JPS61118659A - Column chromatography apparatus - Google Patents

Abstract

PURPOSE:To perform the analysis of an objective component with good accuracy and efficiency, by performing analysis by extraction and concentrating only the objective component present in a concn. range lower than an analytical limit. CONSTITUTION:The carrier gas from piping 9 reaches an analytical column 3 along with the specimen to be analyzed received in a measuring tube 12 and said specimen is separated at every components to be detected by a detector 7 and recorded. In order to determine the holding time of a minute amount of an objective component equal to or less than a detection limit, the standard specimen containing said component is injected. After the elapse of a predetermined time, the objective component is detected by the detector 7 and the holding time (t), before the objective component is flowed out from the column 3, can be determined. Thereafter, a specimen to be analyzed is flowed into the measuring tube 12 from piping 13 and a circuit connected by broken line is subsequently set to flow the specimen into the column 3 along with the carrier gas. When the circuit shown by the solid line is again set, the objective component reaches the measuring tube 12 and mixed with the specimen to be analyzed while the resulting mixture is again flowed into the column 3 through return piping 16 and the concn. thereof increases in proportion to the number of repetitions.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to various column chromatography devices such as gas chromatography, liquid chromatography, and high-performance liquid chromatography, and particularly to column chromatography suitable for extracting and concentrating only trace components of interest. Regarding equipment.

[Background of the invention]

Conventionally, when analyzing trace components contained in a sample using a column chromatography apparatus, it is necessary to concentrate the trace components to a level exceeding the detection limit before performing the analysis.

As such a column chromatography device, JP-A No. 5
As disclosed in No. 5-37945, before injecting an analysis sample into a gas chromatography separation column, only a trace amount of the target component is adsorbed onto a coolant and concentrated, and then this concentrated trace amount of target component is concentrated. The target components were driven out by heating and then introduced into a column for analysis.

In the above gas chromatography apparatus, when the concentration operation is performed using a coolant, components having a lower melting point than the component of interest are simultaneously cooled and concentrated, making it difficult to separate and concentrate only the component of interest using the coolant. Therefore, if the detection peaks of various components in a concentrated sample are close to each other,
There was a problem in that the bases of the profiles of each component overlapped and the analysis accuracy did not necessarily improve.

Furthermore, depending on the component of interest, it may be necessary to change the temperature of the coolant, so the efficiency of analysis is not necessarily sufficient.

[Purpose of the invention]

The purpose of the present invention is to extract and concentrate only the component of interest in a concentration range lower than the analysis limit of the column, and to concentrate and analyze only the component of interest, thereby reducing the analytical ability of the target component with accuracy and efficiency. An object of the present invention is to provide a column chromatography device suitable for the following.

[Summary of the invention]

The first invention of the present application is to mix the target components in the analytical sample separated by the separation column into the analytical sample added to the carrier that is newly supplied to the separation column, and by performing this operation multiple times, only the Nissei component can be extracted. This column chromatography device is characterized by growing the concentration of target components and analyzing these grown target components together with a detector.

The second invention of the present application stores the target component in the analytical sample separated by the separation column, and performs this storage operation for each newly supplied analytical sample to grow the concentration of only the target component, This column chromatography apparatus is characterized in that these grown target components are analyzed together using a detector.

[Embodiments of the invention]

Next, preferred embodiments of the column chromatography apparatus according to the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a block diagram showing an embodiment of the first invention of the present application, and shows a gas chromatography apparatus.

In the figure, an inlet pipe 1 through which carrier gas is supplied is connected to a pipe 21 via two cocks in a four-way cock 2 and 2B, and this pipe 21 is connected to a separation column 3. This separation column 3 is connected to a pipe 22, and the pipe 22 is connected to a detector 7. This detector 7 is connected to a pipe 23, and this pipe 23 is connected to a pipe 24 via cocks 4A and 4B in the four-way cock 4. Piping 24 is cock 5A in hexagonal cocks 5 and 6.
, 5B, 6A, and 6B to a resistor 18, and this resistor 18 is connected to the outlet pipe 8. A cock 5C in the hexagonal cock 5 is connected to a sample inlet pipe 11, and the sample inlet pipe 11 is connected to a calibration tube 12 via cocks 5C and 5D. This calibration tube 12 is connected to the sample outlet piping 1 via cocks 5E and 5F in the hexagonal cock 5.
Connected to 3.

A carrier gas inlet pipe 14 is connected to the cross section C in the hexagonal cross section, and this carrier gas inlet pipe 14 is connected to a carrier gas outlet pipe 15 having a resistance via the cross section C and 6D within the six-way cross section. A carrier gas inlet pipe 19 is connected to the cross section F in the hexagonal cross section, and this carrier gas inlet pipe 19 is connected to the return pipe 16 via the cross sections F and 6E in the hexagonal cross section. This return pipe 16 is connected via the cocks 2C and 2D in the four-way cock 2 to a carrier gas outlet pipe 17 having resistance.

