JP2001343375A - Liquid chromatograph - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable introduction and analysis of a sample having a high concentration without dilution. SOLUTION: The sample is introduced into a transfer liquid passage 17 from an injector 21, and a sample pump 19 is operated. The sample is carried up to a passage branching part 23 by transfer liquid sent from the sample pump 19, and divided there into an introduction side branch passage 25 and a discharge side branch passage 33 with a ratio determined by a passage resistance ratio shown by resistance tube 33a/(resistance tube 31a + sample loop 29). The sample introduced into the discharge side branch passage 33 is discharged to a drain 37 through the resistance tube 33a and a confluence part 37. The sample introduced into the introduction side branch passage 25 is carried to the sample loop 29 through a passage selector valve 27 (A). The sample loop 29 is connected to the middle between an analytical pump 3 in an analytical passage 7 and a separation column 9 by switching the passage selector valve 27, to introduce the sample introduced into the sample loop 29 into the separation column 9 (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid chromatograph, and more particularly, to a separation column, a liquid sending section for sending a mobile phase to the separation column, and a sample for introducing a sample into an analysis flow path to the separation column. The present invention relates to a liquid chromatograph provided with a detector for detecting a sample component eluted from an introduction part and a separation column.

[0002]

2. Description of the Related Art FIG. 3 is a flow chart showing a conventional liquid chromatograph. In the liquid chromatograph, a sample is introduced into the separation column 9, the analysis pump 3 for sending the mobile phase contained in the mobile phase container 1 through the analysis channel 7 to the separation column 9, and the analysis channel 7 to the separation column 9. And a detector 11 for detecting sample components eluted from the separation column 9. Detector 11 includes detector 1
A data processing unit 13 for identifying and quantifying a sample component based on the detection signal 1 is electrically connected.

In such a liquid chromatograph, the sample introduced into the separation channel 7 at the sample introduction section 5a is sent to the separation column 9 by the mobile phase sent from the analysis pump 3, and the sample is introduced into the separation column 9. It is separated into several components, and the sample components are detected by the downstream detector 11. In liquid chromatography, the separation capacity of the separation column 9 and the detector 1
Due to the detection capability of No. 1, there is an upper limit on the amount of sample that can be analyzed. Therefore, in the case of a sample having a high concentration, it may not be possible to analyze the sample at the same concentration. In such a case, the analysis is usually performed after dilution.

[0004]

However, dilution of a sample is complicated since many instruments such as a dilution vessel and a measuring instrument are required for preparation, and the dilution operation takes a long time and requires a large amount of a diluting solvent. There was such a problem. Also, if the dilution ratio is high, the error of the sample concentration after dilution becomes large,
As a result, there is a problem that errors in the quantitative analysis increase. Accordingly, an object of the present invention is to provide a liquid chromatograph that can introduce and analyze a sample having a high concentration without dilution.

[0005]

The present invention comprises a separation column,
Liquid chromatograph equipped with an analytical liquid sending section for sending the mobile phase to the separation column, a sample introduction section for introducing a sample into the analysis flow path to the separation column, and a detector for detecting sample components eluted from the separation column In the graph, the sample introduction section includes a sample transfer liquid container containing a sample transfer liquid serving as a solvent for transferring a sample, a sample transfer section for transferring the sample transfer liquid, and a sample transfer section. An injector for introducing a sample into the transfer liquid flow path, a flow path branching portion that branches the transfer liquid flow path from the injector into a first branch flow path and a second branch flow path, and transfer of the sample and the sample. A sample loop for temporarily storing a fixed amount of liquid, and a flow path switching valve for connecting the sample loop between the first branch flow path and the drain flow path, or between the analysis liquid sending section of the analysis flow path and the separation column And a sump is provided by a flow path switching valve. A flow path resistance of the first branch flow path side for the sample transfer liquid sent by the sample liquid sending section and a second branch flow in a state where the loop is connected between the first branch flow path and the drain flow path. The amount of sample introduced into the sampling loop is determined with respect to the amount of sample introduced from the injector based on the ratio of the flow path resistance on the road side.

In a state where the sample loop is connected between the first branch flow path and the drain flow path by the flow path switching valve, a sample is introduced from the injector into the transfer liquid flow path, and the sample liquid supply section is operated to activate the sample. When the liquid is supplied, the sample is branched at the flow path branching portion into the first branch flow path side and the second branch flow path side. That is, the amount of the sample introduced into the first branch flow path side, and eventually into the sampling loop, is smaller than the amount of the sample introduced from the injector. The ratio of the amount of the sample branched at the channel branching section is determined by the ratio of the channel resistance on the first branch channel side to the channel resistance on the second branch channel side.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS It is preferable that the flow resistance on the first branch flow path side and / or the flow resistance on the second branch flow path side can be changed. As a result, by changing the ratio of the flow path resistance on the first branch flow path side to the flow path resistance on the second branch flow path side, the sample introduced into the sampling loop with respect to the sample amount introduced from the injector is changed. The quantity can be changed.

