JPH0452555A - Measuring apparatus of amount of carbon - Google Patents

Abstract

PURPOSE:To quickly exchange and supply a reaction solution by separately providing means for feeding a reaction solution for measuring organic carbon and means for feeding a reaction solution for zero point calibration. CONSTITUTION:Inert gas is sent to a sample liquid in 8 to which a reaction solution is fed by a deaerator 7. Organic and inorganic carbons are moved outside together with the gas when the gas is stirred. The sample solution from which the inorganic carbons are removed is heated. The resultant carbon dioxide is analyzed by infrared rays at 24, so that the concentration of the carbons in the sample solution is measured. There are separately provided feeding means 9, 10 of the reaction solution feeding means 8 respectively for measuring organic carbons and for calibration of a zero point. Therefore, each reaction solution is directly supplied, whereby it becomes possible to speedily supply the reaction solution after it is exchanged. An electromagnetic valve for the exchange is not required.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention is a highly accurate carbon amount measuring device (Total Organic Ca) that can measure the amount of organic carbon.
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n) Concerning meters.

"Prior Art" Generally, when testing the quality of ultrapure water, organic matter is oxidized and decomposed and converted into carbon dioxide.1. A carbon amount measuring device is used to measure the amount of carbon dioxide and determine the amount of organic carbon.

This carbon content measurement device consists of a reaction liquid supply means (2) that adds a reaction liquid such as an acidic solution and an oxidizing agent to the sample liquid, and an inert gas that feeds the sample liquid to which the reaction liquid (acidic solution) has been supplied. a deaerator (7) that stirs the sample liquid and expels inorganic carbon contained in the sample liquid to the outside together with an inert gas;
a reactor (20) that heats a sample liquid to which an oxidizing agent) has been added and from which inorganic carbon has been removed to generate carbon dioxide from the organic carbon contained in the sample liquid; It has an extraction means (22) for extracting carbon, and a quantitative means (24) for quantifying carbon dioxide extracted by the extractor using infrared gas (the overall structure of the apparatus will be explained in Examples). .

"Problems to be Solved by the Invention" By the way, in the carbon content measuring device configured as described above, as shown in FIG. The reaction liquid supply means 2 is provided with a reaction liquid supply means 2 for supplying a reaction liquid, and the reaction liquid supply means 2 further includes a reaction liquid supply means 2 for organic carbon measurement consisting of an acidic solution (sulfuric acid, etc.) and an oxidizing agent (sodium beroxonisulfate, etc.). A first storage section 3 where a liquid is stored, a second storage section 4 where a reaction solution for calibration is stored, and a flow path 3A leading to the first storage section 3 and leading to the second storage section 4. A three-way solenoid valve 6 selectively connects the flow path 4A to the flow path 5 that merges with the sample liquid supply path 1, and a three-way solenoid valve 6 provided in the middle of the flow path 5 to supply the reaction liquid to the deaerator 7. Since the structure has a pump 8, when the three-way solenoid valve 6 is operated and the reaction liquid is switched from, for example, a reaction liquid for organic carbon measurement to a reaction liquid for calibration, the flow rate of each reaction liquid is 0 or 2 CmQ. /win), and on the other hand, the capacity in the system (flow path 5 - sample liquid supply path 1 - deaerator 7) is large, so even if the reaction liquid is switched, it takes time to replace it. There were other problems.

The above-mentioned calibration reaction solution is used when adjusting the zero point of the stationary means, and is prepared, for example, with sulfuric acid or phosphoric acid. Note that the overall configuration of FIG. 3 will be explained in the following embodiments.

The present invention has been made in view of the above-mentioned circumstances, and aims to provide a carbon content measuring device that can quickly exchange and supply a reaction solution by switching the reaction solution.

