KR20110128770A - A total organic carbon analyzer - Google Patents

Abstract

PURPOSE: An organic carbon measuring apparatus by the oxidation reaction using ozone are provided to use OH radicals generated from the apparatus for performing the strong oxidation reaction with measuring water. CONSTITUTION: An organic carbon measuring apparatus by the oxidation reaction using ozone comprises the following: a measuring water supplying unit(30) supplying measuring water; a UV lamp for generating ultraviolet rays for oxidizing organic components; an OH radical generator to generate OH radicals for oxidizing the organic components; a matter transfer unit for supplying gas transferring the OH radicals; a reaction unit(50) with a reaction tank(52) generating carbon dioxide by oxidizing the organic components; and a concentration measuring unit(60).

Description

A total organic carbon analyzer

The present invention relates to a total organic carbon measuring apparatus, and more particularly to a total organic carbon measuring apparatus capable of accurately measuring the total organic carbon of the measured water by a strong oxidation reaction because it oxidizes the measured water (waste water, etc.) with ozone.

In general, various methods of measuring the total organic carbon in the measured water are presented.

General organic carbon (TOC) measurement methods proposed by the American Water Association's standard methods include the combustion-infrared method, the sulfate-ultravioletoxidation method, and the wet-oxidation method. method).

The above-described combustion-infrared method is a method of oxidizing an organic carbon to carbon dioxide and water by oxidizing a sample to be measured at a high temperature of about 900 ° C. using an oxidation catalyst such as cobalt oxide. At this time, the generated carbon dioxide is quantified using an infrared analyzer. This method requires a high temperature and an infrared analyzer, so the apparatus is expensive.

The persulfate-ultraviolet method is a method of oxidizing organic carbon by irradiating ultraviolet rays after adding persulfate to a measurement sample. As with the combustion-infrared method, it is quantified by an infrared analyzer.

In addition, wet oxidation is a method of first acidifying a sample to release inorganic carbon into the atmosphere, and then quantifying carbon dioxide generated by heating at 116 to 130 ° C. using a persulfate as a catalyst using an infrared analyzer.

Each of these methods uses an infrared analyzer and has a complex disadvantage.

On the other hand, using UV radiation as a method of oxidizing organic molecules in the measurement water, using a catalyst or a combination of oxidizing agents such as perchloric acid or persulfate to derive the reaction, and measure the CO2 generated accordingly . The CO 2 can be measured as a change in conductivity of the water sample itself, or can be removed therefrom, without a separate separation process. For example, it is well known to remove CO2 by measuring diffusion of a suitable film with known measuring water and measuring the change in conductivity of the measuring water.

However, such a total organic carbon measuring device or measuring method has a problem that it is difficult to accurately measure because the oxidation power to oxidize organic matter is weak.

On the other hand, it was somewhat resolved by the Republic of Korea Patent No. 10-927847 (Total Organic Carbon Analyzer). However, the total organic carbon analyzer according to the prior art is configured to convert organic carbon into carbon dioxide gas by persulfate oxidation of persulfate of organic carbon and reaction reagent in water sample by irradiating UV light with gas / liquid separation. As a result, the oxidizing power for oxidizing organic matters was weak, making accurate measurement of organic carbon difficult.

Republic of Korea Patent No. 10-927847 (November 23, 2009)

The technical problem of the present invention was devised to solve the above problems of the prior art, and provides a means for accurately measuring the total organic carbon of the measured water by oxidizing the measured water with OH radicals. There is.

The technical problem to be achieved by the present invention is not limited to the technical problem mentioned above, and other technical problems not mentioned above may be clearly understood by those skilled in the art from the following description. There will be.

The technical problem, according to the present invention, as a total organic carbon measuring device,

A measurement water supply unit for supplying the collected measurement water;

UV lamp for generating UV required to oxidize the organic matter of the measurement water;

An OH radical generator for generating OH radicals for oxidizing the organic matter of the measurement water together with UV;

A material carrier for supplying a gas for carrying the OH radicals;

A reaction unit including a reaction tank for reacting the measured water with OH radicals and UV to oxidize the organic material included in the measured water to generate carbon dioxide; And

It is achieved by the total organic carbon measuring apparatus comprising a; concentration measuring unit for measuring the total organic carbon by measuring the concentration of carbon dioxide generated in the reaction unit.

According to the present invention, it is possible to generate OH radicals and to oxidatively react the measured water with OH radicals, thereby providing the effect of accurately measuring the total organic carbon of the measured water.

1 is a schematic diagram illustrating a total organic carbon measuring apparatus according to the present invention.
2 is a schematic diagram illustrating a total organic carbon measuring apparatus according to another embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, descriptions of already known functions or configurations will be omitted to clarify the gist of the present invention.

When described in detail with reference to the accompanying drawings a preferred embodiment of the present invention having such features as follows.

