KR20180103248A - Boron concentrations measuring system for correcting error and method using the same - Google Patents

Abstract

An embodiment of the present invention provides an error correcting type boron concentration measuring system and a boron concentration measuring method using the same. The error correcting type boron concentration measuring system and the boron concentration measuring method using the same according to an embodiment of the present invention include a main flow path, a bypass flow path, a main measuring portion, a sub-measuring portion, a filter, a valve portion, a set converting portion, and an operation control portion. A scale of boron concentration measurement data of the main measuring portion can be corrected by a set cycle by correction data calculated from the set converting portion. Accordingly, distortion of measurement data due to accumulated errors can be prevented, thereby capable of providing a highly precise and highly reliable error correcting type boron concentration measuring system and a boron concentration measuring method using the same.

Description

Technical Field [0001] The present invention relates to a boron concentration measuring system,

The present invention relates to an error-compensating boron concentration measuring system and a boron concentration measuring method using the same, and more particularly, to an error compensating boron concentration measuring system with error corrected for measuring a precise boron concentration in reactor coolant, And a boron concentration measuring method.

In the light water reactor type nuclear power plant, natural boric acid water is added to the reactor coolant to control the long-term response to the combustion of the fuel. Since the criticality varies with the concentration of boric acid, accurate measurement of the boric acid concentration of boric acid is very important for safe operation of nuclear power plants.

For safe and continuous use of nuclear power plants, conventional light water reactor nuclear power plants use a boronometer that measures the boron concentration in the reactor coolant by the neutron absorption method.

Boronometer is a device to measure boron concentration from 0ppm to 5000ppm. It is installed in the outflow system of Chemical & Volume Control System (CVCS) to measure the boron concentration in the coolant flowing out of the reactor coolant system. It can be measured in real time.

However, the conventional boronometer has a disadvantage that detection is difficult at a small error range, and errors are accumulated in the boron concentration measurement data depending on the operation time of the equipment, and the result data is corrected.

Accordingly, in the Korean Registered Patent No. 10-1178707 (entitled "Boron Dilution Accident Alert System and Method Using the Cumulative Deviation Sum Control Chart, Patent Holder: KHNP), the neutron counting rate is continuously measured and the deviation Discloses a boron dilution accident warning system and method using a cumulative deviation sum management chart capable of early detection of an increase in the neutron count rate having a linear trend pattern using a sum.

However, in the conventional Voronometry error correction system using the cumulative deviation sum management chart, it is required to stop the equipment when measuring the neutron counting rate, and accordingly, the disassembling work of the equipment is required. Therefore, there is a disadvantage that time and cost are consumed, and a radiation shielding facility is additionally required.

Korean Patent No. 10-1178707

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a high-accuracy, error-correcting boron concentration measuring system and a boron concentration measuring method using the same.

Another object of the present invention is to provide a high-efficiency, error-correcting boron concentration measuring system and a boron concentration measuring method using the same.

Another object of the present invention is to provide a high-reliability, error-correcting boron concentration measuring system and a boron concentration measuring method using the same.

Another object of the present invention is to provide a high-precision, error-correcting boron concentration measuring system and a boron concentration measuring method using the same.

Another object of the present invention is to provide a low-cost error-correcting boron concentration measuring system and a boron concentration measuring method using the same.

In order to solve the above technical problems, the present invention provides an error-correcting boron concentration measurement system.

According to one embodiment, the error-correcting boron-concentration measuring system includes a main measuring unit, a sub-measuring unit, and a setting converting unit. The main measuring part is located on the main flow passage through which the measurement sample passes. The main measuring unit measures the concentration of boron in the measurement sample in real time using a neutron measurement method. And the sub measurement unit is located on the bypass flow path. At this time, the bypass flow path is branched from the main flow path. The sub-measuring unit measures the concentration of boron in the sample to be measured which passes through the bypass flow path at regular intervals by an electricity quantity titration method. The setting conversion unit compares the boron concentration data measured from the main measurement unit and the sub measurement unit, and adjusts the scale of the main measurement unit.

