JPS59157564A - Liquid chromatograph - Google Patents

Abstract

PURPOSE:To eliminate the need for a laborious treatment for removing a suspended material with a sample contg. the suspended material by providing a precolumn packed therein with porous glass beads in a liquid feed line connecting a sample introducing device and a sepn. column. CONSTITUTION:A precolumn 11 packed therein with porous beads having 80- 120 mesh grain size and 3,000Angstrom average pore size is provided in a liquid feed line between a sample introducing device 8 and an anion sepn. column 13. The suspended material in a sample is virtually automatically removed by the column 11. The need for a laborious treatment for removing the suspended material is thus eliminated with the sample contg. the suspended material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid chromatographs, and more particularly to liquid chromatographs that can be used even when the sample lacks a solid suspension.

As is well known, liquid chromatographs are used for qualitative and quantitative analysis in a wide range of fields, such as analysis of organic and inorganic storage and analysis of biological storage, and its application fields are increasingly expanding.

By the way, some fields that require qualitative and quantitative analysis include, for example, purchasing management of muddy water used in muddy water construction methods in civil engineering and construction, analysis of sludge, management of graded concrete for ready-mixed concrete, and management of individual water and wastewater. In addition, the liquid to be measured often contains solid suspended substances. In such cases, conventionally, the sample has been subjected to pretreatment such as centrifugation or filtration to remove suspended matter, and then subjected to analysis by body chromatography. However, the above-mentioned pretreatment requires a lot of effort and time, and there is a problem that the analysis operation becomes complicated and inefficient. %, when analyzing samples containing suspended solids, the analytical operations are often carried out at the work site, for example when managing muddy water or managing ready-mixed concrete.
There was a desire for an analysis method that did not require complicated operations.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid chromatograph that can measure samples containing suspended solids without requiring complicated pretreatment. It is something.

In order to achieve this objective, the present invention provides a pre-column filled with porous glass beads in front of a separation column in a liquid chromatograph, and uses this pre-column to remove suspended substances in a sample. It's something.

The present invention will be explained below based on embodiments shown in the drawings.

1 to 3 are diagrams showing one embodiment of the present invention, and show an example in which the present invention is applied to an ion exchange chromatograph.

First, the general structure will be explained. In FIG. 1, reference numeral 1 is a bath liquid tank, and 2 is a regeneration tank.

The feed pipes 3 and 4 drawn out from each tank 1.2 are each connected to a three-way valve 5, and the three-way valve 5 is further connected to the introduction side of a liquid feed pump 7 via a diffusion pipe 6. . The three-way pulp 5 selectively switches between the liquid feeding path from the swamp waste tank 1 to the liquid feeding pump 7 and the liquid feeding path from the reclaimed liquid tank 2 to the liquid feeding pump 7.

The liquid sending pump 7 sends out the liquid or the regenerating liquid using a rectangular flowmeter, and a sample introduction device 8 is connected to the discharge side of the pump 7.

Furthermore, a pressure belt 9 and a damper 10 are provided in parallel between the liquid feeding pump 7 and the sample introduction device 8. The damper 10 is provided to prevent pulsating flow of the liquid sent out from the pump 7, and may be an air damper, a plunger damper, or a combination thereof. can be used. As the pressure gauge 9, one with an upper limit limiter can be suitably used, so that the device can be protected in the event of excessive pressure.
It is desirable to plan for a long time.

A precolumn 11, a cation removal column 12, and an anion separation column 13 are connected in series after the sample introduction device 8. After the anion separation column 13,
A detector 14 is provided to detect the ionized yuzu separated by the column 13. A drain tank 15 is provided downstream of the detector 14 for storing the eluted liquid and the regenerating liquid after measurement. Further, the output of the detector 14 is supplied to a recorder 16.

Next, the precolumn 11 will be explained in more detail with reference to FIG. The precolumn 11 is formed by filling a column container 20 with porous glass beads 21 as a filler. The empty container 20 has a column stopper 23.24 and a joint 25.25 at both ends of a stainless steel cylindrical part 220, and a stainless steel tube 26.26 is connected to each end via a joint 25. is now connected.