[0008]

FIG. 1 is a flow chart showing one embodiment. Portions performing the same functions as those in FIG. 3 are denoted by the same reference numerals, and description thereof will be omitted. A mobile phase container 1, an analysis pump (analysis liquid sending section) 3, an analysis flow path 7, a separation column 9, a detector 11, and a data processing section 13 are provided in the same manner as the liquid chromatograph shown in FIG. A sample introduction unit 5 is provided between the analysis pump 3 and the separation column 9 in the analysis channel 7.

The sample introduction section 5 will be described. Sample transfer liquid container 15 containing a sample transfer liquid for transferring a sample
Is provided. A sample pump (sample sending section) 19 for sending the transfer solution to the transfer solution channel 17 from the sample transfer solution container 15, and an injector for introducing a predetermined amount of sample into the transfer solution channel. 21 and a flow path branching portion 23 that branches the transfer liquid flow path 17 into an introduction-side branch flow path (first branch flow path) 25 and a discharge-side branch flow path (second branch flow path) 33 They are provided in order from the container 15. A discharge pipe 33a for adjusting the flow resistance is provided in the discharge side branch flow path 33 from the flow path branch part 23.

[0010] Introductory branch flow channel 25 from flow channel branch portion 23
Is connected to one port of a flow path switching valve 27 composed of a 2-position 6-port valve. Of the other ports of the flow path switching valve 27, two of the ports are connected to the analysis liquid sending pump 3 and the analysis flow path 7 between the separation columns 9, and the other two ports are for the sample and the sample transfer liquid. Both ends of a sample loop 29 for temporarily storing a fixed amount are connected, and a drain channel 31 connected to the drain 35 is connected to the remaining ports. Flow path switching valve 27
The load position connects the sample loop 29 between the sample introduction side branch flow path 25 and the drain flow path 31 and connects the analysis liquid sending pump 3 and the separation column 9 in the analysis flow path 7 (see (A)). ), And an injection position (((a)) that connects the analysis liquid feed pump 3 and the separation column 9 in the analysis flow path 7 via the sample loop 29 and connects the sample introduction side branch flow path 25 to the drain flow path 31 side. B))
Can be switched between. The drain passage 31 is provided with a resistance tube 31a for adjusting the flow resistance. The branch channel 31 merges at the junction 37 between the resistance tube 31 a and the drain 35 of the drain channel 31.

The operation of this embodiment will be described with reference to FIG. (A) A sample is introduced from the injector 21 into the transfer liquid flow path 17 and the sample pump 19 is operated. The sample is transported from the sample pump 19 by the transfer liquid,
To the resistance tube 33a / (resistance tube 31a +
The inlet-side branch channel 25 and the discharge-side branch channel 33 are divided at a ratio determined by the channel resistance ratio of the sample loop 29). The sample introduced into the discharge side branch channel 33 is discharged to the drain 37 via the resistance tube 33a and the junction 37. The sample introduced into the introduction-side branch flow path 25 is supplied to the flow path switching valve 27.
To the sample loop 29.

(B) After the sample introduced into the introduction-side branch flow path 25 reaches the sample loop 29, the flow path switching valve 27 is switched so that the sample loop 29 is separated from the analysis pump 3 of the analysis flow path 7 by the analysis pump 3. Connect between columns 9. The sample introduced into the sample loop 29 is introduced into the separation column 9 by the mobile phase sent from the analysis pump 3 and separated. The sample component eluted from the separation column 9 is detected by the detector 11 and the data processing unit 13
To identify and quantify the sample. As described above, the sample is supplied to the sampling loop 29 at a predetermined ratio with respect to the amount of the sample introduced from the injector 21, and thus the analysis channel 7.
Therefore, even a sample having a high concentration can be introduced from the injector 21 and analyzed without being diluted.

FIG. 2 is a flow diagram showing another embodiment. In the drain channel 31, via the selection valve 31b,
Resistance tubes 31c, 31d, 31 having different flow path resistances
e is connected to one end of each of the resistance tubes 31c, 31d, 31e.
Are joined at a junction 31 f and connected to the drain 35 via a junction 37. The flow path selection valve 31b is switched so as to connect the drain flow path 31 to any one of the resistance tubes 31c, 31d, and 31e. One ends of resistance pipes 33c, 33d, and 33e having different flow path resistances are connected to the discharge-side branch flow path 33 via a selection valve 33b, and the other ends of the resistance pipes 33c, 33d, and 33e join at a junction 33f. Then, it is connected to the drain 35 via the junction 37. The flow path selection valve 33b is switched so that the discharge side branch flow path 33 is connected to one of the resistance pipes 33c, 33d, and 33e, or is not connected to any of the resistance pipes.