According to one embodiment, the error-correcting boron concentration measuring system may further include a filter and a valve unit. The filter may be disposed in series with the sub-measurement unit on the bypass flow path. Accordingly, the filter can filter an exhausted sample, which is a product of the sub-measuring unit. The valve unit may adjust the amount of the sample to be injected.

According to an embodiment, the error correction type boron concentration measurement system may further include an operation control unit. The operation control unit may control operations of the sub-measurement unit, the valve unit, and the setting conversion unit.

According to one embodiment, the sub-measurement unit of the error-correcting boron concentration measurement system may include a reaction unit, an injection unit, a power source unit, a current meter, a pH meter, and an analysis unit. The reaction unit may include a reaction tank and an electrode unit. The reaction tank can accommodate a measurement sample introduced from the outside. The electrode unit may be accommodated in at least a part of the reaction vessel. The electrode unit may include an oxidizing electrode and a reducing electrode. The injector may include a first material, a second material, and a third material. The first material may be an electrolyte that dissociates hydrogen ions. The second material may have a standard oxidation potential of 0.8 V or less. The second material may be an electrolyte that reacts with the oxidation electrode to produce a precipitate. The third material may be an electrolyte not participating in a chemical reaction in the reaction tank. The power supply unit may supply an electric current to the electrode unit to control the electrolysis of the measurement sample and the second mixed sample in which the first to third materials are mixed. The current meter may measure an amount of current during electrolysis of the second mixed sample. The pH meter can measure the concentration of hydrogen ions in the measurement sample in the water tank. The analyzer may analyze data measured from the current meter and the pH meter to derive the concentration of boron ions in the measurement sample.

According to an embodiment, the amount of the measurement sample injected into the main channel of the error-correcting boron concentration measuring system may be 50 ml or less.

According to one embodiment, the oxidation electrode of the error-correcting boron concentration measuring system may be at least one of silver (Ag), copper (Cu), and zinc (Zn).

According to one embodiment, when the oxidation electrode of the error compensating boron concentration measuring system is silver (Ag), the second material is selected from the group consisting of sodium bromide (NaBr), sodium chloride (NaCl), potassium chloride (KCl) CaCl _2), sodium sulfide (Na ₂ S), sulfide, potassium (K ₂ S), calcium sulfide (CaS), sodium sulfate (Na ₂ SO _4), potassium sulfate (K ₂ SO _4), calcium sulfate (CaSO _4), The second material may be at least one of sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), or calcium carbonate (CaCO ₃ ). When the oxidation electrode is copper (Cu) (Na ₂ S), potassium sulfide (K ₂ S), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ) or ammonium carbonate ((NH ₄ ) ₂ CO ₃ ) When the oxidation electrode is zinc (Zn), the second material is selected from the group consisting of sodium sulfide (Na ₂ S), potassium sulfide (K ₂ S), ammonium sulfide ((NH ₄ ) ₂ S), magnesium sulfide Barium (BaS), or calcium sulfide (CaS). Can the Nile.

According to one embodiment, the first material of the error compensating boron concentration measurement system is selected from the group consisting of d-mannitol, sorbitol, xylitol, erythritol, or isomalt. Or the like.

According to an embodiment of the present invention, the cathode of the power source unit of the error correction type boron concentration measurement system may be connected to the oxidation electrode, and the anode of the power source unit may be connected to the current meter.

According to one embodiment, the pH meter of the error-correcting boron concentration measuring system may be at least one of a pH meter or an indicator.

According to one embodiment, in the error-correcting boron concentration measuring system, when the current measurement range by the current measuring instrument is less than 50 mA from 10 mA or more, the pH meter may be used as the pH meter.

According to one embodiment, in the error-correcting boron concentration measurement system, when the current measurement range by the current meter is 50 mA or more, the indicator may be used as the pH meter, And may further include a spectroscope for analyzing the color change of the indicator.

In order to solve the above technical problems, the present invention provides a method for measuring a boron concentration.

