JPH0812182B2 - Concentrator - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a concentrating device for concentrating a trace component in a solution, and more particularly to a concentrating device suitable for ionizing and concentrating a nonionic substance in a solution. .

[Background of the Invention]

Conventionally, atomic absorption method, absorptiometry method, electrochemical method and the like have been put into practical use as a quantitative analysis method for trace components in a solution. Then, applying each of these analysis methods, automatic quantitative analysis of trace components in a solution is performed by a flow injection analysis method or a liquid chromatography analysis method.

The detection limit of trace components in the flow injection method and liquid chromatographic analysis method is ppb level. Therefore, when analyzing a component having a concentration lower than the detection limit, it is necessary to concentrate the target trace component in advance. As one of the concentration methods, as disclosed in Japanese Patent Laid-Open No. 59-87559, a sample solution is concentrated with an ion exchange resin before quantitative analysis of a target trace component by liquid chromatography. A small amount of the target component will be concentrated through the column.

However, the above-mentioned conventional concentration method can be effectively used when the trace amount target component in the sample solution exists in an ionic state, but it can be used as it is for the trace amount target component which is nonionic. There was a problem that it could not be done.

Therefore, as a method of ionizing a nonionic substance dissolved in water as a complex or an organic compound, or a nonionic substance existing as a colloid or a suspended substance, in the industrial water test method (JIS kolol-1979), Sample water is heated with an oxidant in the presence of acid or alkali, or the sample water is evaporated to dryness and the residue is heated to 450-500 ° C to ash and then dissolved in acid or melted with alkali. Non-ionic substances are ionized by acid melting.

However, this ionization method has a problem that impurities are mixed into the reagent and the analyzer used from the outside.

[Object of the Invention]

An object of the present invention is to enable highly sensitive analysis of low-concentration nonionic substances by chemically ionizing the nonionic substances, and to perform operations from ionization of nonionic substances to introduction into the analysis unit. It is to measure simplification.

[Outline of Invention]

The present invention relates to an apparatus for supplying a sample solution containing a nonionic substance, an apparatus for supplying an ionization reaction solution containing a chemical ionizing agent, a reaction tube through which the sample solution is circulated, and a reaction tube A reaction part having a heating means for heating to a temperature suitable for the ionization reaction of a substance, a mixing part arranged upstream of the reaction tube, for mixing the sample liquid and the ionization reaction liquid, and the reaction A concentration column disposed downstream of the tube, for capturing the ionized substance ionized in the reaction tube, a device for supplying an eluent for desorbing the ionized substance concentrated in the concentration column, and A switching valve, which is disposed on the upstream side of the concentration column, selectively connects the supply channel of the liquid containing the ionized substance and the supply channel of the eluent to the concentration column, and the concentration valve. Kara A device for supplying the sample liquid, a device for supplying the liquid for ionization reaction, the reaction tube, the reaction unit, the mixing unit, the concentration column, the eluent. Is connected to the switching valve by a pipe and is closed to prevent contamination from the outside to form a closed flow path.

As described above, the use of the configuration of the present invention enables highly sensitive analysis of low-concentration nonionic substances and simplifies the operation from ionization of nonionic substances to introduction into the analysis unit. .

Further, if the sample liquid and the reaction liquid are mixed in a continuous flow system, the amount of the reaction liquid which is likely to contain impurities can be reduced. Further, as shown by the Arrhenius equation, the reaction rate is more advanced when the temperature is higher, and thus the amount of the reaction solution can be further reduced by mixing the sample and the reaction solution at high temperature. it can. However, when the sample solution is an aqueous solution, there is a risk that the water will boil and the flow system will be disturbed if the temperature is raised to 100 ° C. or higher at 1 atm. Therefore, in order to prevent this, it is necessary to pressurize the reaction system above the critical pressure.

Further, by providing an impurity removal column before the injection of the reaction solution into the sample solution and removing impurities contained in the reaction solution with this column, the amount of impurities contained in the reaction system can be reduced. .

Example of Invention

Next, preferred embodiments of the concentrating device according to the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a block diagram showing an embodiment of a concentrating device for ionizing and concentrating a nonionic substance contained in water.

In FIG. 1, a sample water storage tank A in which sample water is stored
Is connected to a pipe 12, and this pipe 12 is connected to the sample water feeding pump 1.

