KR20110077599A - A total organic carbon analyzer and a method thereof - Google Patents

Abstract

PURPOSE: An apparatus for measuring total organic carbons is provided to accurately measure total organic carbons by strong oxidation reaction. CONSTITUTION: An apparatus for measuring total organic carbons comprises: a material supply unit(20) for providing a material which is necessary for delivery and oxidation reaction; a measurement water supply unit(30) for supplying collected measurement water; a reagent supply unit(40) for proving necessary reagent for oxidation reaction; a reaction unit(50) for generating carbon dioxide by oxidizing organic materials; a concentration measuring unit(60) for measuring the concentration of the generated carbon dioxide and total organic carbons; and an ozone generator(24) for generating necessary ozone for oxidation reaction.

Description

A total organic carbon analyzer and a method

The present invention relates to a total organic carbon measuring apparatus and method thereof, in particular, the total organic carbon measuring apparatus that can accurately measure the total organic carbon of the measured water by a strong oxidation reaction because the oxidation of the measured water (waste water, etc.) with ozone; It's about how.

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.

In order to solve the problems of the prior art as described above, the technical problem of the present invention is to provide a means capable of accurately measuring the total organic carbon of the measurement water by oxidizing the measurement water with ozone. There is.

In order to solve the above technical problem, the present invention,

Total organic carbon measuring device

A material supply unit for supplying materials required for transport and oxidation reactions;

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

A reagent supply unit for supplying a reagent required for the oxidation reaction;

A reaction unit for generating carbon dioxide by reacting the gas supplied from the material supply unit with the measurement water supplied from the measurement water supply unit and the reaction reagent supplied from the reagent supply unit in a reaction tank; And

And a concentration measuring unit for measuring total organic carbon by measuring the concentration of carbon dioxide generated in the reaction unit.

The material supply unit,

And an ozone generator for generating ozone with oxygen supplied from the oxygen supply,

In the reaction tank of the reaction unit is a total organic carbon measuring device, characterized in that the mixed solution of the mixed water and the reagent is mixed with the ozone generated from the ozone generator to the lower portion of the reaction tank to bubble the organic matter is oxidized to produce carbon dioxide. to provide.

The concentration measuring unit, a gas-liquid separator for separating a small amount of liquid supplied with the gas supplied from the reaction tank with the gas; And

A dryer for removing water contained in the gas passing through the gas-liquid separator; And

Characterized in that the carbon dioxide meter for measuring the concentration of carbon dioxide in the gas passing through the dryer.

The reagent supply unit is configured to supply sodium hydroxide and sulfuric acid to the reaction tank,

Sodium hydroxide storage tanks for storing sodium hydroxide;

A first pump for supplying sodium hydroxide from the sodium hydroxide storage tank to the reaction tank;

Sulfuric acid storage tank for storing sulfuric acid; And

And a second pump for supplying sulfuric acid stored in the sulfuric acid storage tank to the reaction tank.

On the other hand, the sodium hydroxide is characterized in that 1.2N, sulfuric acid is 1.8N, the sodium hydroxide and sulfuric acid is supplied to the reaction tank in the same ratio.

The ozone generator is further characterized by comprising a cooler.

In addition, the reaction tank is provided with a discharge portion for discharging the substance including the ozone discharged from the mixture and the concentration measuring unit, the reaction is completed,

The discharge portion,

A drain tank for temporarily storing the reaction in which the reaction is completed;

A fourth pump installed in a pipe installed by connecting the reaction tank and the drain tank to discharge the mixture to the drain tank; And

It is installed in the pipe installed on the upper side of the drain tank is characterized in that it comprises an ozone remover for removing the ozone from the gas discharged from the drain tank to discharge to the outside.

In this case, the gas-liquid separator and the carbon dioxide meter is connected to the drain tank and the pipe is characterized in that the liquid discharged from the gas-liquid separator and the gas discharged from the carbon dioxide meter is discharged to the drain tank.

The present invention is a method for measuring the total organic carbon in water,

Collecting the measurement water to be measured;

Preparing a reaction reagent;

Supplying oxygen to the ozone generator to generate ozone with the ozone generator;

Supplying the measured water and the reaction reagent to the reaction tank and then supplying ozone to the reaction tank, and supplying ozone and a carrier material to the lower portion of the reaction tank to react by mixing the measured water, reagent and ozone by bubbling; And

After removing impurities from the gas generated by the reaction in the reaction tank provides a total organic carbon measurement method comprising the step of measuring the concentration of carbon dioxide with a carbon dioxide meter.

At this time, the liquid is completed after the reaction in the reaction tank, and the material discharged from the carbon dioxide measuring device to discharge the liquid and the substance, the gas further comprises the step of removing after removing the contained ozone with ozone remover; It is characterized in that the configuration.