As shown in the accompanying drawings, the total organic carbon measuring apparatus according to the present embodiment is to measure carbon dioxide generated by oxidizing the organic matter of the measurement water with strong ozone (O₃). The material supply unit 20 for supplying, the measurement water supply unit 30 for supplying the collected measurement water, the reagent supply unit 40 for supplying the reagents required for the oxidation reaction, and the material supply unit 20 Reaction unit 50 and reaction unit 50 for generating carbon dioxide by reacting the gas and the measurement water supplied from the measurement water supply unit 30 and the reaction reagent supplied from the reagent supply unit 40 in the reaction tank 52. Concentration measuring unit 60 for measuring the total organic carbon by measuring the concentration of carbon dioxide generated from the.

The substance supply unit 20 is composed of an oxygen supplier 22 for supplying oxygen at a concentration of 99.9% and an ozone generator 24 for generating a high concentration of ozone with a high concentration of oxygen supplied from the oxygen supply 22. . At this time, since the ozone generator 24 generates high temperature heat, the ozone generator 24 further includes a cooler 26 for cooling the heat. It is preferable that this cooler 26 is comprised by water cooling. In the present embodiment, about 200 cc of ozone generated in the ozone generator 24 is supplied to the reaction tank 52. The ozone generator 24 and the reaction tank 52 are connected to the pipe, the end of the pipe is connected to the bottom of the reaction tank (52). Therefore, ozone bubbles the liquid filled in the reaction tank 52.

The measurement water supply unit 30 is configured to supply the collected measurement water to the reaction tank 52 using the third pump 32. The measurement water supply unit 30 filters the collected measurement water with an auto sampler 36. That is, the portion of the measurement water sampled and supplied is overflowed in the auto sampler 36 to control the amount of sample water to prevent the inhalation of suspended substances in the device unnecessary for measurement. On the other hand, the measurement water supply unit 30 mixes the dilution water and the measurement water. This is to measure the concentration of TOC that can be measured in the measuring device increases the concentration. That is, if the amount of dilution water can be known, the concentration of the measured water can be known through the calculation with the value and the measured value. Measured water passed through this process is supplied to the reaction tank 52 through the third pump (32). The amount supplied at this time is 5 cc / m. But it is not limited to this.

The reagent supply unit 40 is configured to store a reagent for assisting the oxidation reaction of the measurement water and then supply the reagent to the reaction tank 52. The reagent consists of sodium hydroxide (NaOH) and sulfuric acid (H₂SO₄). The reagent supply unit 40 includes a sodium hydroxide storage tank 42 for storing sodium hydroxide, a first pump 43 for supplying sodium hydroxide from the sodium hydroxide storage tank 42 to the reaction tank 52, A sulfuric acid storage tank 44 for storing sulfuric acid and a second pump 45 for supplying sulfuric acid stored in the sulfuric acid storage tank 44 to the reaction tank 52.

And the preparation of the reagent is as follows.

Preferably, the water used for the production of sulfuric acid as a reagent is always made of sulfuric acid specified in JIS K 8951 by using water of A3 specified in JIS K 0557 which does not contain inorganic carbon and organic matter. This sulfuric acid has a concentration of 1.8N, which consists of 88.27 g (48 ml) of 100% sulfuric acid solution per liter of water.

On the other hand, sodium hydroxide as a reagent has a concentration of 1.2 N and is composed of 48 g of sodium hydroxide per 1 L of solution. Therefore, 96 g per L is required when using sodium hydroxide concentrated to 50%.

Such sodium hydroxide and sulfuric acid are controlled to be supplied to the reaction tank 52 in the same ratio.

The reaction unit 50 is composed of a reaction tank 52 and a valve for controlling the measured water and each reagent when the reagent is supplied to the reaction tank 52. In the reaction tank 52, ozone generated from the ozone generator 24 is supplied together with the carrier gas to the mixed solution in which the measured water and the reagent are mixed to oxidize the organic material of the measured water. In particular, the reaction tank 52 is formed in a rectangular shape as shown in FIG. 1 to have a vertical shape, and further includes a pipe connected to the discharge part 70. The bottom of the reaction tank 52 is provided with a bubbling member 54 for bubbling by supplying the carrier gas and ozone into the mixed solution. The bubbling member 54 has a disk-shaped upper end so that ozone and gas are dispersed in all directions, and a lower end thereof is provided with a pipe connected to the ozone generator 24.

Concentration measuring device 60 is for measuring the carbon dioxide generated in the reaction unit 50, the gas-liquid separator 62 for separating a small amount of liquid contained in the gas supplied from the reaction tank 52 with the gas, A dryer 64 for removing moisture contained in the gas passing through the gas-liquid separator 62, and a carbon dioxide meter 66 for measuring the concentration of carbon dioxide in the gas passing through the dryer 64. Carbon dioxide meter 66 is described based on the measurement by non-dispersive infrared spectrometry (NDIR), but is not limited thereto, and various meters may be used.

