path 8 and is introduced into the MS detector 7.

Thereafter, when the first set start time T2 (18.0 minutes) is reached, the outlet end of the first column 5 and the inlet end of the second column 6 are connected so as to flow. That is, the sample gas passes through the first column 5 and the second column 6. At this time, since the temperature of the main portion 6b of the second column 6 is controlled at a temperature of 40 ° C., the sample gas entering the second column 6 is aggregated and held in a narrow band near the inlet of the main portion 6b. Will be. On the other hand, the sample gas that has entered the branch path 8 from the measurement start time T1 to the first set start time T2 moves at a certain speed and is introduced into the MS detector 7. .
When the first set end time T3 (for example, 18.5 minutes) is reached, the outlet end of the first column 5 and the inlet end of the branch path 8 are connected so as to flow. That is, the sample gas passes through the first column 5 and the branch path 8 again. At this time, the sample gas that has entered the branch path 8 moves at a certain speed, and is introduced into the MS detector 7.

Thereafter, when the second set start time T4 (19.8 minutes) is reached, the outlet end of the first column 5 and the inlet end of the second column 6 are connected so as to flow. That is, the sample gas passes through the first column 5 and the second column 6. At this time, since the temperature of the main portion 6b of the second column 6 is controlled at a temperature of 40 ° C., the sample gas that has entered the second column 6 is changed from the first setting start time T2 to the first setting end time T3. In the meantime, following the sample gas that enters and is held in the second column 6, it is aggregated and held in a narrow band near the inlet of the main portion 6b of the second column. On the other hand, the sample gas that has entered the branch path 8 from the first setting end time T3 to the second setting start time T4 moves at a certain speed and is introduced into the MS detector 7. ing.
When the second set end time T5 (20.3 minutes) is reached, the outlet end of the first column 5 and the inlet end of the branch path 8 are connected so as to flow. That is, the sample gas passes through the first column 5 and the branch path 8 again. At this time, the sample gas that has entered the branch path 8 moves at a certain speed, and is introduced into the MS detector 7.

After that, when almost all the sample gas entering the branch path 8 is introduced into the MS detector 7 (21.0 minutes), it is within the first set time T2 to T3 and within the second set time T4 to T5. The sample components agglomerated inside the vicinity of the inlet of the main portion 6b of the second column 6 are moved at a certain speed by controlling the temperature rise of the temperature of the main portion 6b of the second column 6. The MS detector 7 is introduced. At this time, since the temperature of the central part of the rear part 6c of the second column 6 is controlled to a high temperature such as 180 ° C. or higher, the sample gas entering the rear part 6c of the second column 6 has a speed at which each component has a certain speed. While being moved, the MS detector 7 is introduced.
The measurement start time T1, the setting start times T2, T4, and the setting end times T3, T5 are determined in advance by confirming the time during which the sample gas is discharged from the outlet end of the first column 5. It is stored in the memory 12 or the like (see FIG. 2). In the case of this example, in the total ion chromatograph of FIG. 2, two circled marks are overlapped, overlapping peaks (near 18.3 minutes and around 20.0 minutes) Each set time was selected in order to perform the separation by the second column 6 of the components to be performed. Thus, the time zone including at least the detection time of the component to be separated in the second column 6 may be set as the time for connecting the outlet end of the first column 5 and the inlet end of the second column 6. .
Further, the set time is not limited to the above two times, and may be set according to the number of components of the sample gas to be separated in the second column 6. In this case, the temperature control of the main portion 6b of the second column 6 is performed after the entire set time is completed, and after the sample gas that has entered the branch path 8 is introduced into the MS detector 7, the temperature of the second column 6 is increased. What is necessary is just to set so that control may be started.

Based on the ion intensity signal detected by the MS detector 7, the MS detector control unit 23 performs control to create a chromatogram having time t versus ion intensity I.
The measurement unit 24 performs control to calculate the concentration of each component based on the chromatogram created by the MS detector control unit 23.

  As described above, according to the multidimensional GC1 of the present invention, the sample that has passed through only the first column 5 and the sample that has passed through both the first column 5 and the second column 6 are detected by the MS detector 7. Can be analyzed accurately in a short time.

(Other embodiments)
In the multi-dimensional GC1 described above, a configuration in which a stationary phase (for example, trifluoropropylmethylpolysiloxane) is applied to the rear portion 6c of the second column 6 is shown. It is good also as a structure where fluoropropyl methyl polysiloxane etc.) are not apply | coated.

  The present invention can be used for multi-dimensional GC using a plurality of columns.

1, 101, 151 Multi-dimensional gas chromatograph 3 First oven 4 Second oven 5 First column 6 Second column 7 MS detector (mass spectrometer)
8, 108, 158 Branch 10, 110, 160 Computer (control unit)
24 Measuring Unit 40 Channel Change Connection Mechanism

Claims (1)

A first column that separates the sample into each component contained in the sample by introducing the sample into the interior from the inlet end, and sequentially discharges the component from the outlet end;
When the sample is introduced into the inside from the inlet end, the sample is separated into each component contained in the sample, the components are sequentially discharged from the outlet end, the front stage part from the inlet end toward the outlet end, the main part A second column comprising a part and a rear part;
A branch that sequentially discharges components contained in the sample from the outlet end by introducing the sample into the interior from the inlet end;
A mass spectrometer connected to the outlet end of the branch and connected to the outlet end of the second column;
Either the outlet end of the first column and the inlet end of the second column are connected so as to flow, or the outlet end of the first column and the inlet end of the branch path are connected so as to flow. A flow path changing connection mechanism that can be switched so as to become
The first oven,
A multi-dimensional gas chromatograph apparatus comprising a second oven,
The first column, the branch path, the front part and the rear part of the second column, and the flow path changing connection mechanism are arranged inside the first oven,
A multi-dimensional gas chromatograph apparatus, wherein a main part of the second column is disposed in the second oven.

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