JP2007017313A - Dissolving treatment apparatus of sample liquid and dissolving treatment method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To quantitatively supply a sample liquid of wastewater or the like by dissolving a suspension in a suspension-containing wastewater or the like. <P>SOLUTION: A dissolving treatment apparatus of the sample liquid has a dissolving tank for receiving the suspension-containing sample liquid, a means for supplying a dissolving solution of the suspension to a dissolving tank, a means for supplying the sample liquid of the dissolving tank to an analyzer, a means for quantifying the sample liquid in the dissolving tank, a means for quantitatively supplying the dissolving liquid to the dissolving tank and a means for quantifying the sample liquid supplied to the analyzer to quantitatively supply the sample liquid, in which the suspension is dissolved in the dissolving tank, to the analyzer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a sample solution dissolution treatment system (dissolution treatment apparatus and dissolution treatment method) that can dissolve a suspension and quantitatively supply a sample solution such as wastewater for wastewater containing suspension. The dissolution treatment system of the present invention is useful for analysis of harmful metal ions contained in wastewater, etc., for example, by connecting to a continuous flow analyzer, the concentration of harmful metal ions contained in wastewater at a factory. This is useful for management and surveys that monitor changes in the concentration of harmful metal ions in rivers and seawater.

An “industrial wastewater test method” defined in the standard (JIS K 0102) is known as a method for measuring harmful metal ions contained in wastewater. In this analysis method, when wastewater contains suspension, after collecting a certain amount of wastewater, etc., acid (nitric acid or hydrochloric acid) is added to the wastewater sample as a pretreatment, and the suspension is dissolved. Elute ions. However, performing this series of operations manually is difficult because of the long melting time, and there are problems such as sample contamination due to the working environment. Furthermore, it takes time and labor to dissolve the sample quantitatively and to send a precise amount to the analyzer.

For the analysis of a sample solution containing such a suspension, for example, the following analysis means are conventionally known.
(A) In flow injection analysis, a pretreatment unit is provided in front of the analysis unit, and an acid or alkali that dissolves the suspension is injected into the sample solution flowing through the pipeline by the carrier liquid in the pretreatment unit. The suspension is dissolved and introduced into the analysis section while flowing through the pipeline (Patent Document 1).
(B) An in-line filter and a washing means for flowing the eluent from the direction opposite to the sample passing direction are provided immediately before the analyzer, and the suspension adhering to the filter is washed with the eluent (Patent Document 2).

However, the analysis means of Patent Document 1 dissolves the suspension while the sample solution flows through the pipe. However, since the dissolution time cannot be sufficiently secured, the suspension tends to remain, and the pipe In order to inject acid or alkali for decomposition into the sample solution flowing through the sample solution, it cannot be quantitatively dissolved. On the other hand, since the analysis means of Patent Document 2 does not dissolve the suspension, high-precision analysis including metal ions and the like adhering to the suspension cannot be performed, and the suspension is further included. Since the sample liquid flows through the pipeline in the state, the pipeline is likely to be blocked, and is not suitable for quantitative analysis of the sample solution.
JP-A-11-64343 JP 2003-202331 A

The present invention solves the above-mentioned problem in the conventional analysis system, and for the sample liquid containing the suspension, the suspension is quantitatively dissolved, and the concentration of the sample liquid is kept constant and the solution is sent to the analyzer. Furthermore, a dissolution processing system capable of automatically performing quantitative sampling of a sample solution, dissolution of a suspension, and quantitative supply to an analyzer is provided.

