JPH03242549A - Metallic component analyzer - Google Patents

Abstract

PURPOSE:To supply a reference liquid for calibration efficiently to a concentration column by providing a treating liquid supply means immediately before a concentration means to selectively supply an eluate or the reference liquid to the concentration means selectively. CONSTITUTION:First, a reference liquid stored in a reference liquid storage section 47 is supplied to a concentration column 8 via a reference liquid supply path 48, a treating liquid supply path 31 and an inflow path 8a. Thereafter, an eluate stored in an eluate storage section 43 is supplied to the concentration column 8 via an eluate supply path 44, the treating liquid supply path 31 and the inflow path 8a. As a result, metal ions of the reference liquid trapped in the concentration column 8 are dissociated to be guided to a line 33 and analyzed by an analysis means 32 to be used for the calculation of efficient of the concentration column 8. The same operation is performed for a concentration column 9 to calculate efficiency thereof. The arrangement of the treating liquid supply means 100 achieves a higher working efficiency.

Description

[Detailed Description of the Invention] "Industrial Application Field" This invention relates to a metal component analyzer that can efficiently analyze minute amounts of metal components in ultrapure water using ion exchange separation. be.

"Prior art" As a conventional liquid component analyzer, for example,
A technique disclosed in Japanese Patent No. 80521 is known.

This liquid component analyzer will be described with reference to FIG. 3. First, reference numeral 1 in the figure is an automatic flow path switching valve.

A sample supply channel 30 is connected to the outlet of the automatic flow path switching valve 1, and the sample supply channel 30 is equipped with a pressurizing pump 2, a reaction so-called 3, An overflow capacity 4, a three-way automatic switching valve 5, a pressurizing pump 6, and a pressure switch 6A are attached. This sample liquid supply path 30 is finally connected to the first four-way switching valve 7.

This first four-way switching valve 7 has an inflow path 8a to the 1a condensation column 8, an inflow path 9a to the second concentration column 9, and a treatment i(l
The supply path 31 is also connected. The processing liquid supply path 31 includes
Pressure switch 17A, pressurization pump 17, and eluent reservoir 1
There are 8 each.

The outflow path 8b from the eleventh agricultural contraction column 8 and the outflow path 9b from the twenty-first agricultural contraction column 9 are connected to a second four-way switching valve 10. This second four-way switching valve 10 further includes a line 33 connected to an analysis means 32 consisting of a separation column 11 and an absorption photometer 12, and a line 35 connected to a drainage channel 34.
or connected.

A flow meter 19 is attached to the line 35.

Further, a reaction liquid di: supply path 37 is connected to the upstream side of the reactor 3 of the sample liquid supply path 30 to supply a reagent for ionizing metals in the sample liquid. And this reaction liquid supply path 37
A pressurizing pump 16 and a reaction sour distillation section 15 are provided therein.

Furthermore, the separation column 11 of the analysis means 32 and the spectrophotometer 12
A coloring liquid supply path 38 for supplying a reagent for coloring metal ions is connected between the two. This coloring liquid supply path 38 is provided with a pressure pump 20 and a coloring liquid storage section 21 .

Next, the operation of this metal component analyzer will be explained.

Six sample 1ffl inflow paths IA to IF are connected to the automatic flow path switching valve 1. One of the night seat entry paths IA-IF is selectively connected to the sample liquid supply path 30 for these samples.

The sample flowing into the sample liquid supply path 30 is sent to the reactor 3 by the pressurizing pump 2. During this time, a reaction liquid is added to the sample liquid from the reaction liquid supply path 37.

The reaction solution and the sample solution added thereto are mixed in the reactor 3 at a predetermined blackness.

The sample liquid that has passed through this reactor 3 is transferred to an overflow container 4.
The sample liquid that exceeds a certain storage amount is temporarily stored in
l: Served. The sample liquid that has passed through the overflow container 4 reaches the three-way switching valve 5. The three-way automatic switching valve 5 guides a part of the sample liquid flowing through the sample liquid supply path 30 to the υ water channel 34 through a line indicated by the symbol L3. That is, when the automatic flow path switching valve 1 is switched and another sample liquid is supplied, the flow path is first switched to the line L side, and the flow path is switched between the automatic flow path switching valve 1 and the three-way switching valve 5. Completely wash away any remaining sample solution. Thereafter, the flow path is switched to allow the sample liquid to flow along the sample liquid supply path 30.

The sample liquid that has passed through the three-way switching valve 5 is pressurized again by the pressure pump 6. The sample liquid pressurized by the pressurizing pump 6 is transferred to the first four-way switching valve 7 by the first four-way switching valve 7. It is supplied to a condensation column 8 or a second concentration column 9.