"Means for Solving the Problem" In order to achieve the above object, the first invention provides a reaction liquid supply means for adding a reaction liquid such as an acidic solution and an oxidizing agent to a sample liquid, and a reaction liquid supply means for adding a reaction liquid such as an acidic solution and an oxidizing agent to a sample liquid. It has a deaerator that feeds and stirs an inert gas into the sample liquid and expels the inorganic carbon contained in the sample liquid to the outside together with the inert gas, and the reaction liquid is added and the inorganic carbon is removed. In the carbon amount measuring device, the carbon content measuring device heats a sample liquid to generate carbon dioxide from the organic carbon contained in the sample liquid, and further measures the carbon concentration of the sample liquid from the generated carbon dioxide. The liquid supply means includes a first supply means that is connected to the deaerator and supplies a reaction liquid for organic carbon measurement, and a second supply means that is connected to the deaerator and supplies a reaction liquid for zero point calibration.
supply means, and these first supply means and second supply means.
The supply means for the above are provided independently.

According to the second invention, a guide member having an opening formed at the bottom and a space inside is provided in the sample liquid of the deaerator, and the space part of the guide member is provided with the first guide member. The supply means and the reaction liquid discharge port of the second supply means are connected to each other.

"Operation" According to the first invention, the first supply means supplies the reaction solution for organic carbon measurement to the deaerator, and the second supply means supplies the reaction solution for zero point calibration. Since the supply means are separately provided, the reaction liquid from the first and second supply means is directly supplied to the deaerator, and when the reaction liquid is switched, the reaction liquid is The reaction solution is immediately supplied to the deaerator. In addition, since the reaction liquid for organic carbon measurement and the reaction liquid for zero point calibration are respectively supplied by the first supply means and the second supply means, it is possible to switch the reaction liquid. No solenoid valve is required.

According to the second invention, a guide member having an opening formed at the bottom and a space formed inside is provided in the sample liquid of the deaerator, and the space of the guide member is filled with the first supply. Since the reaction liquid discharge ports of the means and the second supply means are connected to each other, the reaction liquid supplied from the reaction liquid discharge ports is
Direct contact with the sample liquid in the deaerator is prevented, and the reaction liquid can be added to the sample liquid little by little.

"Example" Hereinafter, an example of the present invention will be described with reference to FIGS. 1 and 2.

The deaerator indicated by the reference numeral 7 in FIG. 1 is provided with a reaction liquid supply means 8 according to the present invention (differences from FIG. 3 are shown by dashed lines).

The reaction liquid supply means 8 includes a first supply means 9 that is connected to the deaerator 7 and supplies a reaction liquid for measuring organic carbon;
A second supply means 10 is connected to the deaerator 7 and supplies a reaction liquid for zero point calibration.

The first supply means 9 contains an oxidizing agent such as potassium belloxonisulfide for generating carbon dioxide, which is inorganic carbon, from the organic carbon contained in the sample liquid, and an oxidizing agent such as potassium belloxonisulfide, and the inorganic carbon initially contained in the sample liquid. a first storage section 11 in which a reaction solution for organic carbon measurement consisting of an acidic solution such as a sulfuric acid solution for expelling carbon dioxide, which is a weak acid, is stored, and this first storage section 11 and a deaerator 7. A connecting channel 12;
It is composed of a pump 13 that transports the reaction liquid in the first storage section 11 to the deaerator 7.

The second supply means 10 includes a second storage section 14 in which a calibration reaction solution prepared with, for example, sulfuric acid or phosphoric acid and used when performing zero point calibration of an infrared analyzer 24, which will be described later, is stored. A flow path 15 connects the second storage section 14 and the deaerator 7, and the reaction liquid in the second storage section 14 is transferred to the deaerator 7.
It consists of a pump 16 that transports the

Further, as shown in FIG. 2(A) and FIG. 2(B), the reaction liquid discharge port 12A, which is the end of the flow path 12 of the first supply means 9, and the flow of the second supply means 10, The reaction liquid discharge ports 15A, which are the ends of the passages 15, are each connected to a guide member 100 having an opening formed at the bottom and a space formed inside. Note that the guide member 100 is provided in the sample liquid of the deaerator 7.