According to the present invention, the following dissolution processing system is provided.
(1) In a sample solution processing apparatus having a dissolution tank for receiving a sample solution containing a suspension, means for supplying the suspension solution to the dissolution tank, and means for supplying the sample solution in the dissolution tank to the analyzer, It has means for quantifying the sample solution in the dissolution tank, means for quantitatively supplying the solution to the dissolution tank, and means for quantifying the sample solution supplied to the analyzer, and dissolves the suspension in the dissolution tank. A sample solution dissolution treatment apparatus characterized in that the sample solution is quantitatively supplied to an analyzer.
(2) The cushion tank is connected to the dissolution tank through the suction pipe L1, the pipe end of the suction pipe L1 is inserted into the dissolution tank, and the amount of the sample liquid is calculated as the pipe end length of the suction pipe L1. (1) The sample solution dissolution treatment apparatus according to (1), wherein means for quantifying the sample solution in the dissolution tank is formed by controlling the liquid level according to the above.
(3) The dissolution tank is connected to the analyzer through the suction line L2, and the tube end of the suction line L2 in the dissolution tank extends below the tube end of the suction line L1 leading to the cushion tank. (2) The sample solution dissolution processing apparatus according to (2) above, wherein a quantitative supply means for sucking the amount of liquid corresponding to the difference between the tube end lengths of the conduit L1 and the conduit L2 and sending it to the analyzer is formed.
(4) A switching valve is provided in the pipeline for supplying the dissolution liquid to the dissolution tank. The switching valve is provided with a loop of a certain length for storing the dissolution liquid, and the loop is connected to the supply pipeline. Then, the sample solution dissolution processing apparatus according to any one of the above (1) to (3), wherein a quantitative supply means for supplying a fixed amount of the solution to the dissolution tank is formed.
(5) In the apparatus of (4) above, the cushion tank is connected to the switching valve through the suction line L3, and the solution is sucked through the suction line L3 and introduced into the loop. A sample solution dissolution processing apparatus in which a dissolution liquid quantification means is formed that accumulates in the loop and guides the excessively sucked solution to a cushion tank.
(6) Means are provided for cleaning the pipe (sample liquid supply pipe S1) for supplying the sample liquid to the dissolution tank and the pipe (solution supply pipe S2) for supplying the dissolution liquid to the dissolution tank. The sample solution dissolution treatment apparatus according to any one of (1) to (5) above.
(7) Means for selecting and supplying a plurality of sample liquids to the dissolution tank, and means for selecting a plurality of dissolution liquids and quantitatively supplying them to the dissolution tank are provided (1) to (6). apparatus.
(8) The sample solution dissolution treatment apparatus according to any one of (1) to (7), wherein the dissolution tank is connected to the continuous flow analyzer through the suction line L2.
(9) An automatic control system for controlling the supply of sample liquid, the supply of dissolved liquid, and the washing means is provided to automatically dissolve the suspension from the supply of the sample liquid and supply the sample liquid quantitatively to the analyzer. The sample solution dissolution treatment apparatus described in any one of (1) to (8).
(10) Dissolution tank for receiving a sample solution containing a suspension, means for supplying the suspension solution to the dissolution tank, means for supplying the sample solution in the dissolution tank to the analyzer, and quantifying the sample solution in the dissolution tank Means for quantitatively supplying the dissolution liquid to the dissolution tank, and means for quantitative determination of the sample liquid supplied to the analyzer, and quantitatively supplying the sample liquid in which the suspension is dissolved in the dissolution tank to the analyzer A method for dissolving a sample solution, characterized by

The dissolution treatment system for a suspension-containing sample solution according to the present invention can dissolve a suspension and treat the sample solution by a method in accordance with a standard (JIS K 0102). Since a series of processing operations up to the quantitative supply of the sample solution can be automated, the analysis processing time can be greatly shortened. Furthermore, the dissolution treatment system of the present invention is combined with, for example, a continuous flow analyzer to monitor the concentration of harmful metal ions contained in factory wastewater and monitor changes in the concentration of harmful metal ions in rivers and seawater. Useful for research.

In the dissolution treatment system of the present invention, the sample solution in the dissolution tank is made to be a constant amount, and acids such as nitric acid, sulfuric acid, hydrochloric acid, or alkaline solution that dissolves the suspension contained in the sample solution (these are referred to as solution solution). Is added to the sample solution in a fixed amount, and the sample solution in which the suspension is dissolved is quantitatively supplied to the analyzer, so that analysis including metal ions attached to the suspension is possible. Since the concentration of the liquid can be accurately controlled, highly accurate analysis can be performed.

