JPS59157563A - Molecular sieve type liquid chromatograph - Google Patents

Abstract

PURPOSE:To analyze efficiently a sample contg. a suspended material with a simple operation by disposing precolumns packed therein with porous glass beads in the fore stage of molecular sieve type sepn. columns and removing the suspended material in the sample. CONSTITUTION:The sample from a sample introducing device 6 is conveyed by an eluate such as pure water or the like supplied via a liquid feed pump 4 from a tank 1 and is admitted into the precolumns 9 in a precolumn part 10 which are disposed in the fore stage of molecular sieve type sepn. columns 11, 11', etc. and are selected by corresponding inflow valves. Porous glass beads having 80- 120 mesh grain size and 3,000Angstrom average pore size are packed in the columns 9, by which the suspended material in the inflow sample is satisfactorily and automatically removed. There is therefore no need for performing a pretreatment, etc. for removing the suspended materials and the analysis of the sample contg. the suspended material is efficiently accomplished with the simple operation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a molecular sieve type liquid sieve.

As is well known, the molecular sieve Chroma 1 Hegelaphi
It is an analytical method for separating, identifying, and quantifying components in I according to molecular size, and is widely used in various fields.

By the way, fields in which the molecular sieve chromatography of this scale is desired include the management of muddy water for muddy water construction methods in civil engineering construction, the management of various types of water and wastewater, and the analysis of sludge. may be applied to liquids contaminated with For example, management of muddy water for muddy construction methods has conventionally been carried out based on analysis of physical properties such as funnel viscosity and specific gravity. However, as the volume of muddy water used increases due to larger-scale construction projects, thickeners such as carboxymethyl cellulose (CMC) and polyacrylic acid Chemically analyze the amount of dispersants added, such as sodium and sodium hexametaphosphate, to scientifically refine muddy management methods, thereby improving the quality of muddy water and optimizing its use in mud production. is required. Molecular sieve chromatography, which is difficult to compare the influence of the chemical properties of each substance, is suitable for analyzing the above-mentioned polymeric substances and organic substances, but in the conventional molecular sieve chromatography, When measuring a sample containing suspended solids such as the muddy water mentioned above, it is necessary to remove the suspended solids by means such as centrifugation or filtration, which poses the problem that the analysis operation is extremely cumbersome. .

In view of the above-mentioned circumstances, the present invention was made for the purpose of providing a molecular sieve type liquid chromatograph capable of measuring samples containing suspended solids without the need for complicated pretreatment. It is.

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

FIG. 1A to FIG. 3 are diagrams showing an embodiment of the molecular sieve type liquid chromatograph of the present invention.

In these figures, the outline (711 configuration) will first be explained with reference to FIG.

In FIG. 1, reference numeral 1 indicates a solution tank.

This pre-solution solution tank//1 contains pure water or a salt solution <Na CR, Ca C92, K C9, etc.) as the solution H1 solution, and the solution pipe 2 is used to send out the solution H1 solution.
is connected. A deaerator 3 is connected to the delivery side of the liquid feed pipe 2. This deaerator 3 removes oxygen in the eluent, which is the cause of fluctuations in the baseline and intensities of the detector, which will be described later. It is set up for the purpose.

A liquid feed pump 4 is connected to the delivery side of the deaerator 3. In this case, a single plunger pump is used as the liquid pump 4, which facilitates maintenance and inspection. A sample introduction device 6 is connected to the discharge side of the liquid feeding pump 4 via a liquid feeding pipe 5. Further, a pressure gauge 7 and a damper 8 are connected to the intermediate portion of the liquid sending pipe 5, respectively.

The above-mentioned pressure) J ff+ 7 is of a type equipped with an upper pressure limiter, and the operation control of the pre-distribution liquid pump 4 etc. is performed in conjunction with this limiter, so that it can be used in the event of excessive pressure. The equipment is protected. Further, the damper 8 is provided to prevent pulsating flow of the eluent sent from the liquid delivery pump 4, and in this case, since a single plunger pump is used as the pre-delivery liquid pump 4, An air damper 8a that is effective at low pressures and a plunger damper 8b that is effective at high pressures are used together.