A carrier gas inlet pipe 9 is connected to the cock 4C in the four-way cock 4.
is connected to a carrier gas outlet pipe 10 having a resistance via 40, 4D in the four-way cock 4.

The portions indicated by broken lines in the four-way cocks 2 and 4 and the six-way cocks 5 and 6, that is, the two cocks in the four-way cock 2 and the 2D
Between 2B and 2C, between cocks 4A and 4 of the four-way cock 4
Between D, between 4B and 4C, between cocks 5A and 5D of the six-way cock 5, between 5B and 5B, between 6A and 6E of the six-way cock
Between 6B and 6C, piping indicated by the solid lines of each cock and piping whose flow paths can be selectively switched are connected.

Next, the operation of this embodiment will be explained.

First, before sample analysis, the circuit connected by the solid line in FIG. 1 is activated, and carrier gas flows through each four-way cock or six-way cock to remove impurity gas in the piping. On the other hand, the analysis sample is supplied from the sample supply pipe 11,
Calibration tube 1 passes through cocks 5C and 5D in hexagonal cock 5.
2 and after a predetermined amount of the analysis sample is accumulated in the calibration tube 12, the excess sample is discharged from the pipe 13 with carrier gas via the cocks 5C and 5B.

Next, when analyzing the sample stored in the calibration tube 12, first, the four-way cock 2,
4 or the hexagonal cocks 5 and 6, the dashed line portions in each cock are connected, and the solid line portions are closed. The carrier gas flowing in from the carrier gas inlet pipe 9 passes through the cocks 4C and 4B in the four-way cock 4 and reaches the six-way cock 5, and then passes through the cocks 5A and 5D in the six-way cock 5 to the test pipe 12.
leading to. The carrier gas that has passed through the calibration tube 12 passes through the cocks 5B and 5D in the hexagonal cock 5 together with the analysis sample in the calibration tube 12, and reaches the hexagonal cock 5, where it reaches the hexagonal cock A.

6E and reaches the four-way cock 2 from the return piping 16.

In the four-way cock 2, the carrier gas containing the analysis sample passes through the cocks 2C and 2B and reaches the analysis column 3, where each component is separated. At this time, at the outlet of the analytical column 3, various components contained in the analytical sample are separated for a constant retention time by keeping the type and flow rate of the carrier gas, or the material and temperature of the column constant. The peaks of the various components separated by the analysis column 3 are detected by the detector 7 and recorded. An example of this detected peak will be explained with reference to FIG. The horizontal axis of FIG. 2 shows the retention time, and the vertical axis shows the intensity proportional to the concentration of the component. Now, by determining the sample injection conditions, the retention time of each component can be uniquely determined.In the figure, the components with the shortest retention time are numbered 200, 201, 202, 203, and 204, and number 200 is the component of the normal carrier gas. It often shows a peak.

Now, assuming that the trace amount target component to be concentrated and measured above the detection limit of column 3 and detector 7 is the peak indicated by number 203, the operation of concentrating this target component will be described below.

As a first step, consider the state of the flow paths connected by solid lines in FIG. In this case, the detector 7 outputs only a background signal of the carrier gas. First, in order to determine the retention time of the target component in the sample, in column 3,
A standard sample containing this target component is injected. For this purpose, a standard sample 203 of the target component is previously introduced into the circuit leading to the calibration tube 12 in the hexagonal cock 5. Next, the four-way cocks 2 and 4 and the six-way cocks 5 and 6 are switched simultaneously to form a flow path connected by broken lines.

Then, the standard sample flows into column 3 via column 2. After a predetermined period of time has elapsed, each cock is switched on at the same time again, and the circuit is connected with a solid line. In this case, the carrier gas peak 200 and the target component 20 shown in FIG.
3 is detected by the detector 7. With this operation,
After injecting the sample, the retention time during which the target component flows out of the column 3 can be determined. By applying this operation to components other than the target component, such as 201, 202, and 204, their retention times can also be determined. FIG. 3 shows an example of the determination of the retention time of the target component 203 using a standard sample. In the figure, the time from sample injection to the center point of the peak value of the target component, that is, the time (retention time) t until the target component in the sample passes through the analytical column 3 and piping 22 and reaches the detector 7, is determined. . - Concentrate the target component by switching the cock based on this holding time t.