In this case, a filter is not provided at the entrance side opening of the cylindrical part 220 (the opening on the left side in the figure), and a filter is not provided inside the column stopper 23 on the entrance side toward the opening of the cylindrical part 22. A tapered portion 23a whose diameter is gradually expanded is formed.

This tapered portion 23a is provided for the purpose of preventing turbulence from occurring in the liquid flow near the opening of the cylindrical portion 22 due to the omission of the filter. Furthermore, a filter 28 is provided at the exit side opening of the cylindrical portion 22 to prevent the filler from flowing out.

The packing material 21 used in the precolumn 11 is porous glass beads, and its particle size and pore diameter are set in consideration of the appearance and properties of suspended solids in the sample to be measured. When using muddy water for muddy construction method or fresh concrete as a sample, it is suitable that the grain size is usually 80 to 120 mesh and the average pore size of oil is about 300 OA.

The inner diameter and column length of the pre-column 11 described above can be set according to the amount of suspended solids in the sample, but in order to improve separation performance, the inner diameter and column length should be set small. is desirable.

Next, the sample introduction device 8 will be explained with reference to FIG.

In FIG. 3, reference numeral 30 indicates a switching valve, and this switching valve 30
are provided with first to sixth 6 (face openings 31 to 36).The first opening 31 has an inlet conduit 37 connected at one end to the liquid feeding pump 7. Connected.Second
A sampling loop 38 whose internal capacity is set to a predetermined value is provided between the mouth portion 32 and the fifth mouth portion 35 . The third opening 33 has one end or a pressure reducing pump 39.
A sample suction tube 40 connected to is connected. A sample introduction tube 42 for introducing the sample from the sample container 41 is connected to the fourth opening 34 . The sixth port 36 is connected to an outlet conduit 43 that delivers the eluent and sample toward the separation column 13 .

Further, the valve body 30a of the switching valve 30 is formed with three passages 44, 45, 46 that open and close between the adjacent mouth portions, and by rotating the valve body 30a, the adjacent mouth portions communicate with each other. It is possible to select a suitable combination of mouth parts 31 to 360. That is, the passages 44 to 46 are
When set to the state shown by solid lines in the figure, each of the first and second openings 31, 32, third and fourth openings 33.34, and fifth and sixth openings 35.36 The parts communicate with each other, and the inlet conduit 3
A measurement state path is set from 7 to the output conduit 43 via the sampling loop 38. In addition, in the state shown by broken lines in FIG. 3, the second and third openings 32, 33,
fourth and fifth mouth parts 34, 35, sixth and first mouth parts 36,
31 are in communication with each other, and a sampling path is set from the sample container 41 to the vacuum pump 39 via the sample introduction tube 42, the sampling loop 38, and the sample suction tube 40.

Next, the operation of the above body donation chromatograph will be explained.

During measurement, the eluent in the eluent tank 1 is constantly sent to the separation column 13 at a predetermined flow rate by the liquid feed pump 7, as in a normal adult chromatograph. A predetermined amount of sample is introduced from the sample introduction device 8 into this steady flow of eluent. The samples used here do not require treatment to remove suspended solids. This introduction of the sample is performed by the following operations of the sample introduction device 80.

First, the switching valve 30 is connected to its passages 44, 45, 46 or to the second and third openings 32, 33 as shown by broken lines in FIG.
, fourth and fifth openings 34.35, sixth and tenth openings s36
．． 31 are set to communicate with each other. In this state, t6?a flows from the first port s31 to the sixth port 36 through the passage 46. In this state, timer 5
0, the decompression pump 39 operates for the time set in the timer 50, and as a result, the sample inside the sample container 41 flows into the sample introduction tube 4 as shown by the dashed arrow in the figure.
2 - channel 45 - sampling loop 38 - channel 44 - sample aspiration v40. Here, the set time of the timer 50 may be set to a value equal to or longer than enough to fill the inside of the sampling loop 38 with the sample to be measured.

Next, rotate the valve body 30a. Passage 44°45.4
6 to the position shown by the solid line in FIG.