On the other hand, a pipe 13 is connected to a reaction liquid storage tank B that stores a reaction liquid that ionizes a nonionic substance in the sample water, and this pipe 13 is connected to the reaction liquid sending pump 2. . A pipe 14 is connected to the sample liquid feed pump 1, and a pipe 15 is connected to the reaction liquid feed pump 2. The pipes 14 and 15 are connected by the mixer 3, and the mixer 3 is connected to the pipe 16. This pipe 16 is connected to a reaction tube 5 surrounded by a heating tank, and this reaction tube 5 is connected to a pipe 17 having a pressure adjusting valve 6 in the middle thereof. The pipe 17 is connected to the cooler 7, and the cooler 7 is connected to the three-way valve 8. The three-way valve 8 is connected to a storage tank C that stores an eluent, and a pipe 18 having an eluent liquid feed pump 11 is connected to the three-way valve 8. This three-way valve 8
Is connected to the concentration column 9 by opening the pipe 19, and the concentration column 9 is connected to the three-way valve 10 via the pipe 19. A pipe 20 for discharging the waste liquid to the outside of the system is connected to the three-way valve 10, and a pipe 21 for introducing a trace amount of concentrated components into the analysis system is connected to an analysis system inlet 25.

The pipes 12, 13, and 18 connected to the sample water storage tank A, the reaction liquid storage tank B, and the eluent storage tank C are closely attached to each other at the connection with each storage tank in order to prevent contamination from the outside. Has become. Further, each pipe, pump, valve, column, etc. are also closed.

 Next, the operation of this embodiment will be described.

After driving the sample water feed pump 1 and the reaction liquid feed pump 2 to mix the reaction liquid and the sample liquid in the mixer 3, the reaction tube 5
And the non-ionic substance is ionized by heating in the heating tank 4. The pressure in the reaction tube 5 is kept above the critical pressure of water by the pressure control valve 6, and the temperature in the reaction tube 5 is kept at the heating tank 4
Through the reaction tube 5 which is heated by. Reaction tube 5
The sample water that has passed through is cooled by the cooler 7 and then introduced into the concentration column 9, where the ionized target component is concentrated in the concentration column 9. After the ionized target component is adsorbed in the concentration column 9, the remaining sample water is discharged from the system as a drainage through the pipe 20 through the three-way valve 10.

Next, after the trace amount target component in the sample water is adsorbed and concentrated by the column 9, the sample water feed pump 1 and the reaction liquid feed pump 2 are stopped, and the eluent feed pump 11 is driven to pass through the three-way valve 8. And introduce it into the concentration column. The target component in the sample water eluted by the eluent is the three-way valve 10
Is supplied to the analysis system inlet 25 via the pipe 21.

As the above reaction liquid, a sodium peroxodisulfate solution was used, and the pressure in the reaction tube 5 was adjusted to 10 kg by the pressure adjusting device 6.
It was experimentally confirmed that, for example, iron-based suspended solids and aromatic hydrocarbons decompose and ionize when the reaction temperature is kept at 100 ° C / cm ² or higher and the reaction temperature is 100 ° C or higher. The reaction tube preferably has an inner diameter of 1 mm and a length of 10 mm at a flow rate of 5 ml / min. The concentration column 9 is used by being filled with an ion exchange resin or a chelate resin. Further, the reaction tube 5 can be made of quartz, but if it is 150 ° C. or lower, it can be made of tetrafluoroethylene.

Next, another embodiment of the concentrating device according to this embodiment will be described. FIG. 2 is a constitutional view showing another embodiment of the concentrating device. The difference from the embodiment shown in FIG. 1 is that the reaction liquid is contained in the reaction liquid in the middle of the pipe 15 for guiding the reaction liquid to the mixer 3. The point is that an impurity removal column 22 for removing impurities is provided. By thus providing the impurity removal column 22, it is possible to remove impurities that may be carried by the reaction solution into the sample solution.

For the impurity removal column 22, a porous polymer resin that adsorbs an organic substance, an ion exchange resin, or a chelate resin can be used, but when an ion exchange resin is used, the reflux exchange capacity decreases when the reagent concentration is high. .

A catalyst for promoting the decomposition reaction of nonionic components in the sample water, that is, ionization, may be mixed in the reaction tube 5. The catalyst preferably has a property of not being attacked by a reaction liquid such as a platinum wire, but a component having a catalytic action such as cobalt (II) ion may be mixed in the reaction liquid. In this case, since the mixed components cannot be quantified, a certain amount of the mixed catalyst is previously measured and then added. The addition of the catalyst in this way has the effect of promoting the decomposition reaction of the nonionic components.

Further, instead of heating the reaction tube 5, it is possible to irradiate ultraviolet rays to decompose the nonionic substance. In this case, the pressure regulating valve 6, the cooler 7 and the heating tank 4 can be omitted, but the reaction tube 5 needs to be one that does not absorb ultraviolet rays such as synthetic quartz. Further, the reaction solution storage tank B can be omitted by selecting the conditions for generating radicals of dissolved oxygen in water by ultraviolet rays. As described above, according to the concentrating device that decomposes nonionic substances by irradiating with ultraviolet rays, the reaction system does not need to be at high temperature and high pressure, and thus the structure of the device is simplified. Further, when the reaction liquid is not mixed, the mixing of impurities from the reaction liquid can be ignored.

