JPS6263855A - Anion analyzing instrument - Google Patents

Abstract

PURPOSE:To make exact measurement with high accuracy by conducting the removal liquid discharged from the outside chamber of the 1st suppressor to the outside chamber of the 2nd suppressor, conducting liquid to be measured into the inside chamber and removing the metallic ions in the liquid to be measured by an ion exchange. CONSTITUTION:A pump 2a is driven and the eluate in a vessel 1a flows in the flow passage of a pump 2a the 1st, 2nd connecting ports 3a, 3b of an injector 3 a precolumn 4 a sepn. column 5 the inside chamber 6b of the suppressor 6 detector 7 a discharged liquid tank 1d. A pump 2b is driven and the removal liquid in the tank 1b flows via the outside chambers 6c, 9c of the 1st and 2nd suppressors 6, 9 to a discharged liquid tank 1e. A pump 2c is driven in this state and the liquid to be measured in the tank 1c flows via the inside chamber 9b of the 2nd suppressor 9 and a concentration column 3g to the discharged liquid tank 1f. The liquid to be measured of the volume meeting the driving pump of the pump 2c is concentrated in the column 3g.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an anion analyzer fiK that chromatographically analyzes anion species in a liquid to be measured.

<Prior Art> Conventionally, the following anion analyzer u has been used to chromatographically analyze anion species in a liquid to be measured. That is, a certain amount of the sample liquid that has been condensed in a concentration column is collected, and the sample liquid is transported to a separation column using an eluent to chromatographically separate the anion species in the sample liquid. After the eluate from the column was introduced into a suppressor with a double tube structure to remove background, the conductivity of the eluate was detected and the entire anion analysis was performed.

However, in the above conventional example, neutral to acidic and soluble metal ions (for example, Al-3" r
When the test solution contains substances such as F"", Cu2", etc., colloidal or sedimentary substances are generated when the sample solution comes into contact with an alkaline eluent. This causes problems such as adsorption of the ion species to be measured and blockage of the flow path.In particular, when attempting to perform high-sensitivity measurements, a large amount of the analyte liquid is deposited in the concentration column. This phenomenon became more pronounced as the supply increased.Incidentally, when measuring F- in a test solution containing human t3+ and F-, At3+ is mixed with an alkaline eluent (e.g., Na2 CO3, Ni2 CO3+
NaHCO3 or NaHCO3, etc.] and the following formula (1)
The precipitating substance u(OHh
This results in deposition on the upstream side of the concentration column and precolumn. Further, when F- is ν, it causes a reaction as shown in the following formula (2) and is captured, failing to reach the separation column and ultimately causing a large measurement error.

Ai" + 30H-=Go At (OH fan...
・・・・・・・・・(1) 2kl” + 6F--1→A
t(AZF6)↓・・・・・・・・・・・・(2) Furthermore, metal ions such as u" + Fe" + Be2+* Cr" * or Ti'+ are separated at a pH value of 9, for example. soluble precipitates (hydroxides) and these precipitates fFx
Ultimately, large measurement errors occur due to adsorption of ions to be measured by objects or blockage of the concentration column or precolumn.

<Problems to be Solved by the Invention> The present invention has been made in view of the above circumstances, and its purpose is to react with an alkaline eluent in a liquid to be measured to produce colloidal or sedimentary substances. An object of the present invention is to provide an anion analyzer capable of accurately and highly sensitively measuring anion species in a liquid to be measured, even when the liquid contains metal ions that cause oxidation.

Means for Solving the Problems> A feature of the present invention which solves all of the above-mentioned problems is that, in an arbitrary ion analyzer, a second sagre sensor is used, the interior of which is partitioned into an inner chamber and an outer chamber by a cation exchange membrane. A suppressor is provided in the anion analyzer main body to introduce the removal liquid discharged from the outer chamber of the first suppressor in the main body of the anion analyzer, and to introduce the liquid to be measured into the inner chamber where it is removed by ion exchange. The gold ions in the pressed electrolyte are completely removed, and the liquid to be measured from which the gold 4 ions have been removed is concentrated in a concentration column.

<Example> Hereinafter, the present invention will be explained in detail using the drawings. The figure is an explanatory diagram of the configuration of an embodiment of the present invention. In the figure, 1a is a container for storing an alkaline eluent, 1b is a tank for storing a removal liquid such as dodecylbenzenesulfonic acid, and IC is a liquid to be measured. 3 has, for example, first to sixth connection ports 3a to 3f and a concentration column 3), and its internal flow path alternates between a solid line connection state and a broken line contact a state. Injector switched to 4.5
6 is, for example, a pre-column and a separation column filled with an anion exchange resin, 6 is a first suppressor with a double-tube structure whose interior is divided into an inner chamber 6b and an outer chamber 6C by a cation exchange membrane 6&, and 7 is a first suppressor having a double-tube structure. For example, a director consisting of a conductivity meter, 8 is a blur column 41 a separation column 5. A thermostatic chamber 9 houses the first suppressor 6° and the detector 7 and keeps them at a constant temperature;
This is a second suppressor that is divided into an outer chamber 9C and an outer chamber 9C. The ion exchange membrane 9a is, for example, a Nafion tube of R-803H type, but the present invention is not limited to this, and various modifications are possible. Alternatively, the liquid to be measured may be allowed to flow between the membranes, and the removal liquid may be allowed to flow outside the membrane. Furthermore, the removal liquid supplied to the second suppressor 9 does not necessarily have to be the discharged liquid from the first suppressor 6, but can be supplied independently using a pump and removal liquid Jll exclusively for the second suppressor 9. It is also good.