The present invention will be specifically described below.
An outline of the sample solution dissolution processing system of the present invention is shown in FIG. As shown in the figure, the sample solution dissolving system of the present invention includes a dissolving tank 10 that receives a sample solution containing a suspension, means 20 for supplying a dissolving solution for dissolving the suspension to the dissolving tank 10, and a sample in the dissolving tank 10. Means 30 for supplying the solution to the analyzer, means 40 for quantifying the sample solution in the dissolution tank, means 50 for supplying the solution to the dissolution tank 10 in a fixed amount, and sample solution supplied to the analyzer. A sample solution dissolution processing apparatus is provided with means 60 for quantification and quantitatively supplies a sample solution in which a suspension is dissolved in the dissolution tank 10 to an analyzer.

The dissolution treatment system of the present invention has a dissolution tank 10 for dissolving a suspension contained in a sample solution. The dissolving tank 10 is provided with a stirrer 11 and a heater 12, a drain pipe is connected to the bottom of the tank, and a valve F is provided on the drain pipe.

A line S1 for supplying a sample solution is connected to the dissolution tank 10. A valve D is attached to the pipe line S1. As shown in the figure, the pipe S1 is provided with pipes for supplying a plurality of sample liquids (sample A, sample B, sample C,... Sample n), and these sample liquids are selected and supplied to the dissolution tank 10. Means for supplying may be formed. These pipes are equipped with open / close valves (A-1, A-2,..., A-n), are selectively communicated with the pipe S1, and each sample solution is supplied to the dissolution tank 10, respectively.

A cushion tank 41 is connected to the dissolution tank 10 through a suction line L1. The pipe end of the pipe L1 is inserted into the tank of the dissolution tank 10, and the sample in the dissolution tank is controlled by controlling the amount of the sample liquid to the liquid level according to the pipe end length of the pipe L1. A means for quantifying the liquid is formed. The pipe line L1 opens to the upper part in the tank of the cushion tank 41, and is further connected to the air pump P3 via the cushion tank 41. On the other hand, a drainage pipe and an exhaust pipe are connected to the tank bottom of the cushion tank 41, and a valve I and a valve J are provided respectively. Excess sample liquid introduced into the cushion tank 41 is discharged out of the system through a drain pipe.

The dissolution tank 10 is connected to the analyzer through the suction line L2. The pipe end of the pipe line L2 is inserted into the tank of the dissolution tank 10 and extends below the pipe end of the pipe line L1 leading to the cushion tank 41. The pipe ends of the pipe line L1 and the pipe line L2 A fixed amount supply means for sucking the amount of liquid according to the difference in length and sending it to the analyzer is formed.

The dissolution tank 10 is connected to a pipeline S2 for supplying a solution. The other end of the pipe line S2 is connected to a solution storage tank 53. The pipe S2 is provided with means 50 for supplying a fixed amount of the solution. The fixed amount supply means 50 shown in FIG. 2 is formed by a switching valve 51 provided in the pipeline S2 and a loop 52 of a fixed length attached to the switching valve 51. As the illustrated switching valve 51, a six-way valve having six through holes may be used. The two opposing holes are connected by a loop 52, and the other holes are formed so as to be connected to the solution supply line S2, the washing liquid line S3, and the suction line L3. The amount of the solution can be adjusted by the length of the loop 52.

By turning the valve 51, one end of the loop 52 is connected to the pipe line S2 on the storage tank 53 side, the other end of the loop 52 is connected to the suction pipe line L3, and the solution is sucked into the loop 52 to be constant in the loop 52. An amount of lysate can be retained. Next, the valve 51 is turned to switch the connection of the pipelines, and the dissolution liquid held in the loop 52 is supplied to the dissolution tank 10.

In the illustrated example, the cushion tank 54 is connected to the switching valve 51 through the suction pipe L3. The pipe line L3 opens at the upper part of the cushion tank 54 and is connected to the air pump P2 via the cushion tank 54. The solution is sucked through the pipe L3 and introduced into the loop 52, and a fixed amount of the solution is accumulated in the loop 52, and the excessively sucked solution is guided to the cushion tank 54 through the pipe L3. A drain pipe and an exhaust pipe are connected to the bottom of the cushion tank 54, and a valve L and a valve M are provided, respectively. Excess dissolved solution introduced into the cushion tank 54 is discharged out of the system through the drainage pipe.