FIG. 3 is a block diagram showing another embodiment which is a modification of the concentrating device shown in FIG. An ascorbic acid storage tank 103 is connected to the three-way valve 8, and an ascorbic acid addition pump 101 is provided in the middle of the pump. An acid neutralizer 102 is provided downstream of the three-way valve 8. Here, the ascorbic acid 103 is added in order to convert ferric ions into ferrous ions and make all the chemical forms of iron into ferrous ions. Further, the acid neutralizer 102 is for neutralizing a part of the acid added excessively so that the acid is easily adsorbed to the concentration column.

The sample neutralized by the acid neutralizer 102 flows into the analysis system 26. In this embodiment, the analysis system 26 is a liquid chromatograph, which includes concentration columns 9-1 and 9-2, an eluent liquid feed pump 11, a flow path switching valve 104, a separation column 105, an absorption detector 106, and a reaction liquid feed liquid. It comprises a pump 107, an eluent C and a reaction liquid D.

The ionized sample water is flow path switching valves 104-1 and 104.
When water is passed through the concentration column 9-1 via -2, the target component is concentrated. Next, when the flow path switching valves 104-1 and 104-2 are switched, the eluent C is sent by the eluent liquid feed pump 11, and the separation column 105, from the broken line of the flow path switching valves 104-1 and 104-2. It is drained through the absorption detector 106. The reaction liquid D is sent by the reaction liquid feed pump 107 and mixed at the downstream side of the separation column. The components concentrated in the concentration column 9-1 are expelled by the eluent C, and each component is separated and eluted in the separation column 105, so that the components are mixed with the reaction liquid on the downstream side of the separation column 105 to develop color, The absorbance at this time is detected by the absorption detector 106.

While the concentration column 9-1 is being analyzed, the ionized component is passed through another concentration column 9-2 to concentrate the next component. By alternately performing concentration and analysis in this way, the analysis time can be shortened. The separation column 105 can be filled with a strongly acidic cation exchange resin, a sodium tartrate solution can be used as an eluent, and a PAR (pyridylazoresorcinol) solution can be used as a reaction solution.

〔The invention's effect〕

According to the present invention, a nonionic biomaterial contained in a sample solution is chemically ionized while flowing the sample solution, and the ionized material is concentrated to obtain a sample for analysis, whereby a low concentration of non-ionic substances is obtained. Enables highly sensitive analysis of ionic substances,
It is possible to simplify the operation from ionization of the nonionic substance to introduction into the analysis unit.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a constitutional view showing an embodiment of the concentrating device according to the present invention, and FIG. 2 is in the middle of a pipe for supplying the reaction liquid of the concentrating device shown in FIG. FIG. 3 is a configuration diagram showing an embodiment in which a removal column for removing impurities contained in the reaction liquid is provided.
The drawing is a block diagram of another embodiment which is a modified example of FIG. 1 ... Sample water delivery pump, 2 ... reaction solution delivery pump, 3 ...
Mixer, 4 ... Heating tank, 5 ... Reaction tube, 6 ... Pressure adjusting valve, 7
... Cooler, 8 ... Three-way valve, 9 ... Concentration column, A ... Sample water storage tank, B ... Reaction liquid storage tank, C ... Eluent storage tank, 22 ... Impurity removal column.

Claims (1)

[Claims] 1. A device for supplying a sample solution containing a nonionic substance, a device for supplying an ionization reaction solution containing a chemical ionizing agent, and a sample liquid for circulation. A reaction tube and a reaction part having a heating means for heating the reaction tube to a temperature suitable for the ionization reaction of a nonionic substance; and (d) a sample solution and the ion which are arranged upstream of the reaction tube. A mixing section for mixing with a reaction liquid; (e) a concentration column arranged downstream of the reaction tube for capturing ionized substances ionized in the reaction tube; and (f) a concentration column. And a device for supplying an eluent for desorbing the ionized substance concentrated and concentrated, and (g) a supply channel for the liquid containing the ionized substance and a supply channel for the eluent which are arranged on the upstream side of the concentrated liquid column. The flow channel and A switching valve that selectively communicates with the column, and (h) an analysis unit arranged downstream of the concentration column, (i) a device for supplying the sample liquid, a device for supplying the ionization reaction liquid. The reaction tube, the reaction section, the mixing section, the concentration column, the device for supplying the eluent, and the switching valve are connected by piping, and are closed to prevent contamination from the outside and a closed flow path. A concentrating device characterized in that