On the other hand, the total organic carbon measuring apparatus according to the present embodiment includes a discharge unit 70 for discharging the mixture is completed from the reaction tank 52 and the concentration measuring unit 60. The discharge unit 70 is connected to the reaction tank 52 and the pipe, the drain tank 72 for temporarily storing the mixture is completed, the reaction tank 52 and the drain tank 72 is connected to the pipe installed Installed in the fourth pump 74 for discharging the mixture to the drain tank 72 and a pipe installed at an upper side of the drain tank 72 to remove ozone from the gas discharged from the drain tank 72, and then It is composed of an ozone remover 76 to discharge the furnace.

In the concentration measuring unit 60, the gas-liquid separator 62 and the carbon dioxide meter 66 are connected to the drain tank 72 by a pipe. Therefore, the liquid discharged from the gas-liquid separator 62 and the gas discharged from the carbon dioxide meter 66 are configured to be discharged to the drain tank 72.

Although not shown in the drawings, the respective valves and pumps, the material supply unit 20, the measurement water supply unit 30, the reagent supply unit 40, the reaction unit 50, the concentration measurement unit 60, and the discharge unit ( 70) may be further provided with a control unit and other means for controlling the light electronically and electronically and for storing the measured value or for displaying on the transmission and display.

Referring to the operation of the total organic carbon measuring apparatus according to this embodiment configured as described above are as follows.

First, the water to be measured is collected and supplied to the measurement water supply unit 30, and impurities and the like are treated in advance, and dilution water may be supplied by using a separate pump to mix the measurement water and the dilution water as necessary.

Subsequently, sodium hydroxide and sulfuric acid as reagents are prepared at the above-mentioned concentrations and stored in the respective storage tanks 42 and 44.

Then, oxygen is supplied to the ozone generator 24 as a carrier gas to generate high concentration ozone in the ozone generator 24.

At this time, various methods for generating ozone have been disclosed. For example, there are a silent discharge method, an electrolysis method, a photochemical reaction method, a radiation method, other high frequency electric fields, a chemical method, and the like. In this embodiment, ozone is generated using a photochemical reaction method, but is not limited thereto.

In this state, the valve installed in the reaction tank 52 is opened, and the first pump 43 and the second pump 45 are operated to supply sodium hydroxide and sulfuric acid to the reaction tank 52, but at the same rate. Then, the third pump is operated to supply the measured water to the reaction tank 52.

As described above, when the reagent and the measured water are supplied to the reaction tank 52 at a constant ratio, the ozone generated by the ozone generator 24 is then transferred to the reaction tank 52 through the bubbling member 54 using a carrier material. Supply. That is, the carrier gas and ozone are supplied to the reaction tank 52 together.

At this time, the bubbling member 54 installed at the inner bottom of the reaction tank 52 is in a state of being immersed in the mixed solution in which the reagent and the measured water are mixed. When ozone is supplied in this state, the ozone passes through the bubbling member 54. While being discharged into the mixed solution to form a large number of gas bubbles to bubble.

In this way, the ozone supplied into the mixed solution mixed with the measured water and the reagents floats while forming a large number of bubbles, resulting in the effect of stirring the mixed solution.

In this process, since ozone encounters organic matter in the mixed solution in a number of bubbles, the organic matter is oxidized, and carbon dioxide is generated by the oxidation reaction of the organic matter.

In other words, ozone is unstable and tends to return to oxygen. When ozone is converted into oxygen, oxygen atoms released from ozone combine with other substances (organic matters) to oxidize the substances. In this process, CO2 gas is generated by oxidizing organic matter and combining organic matter (C) with O₂ generated during ozone decomposition.

For example, as follows.

After supplying the measured water to the reaction tank 52 and adding sulfuric acid and sodium hydroxide, the acid and inorganic carbon is combined to remove the inorganic carbon. Complete removal of inorganic carbon implies accurate total organic carbon measurements.

As an example,

H₂SO₄ + Na2CO₃-> Na₂SO₄ + CO₂ + H₂O

H₂SO₄ + CaCO₃-> CaSO₄ + CO₂ + H₂O

And, all the organic matter contained in the measured water is changed to CO₂.

In other words, all organic matter in the water should be completely oxidized. Even in very small amounts, it must be fully oxidized. Oxidizers should not be neutralized due to pH changes in acids, organics or samples. By adding O₃ and NaOH to the sample, the pH is raised to 12, and O₃ produces OH in high pH environments. And the organic carbon reacts with OH.

                              O₃

NaOH + Org. Carbon (e.g. CH₃COOH)-> Na₂CO₃ + H₂O

pH> 12

When the organic carbon is changed to carbonate, acid is added to yield CO2.