The sample introduction device 6 includes a sample introduction port 6a for introducing the sample toewise into the eluent in the measurement channel, and a quantification section 6b for quantifying the sample sent to the sample introduction port 6a. For example, a plurality of pre-columns 9, 9, .
A pre-column section 10 having a pre-column section 10 is connected thereto. As will be described in detail later, the pre-column section 10 has switching valves on its inlet side and outlet side, respectively, and by operating the switching valves, any one of the plurality of pre-columns 9.9... , are selectively installed in the measurement flow path. Also,
Each precolumn 9.9... has a porous glass plate inside.
These porous glass beads have the function of removing suspended solids from the sample.

On the delivery side of the pre-column section 10, two molecular sieve type separation columns 11, 11' are connected in series. These separation columns 11,11' are filled with porous glass beads as packing material. The reason why porous glass beads were used as the packing material for the separation column is that porous F1 glass beads have cavities (so-called water channels) in the column and move even when air is mixed in, which deteriorates separation performance. By not inviting. Therefore, porous glass beads can be used for viscous samples such as muddy water that easily entrains air during sample introduction.
Suitable for molecular sieve type columns where IL is the measurement target.

Furthermore, a detection means 12 for detecting each component in the eluent separated through the separation column 11.11' is connected to the delivery side of the separation column 11'. In this embodiment, d5 uses a high-sensitivity differential refractometer 12 as a detector.
a and the ultraviolet absorption detector 121) are used for (jf).

The differential refractometer 12a performs qualitative and quantitative determination of the component based on the difference in refractive index between the component separated by the separation 1 column 11.11' and the eluent. As the ultraviolet absorption detector 121), one that can be set to any wavelength can be suitably used, and it is usually set in the range of 200 to 220 μm, and if necessary, it can be set to any wavelength. By setting the wavelength to 1 (for example, 280 .mu.m when detecting aromatics), it is possible to detect various substances in a partial manner.

Detection outputs from each of the detection means 12a and 1211+ described above are input to a recorder 13, and this recorder 13 is used to obtain a 3° clontogram based on retention time and retention capacity. Note that reference numeral 14 in the figure is a drain tank for storing the drain after passing through the detection means 12.

Next, the precolumn 9 alone will be explained with reference to FIG. The precolumn 9 is formed by filling a column container 20 with porous glass beads 21 as a filler. The empty container 20 has a cylindrical portion 22 made of stainless steel.
Column plugs 23.24 and joints 25. are installed at both ends of the column.
25, each end of which is connected to an inlet pipe 26 and an outlet pipe 27 via the joints 25, 25, respectively.

In this case, the inlet opening of the cylindrical part 22 (the opening on the left side in the figure) is not provided with a filter, and the inside of the column stopper 23 on the inlet side is directed 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 a filter.
A filter 28 for preventing the charging agent 21 from flowing out is provided at the opening on the exit side of the tank.

The packing material 21 used in the pre-column 9 is porous glass beads, and its particle size and pore diameter are set in consideration of the suspension and properties of the suspended solids to be measured. For example, when testing muddy water or ready-mixed concrete for muddy water construction, a particle size of 80 to 120 pores and an average pore diameter of about 3,000 pores is usually suitable.

In addition, the inner diameter and column length of the above-mentioned precolor l\9 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. It is desirable to do so.

Next, a pre-column section 1 including a plurality of the above-mentioned pre-columns 9 is prepared.
0 will be explained with reference to FIG.

The pre-column section 10 has an inlet side switching valve 30 and an outlet side switching valve 31 on the inlet side and the outlet side, respectively. The inlet side switching valve 30 has one inlet port 32 and six outlet ports 3.
3a, 33b, 33c, 33d.