As a result, the eluent sent from the liquid pump 7 pushes the sample in the sampling loop 38 to the outlet pipe 43 through the inlet pipe 37 and the passage 44, and the sample is sent toward the next precolumn 11. .

The eluent into which a predetermined amount of sample is introduced by the sample introduction device 8 is
It is then introduced into a precolumn 11, where suspended solids that may be present in the sample are removed.

Components with large particle sizes in the suspended solids are trapped between the particles of porous glass beads, and components with small particle sizes are trapped between the particles of porous glass beads.
It is trapped and stratified within the pores of porous glass beads. Here, the reason why porous glass beads were used as the packing material for the pre-column 11 is that they are highly rigid materials and are not easily affected by the packing state between the glass beads particles even when suspended substances are stratified. 'Therefore, it is difficult to cause blockage in the pipe.

The common components in the sample pass through the pre-column 11 and are sent to the cation removal column 12 in a bath. In this cation removal column 12, a cation package that serves as a barrier to the separation of anions in the next-stage separation column 13 is removed. fI Kasumi 1 handles the sample that has passed through the cation removal column 12
The f liquid is sent to the anion separation column 13, where it is separated into individual ions by the ion exchange action with the packing material and sent out.

Each ion column separated by the separation column 13 is placed in the bath l! l1
1. It is sent to the detector 14 together with e, and is commonly used for determining ion concentration and the like. The detection output of the detector 14 is detected by the recorder 16.
This provides a chromatogram based on retention time and retention capacity.

According to the adult chromatograph of the present invention as described above, even samples containing suspended solids can be subjected to measurement without the need for complicated pretreatment of removing suspended solids. Analytical operations become very simple. In addition, as the sample introduction device is equipped with a device that guides the sample loosely introduced with a predetermined Sm into the measurement path by operating a valve, it is easier to introduce the sample than the conventional sample introduction operation using a microsyringe. Does it require operations that require skill? Therefore, analysis can be easily performed with good reproducibility.

In the above embodiments, an example in which the present invention is applied to an ion crossing chromatograph has been described, but the present invention is not limited to this, and can be applied to various systems such as a partition chromatograph, a molecular sieve chromatograph, an affinity chromatograph, etc. It can also be applied to chromatography.

Further, although an example has been shown in which the sample introduction device includes one sampling loop, a structure may also be adopted in which a plurality of sampling loops with different capacities are provided and a desired sampling loop is selected by operating a valve.

As explained above, the adult chromatograph of the present invention is provided with a pre-column filled with porous glass beads between the sample introduction device and the separation column, and this pre-column allows the sample to be impregnated. Since suspended solids are removed before being subjected to separation in a separation column, there is no need for complicated sample pretreatment, and therefore samples containing suspended solids can be analyzed efficiently with simple operations. I can do it.

In particular, the sample introduction device is configured to switch between the sampling route, which introduces the sample loosely in the amount of sampling, and the measurement route, which incorporates the sampling loop into the meridian from the liquid pump to the separation column, by operating a valve. , it is possible to introduce a predetermined volume of sample with good reproducibility without requiring any skill or causing individual differences, and therefore, in combination with the above-mentioned advantage that pretreatment is unreliable, it is possible to introduce a sample of a predetermined volume with good reproducibility without requiring any skill or causing individual differences. It has the advantage of being able to analyze samples efficiently and at a high degree of accuracy through quantitative operations, and is suitable for use in various sites where complicated operations must be minimized.

Next, the present invention will be explained in more detail by showing experimental examples.

[Experimental Example 1] Anion and cation analysis of mud water (bentonite mud water) for mud construction method was carried out using an ion father exchange chromatograph having the configuration shown in FIG.

The precolumn used was a column container with an inner diameter of 7.5 mta (if column length of 10 crn) filled with porous glass beads having a particle size of 80 to 120 mesh and an average pore diameter of 3000 A as a packing material. Also, °
The components of the sample used are as follows.

0 Sample bentonite 6.0% Sodium hexametaphosphate 0.2% Tap water Residual anion measurement conditions are as follows.

O anion analysis eluent = 7 Potassium hydrogen talate 5mM Sample collection amount:
100111 Flow rate: 1.5 ml/w Ion separation column: Wescan anion column The measurement conditions for cations are as follows.