As shown in the figure, this pipe S2 is provided with pipes for supplying a plurality of dissolution liquids (dissolution liquid A, dissolution liquid B, dissolution liquid C, dissolution liquid D,... Dissolution liquid n). A means for selecting and supplying to the dissolution tank 10 may be formed. These pipes are equipped with open / close valves (N-1, N-2,..., N-n), are selectively communicated with the pipe S2, and each solution is supplied to the dissolution tank 10, respectively.

In the example shown in the figure, means 70 for cleaning the sample solution supply pipe S1 is provided. The cleaning means 70 includes a cleaning liquid storage tank 71 and a pipe line 72 communicating with the sample liquid supply pipe line S1. A liquid feed pump P1 and valves B and C are interposed in the pipe line 72. The cleaning liquid is introduced into the pipe S1 through the pipe 72 and cleaned.

Further, a pipe 73 communicating with the switching valve 51 is connected to the storage tank 71, and a pump P4 is interposed in the pipe 73. When supplying the solution stored in the loop 52 of the valve 51 to the dissolution tank 10, the pipe 73 is connected to the switching valve 51, and washing water is introduced into the loop 52 of the switching valve 51 by the pump P4. Is used as a carrier liquid to be extruded into the dissolution tank 10.

The dissolution processing system of the present invention is provided with an automatic control system (not shown) for controlling the supply of the sample solution, the supply of the solution, and the washing means, thereby dissolving the suspension from the sample solution supply and the analyzer. It is possible to automatically perform a quantitative supply of the sample solution to the.

The dissolution processing system of the present invention can apply the continuous flow analysis to the sample liquid containing the suspension by connecting to the continuous flow analyzer through the suction line L2.

The dissolution treatment system of the present invention has the above configuration. In a specific device design based on the above configuration, the following is preferable.
(1) It is preferable that the melting tank 10 has a specification to which a cover is attached, and it is preferable to use two or more covers. The drainage pipe of the dissolution tank 10 has an inner diameter of 1 mm or more. (2) The stirrer 11 of the dissolution tank 10 is preferably equipped with a stirring rod and stirring blade made of glass or polytetrafluoroethylene, and has a maximum rotation speed of 50 rpm or more. (3) The cushion tank is preferably made of glass or fluorine-processed resin. (4) The piping is suitably a silicon tube having an inner diameter of 2 mm or more, a polytetrafluoroethylene tube, a Tygon tube, or a Tefzel tube. For example, a silicon tube having an inner diameter of 6 mm may be used. (5) A pump for flowing washing water is preferably a liquid feed pump with a large flow rate. In addition, a peristaltic pump or the like may be used as a pump for flowing the solution.

(6) A pinch valve or a diaphragm valve can be used as the valve. (7) A 6-way valve or a pinch valve may be used as the switching valve. The loop has only to have a length of approximately 10 ml, and it is preferable to use silicon, polytetrafluoroethylene, Tygon, Tefzel tube, or the like. (8) A mist trap may be provided between the cushion tank and the air pump so as to smoothly maintain the operation of the air pump. (9) A heating / cooling means for heating and cooling the sample may be provided as necessary. (10) The washing water may be circulated through the pipe 72 at all times when the sample liquid pipe S1 and the solution liquid pipe S2 are not washed. (11) The dissolution solution dissolves the suspension contained in the sample solution and uses acid or alkali suitable for elution of the measurement target element and measurement conditions of the measurement target element.

The operation procedure of the dissolution treatment system is shown below.
(Sample solution supply)
(1) The valves A-1 to An and the valve D of the pipe line S1 are opened, and the sample (about 120 ml) is poured into the dissolution tank 10. After the operation is completed, the valves An and D are closed.
(2) The valve G of the pipe line L1 is opened, the air pump P3 is operated, an excessive amount of sample liquid is sucked through the pipe line L1, and the liquid sample corresponding to the pipe end length of the pipe line L1 is drawn. By making the surface height, the sample solution in the dissolution tank is made a fixed amount. After the operation is completed, the valve G is closed, the pump P3 is stopped, the valves I and J are opened, and the sample liquid in the cushion tank 41 is discharged. Thereafter, the valve I and the valve J are closed.