9-338.33f, and the valve body 34 has a passage 35 for selectively communicating between the inlet port 32 and any one of the outlet ports 33a to 33f. It is formed. Further, the outlet side switching valve 31 has six inlet ports 3.
6a, 36b, 36c.

36 (1, 36e, 36f) and one outlet port 37, and the valve body 38 has the inlet ports 36a to 36f.
A passage 39 is formed for selectively communicating between one of them and the outlet portion 37.

The introduction side switching valve 30 has an inlet port 32 connected to the above-mentioned trial introduction charge 6, and also connects to an outlet port 33a.
3r is connected to one end of a precolumn 9 via an inlet pipe 26, respectively. The other end of each pre-collar l\9 is connected to each inlet port 3 of the outlet side switching valve 31 via the outlet pipe 27.
6a to 361'. At the outlet portion 37 of the outlet side switching valve 31, the previously blown separation column 11 is connected.

Thus, in the above configuration, the Breno J ram section 10 switches the six precolumns 9, 9, .
Any one of the precolumns 9 can be selectively placed in the measurement channel.

Note that the switching valve 30 on the inlet side and the outlet side mentioned above. .

31 is, for example, driven by a motor,
In addition, the selection and setting operations of the pre-column 9 can be performed electrically by interlocking each motor. Furthermore, the drive control of the motor is performed based on the detection signal of the pressure inside the flow path, so that the adsorption amount of turbid substances inside the pre-column 9 in use is constant, and the pressure is kept at a predetermined value. It is also possible to switch to another spare precolumn when the precolumn rises above this level.

Next, the operation of the above molecular sieve chromatograph will be explained.

The operation of W during measurement is almost the same as that of a conventional chromatograph. Trial is carried out by introducing the trial Fl introduction device 6.If the sample used for this contains suspended solids, it is necessary to remove them!r<, if necessary, dilute and stir the sample before stirring. After pre-processing during the song, direct measurement (
You can donate.

The introduced trial is Solu I! Lucarano \ part 10f7) with il'a? After removing the turbid substances, the components are removed by the pre-column 11.11'. A detector 12a,
1211, where each component is detected at a constant rate. The outputs of the detectors 12a, 12b are fed to the recording Mt 13, which allows molecular sieving! ] 7 tograms are obtained 1
゜The action of the precolumn 9 in the above measurement operation is as follows ^7.
As mentioned above, this is the effect of removing suspended solids during sampling.

Components with large particle diameters in the suspended solids are captured and adsorbed between the ladles of porous glass beads, and components with small flow diameters are captured and adsorbed within the pores of porous glass beads. Ru.

The reason why porous glass beads were used as the packing material in the pre-column 9 is that they are highly rigid materials, and even when suspended substances are adsorbed, the packing state between the glass beads particles is not easily affected. This is because it is difficult to cause blockage in the pipe.

In the above-mentioned pre-column 9, as the number of measurements is increased, the amount of suspended solids adsorbed to the internal porous glass beads increases, and the flow resistance gradually increases accordingly. Therefore, the pressure in the front flow path of the precolumn 9 is to a certain extent (usually 100 ka/c).
m' culm degree) or more, the pre-column 9 is switched. In the above chromatograph, the switching valves 30 on the inlet side and outlet side of the precolumn section 10. ．． 31
By operating the pre-column 9, the pre-column 9 can be switched. This switching operation can be performed simply by rotating the valve bodies 34 and 38, so it can be performed without requiring much time while the device is in operation.
- It is preferable to carry out the end of the measurement before the measurement of the tangential method is carried out.

The used precolumn 9 can be replaced with a new precolumn even when the device is in operation. Therefore, the precolumn installed in the precolumn section 10 and 13- can be replaced by separately preparing the required number of similar precolumns. , it is possible to perform continuous measurements many times. In fact, according to the experiments of the inventors (later J.D.), it is possible to perform several tens of measurements with one wooden precolumn, and in an apparatus equipped with six precolumns 9 as in the illustrated embodiment. b, Breno J
Hundreds of measurements can be made without changing the ram.

