JP2012150032A - Column system and method for measuring component using column system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To shorten a time for a timing adjustment.SOLUTION: The column system includes: means for removing non-measuring objects of which separation speed is slow in a plurality of components; means for trapping components of which separation speeds are slower than those of other plurality of measuring components in the measuring components obtained by removing the non-measuring components; separation means that is disposed in a subsequent stage of the trapping means and separates the other plurality of measuring components respectively that separate earlier than the components of which separation speed is slow among th measuring components; and means that introduces the trapped components of which separation speed is slow, to a detector at a timing being not overlapped with the components that are introduced to the detector.

Description

  The present invention relates to a column system such as gas chromatography and a component measurement method using the column system, and more particularly to a column system that shortens an analysis time and a component measurement method using the column system.

  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. In addition, if a single column is used for quantitative analysis of a plurality of components, the separation time differs depending on the components, so that it may take a long time for the measurement time to separate and come out of the column.

FIG. 2A and FIG. 2B are a system configuration diagram (a) showing an example of a conventional column system for shortening the measurement time and a time chart (b) showing a separation state in each column.
In FIG. 2 (a), 1 is the first 6-way valve into which the sample flows, 2 is the second 6-way valve into which the carrier flows, and the port 2 of the first 6-way valve and the port of the second 6-way valve 2 A first column 3 is arranged with 52 connected. The port 1 of the first 6-way valve and the port 56 of the second 6-way valve 2 are connected by piping.

  Reference numeral 4 denotes a first four-way valve, and the second column 5 is arranged by connecting the port 15 of the four-way valve and the port 53 of the second six-way valve 2. Reference numeral 6 denotes a second four-way valve, and a third column 7 is disposed between the port 19 of the second four-way valve and the port 16 of the first four-way valve.

10 is a detector, which connects the sample inlet (hereinafter referred to as the inlet) 10a of this detector to the port 22 of the second four-way valve 6, and the fourth column 8 is connected. Further, the detector inlet 10a and the first four-way A fifth column 9 is arranged connecting the port 18 of the valve 4.
In addition, the first capillaries 11 are connected by connecting the ports 51 and 54 of the second 6-way valve 2, and the second 51 is also connected by connecting the port 51 of the second 6-way valve 2 and the port 17 of the first 4-way valve 4. The capillary 12 is connected, and the third capillary 13 is connected by connecting the port 51 of the second 6-way valve 2 and the port 21 of the second 4-way valve 6.
Note that the apparatus shown in FIG. 1 (a) is disposed in a thermostat and maintained at a predetermined temperature.

  In the above-described configuration, in the non-measurement mode, the first and second 6-way valves 1 and 2 and the first and second 4-way valves 4 and 6 are in an off state indicated by a solid line, and the second 6-way valve 2 The carrier that has flowed into the port 51 of the first through the port 52 → first column 3 → port 2 of the first 6-way valve 1 → 1 → port 56 → 55 of the second 6-way valve 2 to the wrist lifter (flow control valve) Released from RR. The carrier that has flowed into the first capillary 11 is the port 54 → 53 of the second 6-way valve → the second column 5 → the port 15 → 16 of the first 4-way valve → the third column 7 → the second 4-way valve 6 It is discharged from the fourth capillary 14 via port 19 → 20.

The carrier flowing into the second capillary 12 is discharged via the ports 17 → 18 → the fifth column 9 → the detector 10 of the first four-way valve 4.
The carrier that has flowed into the third capillary 13 is discharged via the ports 21 → 22 → the fourth column 8 → the detector 10 of the second four-way valve 5.
The sample flowing into the first six-way valve 1 is discharged via the port 4 → 3 → the measuring pipe 18 → the port 6 → 5.

