KR20060012960A - A highly detective apparatus and method for leaked carbonaceous species form the ion exchange tower in nuclear power plants - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbonic acid species detecting apparatus and a detection method, and more particularly, to a detection apparatus and a method for detecting carbon dioxide leaking from an ion exchange resin tower of a heavy water reactor type nuclear power plant with high sensitivity.

The present invention,

1) obtaining a sample water by taking a part of the treated water that has passed through the ion exchange resin tower;

2) converting the bicarbonate ions in the sample water into sodium chloride by passing the sample water through a mixed column;

3) converting the sample water containing sodium chloride into hydrochloric acid through a cationic column;

4) provides a method for detecting carbonate species, including the step of measuring the concentration of hydrochloric acid using an electrical conductivity cell.

Nuclear power plant, system water, ion exchange resin tower, carbonate ion, bicarbonate ion

Description

{A HIGHLY DETECTIVE APPARATUS AND METHOD FOR LEAKED CARBONACEOUS SPECIES FORM THE ION EXCHANGE TOWER IN NUCLEAR POWER PLANTS}

1 is a conceptual diagram showing the configuration of a carbonate species high sensitivity detection apparatus according to an embodiment of the present invention.

Figure 2 is a process chart showing each process of the high sensitivity detection method for carbonate species according to the embodiment of the present invention.

3 is a graph showing the equivalent conductivity of various ions.

4 is a graph showing the presence of carbonate species according to the pH of water.

5 is a graph showing the bicarbonate ion detection characteristics for each detection method.

6 is a graph showing detection characteristics according to bicarbonate concentration.

<Description of Symbols for Major Parts of Drawings>

10: sample water supply unit 20: mixing column

30: cation column 40: sample water reuse section

50: electrical conductivity measuring unit 60: anion column

T: ion exchange resin tower T1: treated water outlet

T2: System water inlet V1, V2: Valve

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbonic acid species detecting apparatus and a detection method, and more particularly, to a detection apparatus and a method for detecting carbon dioxide leaking from an ion exchange resin tower of a heavy water reactor type nuclear power plant with high sensitivity.

In general, in a hydro channel nuclear power plant, a radionuclide C-14 is generated in a primary moderator system during operation of a nuclear power plant. Therefore, an ion exchange resin tower is installed in the purification system to remove carbon dioxide (CO ₂ ) containing the C-14. The ion exchange resin tower is filled with an ion exchange resin, and the ion exchange resin removes carbonic acid ions containing C-14 in the system water passing through the ion exchange resin tower. However, if the ion exchange resin continues to be used, the performance of the resin is exhausted, and the carbonate ions cannot be adsorbed or removed, and they start leaking. This release of C-14 can cause problems with general environmental exposure of radioactive material and the generation of radioactive waste. Therefore, the ion exchange resin should be replaced in a timely manner to prevent the leakage of radioactive material.

However, until now, a small amount of bicarbonate ions begin to leak at the time the exchange performance of the ion exchange resin that fulfills (HCO ₃ ^-), or because of carbonate ion (CO ₃ ^2-) did not have a way to direct detection, the safe plants As long as the ion exchange resin tower is operated after a certain period of time, the ion exchange resin is replaced and not only increases the amount of radioactive waste, but also requires high operating costs.

Therefore, it is necessary to quickly identify the saturation time of the ion exchange resin and to prevent the occurrence of such a problem by exchanging the ion exchange resin at an appropriate time. It was developed as a method of detecting a bicarbonate ion (HCO ₃ ^{-) -} Accordingly, carbonate ions leaking from the ion exchange resin column (CO ₃ ^2-) or bicarbonate ions (HCO ₃₎ ^- switch to the chloride ion (Cl) It is a method of detecting the concentration of chlorine ion by the electrical conductivity method after making it. That is, since bicarbonate or carbonate itself is difficult to measure its concentration by the electroconductivity method, after converting them to chlorine ion, the concentration of this chlorine ion is detected through the electroconductivity method, and the concentration of the chlorine ion is used. Conversely, the concentration of bicarbonate ions or carbonate ions is measured.

In such a bicarbonate ion detection method, only chlorine type anion exchange resin is used. However, the lower the concentration of bicarbonate ions, there is a problem that can not detect the time of saturation of the ion exchange resin in a timely manner due to the characteristic that the response time is slow.