In addition, since the column column A11.11' is filled with porous glass beads or syringel as a packing material, even if air enters the column 11.11' when introducing the sample, etc. No cavities are formed inside, and separation performance is not impaired.

According to the molecular sieve type liquid chromatograph of the present invention as described above, a pre-column packed with porous glass beads is disposed before the molecular sieve type liquid chromatograph, and this pre-column allows the concentration of particles in the sample to be detected. Since the suspended solids are sent to the separation column after being removed, there is no need to pre-process the sample even when the sample containing suspended solids is to be measured. It is possible to efficiently carry out trial analysis including analysis with simple operations. In addition, multiple Preno J rams are arranged between the switching valves on the inlet side and the outlet side, making it possible to selectively set any precolumn in the measurement flow path. A large number of measurements can be performed continuously, and the number of maintenance operations such as pre-column replacement can be reduced accordingly. Furthermore, since porous glass beads or silinocogel are used as the packing material for the molecular sieve separation column, even if air enters the measurement flow path, water will not form inside the column. , without impairing separation performance.

Therefore, it can be suitably used for analyzing samples containing suspended substances that tend to entrain air.

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

[Experimental Example 1] Using a molecular sieve chromatograph having the configuration shown in FIG. 1, CMC added as a thickener to muddy water for muddy water construction was analyzed and its fixed loss property was investigated.

As a precolumn, the inner diameter is 7.5nnnφ and the column length is 1.
Particle size 80~ as packing material in 0 CTll column container
A material filled with porous glass beads having a diameter of 100 mm and an average pore diameter of 3000 mm was used. In addition, the trial r1 used
The components of are as follows.

○Sample CMC: 0.3% Pen 1~Night: 3.0% Shielding clay = 3.0% Tap water: Remaining part ○Measurement strip A'1 Separation collar l\\1 Nia, 5mmφX50CT11m
m side: porous glass beads particle size 200-40
0 mesh, 3000 pore diameter, human-soluble l1lIi liquid: Pure water flow rate: 1,5 ti/min Under the above conditions, the sample sample amount was (△) 30μ! and (B) 6011f
Measurements were performed using the following settings, and the chromatograms shown in FIGS. 71(A) and (B) were obtained.

However, in Fig. 4 (A), the trial sampling amount is 30μ, (F3>
is the result for a trial sampling amount of 60μ).

Regarding the obtained chromatogram, we investigated the relationship between the spectral area and the sampling amount (i.e., CM Cffl: ), and found that there was a proportional relationship, and it was found that for samples containing suspended substances such as bentonite and shielding clay, It was confirmed that it is possible to quantitatively analyze right Ia components such as CMC.

[Experimental Example 2] Using the same molecular sieve chromatograph as in Experimental Example 1, the following water distribution was analyzed as Trial F1: one immediately after muddy water preparation, and one that had deteriorated after being used in the field.

○Trial bentonite 2 0.6% CMC: 0.2% Sodani polyacrylate 0.2% Tap water: Remainder 17- ○Measurement strip A'J Separation column 1 method: 7.5nrmφX50cm Packing material: Porous glass beads Particle size 200~/l OO Metsy I Pore size 240 Eluent: @Water flow rate: 1. Oy! /min Sample sampling rate: 00 μm Under the above conditions, analysis of mud water before and after use was carried out, and the mud before use was shown in Figure 5 (A).
5(B) after use of 1:1.

Regarding each of the above chromatograms, each peak was identified using a chromatogram previously measured on pure products of CMC and sodium polyacrylate.Beak C in Figure 5 (A) is a CMC polymer component, and beak D is a CMC polymer component. It was found that 18- is sodium polyacrylate, beak E is a CMC low-molecular component, and beak F in FIG. 5(B) is a CMC high-molecular component. By comparing these chromatograms, it can be seen that in the degraded mud water, the peaks of CMC and sodium polyacrylate decrease, and a large spectrum is observed at a retention time of 25 to 30 minutes. This is because CMC is hydrolyzed by fungi etc. and low molecular weight substances are generated.
It can be concluded that the sodium polyacrylate reacted with salts (Ca2'', -2'', etc.) eluted from the soil during excavation and precipitated.