  Next, in the measurement mode, the first and second six-way valves 1 and 2 are simultaneously switched to an ON state indicated by a dotted line based on a V1 command issued by a control device (not shown). At this time, the first four-way valve and the second four-way valve 4 are in the off state. As a result, the carrier flowing into the second 6-way valve 2 is port 51 → 56 → port 1 of the first 6-way valve 1 → port 6 → measuring tube 18 → port 3 → 2 → first column 3 → second 6 direction Valve port 52 → 53 → Second column 5 → First four-way valve 4 port 15 → 16 → Third column 7 → Second four-way valve 6 port 19 → 20 → Discharge via fourth capillary 14 Has been.

  Here, the component A includes a non-measurement component that is separated relatively quickly among the components separated in each column, the component B that is separated following the component A, and the component C that is separated later than the component B. Suppose that component D separated later than component C and non-measurement component separated later than component D are included.

  In the second 6-way valve 2, when the sample of the components A to D contained in the sample passes through the first column, the on / off switching from the valve V1 to the second 6-way valve 2 is performed, as shown in FIG. As shown in the time chart, when the sample passes through the first column 3, the carrier is port 51 → 52 → first column 3 → first 6-way valve 1 port 2 → 1 → second 6-way valve 2 port. Flow through 56 → 55, and perform backflushing to remove components other than components A to D.

  The first four-way valve 4 is in an off state, and the components A to C that have passed through the second column 5 flow into the third column 7 via the ports 15 → 16. At this time, the second four-way valve 6 is in an OFF state, and the non-measurement component including the A component that is quickly separated is fore-flashed from the fourth capillary 14 via the port 19 → 20. Thereafter, the second four-way valve 6 is turned on, and the B and C components other than the non-measurement components including the A component are carried to the carrier flowing in from the third capillary 13 via the ports 21 → 22, and the ports 19 → 22 → the second It flows into the detector 10 via 4 columns.

  On the other hand, after the components A to C have passed through the first four-way valve 4, an on command is issued by the valve V2, and the slow-separated D component is the first capillary 11 → the port 54 → 53 → second of the second six-way valve 2. It is carried by the carrier flowing in through the column 5 and flows into the fifth column 9 through 15 → 18.

Here, as shown in FIG. 2 (b), the relationship between the separation rates of the components B, C, and D in the fourth column 8 and the fifth column 9 (component A is removed by foreflash) is as follows. Flows into the detector 10, then component D is adjusted so that component C finally flows.
In this way, the component D having a slow separation is separated at the stage of the second column 5, and is interrupted between the B and C components separated from the fourth column 8 through the first four-way valve 4 and the second capillary 13. As a result, the speed of component analysis as a whole can be improved.

JP 2006-064646 A JP 2010-271241 A

As described above, in process gas chromatography, a column is used to separate a sample, and a column to be used depending on a component is switched using valves V1 to V3, and a measurement component is separated from other components to be a detector. Introduce.
In that case, in order to prevent components from different routes from overlapping, a method is adopted in which a 1/8 inch pipe called a timing column is inserted in the front stage of the fifth column 9 and the timing of introduction to the detector 10 is adjusted. It was.

  However, in the method of inserting a timing column, it is necessary to change the length of the timing column for timing adjustment. In order to change the length, it is necessary to drop the heater of the thermostatic bath whose temperature is controlled and replace the timing column, and there is a problem that it takes time to stabilize the temperature of the thermostatic bath again.

  Therefore, the present invention changes the column system, and inserts the third and fourth 6-way valves instead of the first four-way valve conventionally disposed between the second column and the third column. It is an object of the present invention to provide a column system that can shorten the time for adjusting the timing without opening the thermostat by holding the components in the sixth column connected to.

The present invention has been made to solve the above problems, and in the column system according to claim 1,
In a column system for carrying a sample by a carrier, separating a plurality of components contained in the sample by a column provided in the middle of the sample and sequentially introducing the components into a detector,
Means for removing a non-measurement component having a slow separation speed among the plurality of components;
Means for trapping in the initial stage a component whose separation rate is slower than other measurement components among the measurement components excluding the non-measurement component;
Separating means that is arranged downstream of the means for trapping and separates a plurality of other measurement components that separate faster than components having a slow separation speed among the measurement components;
It has means for introducing the trapped component having a low separation speed into the detector at a timing that does not overlap with the component introduced into the detector.