[Supply of solution]
(3) Open the valves N-1 to Nn of the pipe line S2 and the valve K of the pipe line L3, operate the air pump P2, suck the solution, and introduce a certain amount of solution into the loop 52 of the switching valve 51. To do. After the operation is completed, the valve Nn and the valve K are closed, the air pump P2 is stopped, the valve L and the valve M are opened, and the excess dissolved solution flowing into the cushion tank 54 is discharged. Thereafter, the valves L and M are closed.
(4) The switching valve 51 is rotated to connect the loop 52 to the dissolution tank side pipe line S2 and the pipe line 73, the valve E of the pipe line S2 is opened, and the liquid feed pump P4 is operated. The water is introduced into the loop 52 and the solution in the loop is sent out to the dissolution tank 10. After the operation is completed, the valve E is closed and the pump P4 is stopped.

[Dissolution / Quantitative supply]
(5) The dissolution tank 10 is heated to about 80 ° C. with the heater 12, and the stirrer is rotated (about 300 rpm) to dissolve the suspension contained in the sample solution in the tank. After the dissolution operation is completed, the stirrer is stopped, the valve H of the pipe line L2 is opened, and the sample solution in the dissolution tank is introduced into the analyzer. Since the pipe end of the pipe line L2 extends below the pipe end of the pipe line L1, a certain amount of sample liquid corresponding to the difference in the pipe end length between the pipe line L1 and the pipe line L2 is supplied to the analyzer. Sent. After the introduction is completed, the valve H is closed.
(6) Open the valve F of the dissolution tank 10 and discharge the sample liquid and insoluble components remaining in the tank. After the discharge is completed, the valve F is closed.

[Cleaning work]
(7) The valve B of the pipe line 72 is closed, the valves A-1 to An of the pipe line S1 and the valve C of the pipe line 72 are opened, and the pump P1 is operated to supply the cleaning liquid to the pipe line S1. The path S1 is washed.
(8) The valves A-1 to An are closed, the valve D is opened, and the cleaning liquid (about 400 ml) is poured into the dissolution tank 10. Thereafter, the valve F at the bottom of the tank is opened to discharge the washing water. After the discharge is completed, the valve F is closed.
(9) The above operations (7) and (8) are repeated to wash the pipe line S1 and the dissolution tank 10.
(10) After washing, the valve C of the pipe line 72 and the valve D of the pipe line S1 are closed, and the valve B of the pipe line 72 is opened to circulate the washing water.
The series of operations (1) to (10) may be fully automatic operation by a programmable controller (sequencer, PLC). The dissolution time may be about 15 minutes per sample.

For sample solutions A to E, the suspension was dissolved based on the dissolution treatment system shown in FIG. 1, and the concentrations of cadmium, arsenic, selenium and antimony in each sample solution were measured by continuous flow analysis. The amount of the sample solution introduced into the dissolution tank was 120 ml, and an excess amount of 20 ml was sucked into the cushion tank 41. On the other hand, 10 ml of nitric acid was sucked as a dissolving liquid and held in the loop 52 of the valve 51, the pipe connection was switched, the nitric acid was introduced into the dissolving tank, and the liquid in the tank was stirred to dissolve the suspension. . For antimony, 10 ml of hydrochloric acid was used as a solution. The sample solution was introduced into the analyzer after the dissolution treatment. The residual liquid and insoluble components in the dissolution tank were discharged out of the system from the bottom of the tank. The results are shown in Table 1. For reference, Table 1 also shows the analysis results by the official method (JIS K 0102 analysis method) and the analysis results measured without adding nitric acid or hydrochloric acid (comparative method: suspension undissolved). It was.

As shown in Table 1, the analysis to which the dissolution processing system of the present invention is applied gives a result almost in agreement with the official method. On the other hand, the analysis result of the comparative method that does not dissolve the suspension is greatly different from the official method and the method of the present invention, and the reliability is low.