According to one embodiment, the boron concentration measuring method includes the steps of injecting a measurement sample into a main flow path, injecting at least a portion of the measurement sample into a bypass flow path in a specific cycle, Measuring a concentration of boron in the measurement sample passing through the bypass passage in the sub-measurement unit by an electrometric titration method, measuring a concentration of boron in the measurement sample passing through the bypass passage, And calculating the correction data by comparing the boron concentration data measured from the sub-measurement unit and correcting the scale of the main measurement unit by the calculated correction data.

According to one embodiment, in the step of calculating the correction data among the boron concentration measuring methods, the correction data can be calculated by the data interpolation method.

According to one embodiment of the present invention, in the step of measuring the concentration of boron in the measurement sample by the electrometric titration method in the sub-measurement unit, at least one of the electrode unit including the oxidation electrode in the sub- A step of injecting a measurement sample into a reaction tank containing a part of the sample, a step of injecting a first substance, which is an electrolyte for dissociating hydrogen ions, from the injection unit into the reaction tank into which the measurement sample flows, Is injected into the first mixed sample from the injection unit through a second material which is an electrolyte which reacts with the oxidation electrode to generate a precipitate and an electrolyte which is not involved in a chemical reaction in the reaction tank A step of producing a second mixed sample, a step of supplying an electric current by the power source unit and electrolyzing the second mixed sample Measuring a hydrogen ion concentration of the second mixed sample with respect to time using a pH meter during the electrolysis, measuring a current amount of the second mixed sample with a current meter during the electrolysis, Measuring the amount of ions and transmitting the respective concentration data and current data measured in the step of measuring the amount of current to the analyzing unit and based on the received concentration data and the current data, And calculating the concentration.

According to an embodiment of the present invention, the step of calculating the concentration of boron in the measurement sample in the analysis unit among the boron concentration measurement method may include graphing the concentration data measured from the pH meter, A step of extracting a time point, a step of graphing the current data measured from the current measuring device, extracting the amounts of current measured until the appropriate time point, integrating the extracted time point and the amounts of current extracted, 2 mixed sample, calculating the number of moles of free electrons by dividing the amount of charge by a Faraday constant, and correlating the number of moles of the free electrons with the boron concentration .

The system for measuring the boron concentration of the error-compensating type according to the embodiment of the present invention and the method for measuring the boron concentration using the same may be capable of real-time boron concentration measurement in the measurement sample by operating the main measurement unit in real time.

In addition, the system for measuring the boron concentration of the error-correcting type according to the embodiment of the present invention and the method for measuring the boron concentration using the same may further include a boron concentration measurement data for the cumulative error generated when the main measurement unit is operated for a long time by the sub- It is possible to measure the boron concentration with high reliability.

Further, the error-correcting boron concentration measuring system and the boron concentration measuring method using the same according to the embodiment of the present invention can accurately measure the concentration of boron by measuring the boron concentration in the sample to be measured with a fully- Boron concentration measurements may be possible.

The boron concentration measuring system of the present invention and the boron concentration measuring method using the same according to the embodiment of the present invention can utilize the conventional boronometer facility and thus can measure the boron concentration at a low cost.

Further, the system for measuring the boron concentration of the error-compensating type according to the embodiment of the present invention and the method for measuring the boron concentration using the same may further include a step of measuring the concentration of boron in the measurement sample, , Low-cost and high-stability boron concentration measurement can be made possible.

FIG. 1 is a conceptual diagram for explaining the structures of an error-correcting boron concentration measurement system according to an embodiment of the present invention.
FIG. 2 is a conceptual diagram for explaining a sub-measuring unit of the error-correcting boron-concentration measuring system according to an embodiment of the present invention.
3 is a flowchart for explaining the boron concentration measurement method according to an embodiment of the present invention.
FIG. 4 is a flowchart for explaining a method of measuring a boron concentration in a sub-measuring unit in a method of measuring a boron concentration according to an embodiment of the present invention.
5 is a flowchart for explaining a boron concentration calculating method by the analyzer in the boron concentration measuring method according to the embodiment of the present invention.