In the second step, after determining the retention time using the standard sample, the sample to be analyzed is flowed into the calibration tube 12 in the cock 5 from the piping 13, and first the column 3 is connected by the circuit connected by the solid line.
Only carrier gas is allowed to flow into the inlet pipe 1.

Next, each cock is switched at the same time to form a circuit connected by a broken line.

In this case, the sample to be analyzed will flow into the column 3 together with the carrier gas introduced from the inlet pipe 9 through the cocks 4, 5 and 6.2 in sequence. After the analysis sample has flowed into column 3, each cock is switched again to form a solid line circuit. The timing at which the analysis sample flows into the column 3 is determined by the flow rate of the carrier gas and the length of the piping channel. In the solid line flow path, the column 3 separates each component as shown in FIG. Before and after the region of the target component, there are regions a and c containing components other than the target component.
exists, and from column 3, the components in region a flow out first. In the circuit shown by the solid line inside each cock, the component in area a is the piping 24 that exits through cocks 4 and 5.6.
The sum of the length of the pipe passing through A and 4B and reaching the cock 5A divided by the carrier gas flow rate (hereinafter referred to as H time). ), the circuit inside each cock is switched from the solid line to the broken line inside each cock. After time Δt+H, the circuit is switched from the broken line to the solid line again. As a result, the target component present in the area reaches the calibration tube 12 from the cock 5A, mixes with a new sample to be analyzed, and flows into the column 3 via the return pipe 16. Further, the component in the C region that flows out after the target component passes through the detector 7 and is released into the atmosphere. By repeating the above series of operations, components other than the target component are released into the atmosphere, and only the target component is extracted together with a new sample to be analyzed. Therefore, the concentration of the target component flowing out from the column 3 becomes larger in proportion to the number of repetitions than the concentration of other components. This relationship is schematically shown in (4th
It will look like the figure. In FIG. 4, the value indicated by the broken line represents the lower detection limit of 8/N. By repeating the above-described operation several times until this lower limit is exceeded, analysis in the sample becomes possible.

The repetition time for extracting the target component is the time required for all the components of the sample injected into column 3 to flow out from column 3;
That is, the holding time t shown in FIG. 3 is required to be much longer. Furthermore, the shorter the time Δt for extracting the target component, the more pure the target component can be extracted, but the ratio of increase in 87H to the number of repetitions of the concentration operation becomes smaller. Therefore, the extraction time Δt needs to be selected depending on the chromatographic analysis conditions.

For example, when analyzing oxygen, nitrogen, methane, and carbon oxide in a gas, the analysis conditions are as follows: The column packing material is Molecular Sheep 5A, the temperature is approximately 90C, and when He is used as the carrier gas, the retention time is 1. is approximately 10 minutes deep. In this case, the retention time interval for each component is 2 to
Since they are about 3 minutes apart, it is sufficient to set the extraction time Δt to within 0.5 minutes. Furthermore, if the lower limit of analysis of oxygen etc. of the analyzer is approximately IP, if the expected oxygen concentration in the sample to be analyzed is 0.1 plP, the above operation should be performed once.
Analysis is possible by repeating 0 times.

As explained above, according to this embodiment, there is no need for the concentration operation using a coolant before injecting it into the column as in the conventional example, and the method of heating the coolant and flowing it into the column, thereby reducing analysis errors. It becomes less. Furthermore, when concentrating with a coolant, it is necessary to determine the concentration of the coolant that corresponds to the target component, and since components with a longer retention time than the target component will be concentrated in the coolant together with the target component, heating Even if this is injected into the column, the S/N will not increase, but in this example, the components before and after the target component are released outside the system, and only the target component is extracted. /N
increases in proportion to the number of repetitions of the operation. Therefore, it is particularly effective for separating samples in which the target component and other components have very close retention times.

Furthermore, if the retention time t of each component is determined in advance, concentration and analysis of any component can be carried out online by simply switching the cock according to each retention time.

Next, another embodiment of the first invention of the present application will be described.

FIG. 5 is an overall configuration diagram showing another embodiment of the first invention of the present application.

This embodiment differs from the embodiment shown in FIG. 1 in that the detector 7 is installed between the column 3 and the cock 4 in the embodiment shown in FIG. In this example, the detector 7 is installed between the piping and the outlet pipe 8. In this embodiment, the same components as those in the embodiment shown in FIG. 1 are denoted by the same reference numerals, and the explanation thereof will be omitted.

Next, the characteristic parts of the operation of this embodiment will be explained.

In this embodiment, the operation of extracting and concentrating the target component using the column 3 is repeated a necessary number of times, and the target component is introduced to the detector 7 only when an analysisable S/H is reached. At this time, since the retention time of the target component is determined in advance using a standard sample, switching between the flow path indicated by the solid line and the dashed line in each cock is performed using the dashed line within each cock. By opening the flow path of the detector, there is no need to switch the flow path since detection peaks are extracted for each target component as in the embodiment shown in FIG.