Conceptual diagram of the dissolution treatment system of the present invention Schematic diagram of switching valve

Explanation of symbols

10-dissolution tank, 11-stirrer, 12-heater, 20-solution supply means, 30-analyzer supply means, 40-sample liquid quantification means, 41-cushion tank, 50-solution quantification supply means, 51-switching Valve, 52-loop, 53-solution storage tank, 54-cushion tank, 60-sample liquid quantification means, 70-cleaning means, 71-cleaning liquid storage tank, 72-line, 73-line, S1-sample liquid supply pipe Path, S2-solution supply line, L1, L2, L3-suction line,

Claims (10)

In a sample solution processing apparatus having a dissolution tank for receiving a sample solution containing a suspension, a means for supplying the suspension solution to the dissolution tank, and a means for supplying the sample solution in the dissolution tank to the analyzer. A sample solution in which the suspension is dissolved in the dissolution tank, and a means for quantitatively supplying the solution to the dissolution tank, and a means for quantitatively determining the sample solution supplied to the analyzer. A sample solution dissolution treatment apparatus characterized in that the sample solution is quantitatively supplied to an analyzer.
A cushion tank is connected to the dissolution tank through the suction pipe L1, and the pipe end of the suction pipe L1 is inserted into the dissolution tank, and the amount of the sample liquid is determined according to the pipe end length of the suction pipe L1. The sample solution dissolution treatment apparatus according to claim 1, wherein means for quantifying the sample solution in the dissolution tank is formed by controlling the height of the solution.
The dissolution tank is connected to the analyzer through the suction line L2, and the tube end of the suction line L2 in the dissolution tank extends below the tube end of the suction line L1 leading to the cushion tank. 3. The sample solution dissolution processing apparatus according to claim 2, wherein a fixed amount supply means is formed for sucking the amount of liquid corresponding to the difference between the tube end lengths of the passage L1 and the passage L2 and sending it to the analyzer.
A switching valve is provided in the pipeline for supplying the lysis solution to the lysis tank, and the switching valve is provided with a loop of a certain length for storing the lysis solution, and the loop is connected to the supply pipeline to be constant. The sample solution dissolution treatment apparatus according to any one of claims 1 to 3, wherein a quantitative supply means for supplying an amount of the dissolution solution to the dissolution tank is formed.
5. The apparatus according to claim 4, wherein a cushion tank is connected to the switching valve through a suction line L3, and a solution is sucked through the suction line L3 and introduced into the loop, and a certain amount of solution is stored in the loop. At the same time, a sample solution dissolution treatment apparatus in which a quantification means for the solution is formed to guide the excessively sucked solution to the cushion tank.
A means for cleaning a pipe (sample liquid supply pipe S1) for supplying the sample liquid to the dissolution tank and a pipe (solution supply pipe S2) for supplying the dissolution liquid to the dissolution tank are provided. The sample solution dissolution treatment apparatus according to any one of 1 to 5
7. The sample solution dissolution treatment apparatus according to claim 1, further comprising means for selecting and supplying a plurality of sample solutions to the dissolution tank and means for selecting and supplying a plurality of dissolution solutions to the dissolution tank.
The sample solution dissolution treatment apparatus according to any one of claims 1 to 7, wherein the dissolution tank is connected to the continuous flow analyzer through the suction line L2.
An automatic control system is provided to control sample solution supply, solution supply, and cleaning means, and it automatically performs sample solution supply to suspension dissolution and sample solution quantitative supply to the analyzer. The sample solution dissolution treatment apparatus according to claim 1.
Dissolution tank for receiving a sample solution containing a suspension, means for supplying the suspension solution to the dissolution tank, means for supplying the sample solution in the dissolution tank to the analyzer, means for quantifying the sample solution in the dissolution tank And a means for quantitatively supplying the dissolution liquid to the dissolution tank and a means for quantitatively determining the sample liquid supplied to the analyzer, characterized in that the sample liquid in which the suspension is dissolved in the dissolution tank is quantitatively supplied to the analyzer. A method for dissolving the sample solution.

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