According to the total organic carbon measuring apparatus and the measuring method according to the present invention, by introducing oxygen into the ozone generator to generate a high concentration of ozone, the total organic carbon of the measured water is accurately Measurable effects are provided. In other words, because ozone is unstable and very strong in returning to oxygen, the oxygen atom that is released while ozone is converted to oxygen combines with other substances to oxidize, and has a strong oxidizing power compared to other organic carbon measurement methods. The effect is to get faster, more accurate measurements.

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 are prepared as the reagents at the concentrations described above 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 52 installed on the inner bottom of the reaction tank 52 is 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.

The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by those skilled in the art without departing from the gist of the present invention as claimed in the claims. Of course, such changes will fall within the scope of the claims.

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

Figure 2 is a schematic diagram for explaining the total organic carbon measuring apparatus according to another embodiment of the present invention.

<Description of the symbols for the main parts of the drawings>

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 (10)

Total organic carbon measuring device A material supply unit for supplying materials required for transport and oxidation reactions; A measurement water supply unit for supplying the collected measurement water; A reagent supply unit for supplying a reagent required for the oxidation reaction; A reaction unit for generating carbon dioxide by oxidizing an organic substance by reacting a material supplied from the material supply unit with a measurement water supplied from the measurement water supply unit and a reaction reagent supplied from the reagent supply unit in a reaction tank; And And a concentration measuring unit for measuring total organic carbon by measuring the concentration of carbon dioxide generated in the reaction unit. The material supply unit, An oxygen supplier and an ozone generator for generating ozone necessary for an oxidation reaction with oxygen supplied from the oxygen supplier, In the reaction tank of the reaction unit is a total organic carbon measuring apparatus characterized in that the mixed solution of the mixed water and the reagent is mixed with the ozone generated from the ozone generator to the lower portion of the reaction tank to bubble the organic matter is oxidized to produce carbon dioxide. 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. According to claim 1, wherein the concentration measuring unit, Gas-liquid separator for separating a small amount of liquid contained in the gas supplied from the reaction tank with the gas; A dryer for removing water contained in the gas passing through the gas-liquid separator; And Total organic carbon measuring device comprising a carbon dioxide meter for measuring the concentration of carbon dioxide in the gas passing through the dryer. The method of claim 1, wherein the reagent supply unit is configured to supply sodium hydroxide and sulfuric acid to the reaction tank, Sodium hydroxide storage tanks for storing sodium hydroxide; A first pump for supplying sodium hydroxide from the sodium hydroxide storage tank to the reaction tank; Sulfuric acid storage tank for storing sulfuric acid; And And a second pump for supplying sulfuric acid stored in the sulfuric acid storage tank to the reaction tank. 5. The total organic carbon measuring apparatus according to claim 4, wherein the sodium hydroxide is 1.2N, the sulfuric acid is 1.8N, and the sodium hydroxide and sulfuric acid are supplied to the reaction tank at the same ratio. The total organic carbon measurement apparatus according to claim 1, wherein the ozone generator further comprises a cooler. According to claim 3, wherein the reaction tank is provided with a discharge portion for safely discharging the mixture containing the reaction and ozone discharged from the concentration measuring unit, The discharge portion, A drain tank for temporarily storing the reaction in which the reaction is completed; A fourth pump installed in a pipe installed by connecting the reaction tank and the drain tank to discharge the mixture to the drain tank; And Total organic carbon measuring apparatus is installed in a pipe installed on the upper side of the drain tank and comprises an ozone remover for removing the ozone from the gas discharged from the drain tank to discharge to the outside. The total organic carbon of claim 7, wherein the gas-liquid separator and the carbon dioxide meter are connected to the drain tank by pipes, and the liquid discharged from the gas-liquid separator and the gas discharged from the carbon dioxide meter are discharged to the drain tank. Measuring device. As a method for measuring total organic carbon in water, Collecting the measurement water to be measured; Preparing a reaction reagent; Supplying oxygen to the ozone generator to generate ozone with the ozone generator; Supplying the measured water and the reaction reagent to the reaction tank and then supplying ozone to the reaction tank, and supplying ozone and a carrier material to the lower portion of the reaction tank to react by mixing the measured water, reagent and ozone by bubbling; And And removing impurities from the gas generated by the reaction in the reaction tank and measuring the concentration of carbon dioxide with a carbon dioxide meter. 10. The method of claim 9, wherein after the reaction is completed in the reaction tank and the material discharged from the carbon dioxide measuring device, the liquid and the material are discharged, and the gas is removed after the ozone is removed by removing the contained ozone. Total organic carbon measurement method, characterized in that further comprises.

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