The first four-way switching valve 7 and the second four-way switching valve 10 allow the sample liquid supplied from the sample liquid supply path 30 to pass through the concentration column 8 or 9, and then lead to the drain path 34 via the line 35. Agricultural shrinkage process flow path and processing liquid supply path 31
Concentrate the elution ill supplied from A 9 or 8
A flow path for the metal ion elution step, through which the metal ions pass through and then leads to the analysis means 32, is formed alternately with respect to the concentration columns 8 and 9. This four-way switching valve7. The IO switching is performed by a signal sent from the control section C when the flow rate 4iff of the sample liquid passing through the flowmeter 19 reaches a set value.

When the sample liquid passes through the concentration column 8 or 9, metal ions in the sample liquid are adsorbed by the column 8 or 9. The metal ions adsorbed on the column 8 or 9 are eluted from the column 8 or 9 by the eluent supplied from the processing liquid supply path 31 and transported to the analysis means 32.

The metal ions carried to the analysis means 32 are transferred to the separation column 11
After separation, each component is eluted in time series, and the color is developed by the coloring liquid from the coloring liquid supply path 38.
The concentration is measured at

"Problems to be Solved by the Invention" By the way, in the metal component analyzer configured as described above, the concentration efficiency of the concentration columns 8 and 9, that is, the concentration efficiency of the concentration columns 8 and 9, that is, the concentration efficiency of the concentration columns 8 and 9, that is, the concentration efficiency of the concentration columns 8 and 9, that is, the concentration efficiency of the concentration columns 8 and 9, There was a problem in that the efficiency with which the particles were captured was different, which caused detection errors in the spectrophotometer 12, making accurate analysis impossible.

In order to solve such a problem, the metal component analyzer described above injects a standard solution containing a metal with a known concentration from one of the (-) sample liquid flow paths IA to IF.
d) The standard is supplied to each of the concentration columns 8 and 9 through the sample liquid supply path 30 at night; (3) The metal ions in the standard solution captured in each of the concentration columns 8 and 9 are
After sequentially repeating the steps of separating the columns and measuring their absorbances in the analysis means 32, the subsequent detected values are calibrated for each agricultural contraction column 8 and 9 based on the absorbance measured in the analysis means 32. That's what I do.

However, in the metal component analyzer configured as above, as shown in (-) and (d) above, standard solutions whose metal ion concentrations are known are not supplied to the concentration columns 8 and 9 (co-fed). There are many steps required to prepare the product, and therefore, it takes a long time to supply the product, resulting in a problem of decreased work efficiency.

This invention was made in view of the above circumstances, and it is possible to efficiently supply a standard solution for calibrating the detection value of the analysis means to the final phase column, and to prepare for the start of determination of metal components. The purpose of this invention is to provide a metal component analyzer that reduces time and improves work efficiency.

In order to achieve the above object, the present invention provides a sample liquid supply means for supplying a sample liquid containing metal ions, and a concentration means for adsorbing metal ions in the sample liquid. , a processing liquid supply means for supplying a processing liquid such as an eluent for eluting the metal ions adsorbed by the concentration means, an analysis means for analyzing the metal ions eluted from the concentration means, and immediately before the concentration means. a switching valve that selectively supplies the sample liquid from the sample liquid supply means and the processing liquid from the processing liquid supply means to the concentration means;
The night supply means is provided with an eluent supply means for supplying an eluent to the concentration means, and a standard solution supply means for supplying a standard solution containing metal ions of a known concentration to the concentration means. I have to.

"Operation" According to the present invention, immediately before the concentration means, the processing liquid supply means selectively supplies the elution i(t) or the standard solution lj containing a known concentration of metal ions to the concentration means. Since this is provided, a standard solution is supplied and the metal ions in the standard solution are captured by the concentration means before the start of the judgment, and after this, an eluent is supplied in place of the standard solution. The metal ions captured by the concentration means can be eluted and supplied to the analysis means.Then, the analysis means can measure the concentration of metal ions of known concentration contained in the standard solution, and The concentration efficiency of the concentration means can be determined, and the measured value of the analysis means at the time of actual measurement can be calibrated based on this 1R reduction ratio.In other words, in this invention, the The processing liquid supply means can efficiently supply a calibration standard solution for calibrating the detection value of the analysis means to the concentration column.

"Example" Hereinafter, the metal component analyzer of the present invention will be described in detail with reference to FIGS. 1 and 2.