This prevents the organic carbon measurement reaction liquid and the calibration reaction liquid supplied through the channels 12 and 15 from coming into direct contact with the sample liquid.

The basic configuration of the carbon content measuring device will be explained below.

The deaerator 7 is connected to a flow path 17 at the bottom for feeding an inert gas such as helium or nitrogen, and the inert gas supplied through the flow path 17 flows inside the deaerator 7. The sample liquid (mixed liquid with sulfuric acid solution) is stirred and mixed with each other, and the carbon dioxide (inorganic carbon) in the sample liquid is
It is designed to degas the air. As shown in FIG. 2(A), a filter 17A is provided at the inert gas discharge port of the flow path 17 to discharge the inert gas in the form of fine bubbles. A flow path 18 is connected to the discharge port of 7, and a pressurizing pump 19 and a reactor 2
0, fixed apertures 21 are sequentially provided.

The pressure pump 19 is for supplying a mixed liquid consisting of the sample liquid and the reaction liquid at a constant pressure and at a constant flow rate into a reactor, which will be described later.
A flow path 18 is spirally wound around the drum heater 2OA, and a thermocouple (path shown) for detecting the temperature inside the tube is attached to the wall of the flow path 18. The temperature is controlled to remain constant at all times. and,
In this reactor 2o, the reaction solution (oxidizing agent) and organic carbon in the sample solution are reacted to generate carbon dioxide from the organic carbon.

The fixed throttle 21 is for increasing the reaction pressure inside the reactor 2o, and prevents vaporization of the reaction liquid even if the temperature of the reactor 20 exceeds the boiling point of water. It is something.

Further, at the end of the flow path 18 and on the downstream side of the fixed throttle 21, an extractor 22 is provided for extracting carbon dioxide from the sample liquid whose reaction has been completed in the reactor 2o.

This extractor 22 is provided facing up and down, and the flow path 18
It consists of an extraction tower that separates the sample liquid supplied through the extraction tower into carbon dioxide and drain water (residue), and a cooling pipe installed around the extraction tower to cool the extraction tower. be.

Further, a mass flow controller 23A is provided in the lower part of the extraction column to control the flow rate, and the fluid supplied from the flow path 18 (reaction is completed in the reactor 20 and the carbon dioxide produced from organic carbon A channel 23 is connected to which an inert gas such as helium or nitrogen is sent to extract carbon dioxide from the carbon containing carbon.
Further, in the upper part of the extraction tower, there is a dehumidifier 23 for drying the carbon dioxide and inert gas separated in the extraction tower, and an infrared analyzer 24 for measuring the concentration of carbon dioxide in the inert gas. A flow path 25 is connected thereto.

Based on the results analyzed by the infrared analyzer 24, the proportion of organic carbon contained in the sample liquid supplied from the sample liquid supply channel 1 is calculated as appropriate. (However, the amount of sample liquid supplied from the sample liquid supply channel 2 is constant per unit time).

Note that reference numeral 26 indicates a gas cylinder for supplying inert gas to the channels 17 and 23, respectively, when measuring organic carbon. Also, the one indicated by numeral 28 is cylinder 2.
Pressure reducing valve for setting the pressure of the inert gas from 6, reference numeral 30
- 31 is a three-way solenoid valve for selectively supplying the inert gas in the gas cylinder 26 to the deaerator 7, the extractor 22, and the infrared analyzer 24.

According to the carbon amount measuring device configured as above, the first supply means 9 supplies the reaction liquid for organic carbon measurement to the deaerator 7, and the reaction liquid for zero point calibration is supplied to the deaerator 7. Since the second supplying means 10 for supplying is separately provided, each reaction liquid from the first and second supplying means 9 and 10 is directly supplied to the deaerator 7, thereby causing the reaction to proceed. When the liquid is switched, the reaction liquid after switching is quickly supplied to the deaerator 7, and the effect that the reaction liquid switching operation can be carried out efficiently can be obtained.