As explained above, according to this embodiment, the target components are finally guided to the detector in one go, so the detector burns the analysis sample like a hydrogen salt ionization detector (FID). In this case, it is impossible to use such a detector in the embodiment shown in Fig. 1 because the structure of the target component changes, whereas in this embodiment, such a hydride ion detector or other heat conduction detector is used. This has the effect that various types of detectors such as a degree type detector (PCP) and an electron capture type detector (ECD) can be freely applied.

Next, an embodiment of the second invention of the present application will be described. 6th
The figure is a conceptual configuration diagram showing an embodiment of a column chromatography apparatus according to the second aspect of the present application. 1 This embodiment is the same as the embodiments shown in FIGS. 1 and 5.

A storage tank 6 filled with a refrigerant that stores only target components in the middle of the flow path through which carrier gas containing nine different analysis samples flows.
0 and analytical column 3, another analytical column 61
is provided between the cock 4 and the detector 7. Components that are the same as those in the embodiment shown in FIG. 1 are designated by the same reference numerals, and their description will be omitted.

Next, the characteristic parts of the operation of this embodiment will be explained.

The carrier gas passes through the inlet pipe 1, passes through the circuit shown by the broken line in the six-way cock 5, and the target component is separated in the separation column 3 together with the analytical sample in the calibration tube 12. This separation of the target component is carried out by determining the retention time in advance using a standard sample, as in the case explained with reference to FIG. Components other than the target components pass through the broken line between the two cocks and 2D in the cock 2 and are discharged into the atmosphere from the piping 62 having resistance. The target component passes through the solid line between the two cocks 2 and 2B in the cock 2 and is dragged into the storage tank 6o. The target component trapped in the storage tank 6o is driven out of the storage tank 6o by heating, flows into the column 61 again, is separated, and is guided to the detector 7. Note that the column 61 is not necessary when only the target component is trapped, but since other components may be trapped in the storage tank 60 in addition to the target component, the column 61 separates them further and the detector 7 Calibration with higher accuracy can be achieved by calibrating with .

Trapping in the storage tank 60 is performed using a refrigerant, and this refrigerant is a filler that can trap the target component by physical adsorption. only will be trapped.

As explained above, according to this embodiment, FIG.

Unlike the embodiment shown in Fig. 5, only the target components are extracted and produced, and then they are stored in a certain area and finally detected by the detector all at once. This embodiment has the advantage that switching the flow path from the solid line to the broken line and vice versa from the broken line to the solid line is easier than in the embodiments shown in FIGS. 1 and 5.

Therefore, it has the effect that the analysis time required for analyzing the target component can be shortened.

〔Effect of the invention〕

As explained above, according to the present invention, it is possible to efficiently extract and concentrate the target component contained in the analysis sample, so that the target component can be detected quickly and accurately at or above the detection limit of the analyzer. It has the effect of being able to.

[Brief explanation of drawings]

Figures 1 and 5 are conceptual configuration diagrams showing one embodiment of the first invention of the present application, Figure 2 is a graph showing an example of separation of a standard sample using a column, and Figure 3 is a diagram showing the separation of a target sample in an analytical sample. A graph explaining the extraction time, FIG. 4 is a graph showing the relationship between the number of repetitions and S/N for extraction and concentration of the target component, and FIG. 6 is a conceptual diagram showing an embodiment of the second invention of the present application. FIG. 3... Separation column, 2.4... Four-way cock, 5, 6
... Hexagonal cock, 7... Calibrator, 12... Calibrator, 16... Return piping, 60... Storage tank.

Claims (1)

[Scope of Claims] 1. A carrier inflow means for flowing the carrier into a separation means capable of separating various components contained in an analysis sample into each component, and a sample for adding a sample containing the target component to be analyzed to the carrier. In a column chromatography apparatus comprising a supply means and a detection means for detecting the target component separated by the separation means, an extraction means for extracting the target component separated by the separation means; A column chromatography apparatus comprising a mixing means for mixing a component with a newly added sample, and detecting the target component by increasing the amount of the target component in the sample. 2. A carrier inflow means for flowing the carrier into a separation means capable of separating various components contained in an analysis sample into each component, a sample supply means for adding a sample containing the target component to be analyzed to the carrier, and the separation means A column chromatography apparatus comprising a detection means for detecting the target component separated by the separation means, an extraction means for extracting the target component contained in the sample separated by the separation means from the sample; A column chromatography apparatus comprising: a storage means for storing the target component extracted by the extraction means; and an introduction means for introducing the stored target component into the detection means.