The metal component analyzer shown in this embodiment has the same basic configuration as the metal component analyzer shown in the conventional example, so parts having the same structure are given the same reference numerals to simplify the explanation.

In FIG. 1, the symbol 100 indicates the concentration column 8.
9 is a processing liquid supply means provided immediately before.

The processing liquid supply means 100 includes an eluent supply means 40 for supplying an eluent to the concentration columns 8 and 9 to elute the metal ions adsorbed in the concentration columns 8 and 9, and an eluent supply means 40 that supplies the concentration columns 8 and 9 with an eluent that elutes metal ions adsorbed in the concentration columns 8 and 9. and a standard solution supplying means 41 for supplying a standard solution to be used, and between the eluent supplying means 40 and the standard solution supplying means 41, an eluent from the eluent supplying means 40, A third four-way switching valve 42 is provided for selectively guiding the reference liquid from the standard solution supply means 41 to the processing 'tR supply path 42.

Specifically, the eluent supply means 40 includes an eluate storage section 43 in which elution and night storage are performed, and an eluent supply path 44 that connects this elution storage section 43 and the third four-way switching valve 42. , a pressurizing pump 45 that transports the eluent in the reservoir 43 , and the eluent? The pressure sensor 46 is provided in the middle of the eluent supply path 44 and detects when the pressure within the eluent supply path 44 exceeds a certain value.

Further, the standard solution supply means 40 connects a standard solution storage section 47 in which a standard solution containing metal ions of a known concentration is stored, and this standard solution storage section 47 and the third four-way switching valve 42. It is composed of a standard supply channel 48 and a pressurizing pump 49 that transports the standard solution in the standard solution storage section 47.

Although a pressure sensor is not particularly provided in the standard solution supply path 48, a pressure sensor may be provided to prevent the discharge pressure of the pressurizing pump 49 from exceeding a certain value. The third four-way switching valve 42 also includes a drainage channel 34.
The line L4 passing through is connected, and this line r,
4, the eluent, which is not introduced into the supply path 31, is discharged.

Next, a process of measuring the concentration efficiency of the first concentration column 8 and the second concentration column 9 using the metal component analyzer configured as described above will be explained. Note that this step is performed before performing a normal metal component analysis step.

First, regarding the concentration efficiency measurement process of the first concentration column 8 (
This will be explained with reference to -) to (3).

(-) The third four-way switching valve 42 is switched to the position shown by the dotted line, the first four-way switching valve 7 is switched to the position shown by the dotted line, and the second four-way switching valve 10 is switched to the position shown by the solid line.
The standard solution stored in 7 is labeled rX, liquid supply path 48,
Processing liquid supply path 31. The standard solution is supplied to the concentration column 8 through the inflow path 8a, and the metal ions in the standard solution are captured in the concentration column 8.

Note that the standard solution (drain) after metal ions have been captured in the concentration column 8 is discharged through the line 35 and the drainage channel 34. Also, the standard for the concentration column 8? The skin is supplied for a certain period of time to keep the supply amount constant.

(d) The third four-way switching valve 42 is switched to the position shown by the solid line, the first four-way switching valve 7 is switched to the position shown by the dotted line, and the second four-way switching valve 10 is switched to the position shown by the dotted line, and the eluent reservoir 43
The eluent stored in is supplied to the concentration column 8 via the eluent supply path 44, the processing liquid supply path 31, and the inflow path 8a. Then, in this concentration column 8, the metal ions that were f;li I'El in the concentration column 8 are eluted, and the eluted metal ions are guided to the outflow path 8b and line 33 together with the eluent. .

(3) The metal ions guided to the line 33 are measured by the analysis means 32, and the degree of In difference is determined from the metal ion concentration of the standard solution stored in the standard solution storage section 47. 1 concentration column 8) is calculated by calculation, and further, the first concentration column 8 calculated in this way,
Based on the concentration efficiency of B, the 'full constant ffE of the analysis means 32 in the actual measurement is calibrated by calculation.

(4) The above-mentioned (-) to (3) treatments are carried out in a second condensing column.
9, the concentration efficiency of the second concentration column 9 is determined by calculation, and further, based on the concentration efficiency of the second concentration column 9 measured in this way, the sub-determined value of the analysis means 32 at the time of actual measurement is determined. It is calibrated by calculation.