Furthermore, from the above experiments, it was confirmed that the molecular sieve chromatograph of the present invention is very effective in managing muddy water.

[Experiment Example 3] Under the same conditions as the measurement of muddy water shown in Experiment Example 2, measurements were repeated for the following trial containing more hanging bentonite than Experiment Example 2, and the pressure in the flow path was investigated for each number of measurements. . The results are shown in FIG.

○Test $+1 Bentonite = 6.0% CMC: 0.2% Sodium polyacrylate: 0.2% Tap water: Remainder From this experiment, the molecular sieve chromatograph according to the present invention can be used for separations containing suspended solids. ,” 50 under the conditions described in Part 2.
The mantissa was measured at a pressure in the flow path of 100 kfl/'c.
−+? It has been confirmed that the following can be done:

Also, the pressure inside the flow path has increased to 120 ka/ci)! After the first measurement, the precolumn in the precolumn part was switched and the same measurement was performed again.
g/cnF, and it was confirmed that most of the suspended matter was trapped in the precolumn.

It has therefore been found that if the pre-column is well maintained, the separation column can be maintained similarly to that of the chroma l-graph applied in conventional suspension-free separations.

[Brief explanation of the drawing]

FIG. 1 shows an example of the present invention; FIG. 2 is a sectional view showing an example of a single pre-column; FIG. 3 shows an example of a single pre-column; Figure (A) is the chromatogram when the sample collection amount was 30 II J according to Experimental Example 1, and Figure 4 (B) is the chromatogram when the sample collection amount was
The chromatogram in the case of 0μ, FIG. 5 (Δ), is the chromatogram I\ of the muddy water obtained in Experimental Example 2 before use, and FIG. 5 (B) is the chromatogram of the muddy water after the same use. 6 is a graph showing the relationship between the number of measurements obtained in Experimental Example 3 and the channel internal pressure angle. 1...Eluent tank, 4...Liquid pump, 6...Test F4 L'lJ device, 8...
...Damper, 9...Precolumn, 10...
...Pre-column section, 11.11'...Molecular sieve type separation column, 12...Detection means, 20.
... Column container, 21 ... Porous glass beads, 23a ... Tapered part, 30 ...
・Inlet side switching valve, 31... Outlet side switching valve, 32
...Introduction port, 33a, 33b, 33c,
33d, 33e, 33f--Outlet port, 35-
...Passage, 36a, 36b, 360. 36d, 36e, 36f...Inlet port, 3
7... Outlet portion, 39... Passage. 21- Ifu faction＼? sect

Claims (1)

[Claims] 1. A sample introduction device for introducing a sample into the eluent is connected to the discharge side of a liquid feeding pump for force-feeding the eluent, and on the delivery side of the sample introduction device, 1. The inlet port of an inlet side switching valve which has a plurality of inlet ports and a plurality of outlet ports and selectively opens a circuit between any one of the inlet ports and the inlet port is connected to the inlet port. Each inlet end of a pre-column filled with porous glass beads is connected to at least two of the outlet ports of the side switching valve, and the outlet end of each pre-column is connected to a plurality of inlet ports and one The respective inlet portions of the outlet-side switching valve are connected to each other, and each of the inlet ports of the outlet-side switching valve is connected to the outlet-side switching valve, which has a plurality of outlet ports and selectively opens a circuit between an arbitrary inlet port and the outlet port. A molecular sieve separation column filled with porous glass beads or porous silica gel for separation is connected to the outlet, and a detection means is connected to the delivery side of the molecular sieve separation column. Molecular sieve type liquid chromatograph. 2. The porous glass beads packed in the pre-column have a particle size of 80 to 120 pores and an average pore diameter of about 3000 pores, according to claim 1. molecular sieve liquid chromatograph.