                   O₃

Na₂CO₃ + H₂SO₄-> Na₂SO₄ + CO₂ + H₂O

pH <12

Carbon dioxide generated by the above-described process is passed through the gas-liquid separator 62 through the pipe to remove a small amount of liquid contained in the carbon dioxide.

The gas (carbon dioxide) that has passed through the gas-liquid separator 62 passes through the dryer 64 to remove a small amount of water contained in the gas.

In this process, carbon dioxide from which impurities such as liquid and water are removed is introduced into the carbon dioxide meter 66, and the concentration thereof is measured.

That is, carbon dioxide (CO₂ carbon dioxide) generated by the above-described ozone oxidation process is the concentration of carbon dioxide separator (66) after measuring the total organic carbon through the gas-liquid separator (62) and dryer (64). It can be measured.

On the other hand, the mixed liquid in which the reaction is completed in the reaction tank 52 is discharged to the drain tank 72 through the fourth pump 74, and the liquid separated from the gas in the gas-liquid separator 62 is also drained through the piping. ) Is discharged to the drain tank 72, the gas of which measurement is completed in the carbon dioxide meter 66.

The mixed liquid discharged to the drain tank 72 is discharged through the valve, and the gas is discharged to the outside while the ozone is removed while passing through the ozone remover 76.

As described above, by measuring the carbon dioxide generated by oxidizing the organic matter in the water of measurement with a high concentration of ozone, the measurement of organic carbon is accurate.

Meanwhile, as shown in FIG. 2, another preferred embodiment of the present invention is presented.

Total organic carbon measuring apparatus according to another embodiment is the same as the above embodiment except that the means for oxidizing the organic material is composed of UV and OH radicals.

That is, to generate the UV required to oxidize the organic material of the measurement water supply unit 30, the measurement water supply unit 30 for supplying the collected measurement water for supplying the material required for the oxidation reaction UV lamp 300 for, the OH radical generating unit 200 for generating OH radicals for oxidizing the organic matter of the measurement water together with the UV, and the measured water and the OH radicals and UV to react to be included in the measurement water A reaction unit 50 including a reaction tank 52 for oxidizing organic matter to generate carbon dioxide, and a concentration measuring unit for measuring total organic carbon by measuring a concentration of carbon dioxide generated in the reaction unit 50 ( 60).

That is, the present embodiment uses an AOP-ADVANCED OXIDATION PROCESS oxidation method, and various advanced oxidation methods may be used. For example, a method of generating and oxidizing a large amount of OH radicals in the process of simultaneously generating 253.7 nm (UV) wavelength and 184.9 nm (AM) wavelength in the discharge lamp and combining the oxygen with air in the photodegradation process can be applied. . In addition, hydrogen peroxide may be added to increase the oxidizing power.

The oxidizing potential (V) of OH radicals is highest (2.80), followed by ozone (2.07), hydrogen peroxide (1.77), potassium permanganate (1.68) and chlorine (1.36). In this way, the oxidizing power of OH radicals is superior to other oxidizing agents. This embodiment is to maximize the oxidizing power of the organic material by using such OH radicals and ultraviolet (UV).

As such, when the oxidizing power of the organic material is improved, the measurement of the total organic carbon of the organic material can be made accurately and quickly. That is, the ability to oxidize the organic carbon and the measurement time can be shortened.

While specific embodiments of the invention have been described and illustrated above, it is to be understood that the invention is not limited to the described embodiments, and that various modifications and changes can be made without departing from the spirit and scope of the invention. It is self-evident to those who have. Therefore, such modifications or variations are not to be understood individually from the technical spirit or point of view of the present invention, the modified embodiments will belong to the claims of the present invention.

20 material supply 22 oxygen supply
24: ozone generator 26: cooler
30: measuring water supply part 32: third pump
40: reagent supply 42: sodium hydroxide storage tank
43: first pump 44: sulfuric acid storage tank
45: second pump 50: reaction unit
52: reaction tank 60: concentration measuring unit
62: gas-liquid separator 64: dryer
66: carbon dioxide meter 70: discharge
72: drain tank 74: fourth pump
76: ozone remover 100: material transport unit
200: OH radical generating unit 300: UV lamp

Claims (1)

Total organic carbon measuring device
A measurement water supply unit for supplying the collected measurement water;
UV lamp for generating UV required to oxidize the organic matter of the measurement water;
An OH radical generator for generating OH radicals for oxidizing the organic matter of the measurement water together with UV;
A material carrier for supplying a gas for carrying the OH radicals;
A reaction unit including a reaction tank for reacting the measured water with OH radicals and UV to oxidize the organic material included in the measured water to generate carbon dioxide; And
Total organic carbon measuring apparatus comprising a; concentration measurement unit for measuring the total organic carbon by measuring the concentration of carbon dioxide generated in the reaction unit.

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