The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing. In the accompanying drawings, the dimensions of the structures may be exaggerated to illustrate the present invention.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprising" or "having ", and the like, are intended to specify the presence of stated features, integers, steps, operations, elements, parts, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, parts, or combinations thereof. In addition, A and B are 'connected' and 'coupled', meaning that A and B are directly connected or combined, and other component C is included between A and B, and A and B are connected or combined .

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.

FIG. 1 is a conceptual diagram for explaining the structures of an error-correcting boron concentration measurement system according to an embodiment of the present invention.

Referring to FIG. 1, the error-compensating boron concentration measuring system may be installed in the outflow system of a chemical and volume control system (CVCS). Here, the chemical and volume control system (CVCS) may be a facility for purifying a measurement sample introduced into a nuclear reactor under operation using a demineralizer.

For example, the measurement sample purified by the Chemical & Volume Control System (CVCS) may be introduced into the error correction boron concentration measurement system. Accordingly, the error-correcting boron concentration measurement system can calculate the boric acid concentration in the introduced measurement sample.

The error correction type boron concentration measurement system may include a main channel 1000 and a bypass channel 2000. In addition, the error-correcting boron concentration measuring system may include a valve unit 3000, a setting conversion unit 4000, and an operation control unit (not shown).

The main channel 1000 may be connected to the outflow pipe of the outflow system as described above. Accordingly, the measurement sample purified from the Chemical & Volume Control System (CVCS) can be passed as described above.

A main measurement unit 1100 may be disposed on the main flow path 1000. Therefore, the measurement sample may be introduced into the main measurement unit 1100 through the main flow path 1000.

The main measurement unit 1100 can measure the concentration of boron in the measurement sample. More specifically, the main measuring unit 1100 can measure the concentration of boron in the measurement sample using a neutron measurement method.

According to the embodiment, the main measuring unit 1100 may be a conventional Voronometer equipment. The boronometer for measuring the concentration of boron by using the neutron measurement method is a well-known technique to those skilled in the art, and a detailed description thereof will be omitted.

The boron concentration data measured from the main measuring unit 1100 may be adjusted by the setting conversion unit 4000 to be described later. This will be described more specifically when the setting conversion unit 4000 is described.

When the measurement of the boron concentration of the main measurement part 1100 is completed, the exhausted sample discharged from the main measurement part 1100 flows along the main flow path 1000 to the chemical and volume control system CVCS Control System). In other words, the measurement sample is circulated in the chemical and volume control system (CVCS) and the main measurement unit 1100, so that the error correction type boron concentration measurement system according to the embodiment of the present invention The concentration of boron in the measurement sample can be measured in real time without taking the measurement sample separately.

The bypass flow path 2000 may be a flow path branched from the main flow path 1000 and bypassing the main flow path 1000. More specifically, the bypass passage 2000 may be branched from the main passage 1000 at the first branch point A and merged with the main passage 1000 at the second branch point B .

At least a part of the measurement specimen passing through the main flow path 1000 may be introduced into the bypass flow path 2000 by the operation control unit (not shown) to be described later.

More specifically, the operation control unit 6000 may open the first valve 3100, which will be described later. Accordingly, at least a part of the measurement specimen passing through the main flow path 1000 can be introduced into the bypass flow path 2000 at the first branch point (A). At this time, the amount of the measurement sample introduced into the bypass channel 2000 may be less than 1L to less than 1L. According to an embodiment, the amount of the measurement sample may be 50 ml. Accordingly, the sub-measuring unit 2100, which will be described later, located on the bypass flow path 2000 can quickly measure the boron concentration in the measurement sample.

As described above, the sub measurement unit 2100 and the filter 2500 may be disposed on the bypass flow path 2000.

The sub-measurement unit 2100 may be operated at regular intervals by the operation control unit (not shown).