An object of the present invention is to provide a high sensitivity carbonate species detection method capable of quickly detecting a low concentration of bicarbonate.

Another object of the present invention is to provide a high-sensitivity carbonate species detecting device capable of quickly detecting a low concentration of bicarbonate.

In order to achieve the above object, the present invention,

1) obtaining a sample water by taking a part of the treated water that has passed through the ion exchange resin tower;

2) converting the carbonic acid in the sample water to sodium chloride by passing the sample water through a mixed column;

3) converting the sample water containing sodium chloride into hydrochloric acid through a cationic column;

4) provides a method for detecting carbonate species, including the step of measuring the concentration of hydrochloric acid using an electrical conductivity cell.

And in another aspect of the present invention,

1) obtaining a sample water by taking a part of the treated water that has passed through the ion exchange resin tower;

2) measuring the electrical conductivity of the sample water using an electroconductivity cell after passing the sample water through a cation column;

3) passing the sample water through a mixed column to convert carbonic acid in the sample water to sodium chloride;

4) converting the sample water containing sodium chloride into hydrochloric acid through a cationic column;

5) measuring the electrical conductivity of the sample water passing through the cation column using an electrical conductivity cell;

6) obtaining a concentration of bicarbonate ions from the difference between the electrical conductivity in step 2) and the electrical conductivity in step 5); providing a method for detecting a carbonate species, comprising sulfate and nitrate ions in the sample water. And carbonate ions can be detected quickly and accurately even when chlorine ions and the like coexist.

In another aspect of the present invention, the sample water providing unit is connected to the treated water outlet of the ion exchange resin tower, taking a portion of the treated water passed through the ion exchange resin tower to provide a sample water; A mixing column connected to one end of the sample water providing unit and converting the carbonic acid in the sample water to sodium chloride; A cation column connected to the mixing column and converting sodium chloride in the sample water into hydrochloric acid; An electrical conductivity measurement unit connected to an end of the cation column and measuring an electrical conductivity of the sample water passing through the cation column; It is connected to the end of the cation column, and the sample water return unit for sending the sample water passed through the cation column to the ion exchange resin tower inlet; provides a high-sensitivity detecting device comprising a carbon dioxide species.

In still another aspect of the present invention, the sample water providing unit is connected to the treated water outlet of the ion exchange resin tower, taking a portion of the treated water passed through the ion exchange resin tower to provide a sample water; A first cation column connected to one end of the sample water providing unit and converting a cation in the sample water into hydrogen ions; A first electrical conductivity measurement unit connected to an end of the first cation column and measuring an electrical conductivity of the sample water passing through the first cation column; A mixing column connected to the end of the first cation column and converting carbonic acid in the sample water to sodium chloride; A second cation column connected to the mixing column and converting sodium chloride in the sample water into hydrochloric acid; An electrical conductivity measurement unit connected to an end of the second cation column and measuring an electrical conductivity of the sample water passing through the second cation column; It is connected to the end of the second cation column, the sample water return unit for sending the sample water passing through the second cation column to the inlet of the ion exchange resin tower; Even when anions such as sulfate ions, nitrate ions, and chlorine ions coexist in the water, carbonate ions can be detected quickly and accurately.

Hereinafter, with reference to the accompanying drawings will be described in detail a specific embodiment of the present invention.

First, the carbonate species high sensitivity detection apparatus according to an embodiment of the present invention will be described.

<Example 1>

1 is a diagram schematically showing the configuration of a carbonate species high sensitivity detection device 1 according to a first embodiment of the present invention.

As shown in FIG. 1, the carbonate species high sensitivity detecting device 1 according to the present embodiment includes a sample water supply unit; Mixing column; Cation column; Electrical conductivity measurement unit; It is configured to include a sample water return unit.

Here, the sample water providing unit 10 takes the sample water from the ion exchange resin tower T and serves to provide the carbonate species high sensitivity detection device 1 according to the present embodiment. That is, one end thereof is connected to the treated water outlet (T1) of the ion exchange resin tower (T), the other end is made of a pipe structure connected to the inlet of the mixing column 20, the ion exchange resin tower (T) A portion of the treated water that has passed is taken and provided to the carbonate high sensitivity detection device 1 as sample water.