As described above in detail, according to the metal component analyzer shown in this embodiment, the analysis means 3
Standard for calibrating the detected value of 2? Since the treatment liquid supply means 100 for supplying the skin is provided, the concentration efficiency of the concentration columns 8 and 9 can be efficiently measured, and the preparation time before starting the actual analysis of metal components can be shortened, improving work efficiency. ■ The standard solution does not pass through other routes such as the sample 1 skin supply route 30, and the routes such as the sample solution supply route 30 are contaminated with the standard solution (for example, the standard solution does not pass through other routes such as the sample 1 skin supply route 30). (e.g., at high concentrations). Similarly, the standard acid does not contaminate the sample liquid remaining in the sample liquid supply path 30 (for example, when a highly concentrated sample liquid remains without being removed). ■ Four-way switching valve By sequentially switching between 7 and 10, the concentration efficiency of multiple concentration columns 8 and 9 can be determined, and by adding four-way switching valves 7 and 10, the concentration efficiency of even more concentration columns can be measured. can get.

Next, a second embodiment of the present invention will be described with reference to FIG.

The metal component analyzer shown in 2nd □□□ is the metal shown in Figure 1! The difference in configuration from that of the component analyzer is the configuration of the processing Z night supply means indicated by reference numeral 101.

This processing i(l supply means 101 is provided with a hexagonal bamboo valve 50 between the processing liquid supply path 31, elution branch supply path 44, and standard solution supply path 48.
Further, a route L leading to the drainage channel 34 and a sampling route 51 are provided. Note that this sampling route 51 has a constant internal capacity and is used when sampling a constant amount of standard solution.

To explain the operation of the processing liquid supply means 101 configured as follows, during normal analysis, the six-way switching valve 50 is set to the solid line position shown in the figure, and the metal in the concentration columns 8 and 9 is Only the eluent that elutes the ions is supplied.

Also, before starting the measurement, (-) with the six-way switching valve 50 set to the solid line position shown in the figure, the pressurizing pump 49 is driven to pump a certain amount of sample/$ into the sampling route 51. Allow fluid to accumulate. Note that the target ifiM supplied in excess of the capacity of the sampling route 51 is discharged to the external system through the line L4.

(d) After this, the hexagonal switching valve 50 is switched to the position shown by the dotted line, and the eluent l &
As a result, the mark Q't& stored in the sampling route 51 at (-) is pushed out to the processing liquid supply path 3■.

In addition, at this time, the first four-way switching valve 7 of the main route is
When the first standard solution and eluent are introduced into the layer line column 8, the positions are shown in dotted lines in the figure, and when the standard solution and eluent are introduced into the second layer line column 9, the positions are shown with solid lines in the figure. Set to position. This operation is the same as that of the metal component analyzer shown in the first embodiment.

According to the metal component analyzer shown in the second embodiment as described above, the same effects as the metal component analyzer shown in the first embodiment can be obtained, and the sampling route provided in the processing liquid supply means 101 is 51, a certain amount of the standard solution is quantified, and the effect is that the concentration efficiency of each concentration column 8, 9 can be determined accurately.

"Effects of the Invention" As explained above, according to the metal component analyzer of the present invention, the processing liquid supply means provided immediately before the concentration means provides a calibration standard for calibrating the detection value of the analysis means. The effect is that the liquid can be efficiently supplied to the concentration column, the preparation time before starting the actual analysis of metal components can be shortened, and work efficiency can be improved.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing a first embodiment of the present invention, FIG. 2 is a schematic diagram showing a second embodiment of the present invention, and FIG. 3 is a schematic diagram showing the configuration of a conventional metal component analyzer. . ■・・・Automatic flow path switching valve (sample branch supply means), 7.
...First four-way switching valve, 8...1a condensation column (4 condensation means), 9...0 2 2 0 1 0 100...2nd concentration column (concentration means), ...1st 2 four-way switching valve, ... analysis means, ... third four-way switching valve, ... elution i (l supply means, ... standard? night supply means, ... six-way switching valve, 101...processing liquid supply means;

Claims (1)

[Scope of Claims] A sample liquid supply means for supplying a sample liquid containing metal ions, a concentration means for adsorbing metal ions in the sample liquid,
A processing liquid supply means for supplying a processing liquid such as an eluent to elute the metal ions adsorbed by the concentration means, an analysis means for analyzing the metal ions eluted from the concentration means, and a treatment liquid supply means provided immediately before the concentration means. and a switching valve for selectively supplying the sample liquid from the sample liquid supply means and the processing liquid from the processing liquid supply means to the concentration means, the processing liquid supply means , an eluent supply means for supplying an eluent to the concentration means, and a standard solution supply means for supplying a standard solution containing metal ions of a known concentration to the concentration means. Characteristics of metal component analysis equipment.