In Claim 2, in the measuring method using a column system,
In a measurement method using a column system in which a sample is conveyed by a carrier, a plurality of components contained in the sample are separated by a column provided in the middle of the conveyance and sequentially introduced into a detector, and the component measurement is performed. Among the measurement components excluding the non-measurement component, the component having a slower separation speed than the other plurality of measurement components is trapped in the initial stage, and the other measurement components separated earlier than the component having the lower separation speed are trapped in the latter stage. The trapped component having a slow separation rate is introduced into the detector at a timing that does not overlap with the component that is separated from the column and introduced into the detector.

As is apparent from the above description, according to Claims 1 and 2 of the present invention, means for removing a non-measurement component having a slow separation speed among a plurality of components,
Means for trapping in the initial stage a component whose separation rate is slower than other measurement components among the measurement components excluding the non-measurement component;
Separating means that is arranged downstream of the means for trapping and separates a plurality of other measurement components that separate faster than components having a slow separation speed among the measurement components;
Since it has means for introducing the trapped component having a low separation rate into the detector at a timing that does not overlap with the component introduced into the detector, the time for adjusting the timing can be shortened without opening the thermostat. be able to.

It is a block diagram of the column system of this invention. It is a block diagram of the conventional column system.

  FIG. 1 (a, b) shows a column system of the present invention, and is a system configuration diagram (a) and a time chart (b) showing a separation state in each column. In these drawings, the same elements as those in FIG.

  In the present invention, the first four-way valve 4 (see FIG. 2) arranged between the second column and the third column constituting the conventional column system is removed, and instead, the third six-way valve 15 and A fourth column 16 is arranged between the ports 23 and 24 of the third six-way valve 15 by arranging the fourth six-way valve 17. The fifth capillary 20 connecting the port 26 of the third 6-way valve and the port 74 of the fourth 6-way valve 17 functions as a resistance for adjusting the carrier flow rate at the time of valve switching.

  In the above-described configuration, in the non-measurement mode, the first and second 6-way valves 1 and 2 and the first and second 4-way valves 4 and 6 are in an off state indicated by a solid line, and the second 6-way valve 2 The carrier that has flowed into port 51 of the first port 3 → the first column 3 → the port 2 of the first 6-way valve 1 → the port → 1 → the port 56 → 55 of the second 6-way valve 2 through the wrist lifter (flow control) Valve) is released from RR. Further, the carrier flowing into the first capillary 11 is port 54 → 53 of the second 6-way valve → second column 5 → port 28 → 27 of the third 6-way valve 15 → port 75 → 76 of the fourth 6-way valve 17 → It is discharged from the fourth capillary 14 via the third column 7 → the port 19 → 20 of the second four-way valve 6.

The carrier flowing into the second capillary 12 is discharged via the port 73 → 74 of the fourth 6-way valve 17 → the port 26 → 25 of the third 6-way valve 15 → the fifth column 9 → the detector 10. . The second capillary 12 functions as a resistor for adjusting the carrier flow rate when switching the fourth 6-way valve.
The carrier flowing into the third capillary 13 is discharged via the ports 21 → 22 → the fourth column 8 → the detector 10 of the second four-way valve 6. The third capillary 13 functions as a resistor for adjusting the carrier flow rate when switching the second four-way valve.
The sample flowing into the first six-way valve 1 is discharged via the port 4 → 3 → the measuring pipe 18 → the port 6 → 5.

  Next, in the measurement mode, the first and second six-way valves 1 and 2 are simultaneously switched to an ON state indicated by a dotted line based on a V1 command issued by a control device (not shown). At this time, the third 6-way valve 15 and the fourth 6-way valve 17 are off. As a result, the carrier flowing into the second 6-way valve 2 is port 51 → 56 → port 1 of the first 6-way valve 1 → port 6 → measuring tube 18 → port 3 → 2 → first column 3 → second 6 direction Valve port 52 → 53 → 2nd column 5 → 3rd 6 way valve 15 port 28 → 27 → 4th 6 way valve port 75 → 76 → 3rd column 2nd 4 way valve 6 port 19 → 20 → It is discharged via the fourth capillary 14.