Preferably, the sample water providing unit 10 is further provided with a sample water control valve 12 capable of measuring and adjusting the amount of sample water passing through the sample water providing unit at a predetermined portion thereof. If too much sample water passes through the column at a high speed, the column may not function properly. Thus, the sample water control valve 12 measures the amount of sample water passing through the sample water providing unit, thereby measuring an appropriate amount of sample. Adjust the amount of sample water to allow the water to pass through.

Next, the mixing column 20 converts bicarbonate ions (HCO ₃ ⁻ ) in the sample water into chlorine ions (Cl ⁻ ). That is, one end thereof is connected to the end of the sample water providing unit 10 described above, the other end thereof is connected to one end of the cation column 30, and a mixed resin is filled therein, so that the bicarbonate ion (HCO ₃ ⁻⁾ ) to the chloride ion (Cl ^- it is to switch to). Here, the term "mixed column" refers to a column filled with a mixed resin in which sodium type cation exchange resin and chlorine type anion exchange resin are mixed. This mixing column thus converts hydrogen ions to sodium ions and bicarbonate ions to chlorine ions. In this embodiment, the mixed resin filled in the mixing column is a mixed resin formed by mixing a sodium (Na) type cation exchange resin and a chlorine (Cl) type anion exchange resin.

Next, the cation column 30 is a component that converts sodium chloride (NaCl) into hydrochloric acid (HCl) in the sample water passed through the above-described mixing column 20. That is, one end is connected to the end of the mixing column 20, the other end is connected to the inlet of the sample water return portion 40, the cation exchange resin is filled therein, so that the sodium cation (Na ⁺ ) Sodium chloride (NaCl) is converted to hydrochloric acid (HCl) by conversion to hydrogen ions (H ⁺ ). Herein, the term "cationic column" refers to a column capable of converting a specific cation contained in a liquid passing through the hydrogen cation exchange resin into the hydrogen ion. In this embodiment, hydrogen (H) type cation exchange resin is filled in the cation column.

Next, the electrical conductivity measuring unit 50 is a component that is connected to a predetermined portion of the cation column terminal 30 and measures the electrical conductivity of the sample water passing through the cation column 30. In this embodiment, the electrical conductivity measuring unit 50 is installed in a path through which the sample water passing through the cation column 30 passes through the conductive cell 52 in direct contact with the sample water; It is composed of an electrical conductivity measuring device 54 which is electrically connected to the electrical conductivity cell 52 to process data transmitted from the electrical conductivity cell 52 to calculate electrical conductivity and output the electrical conductivity.

Next, in the carbonate species high sensitivity detection device 1 according to the present embodiment, one end thereof is connected to the end of the cation column 30, the other end thereof is connected to the sample water return part 40, and the cation column It is preferable to further provide an anion column 60 for adsorbing and removing chlorine ions (Cl ⁻ ) in the sample water passing through (30). It referred to herein, the anion column "means the hydroxyl ions (OH ^-) in the interior of the said column, which can be removed by adsorption to the anion contained in the liquid to be type anion exchange resin is filled through the inside thereof. In this embodiment, a hydroxide ion (OH ⁻ ) type anion exchange resin is filled in the anion column.

The sample water that has passed through the above-described cation column 30 is sent to the ion exchange resin tower (T) again to be used as system water. However, cation column in the 30 number of samples passed through the chlorine ion (Cl ^{-) a-providing} the anion column 60, chlorine ions (Cl) in order to remove the chloride ion (Cl) because it contains a To remove by adsorption.

Next, the sample water return unit 40 is a component for returning the sample water passed through the carbonate species high sensitivity detection device 1 according to the present embodiment to the ion exchange resin tower T to be reused as system water. That is, one end thereof is connected to the end of the above-described anion column 60, and the other end thereof is connected to the inlet T2 of the ion exchange resin tower to return the sample water to the ion exchange resin tower T.

<Example 2>

On the other hand, when negative ions such as sulfate ion (SO ₄ ^2- ), nitrate ion (NO ₃ ⁻ ), and chlorine ion (Cl ⁻ ) coexist in the sample water, high sensitivity of carbonate species having a structure different from that of the first embodiment described above. A detection device should be used. In other words, there is a need for a device that removes the contribution of electrical conductivity by anion already present and considers only the electrical conductivity by chlorine ions converted from carbonate ions containing C-14 purely.