The sub-measuring unit 2100 can measure the concentration of boron in the measurement sample injected through the bypass channel 2000. According to the embodiment, the sub-measuring unit 2100 can measure the concentration of boron in the sample to be measured by using an electric quantity titration method. At this time, the boron concentration data measured from the sub-measurement unit 2100 may be transmitted to the setting conversion unit 4000, which will be described later.

FIG. 2 is a conceptual diagram for explaining the sub-measuring unit of the error-correcting boron-concentration measuring system according to the embodiment of the present invention.

1 and 2, the sub-measurement unit 2100 includes a reaction unit 100, an injection unit 200, a power source unit 300, a current meter 400, a pH meter 500, and an analysis unit 600 ).

The reaction unit 100 may be a space where electrolysis and chemical reaction occur. The reaction unit 100 may include a reaction tank 110 and an electrode unit 150.

The reaction tank 110 may receive at least one of the external sample or the sediment 235 generated from the measurement sample, the electrolytic material, and the combination thereof introduced from the injection unit 200 to be described later.

According to the embodiment, the reaction tank 110 can receive the second mixed sample and the sediment 235 to be described later. The second mixed sample is a mixture of the measurement sample introduced into the reaction tank 110 and the first to third materials 210, 230, and 250 injected from the injection unit 200 . In addition, the precipitate 235 may be a substance generated from the reaction of the oxidation electrode 151 and the second material 230, which will be described later. The precipitate 235 will be described in more detail in the injection unit 200 to be described later.

The electrode unit 150 may be connected to the power unit 300 and the current meter 400 to form a circuit C. Accordingly, the current generated from the power supply unit 300 can be supplied to the electrode unit 150 through the circuit C.

At least part of the electrode unit 150 may be accommodated in the reaction vessel 110. At this time, at least a part of the electrode unit 150 may be immersed in the second mixed sample contained in the reaction tank 110. Accordingly, when current is supplied to the electrode unit 150 immersed in the power supply unit 300, the second mixed sample can start electrolysis.

The electrode unit 150 may include an oxidation electrode 151 and a reduction electrode 155. The oxidation electrode 151 may be a cathode. Accordingly, when power is supplied from the power supply unit 300, an oxidation reaction may occur in the oxidation electrode 151.

More specifically, the oxidation electrode 151 may emit the free electrons e ^- and be ionized. The emitted free electrons e ^- may be transferred to the reduction electrode 155, which will be described later, along with the circuit C described above. At this time, the number of free electrons (e ^- ) emitted may be equal to the number of hydroxide ions (OH ^- ) to be described later.

On the other hand, as described above, the metal cation of the ionized electrode 151 may react with the second material 230 to form the precipitate 235, which will be described later.

The oxidation electrode 151 may be a metal having a standard electrode potential of 0.8 V or less. In other words, the oxidation electrode 151 may be a metal having a good reducing power.

[Table 1] is a standard electrode potential table in which a half-reaction scheme of some metals whose standard electrode potential is 0.8 V or less is described. Referring to Table 1, the oxidation electrode 151 may be at least one of silver (Ag), copper (Cu), and zinc (Zn).

Half reaction E ⁰ (V) Ag ⁺ (aq) + e ^- ? Ag (s) 0.8 Cu ^{2 +} (aq) + 2e ^- ? Cu (s) 0.34 Sn ^{2 +} (aq) + 2e ^- ? Sn (s) 0.15 2H ⁺ (aq) + 2e ^- ? H ₂ (g) 0 Pb ^{2 +} (aq) + 2e ^- ? Pb -0.13 Zn ^{2 +} (aq) + 2e ^- ? Zn (s) -0.76 Al ^{3 +} (aq) + 3e ^- ? Al (s) -1.66

According to the embodiment, the oxidation electrode 151 may be silver (Ag). Accordingly, during the electrolysis, the silver (Ag) that is the oxidation electrode 151 can be separated into the free electrons e ^- and the silver ions Ag ⁺ (see Chemical Formula 1 below). At this time, the separated free electrons e ^- can be transferred to the reduction electrode 155 described later along the circuit C.

