JPH03242552A - Metal component analyzer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a metal component analyzer, and more particularly to an analyzer that prevents a decrease in the concentration and separation capabilities of a column that concentrates or separates ions to be analyzed.

[Conventional technology]

FIG. 5 shows a metal component analysis apparatus previously proposed by the present inventors in Japanese Patent Application No. 180529/1983. Reference numeral 1 in the figure is an automatic flow path switching valve. A sample liquid supply path 30 is connected to the outlet of the automatic flow path switching valve 1. The sample liquid supply path 30 includes a liquid feeding pump 2 and a reactor 3.
, an overflow container 4, a three-way automatic switching valve 5, a pressure pump 6, and a pressure switch 6A are attached, and this sample liquid supply path 30 is finally connected to a first four-way switching valve 7. An inflow path 8a to the first concentration column 8, an inflow path 9a to the second concentration column 9, and an eluent supply path 31 are connected to the first four-way switching valve 7. A pressurizing pump 17 and an elution reservoir 18 are provided. The outflow path 8b from the first concentration column 8 and the outflow path 9b from the second ′a condensation column 9 are connected to a second four-way switching valve 10. A flow path 33 connected to an analysis means 32 consisting of a separation column 11 and an absorption photometer 12 and a flow path 35 connected to a drainage path 34 are further connected to the second four-way switching valve lO. A flow meter 19 is attached. Next, the operation of the metal component analyzer will be explained. The automatic flow path switching valve 1 includes six sample liquid inflow paths IA-
IF is connected, and one of these sample liquid inflow paths IA to 1F is selectively connected to the sample liquid supply path 30. The sample liquid flowing into the sample liquid supply path 30 is sent to the reactor 3 by the wave sending pump 2. On the upstream side of reactions 2 and 3,
A reaction liquid storage section 15 and a reaction liquid supply path 37 equipped with a supply pump 16 are connected, and a reaction liquid for test 1) for ionizing metal in an acid is added to a sample liquid. The sample i (t) to which this reaction liquid has been added is combined at a predetermined temperature in the reactor 3. The sample liquid exceeding the storage amount is sent to the drainage channel 34 through the channel indicated by the symbol Lt.
Served. The translation liquid that has passed through the overflow container 4 reaches the three-way switching valve 5. Further, the automatic flow switching valve 5 guides a part of the sample liquid flowing through the sample liquid supply path 30 to the drainage path 34 through a flow path indicated by the symbol L3, and is configured to switch between the automatic flow path switching valve 1 and the flow path L3. When another sample liquid is supplied, first, switch the flow path to the flow path L3 side to completely remove the previous sample liquid remaining between the automatic shutoff side switching valve l and the three-way switching valve 5. After rinsing, the sample liquid is made to flow along the sample liquid 1% supply path 30 by switching the flow path. The sample liquid that has passed through the three-way switching valve 5 is pressurized by a pressure pump 6. Note that when the sample liquid is pressurized to a predetermined pressure or higher by this pressure pump 6, the pressure
is turned ON, and a detection signal for stopping the operation of the pressurizing pump 6 is output to the control unit C. The sample liquid pressurized by the pressurizing pump 6 is passed through the first four-way switching valve 7 to the first layer column 8 or the second layer column 8.
IR condensation column 9 is fed. 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
After the eluent supplied from the metal ion concentration step flow path leading to the tJI waterway 34 via the flow path 35 and the eluate supply path 31 passes through the concentration column 19 or 8, the analysis means 3
The flow path for the metal ion elution step leading to step 2 is connected to the concentration column 8.
．． 9 is formed alternately. The switching of this four-way switching valve 7°10 is based on the flow path 3 measured by the flowmeter 19.
This is done by a signal sent from the control unit C when the flow rate value of the sample passing through the flow rate reaches a set value. Then, the sample IN that passed through the concentration column 8 or 9
The metal ions in & are adsorbed to column 8 or 9, and the metal ions adsorbed to column 8 or 9 are
The eluent supplied from the eluent supply path 31 causes the column 8 to
, 9 and transported to the analysis means 32. moreover,
The metal ions carried to the analysis means 32 are transferred to the separation column 11
After being purified, it is colored by a coloring solution supplied from a coloring supply path 38, and the degree of coloring is chromatographed in an absorptiometer 12 and its concentration is measured.