Therefore, the carbonate species high sensitivity detection device according to the present embodiment, the sample water supply unit; First cation column; A first electrical conductivity measurement unit; Mixing column; Second cation column; A second electrical conductivity measurement unit; It is configured to include; sample number measuring unit. Here, the sample water providing unit, the mixing column, and the sample water measuring unit have the same structure and function as those of the first embodiment and will not be described again.

Next, the first cation column is connected to one end of the sample water supply unit, and the other end is connected to one end of the mixing column. The first cation column is filled with a cation exchange resin therein, and serves to adsorb and remove cations in the sample water passing therein. In this embodiment, a hydrogen (H) type cation exchange resin is filled and used in the first cation column.

The first electrical conductivity measurement unit is connected to the end of the cation column. That is, the concentration of anion present in the sample water is determined by measuring the electrical conductivity of the sample water passing through the cation column. The first electrical conductivity measuring unit has the same function and structure as the electrical conductivity measuring unit in the first embodiment.

Next, the sample water passing through the cation column is passed through the mixing column and the second cation column to convert the bicarbonate ions (HCO ₃ ⁻ ) into hydrochloric acid (HCl). Then, a second electrical conductivity measurement unit is provided at the end of the second cation column, and the electrical conductivity of the sample water passing through the second cation column is measured. Electrical conductivity is measured at a second electrical conductivity measuring section is sulfuric acid which has been contained in the sample from the first ion (SO ₄ ^2-), nitrate ion (NO ₃ ^{-) -} electricity by anions such as chloride ion (Cl) The conductivity and the electrical conductivity by chlorine ions (Cl ⁻ ) generated by conversion of bicarbonate ions (HCO ₃ ⁻ ) by the mixed column and the second cation column according to the present embodiment are measured.

Therefore, the concentration of bicarbonate ions (HCO ₃ ⁻ ) in the sample water can be determined using the difference between the electrical conductivity measured by the second electrical conductivity measuring unit and the electrical conductivity measured by the first electrical conductivity measuring unit.

Next, an embodiment of a carbonate species high sensitivity detection method according to the present invention will be described.

First, a step (S110) of obtaining a sample water by taking a part of the treated water discharged through the ion exchange resin tower is performed. Since the present embodiment is to monitor the performance of the ion exchange resin tower by detecting carbonic acid species containing C-14 in the treated water that passed through the ion exchange resin tower, a portion of the treated water that has passed through the ion exchange resin tower It should be taken and detected if it contains carbonate species. Therefore, a portion of the treated water is taken as sample water at a predetermined portion of the outlet of the treated water discharged from the ion exchange resin tower.

Next, the sample water is passed through the mixed column to convert the bicarbonate ions (HCO ₃ ⁻ ) in the sample water into chlorine ions (Cl ⁻ ) (S120). In this embodiment, the concentration of ions in the sample water is determined by the electrical conductivity method. However, bicarbonate ions (HCO ₃ ⁻ ) are ionic species in which concentration is difficult to obtain by the electrical conductivity method. Therefore, hydrogencarbonate ions (HCO ₃ ^{-) -} was converted indirectly bicarbonate ion (HCO ₃ ^-) in the electrical conductivity method in a concentration of chloride ion (Cl) were measured easy intended to measure the concentration of. In converting bicarbonate ions (HCO ₃ ⁻ ) to chlorine ions (Cl ⁻ ), carbonic acid (H ₂ CO ₃ ) is converted to sodium chloride (NaCl) using a mixing column in this step.

Next, a step of converting sodium ions (Na ⁺ ) into hydrogen ions (H ⁺ ) using a cation column to convert sodium chloride (NaCl) into hydrochloric acid (HCl) is performed (S130).

Then, the step of measuring the electrical conductivity of the sample water passing through the cation column (S140) proceeds. That is, through the mixing column with the cation column bicarbonate ion (HCO ₃ ^-) is chloride ion (Cl ^-) bicarbonate ions in the indirectly sample by measuring the electrical conductivity due to the chloride ion in the transition state (HCO ₃ ^-), calculate the concentration.