0 cation analysis bath t'711? [k: p-phenylenediamine
5mM hydrochloric acid 5m [Sample collection amount: 100μ1 tfrt, ijt: 1.5ml/w Cation separation column: Wescan cation column As a result of analyzing anions and cations under each of the above conditions, A chromatogram shown in FIG. 4 was obtained.

In Figure 4, curve A is the anion chromatogram, curve m
It is a chromatogram of BldlN ion. As a result of comparing and analyzing these chromatograms with the chromatograms obtained in advance using standard samples, it was determined that the peak C of curve A was the same as Cl-, and the amount thereof was determined to be 54. Ma7'h song & IB no peak DldMg'+(
511P) was identified and quantified, and the peak E was Oa” (5
flF) was identified and quantified.

From the above results, the liquid chromatograph of the present invention can also be used for samples containing suspended solids (bentonite in this case).
It was confirmed that it is possible to analyze ions with a concentration of less than pa.

For comparison, when we attempted to analyze anions and cations separately under the same conditions as above without using a precolumn, the separation column was clogged after one measurement, and the separation pressure was It reached 25o kg/crd or more and no chromatogram could be obtained. Additionally, the separation column used became unusable.

[Experimental Example 2] Measurement and regeneration were repeated under the same conditions as in the anion measurement shown in Experimental Example 1, and the pressure inside the channel was examined for each measurement. The results are shown in FIG.

From this experiment, the liquid chromatograph according to the present invention was able to carry out more than 50 measurements under the above conditions for a sample containing a suspension (bentonite), and the pressure inside the flow path was 100 kg77.
It has been confirmed that the process can be carried out with the following conditions.

In addition, after the measurement when the pressure in the channel reached 120 to 9/(d), when only the precolumn was replaced and the same measurement was performed, the pressure in the channel decreased to approximately 0 kg/d. ,
It was confirmed that most of the suspended particles were trapped within the precolumn. It has therefore been found that if the precolumn is well maintained, the separation column can be maintained in a manner similar to that of a chromatograph applied to samples without conventional suspension intermediaries.

[Brief explanation of the drawing]

FIG. 1 is a schematic configuration diagram showing an example of the present invention, FIG. 2 is a sectional view showing an example of a precolumn, FIG. 3 is a schematic configuration diagram showing an example of a sample introduction device, and FIG. Figure 8g5, which is a diagram showing a chromatogram of anions and cations obtained in Experimental Example 1, is a graph showing the relationship between the number of measurements obtained in Experimental Example 2 and the pressure inside the channel. 7...Liquid feed pump, 8...Sample introduction device, 11...
- Pre-column, 13... Anion separation column (separation column), 14... Detector (detection device), 20... Column container, 21... Filler, 30... Switching valve, 37
...Inlet conduit, 38...Sampling loop, 39
...Reduction pump, 40...Sample suction tube, 42...
Sample introduction tube, 43...Output conduit, 44°45.46.
··aisle. Applicant Shimizu Corporation

Claims (1)

[Scope of Claims] 1. A rapid-generation pump for constantly pumping the ordinary e.g.;
A sample introduction device for introducing a sample into the adult cattle sent from this rapid generation pump, a separation column connected to the feeder of this sample introduction device, and a detection device connected to the rear stage of this separation column. In a liquid chromatograph comprising a device, a break column filled with porous glass beads is interposed in the rapid formation path connecting the sample introduction device and the separation column. liquid chromatograph. 2. The particle size of the pre-Hpi porous glass beads is 80-1
20 mesh, and the average pore diameter is about 300OA
The adult chromatograph according to claim 1, characterized in that: 3. The sample introduction device or the sample introduction tube connected to the sample container, the sample suction tube connected to the vacuum tube, the sampling loop having a constant internal volume, and the rapid production pump connected an inlet conduit, an outlet conduit connected to the separation column, and a switching valve, the switching valve comprising:
A sampling path from the sample introduction tube to the sample suction tube via the sampling loop, and a measurement path from the input conduit to the output conduit via the sampling loop can be selectively set. Liquid chromatograph according to scope 1 or 2.