[Problem to be solved by the invention] However, in the analyzer having the configuration described in -4-, as the analysis is repeated, the concentration column 8 of the ion chromatography section
, 9, or the exchange capacity of the ion exchange resin packed in the separation column 11 inevitably deteriorates, and this deterioration causes a problem in that the separation of each metal component becomes difficult. Furthermore, due to the deterioration, the chromatogram may have a waveform that is steeply rising from the straight line A as shown in Figure 4, or it may be a waveform that rises slowly from the unstable line B as shown in Figure 5. The waveform becomes all
There was a problem that the quantitative nature of the results was lost. The present invention has been made in view of the above circumstances, and it is an object of the present invention to maintain the exchange capacity of an ion exchange resin in an analyzer at a predetermined level or more to perform stable measurements. [Means for Solving the Problems] In order to achieve the above object, the present invention provides
In reaction 2, the sample solution is placed in a flow path through which the sample liquid flows through the reactor 5, and the reaction preparation process 2 is carried out by the reactor.
[In a metal component analyzer composed of a column that adsorbs a liquid and an analysis means that analyzes ions eluted from the column during elution dk, a translation between the reactor and the column] A first switching valve that is immersed in the first liquid flow path and selectively connects the front one-leg column to the sample liquid flow path or the discharge path; A second switching valve is provided which selectively connects the column further downstream to a flow path or a cleaning supply source. If there is, by operating both switching valves, the column can be placed either in the direct path of the sample liquid from the reactor to the analytical means, or in the flow path from the supply source of the washing liquid to the discharge path. [Example] Hereinafter, the present invention will be described in detail with reference to the drawings.
Components common to the conventional example are given the same reference numerals to simplify the explanation. FIG. 1 shows a first embodiment of the present invention. In this first embodiment, a three-way switching valve 41 is provided in a flow path 40 between a separation column 11 of an analysis means 32 and an absorptiometer 12. The separation column 11 is selectively switched to the spectrophotometer 12 or the washing liquid supply channel 42. A pump 43 is provided in the 'f&Rai&supply stream&W42, and is used to pump column lS (NatSO3+Hcl stored in the purified 'tel storage section 44. Column cleaning liquid such as tartaric acid into the flow path 40). In addition, the three-way switching valve 41
And the pump 43 is controlled by switching control or ON-OFF by the control signal supplied from the control unit C.
It's about to be controlled. The analyzer configured as described above has the three-way switching valve 4.
1 to the position shown by the solid line in the figure, the separation column 11 and the spectrophotometer 12 are connected, and the cleaning liquid supply channel 4
2 is cut off from the flow path 4o, and normal measurements can be performed by supplying the sample liquid to the concentration column 8 or 9 in this state. That is, the four-way switching valve 7, 1o
By operating the sample liquid pump 6 with both positions indicated by the solid line, the sample liquid is fed into the concentration column 8, and the waste liquid is discharged to the drainage channel 34 while being adsorbed by the ion exchange resin in the concentration column B. Next, after a predetermined amount of the sample 1fffi is sent in, the eluent is removed by setting the four-way switching valves 7 and 10 to the positions indicated by the broken lines and operating the pump 17.
The metal components adsorbed in the concentration column 8 are eluted, and the eluted i+& is sent to the separation column 1.
1 to the spectrophotometer 12 for component analysis. Note that the concentration column 9 can also be operated in a similar manner. On the other hand, when attempting to wash the ion exchange resin, the separation column 11 is connected to the washing liquid supply flow path 42 by the three-way switching valve 41, and is cut off from the absorption photometer 12, and the three-way switching valve 5 is connected to the broken line in the figure. By connecting the concentration column 8 and the separation column 11 to the drainage channel 34 by setting them to the positions shown in , and by operating the pump 43 to supply the column washing liquid to the separation column 11 and the concentration column 8 and discharging it to the drainage channel 34. The metal ions adsorbed on the ion exchange resins in the separation column 11 and the concentration column 8 can be separated into a column cleaning solution and removed. Furthermore, when attempting to wash the concentration column 9, the four-way switching valves 7, 1