In an actual flow example of the present invention having such a configuration, the pump 2a is driven, and the eluent in the tank la is transferred from the pump 2a to the first and second connection ports 3m of the injector 3, :(b→precolumn 4→ Separation column 5 → inner chamber 6b of suppressor 6 →
The liquid flows through the flow path from the detector 7 to the waste liquid W11d. In addition, the pump 2b is driven, and the i liquid in the tank lb is transferred from the pump 2b-+outer chamber 6c of the first suppressor 6 to the second suppressor 2cm+inner chamber 9b of the second suppressor 9 to the fourth and fourth injector 3. 3 connection ports 3d and 3e→concentration column 32→sixth and fifth connection ports 3f and 3a of injector 3→drainage tank 1f, and the amount of liquid to be measured according to the drive time of pump 2C is concentrated. It is concentrated in column 3f.

By the way, metal ions ~1n+ (for example) t'', Fe'' that react with the alkaline solution in the liquid to be measured in the lie to produce colloidal or sedimentary substances.

2+ Be etc.), when the liquid to be measured is carried into the inner chamber 9b of the second suppressor 9, a cation exchange membrane is formed between it and the removal liquid in the outer chamber 9C of the second suppressor 9. 9bi
3M"+n (R-803"H")-→n(RS03
H") + nH tag... (3) Through such cation exchange, the above M" (metal ionone moves to the removal liquid side and H (hydrogen ions) moves to the measured liquid side. Therefore, the liquid to be measured flowing out from the inner chamber 9b of the suppressor 9 is in a state in which no colloidal or sedimentary substances are generated even if it reacts with the alkaline eluent. When the concentration column 3y'''C has been concentrated, the injector 3fr is turned on and its internal flow path is switched from the solid line connection state to the broken line connection state.The liquid to be measured in the concentration column 37 is carried by the eluent and separated via the bricolumn 4. The anion species in the liquid to be measured are separated by chromatography.Separation column 5
The effluent is led to the inner chamber 6bK of the first suppressor 6, where cation exchange is performed via the cation exchange membrane 6 and so-called background removal is performed. The effluent from the inner chamber 6b is then led to a detector 7, where its conductivity, for example, is detected, and a chromatogram is drawn on a recorder (not shown) based on the detection signal.

<Effects of the Invention> According to the present invention as described in detail above, the removal liquid discharged from the outer chamber 6c of the first suppressor 6 is guided into the outer chamber 9C of the second suppressor 9, and the inner chamber 9b is covered with Since the structure is such that the measurement liquid is introduced, metal ions in the measurement liquid are removed by ion exchange, and then the measurement liquid is concentrated, colloidal or Even if metal ions that cause sedimentation are contained, anionic species in the liquid to be measured can be measured accurately and with high sensitivity.

[Brief explanation of drawings]

The figure is an explanatory diagram of the configuration of an embodiment of the present invention. 1&～If...tank, 3...injector, 3y...
- Concentration column, 4, 5... Column, 6, 9... Suppressor, 7... Detector, 8... Constant temperature bath.

Claims (3)

[Claims] (1) Collect a certain amount of the concentrated test liquid, transport the test liquid to a separation column using an eluent, chromatographically separate the anion species in the test liquid, and elute the separation column. In an anion analyzer that introduces the liquid into a suppressor with a double tube structure to remove background, and then detects the conductivity of the eluate and analyzes the anion species, the interior is A second suppressor is provided which is partitioned into an inner chamber and an outer chamber, and the removal liquid discharged from the outer chamber of the suppressor is introduced into the outer chamber of the second suppressor, and the concentrated liquid is introduced into the inner chamber of the second suppressor. What is claimed is: 1. An anion analyzer characterized in that the anion analyzer is configured to introduce a liquid to be measured before being analyzed and remove metal ions in the liquid to be measured by ion exchange. (2) The anion analyzer according to claim 1, wherein the second suppressor has a double tube structure in which the inside is divided into two chambers by the cation exchange membrane. (3) The anion analyzer according to claim (1), wherein the second suppressor has an inner chamber and an outer chamber formed by two membranes made of a weakly acidic cation exchange resin.