Moreover, since each reaction liquid is supplied by the first supply means 9 and the second supply means 10,
There is no need for a solenoid valve (6) to switch the reaction solution,
The effect of smoothly supplying the reaction liquid can be obtained.

Further, a guide member 100 having an opening at the bottom and a space inside is provided in the sample liquid of the deaerator 7, and the first supply means 9 and the first supply means 9 are provided in the space of the guide member 100. Since the reaction liquid discharge ports 12A and 15A of the second supply means 10 are connected to each other, the reaction liquid discharge ports 12A and 15A are connected to each other.
The reaction liquid supplied from 15A is prevented from coming into direct contact with the sample liquid in the deaerator 7, the reaction liquid can be added to the sample liquid little by little, and the reaction liquid exchange operation can be performed quickly. You can get the desired effect. In addition, the guide member 10
0, the reaction liquid outlet 15A to which the reaction liquid for calibration is supplied is provided above the reaction liquid outlet 12A to which the reaction liquid for organic carbon measurement is supplied. The calibration reaction solution washes away the organic carbon measurement reaction solution having different components and concentrations, thereby providing the advantage that the calibration work can be performed without being affected by the organic carbon measurement reaction solution.

"Effects of the Invention" As explained in detail above, according to the first invention, the reaction liquids from the first and second supply means are directly supplied to the deaerator, thereby allowing the reaction to take place. When the liquid is switched, the reaction liquid after switching is quickly supplied to the deaerator, and the effect that the reaction liquid switching operation can be carried out efficiently can be obtained.

In addition, since the reaction liquid is supplied by the first supply means and the second supply means, a solenoid valve for switching the reaction liquid is not required, and the reaction liquid can be smoothly supplied. You can get the effect you want.

According to the second invention, a guide member having an opening formed at the bottom and a space inside is provided in the sample liquid of the deaerator, and the space of the guide member is filled with the first supply means. Since the reaction liquid discharge ports of the first and second supply means are connected to each other, the reaction liquid supplied from the reaction liquid discharge port is prevented from directly contacting the sample liquid in the deaerator, and the reaction liquid is prevented from directly contacting the sample liquid in the deaerator. The liquid can be added to the sample liquid little by little, resulting in the effect that the reaction liquid can be replaced quickly.

[Brief explanation of the drawing]

1 to 2 (B) are diagrams showing one embodiment of the present invention, in which FIG. 1 is an overall schematic system diagram of the present invention, and FIG. 2 (A
) is a front sectional view showing the inside of the deaerator, and FIG.
Sectional view along line I[(B)-n(B) of Figure (A), 3rd
The figure is a schematic configuration diagram showing a conventional deaerator. 24... Infrared analyzer (quantification means) 100...
...Guidance means

Claims (2)

[Claims] (1) A reaction liquid supply means for adding a reaction liquid such as an acidic solution and an oxidizing agent to a sample liquid, and an inert gas being fed into the sample liquid to which the reaction liquid has been supplied, stirring it, and inorganic substances contained in the sample liquid. It has a deaerator that expels carbon to the outside together with an inert gas, and heats the sample liquid to which the reaction liquid has been added and from which inorganic carbon has been removed, to remove carbon dioxide from the organic carbon contained in the sample liquid. In the carbon content measuring device which generates carbon dioxide and further measures the carbon concentration of a sample liquid from the generated carbon dioxide, the reaction liquid supply means is connected to the deaerator to supply a reaction liquid for organic carbon measurement. a first supply means for supplying a reaction solution for zero point calibration; and a second supply means connected to the deaerator for supplying a reaction liquid for zero point calibration.
1. A carbon content measuring device characterized in that said supply means are each provided independently. (2) A guide member having an opening at the bottom and a space inside is provided in the sample liquid of the deaerator, and the first supply means and the second supply means are provided in the space of the guide member. 2. The carbon amount measuring device according to claim 1, wherein the reaction liquid discharge ports of the supply means are connected to each other.