Next, the chlorine ion (Cl ⁻ ) contained in the sample water is removed, and the step S150 is returned to the ion exchange resin tower. In this step, the sample water is passed through an anion column to remove chlorine ions. In this case, it is preferable to use a negative ion column filled with a hydroxide ion anion exchange resin so that chlorine ions are replaced with hydroxyl ions. In this way, the sample water from which the chlorine ions have been removed is returned to the ion exchange resin tower (S160).

Therefore, in the high sensitivity detection method according to the present embodiment, a portion of the treated water that has passed through the ion exchange resin tower is continuously sampled into the sample water, the concentration of bicarbonate ions contained therein is measured, and the sample water is again ionized. Return to the exchange resin tower. Therefore, according to this embodiment, the performance of the ion exchange resin tower is monitored by measuring the concentration of carbonate ions in the treated water in real time while continuously circulating some of the treated water.

The sulfuric acid in the sample ion (SO ₄ ^2-), nitrate ion (NO ₃ ^-), chloride ion (Cl ^-), etc. When the co-existence is already using the method described above with some other method to obtain the concentration of carbonate ions shall. That is, with the exception of the electrical conductivity caused by the anions already present in the number of samples contributing purely bicarbonate ion (HCO ₃ ^{-) -} to obtain only the electrical conductivity caused by the contribution of chloride ion (Cl) that is caused by the switching will be.

Therefore, hydrogencarbonate ions (HCO ₃ ^-), chlorine ion (Cl ^-) to the previously measured electric conductivity of the sample number, and the bicarbonate ion (HCO ₃ ^-) before transferring the chloride ions (Cl ^-) number of samples after the conversion to the By measuring the electrical conductivity, the difference in the value can be used to determine the concentration of bicarbonate ions.

In this case, the remaining steps are the same as those of the above-described high sensitivity detection method for carbonate species and are not described again. However, before converting bicarbonate ions into chlorine ions, the electrical conductivity of the sample water is measured once more.

Hereinafter, the present invention will be described an advantage over the prior art while explaining the theoretical background to obtain the concentration of bicarbonate ions by the embodiment of the present invention.

First, the electrical conductivity measuring method used to measure the concentration of carbonate species in the present invention is the most widely used method for determining the degree of containing the ionic substance present in water. That is, as shown in FIG. 3, since a linear relationship is established between the concentration of ions and the electrical conductivity, the concentration of ions in proportion to the electrical conductivity is measured. However, as shown in FIG. 3, chlorine ions (Cl ⁻ ) and sulfate ions (SO ₄ ²⁻ ) have a good linear relationship between ion concentration and electrical conductivity, but in the case of bicarbonate ions (HCO ₃ ⁻ ) Since the linear relationship does not hold, it is impossible to accurately measure the concentration of ions using electrical conductivity. That is, when carbonic acid gas is dissolved in water, its dissociation degree (the degree of becoming ions) is extremely small, so the influence on the electrical conductivity is small and it is difficult to detect using the electrical conductivity method. Therefore, in the present invention, the concentration of bicarbonate ions (HCO ₃ ⁻ ) is indirectly measured by converting bicarbonate ions (HCO ₃ ⁻ ) into chlorine ions (Cl ⁻ ).

Hereinafter, a process of converting bicarbonate ions (HCO ₃ ⁻ ) into chlorine ions (Cl ⁻ ) by an ion exchange resin will be described.

Carbon dioxide (CO ₂ ) is present in various forms when dissolved in water, as shown in FIG. That is, the carbonate species present varies greatly depending on the pH of the water. Below pH 4, most of the carbonate species are present as hydrated carbon dioxide (CO ₂ (aq)). As the pH is increased, the ratio of bicarbonate ions (HCO ₃ ⁻ ) is gradually increased to the maximum near pH 8. As the pH is raised above, the bicarbonate ions (HCO ₃ ⁻ ) gradually decrease, and the carbonates (CO ₃ ^2- ) increase to the maximum at pH 11. However, the carbonate species converted into chlorine ions is not hydrated carbon dioxide (CO ₂ (aq)), but ionic carbonate species such as bicarbonate ions (HCO ₃ ⁻ ) and carbonate ions (CO ₃ ^2- ). Therefore, as the pH of the water increases, the carbonate species present in the ionic phase increases, so the rate of conversion to chlorine ions increases. As a result, even though the concentration of all the carbonate species present in the water is low, many carbonate species exist as ions, so that the carbonate species can be detected more quickly.