In this embodiment, the flow resistance of the drain flow path 31 can be changed by switching the selection valve 31b, and the flow resistance of the discharge side branch flow path 33 can be changed by switching the selection valve 33b. The amount of the sample introduced into the sample loop 29 can be changed with respect to the amount of the sample introduced from the injector 21 by the combination of the flow path resistance of the drain flow path 31 and the flow path resistance of the branch flow path 33. Also,
If the discharge side branch flow path 33 from the flow path branch portion 23 is not connected to any of the resistance tubes by the selection valve 33b, the entire sample amount introduced from the injector 21 can be introduced into the sample loop 29. .

In the above embodiment, the flow path resistance on the introduction-side branch flow path side and the flow path resistance on the discharge-side branch flow path side are adjusted by the resistance tube. However, the present invention is not limited to this. The flow path resistance on the side branch flow path side and the flow path resistance on the discharge side branch flow path side may be adjusted by another flow path adjuster, such as a variable flow path resistance depending on the opening / closing degree of the valve, or the flow path adjuster Alternatively, the flow path resistance may be adjusted according to the size of the inner diameter.

[0016]

According to the liquid chromatograph of the present invention, the sample introduction section includes a sample transfer liquid container containing a sample transfer liquid serving as a solvent for transferring a sample, a sample transfer section for sending the sample transfer liquid. An injector for introducing a sample into a transfer liquid flow path from the sample liquid sending section, and a flow path that branches the transfer liquid flow path from the injector into a first branch flow path and a second branch flow path A branch portion, a sample loop for temporarily storing a fixed amount of a sample and a sample transfer liquid, a sample loop between the first branch flow path and the drain flow path, or an analysis liquid sending section in an analysis flow path, and a separation column. A sample transfer liquid sent by the sample sending section in a state where the sample loop is connected between the first branch flow path and the drain flow path by the flow path switching valve. Flow path resistance on the first branch flow path side with respect to The amount of sample to be introduced into the sampling loop is determined by the ratio of the flow path resistance on the branch flow path side to the amount of sample introduced from the injector. Can be analyzed. In particular, in the case of a sample requiring a high dilution ratio, the error in concentration can be reduced as compared with the case where the sample is diluted externally.

The flow path resistance on the first branch flow path side or the second flow path resistance
If the flow path resistance on the side of the branch flow path or both of them can be changed, by changing the ratio of the flow path resistance on the side of the first branch flow path to the flow path resistance on the side of the second branch flow path, the injector The amount of sample introduced into the sampling loop can be changed with respect to the amount of sample introduced from.

[Brief description of the drawings]

FIG. 1 is a flow chart showing one embodiment.

FIG. 2 is a flow chart showing another embodiment.

FIG. 3 is a flow chart showing a conventional liquid chromatograph.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Mobile phase container 3 Analysis pump 5 Sample introduction part 7 Analysis flow path 9 Separation column 11 Detector 13 Data processing device 15 Sample transfer liquid container 17 Transfer liquid flow path 19 Sample pump 21 Injector 23 Flow path branch part 25 Introduction side Branch flow path 27 Flow path switching valve 29 Sample loop 31 Drain flow path 31a, 33a Resistance tube 33 Discharge separation flow path

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kaoru Murata 9-7-509, Inari-mae, Tsukuba, Ibaraki (72) Inventor Yasushi Ishihama 5-7-3 Misono, Moriya-cho, Kitasoma-gun, Ibaraki (72) Invention Naoki Asakawa 3-26-13 Namiki, Tsukuba City, Ibaraki Prefecture

Claims (2)

[Claims] 1. A separation column, an analysis liquid sending section for sending a mobile phase to the separation column, a sample introduction section for introducing a sample into an analysis flow path to the separation column, and detection of sample components eluted from the separation column. In the liquid chromatograph provided with a detector to perform, the sample introduction unit, a sample transfer liquid container containing a sample transfer liquid serving as a solvent for transferring a sample, a sample liquid transfer unit that sends the sample transfer liquid, An injector for introducing a sample into a transfer liquid flow path from the sample liquid supply unit, and a flow path branch for branching the transfer liquid flow path from the injector into a first branch flow path and a second branch flow path Part, a sample loop for temporarily storing a fixed amount of a sample and a sample transfer liquid, and the analysis liquid sending part of the sample loop between the first branch flow path, the drain flow path, or the analysis flow path Flow path connected between the separation columns A valve instead comprises, in the sample loop by the flow path switching valve of the first branch flow channel, while connected to the drain passage,
The amount of the sample introduced from the injector is determined by the ratio of the flow path resistance on the first branch flow path side to the sample transfer liquid fed by the sample liquid sending section and the flow path resistance on the second branch flow path side. A liquid chromatograph characterized in that an amount of a sample to be introduced into the sampling loop is determined. 2. The liquid chromatograph according to claim 1, wherein a flow path resistance on the first branch flow path side and / or a flow path resistance on the second branch flow path side can be changed.