The same process may be performed by switching 0 to the position indicated by the broken line in the figure. It goes without saying that the switching of the valves in the measurement and cleaning, or the operation and stopping of the pump, is performed by control signals from the control section C. By making decisions based on the rise in
As shown in FIG. 4, the chromatographic baseline can be maintained at a constant linear value. Next, FIG. 2 shows a second embodiment of the present invention. In this embodiment, the coloring liquid pump 20 that sends the coloring liquid stored in the coloring liquid storage section 2I to the flow path 40 is also used to supply the column cleaning liquid. In other words, the coloring liquid pump 20 and the coloring liquid A three-way switching valve 45 is provided in the flow path between the storage section 21 and a flow path 46 branched from the three-way switching valve 45 is connected to the column cleaning liquid storage section 44, and further connected to the inlet of the spectrophotometer 12. An on-off valve 47 is provided. In this second embodiment, the pump 20 is connected to the coloring liquid reservoir 21 with the three-way switching valve 45 at the position indicated by the solid line, and the on-off valve 47 is opened, and the three-way switching valve 5 is set at the position indicated by the solid line. By determining the position, analysis can be performed in the same manner as in the first embodiment. When cleaning the column, the three-way switching valve 45 is set to the position indicated by the broken line, and the cleaning liquid reservoir 44 is connected to the pump 20, and the on-off valve 47 is closed to stop the cleaning liquid from entering the spectrophotometer 12. By operating the pump 20f in this state, the concentration columns 8 and 9 and the separation column 11 can be washed in the same manner as in the first embodiment. It goes without saying that the present invention can be applied not only to the analyzers of the two embodiments described above, but also to the third embodiment shown in FIG. In other words, the analyzer of this embodiment cools the sample liquid by providing a cooling device 52 consisting of a coil-shaped attachment 50 and a joint fan 51 below the reactor 3. Sample i (
After making the sample liquid almost neutral by sending the sample liquid to the pH adjustment section 53 and ion-exchanging it with the neutralization liquid supplied from the neutralization liquid storage section 57 by the pump 58, the sample liquid is transferred to the concentration column 8.
By providing a check valve 59 on the suction side of the pump 6, which sends the fibers to the core column and below, a constant load is applied to the pump 6. In this embodiment, as in the case of the first embodiment, the hair line can be stabilized by supplying cleaning at night. It goes without saying that the washing liquid may be supplied to the analyzer shown in FIG. 3 using the method of the second embodiment. Effects of the Invention As is clear from the above description, according to the present invention, by operating the double-cut patent, the column is placed in the flow path of the sample liquid from the reaction 2g to the analysis means, or in the lj of the washing liquid. - The column can be placed anywhere in the flow path from the supply source to the discharge path, so that the column can be placed anywhere in the flow path of the sample solution, by carrying out the normal analysis and supplying a washing liquid as necessary. This has the effect that the ability of the ion exchange resin in the column, which has decreased in capacity, can be verified once again, and a stable take can be obtained in the absorption light analysis at that stage.

[Brief explanation of drawings]

Fig. 1 is a piping diagram showing a first embodiment of the present invention, Fig. 2 is a piping diagram showing a second embodiment of the invention, and Fig. 3 is a piping diagram showing a third embodiment of the invention.
A piping diagram showing an example, FIG. 4 is a waveform diagram of the measurement signal of the spectrophotometer after cleaning by applying a water head, FIG. 5 is a piping diagram of a conventional example of a metal component analyzer, and FIG. 6 is a waveform diagram of determination No. 13 of a conventional absorption photometer.

Claims (1)

[Claims] a reactor installed in a flow path through which a sample solution containing metal components flows and reacts and prepares the sample solution; a column that adsorbs the sample solution reaction-prepared by the reactor; In a metal component analyzer comprising an analysis means for analyzing eluted ions, a metal component analyzer is provided in a sample liquid flow path between the reactor and the column, and the column is selectively used as the sample liquid flow path or the discharge path. a first switching valve that connects the column to a sample liquid flow path downstream of the column, and a second switch that is provided in a sample liquid flow path downstream of the column and selectively connects the column to a sample liquid flow path further downstream or a washing liquid supply source; A metal component analyzer characterized by comprising a valve.