Therefore, in this embodiment, thereby replacing the hydrogen ions (H ⁺⁾ from an acid gas _{(H 2 CO 3 (aq)} ) hydrated in order to increase the pH of the water with sodium ions (Na ^+). That is, when hydrogen ions are replaced with sodium in hydrated carbon dioxide gas (H ₂ CO ₃ (aq)), sodium bicarbonate (NaHCO ₃ ) is formed to increase the pH of water. Therefore, the rate of bicarbonate ions is increased to replace the chlorine.

The chemical process is as follows.

<Formula 1>

<Formula 2>

Carbon dioxide gas becomes hydrated carbon dioxide when dissolved in water. This carbon dioxide gas has a very small dissociation constant, so that a small amount is dissociated into bicarbonate and hydrogen ions. In this case, when the hydrogen ions (H ⁺ ) are converted to sodium ions (Na ⁺ ) using a cation exchange resin, sodium bicarbonate (NaHCO ₃ ) is generated as shown in Formula 3, thereby increasing the pH of water.

<Formula 3>

At this time, since the mixed column is used in the present invention, as shown in the general formula (4), the bicarbonate ion (HCO ₃ ⁻ ) is substituted with the chlorine ion (Cl ⁻ ) of the chlorine ion exchange resin.

<Formula 4>

As a result, sodium chloride (NaCl) is dissolved in water.

<Formula 5>

R-H + Na + + Cl- ----> R-Na + H + + Cl-

(In Formulas 3, 4, and 5, R represents a resin body.)

Then, by using a hydrogen type cation exchange resin, hydrochloric acid (HCl) is generated by replacing sodium ions (Na ⁺ ) with hydrogen ions (H ⁺ ), as shown in Formula 5. Therefore, the concentration of hydrochloric acid (HCl) produced is proportional to the concentration of bicarbonate ion (HCO ₃ ⁻ ). Therefore, when the hydrochloric acid concentration measured by the electric conductivity measuring method bicarbonate ion (HCO ₃ ^-) can be obtained, the concentration of.

Conventional bicarbonate detection method merely converts bicarbonate ions (HCO ₃ ⁻ ) to chlorine ions (Cl ⁻ ) using a chlorine type anion exchange resin, but hydrogen ions of carbon dioxide gas using a mixed resin according to the present invention. Since the bicarbonate ion (HCO ₃ ^-) faster than the conventional method aggressive bicarbonate ion detection method for increasing the will to detect a concentration of ^- the replaced with sodium ions bicarbonate ion (HCO ₃₎ in the water by increasing the pH of the water .

This can be clearly seen from the bicarbonate ion detection characteristics of each method shown in FIG. 5. That is, in the conventional method, 55 minutes after the sample injection, the electrical conductivity is maximized, and in the case of using two ion exchange resins, the primary electrical conductivity increases after about 6 minutes, and then 35 minutes is hardened again. The electrical conductivity starts to increase and reaches a maximum in about 48 minutes. Therefore, although there is some effect of increasing the detection speed, it is judged that responsiveness is not greatly improved.

On the other hand, in the case of using a mixed column, the electrical conductivity starts to increase immediately after the injection of the sample and reaches a maximum in about 30 minutes, indicating that the responsiveness is remarkably improved.

And Figure 6 is but a mixed column, bicarbonate ion (HCO ₃ ^-) is a graph showing the detection characteristics and different concentrations of. According to FIG. 6, it can be seen that the difference in electrical conductivity is remarkable according to the concentration of bicarbonate ion (HCO ₃ ⁻ ). Therefore, it can be seen that the present invention can be very usefully used for the detection of bicarbonate ions in water.

The present invention is a bicarbonate that leaks when the performance of the ion exchange resin tower of the purification system for removing carbon dioxide (CO ₂ ) containing a radionuclide C-14 generated during operation in the primary system of the heavy water nuclear power plant deterioration By monitoring ions (the first to leak out of performance) and replacing ion exchange resins in a timely manner, they can help minimize C-14, a radionuclide released into the atmosphere, reduce the generation of radioactive waste, and contribute to operating costs. In particular, according to the present invention, there is an advantage that a low concentration of bicarbonate can be detected quickly.