  Here, in the second 6-way valve 2, when the sample of the components A to D contained in the sample passes through the first column 3, the valve V1 is switched on and off with respect to the second 6-way valve 2. As shown in the time chart of b), when the sample passes through the first column 3, the carrier is moved from the second 6-way port 51 → 52 → the first column 3 → the first 6-way port 2 → 1 → It flows through the port 56 → 55 of the second 6-way valve 2 and performs backflushing to remove components other than the components A to D.

The third 6-way valve 15 and the fourth 6-way valve 17 are in an OFF state, and the components A to C that have passed through the second column 5 are connected to the port 28 → 27 → the port 75 → 76 of the fourth 6-way valve 17. Then, it flows into the third column 7. At this time flowing to port 28 → 23 side is passed through the sixth column 16 as trapping means come Component D out behind the second column as on the third 6-way valve 15, port 2 4 → 25 → first Although it flows into the detector 10 via the five columns 9, the component D is adjusted so as to flow into the detector 10 later than the component B and earlier than the component C.

  That is, in the third column 7, the non-measurement components including the component A are quickly separated and come out, but these components are fore flushed from the ports 19 → 20 → the fourth capillary 14 of the second four-way valve 6 in the off state. Is done. Thereafter, the second four-way valve 6 is turned on, and the components B and C that are separated with delay are port 19 → 22 → fourth column of the second four-way valve 6 by the carrier introduced through the third capillary 13. It flows into the detector 10 through 8.

  According to the above-described configuration, it is possible to adjust the timing of holding the component in the column and introducing it to the detector by switching the valve. As a result, it is no longer necessary to open a thermostatic chamber to adjust the length of the pipe called a timing column that has been used in the past. Time can be shortened.

The above description merely shows a specific preferred embodiment for the purpose of explanation and illustration of the present invention. For example, in this embodiment, an example applied to gas chromatography has been described, but liquid chromatography may be used.
Therefore, the present invention is not limited to the above-described embodiments, and includes many changes and modifications without departing from the essence thereof.

1 First 6-way valve
2 Second 6-way valve
3 First column
4 First 4 way valve
5 Second column
6 Second 4-way valve
7 Third column
8 4th column
9 5th column
10 Detector
11 First capillary
12 Second capillary
13 Third capillary
14 4th capillary
15 Third 6-way valve
16 6th column
17 4th 6-way valve
18 Measuring tube
20 5th capillary

Claims (2)

In a column system for carrying a sample by a carrier, separating a plurality of components contained in the sample by a column provided in the middle of the sample and sequentially introducing the components into a detector,
Means for removing a non-measurement component having a slow separation speed among the plurality of components;
Means for trapping in the initial stage a component whose separation rate is slower than other measurement components among the measurement components excluding the non-measurement component;
Separating means that is arranged downstream of the means for trapping and separates a plurality of other measurement components that separate faster than components having a slow separation speed among the measurement components;
A column system comprising: means for introducing the trapped component having a low separation rate into the detector at a timing that does not overlap with the component introduced into the detector.   In a measurement method using a column system in which a sample is conveyed by a carrier, a plurality of components contained in the sample are separated by a column provided in the middle of the conveyance and sequentially introduced into a detector, and the component measurement is performed. Among the measurement components excluding the non-measurement component, the component having a slower separation speed than the other plurality of measurement components is trapped in the initial stage, and the other measurement components separated earlier than the component having the lower separation speed are trapped in the latter stage. A component measurement method using a column system, wherein the trapped component having a low separation rate is introduced into the detector at a timing that does not overlap with the component that is separated from the column and introduced into the detector.

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