Claims (14)

1) obtaining a sample water by taking a part of the treated water that has passed through the ion exchange resin tower; 2) converting the carbonic acid in the sample water to sodium chloride by passing the sample water through a mixed column; 3) converting the sample water containing sodium chloride into hydrochloric acid through a cationic column; 4) measuring the electrical conductivity of the sample water using the electrical conductivity cell; Carbon dioxide species high sensitivity detection method comprising. The method of claim 1, After performing step 4), the sample water is passed through an anion column to remove chlorine ions, and further comprising the step of sending to the ion exchange resin tower inlet detection method. 1) obtaining a sample water by taking a part of the treated water that has passed through the ion exchange resin tower; 2) measuring the electrical conductivity of the sample water using an electroconductivity cell after passing the sample water through a cation column; 3) passing the sample water through a mixed column to convert carbonic acid in the sample water to sodium chloride; 4) converting the sample water containing sodium chloride into hydrochloric acid through a cationic column; 5) measuring the electrical conductivity of the sample water passing through the cation column using an electrical conductivity cell; 6) obtaining a concentration of bicarbonate ions from the difference between the electrical conductivity in step 2) and the electrical conductivity in step 5); Carbon dioxide species high sensitivity detection method comprising. The method of claim 3, After performing step 6), passing the sample water through an anion column to remove chlorine ions, and further comprising the step of sending to the ion exchange resin tower inlet detection method. A sample water providing unit connected to the treated water outlet of the ion exchange resin tower and taking a portion of the treated water that has passed through the ion exchange resin tower and providing the sample water; A mixing column connected to one end of the sample water providing unit and converting the carbonic acid in the sample water to sodium chloride; A cation column connected to the mixing column and converting sodium chloride in the sample water into hydrochloric acid; An electrical conductivity measurement unit connected to an end of the cation column and measuring an electrical conductivity of the sample water passing through the cation column; A sample water return unit connected to an end of the cation column and sending the sample water passing through the cation column to the ion exchange resin tower inlet; Carbonate high sensitivity detection device comprising a. The method of claim 5, wherein the mixed column, A high sensitivity detection device for carbonate species, characterized in that the column is filled with a mixed resin of sodium cation exchange resin and chlorine anion exchange resin. The method of claim 5, wherein the cation column, A high sensitivity detecting device for carbonate species, characterized in that the column is filled with a hydrogen type cation exchange resin. The method of claim 5, One end is connected to the end of the cation column, the other end is connected to the sample water return portion, the carbonic acid species high sensitivity detection device, characterized in that there is further provided an anion column for adsorbing and removing chlorine ions in the sample water. The method of claim 8, wherein the anion column, A high sensitivity detecting device for carbonate species, characterized in that the column is filled with a hydroxide ion anion exchange resin. A sample water providing unit connected to the treated water outlet of the ion exchange resin tower and taking a portion of the treated water that has passed through the ion exchange resin tower and providing the sample water; A first cation column connected to one end of the sample water providing unit and converting a cation in the sample water into hydrogen ions; A first electrical conductivity measurement unit connected to an end of the first cation column and measuring an electrical conductivity of the sample water passing through the first cation column; A mixing column connected to the end of the first cation column and converting carbonic acid in the sample water to sodium chloride; A second cation column connected to the mixing column and converting sodium chloride in the sample water into hydrochloric acid; An electrical conductivity measurement unit connected to an end of the second cation column and measuring an electrical conductivity of the sample water passing through the second cation column; A sample water return unit connected to an end of the second cation column and sending the sample water passing through the second cation column to the ion exchange resin tower inlet; Carbonate high sensitivity detection device comprising a. The method of claim 10, wherein the mixing column, A high sensitivity detection device for carbonate species, characterized in that the column is filled with a mixed resin of sodium cation exchange resin and chlorine anion exchange resin. The method of claim 10, wherein the second cation column, A high sensitivity detecting device for carbonate species, characterized in that the column is filled with a hydrogen type cation exchange resin. The method of claim 10, One end is connected to the end of the second cation column, the other end is connected to the sample water return portion, carbon dioxide species high sensitivity detection, characterized in that an anion column for adsorbing and removing chlorine ions in the sample water is further provided. Device. The method of claim 13, wherein the anion column, A high sensitivity detection device for carbonate species, characterized in that the column is filled with a hydroxide ion anion exchange resin.

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