On the other hand, the silver ions (Ag ^< ⁺ > It can react with the bromine ion (Br ^- ) present therein to form a precipitate of silver bromide (AgBr). Here, the bromine ion (Br ^- ) may be an anion of sodium bromide (NaBr), which is an example of the second material 230.

The reaction of the oxidation electrode 151 and the second material 230 will be described more specifically in the description of the injection unit 200 to be described later.

The reducing electrode 155 may be an anode. In addition, the reducing electrode 155 may be a material having low reactivity with water (H ₂ O). In other words, the reducing electrode 155 may be a material that is not well soluble in water (H ₂ O). For example, the reducing electrode 155 may be at least one of carbon (C), platinum (Pt), titanium (Ti), and iridium (Ir).

When a current is supplied to the electrode unit 150 by the power supply unit 300 to be described later, a reduction reaction may occur in the reduction electrode 155.

More specifically, the reducing electrode 155 may receive the free electrons (e ^- ) emitted from the oxidizing electrode 151 when the power source 300 supplies a current. The transferred free electrons e ^- may be combined with water molecules (H ₂ O) distributed around the reducing electrode 155 to perform a reduction reaction (see Chemical Formula 2 below)

As a product of the reduction reaction, hydrogen gas (H ₂ ) and hydroxide ion (OH ^- ) may be generated. The hydroxide ions (OH ^-) can be carried out for the measurement sample and dissociated by the reaction of the first material 210 will be described later, the hydrogen ions (H ⁺⁾ and the neutralization reaction. At this time, the hydroxide ion (OH ^- ) and the completely dissociated hydrogen ion (H ⁺ ) can be reacted completely. Thus, the second at full neutralization of the mixed sample, the hydroxide ion (OH ^-) can be equal to the amount of the hydrogen ion (H ⁺⁾ dissociation of the full amount.

The injector 200 may receive the first material 210, the second material 230, and the third material 250.

The injection unit 200 may be connected to at least a part of the reaction vessel 110. Accordingly, the first to third materials 210, 230, and 250 contained in the injection unit 200 can be injected into the reaction vessel 110.

The first material 210 may be chemically reacted with the measurement sample when injected into the reaction tank 110, as described above. The hydrogen ion (H ⁺ ) can be dissociated from the measurement sample by the chemical reaction.

In other words, the first material 210 may be a material that helps ionize the hydrogen ions (H ⁺ ) from the measurement sample. At this time, the concentration of the first material 210 injected into the reaction tank 110 may be at least 2 times or more than 10 times the concentration of the measurement sample. Accordingly, the measurement sample can sufficiently receive the hydroxyl group (OH < ^- >) from the first material 210. Therefore, the hydrogen ions (H ⁺ ) can be completely disassociated from the measurement sample without being recombined.

At this time, the production ratio of the dissociated hydrogen ions (H ⁺ ) may be the same as the reaction ratio of the measurement sample. Therefore, the boron (B) concentration in the measurement sample may correspond to the concentration of the hydrogen ion (H ⁺ ).

As noted above, the dissociation of the hydrogen ion (H ⁺⁾ is a reduction reaction of the hydroxide ions produced in (OH ^-) of the reduction electrode 155 can be a full and reaction. Accordingly, the second mixed sample can be neutralized.

Therefore, the sub-measuring unit 2100 can determine the concentration of the boron (B) by calculating the reaction concentration of the hydroxide ion (OH ^- ) at the time when the hydrogen ion (H ⁺ ) is completely neutralized. The process of calculating the concentration of the hydroxide ion (OH < ^- & gt ^; ) will be described in more detail in the analysis unit 600 described later.

The first material 210 may be at least one of d-mannitol, sorbitol, xylitol, erythritol, or isomalt. According to an embodiment, the first material 210 may be d-mannitol.

The second material 230 may be an electrolyte. Thus, it may be present in the second mixed sample in an ionic state.

The anion (-) of the second material 230 may be combined with the positive (+) electrode of the oxidation electrode 151 in the reaction tank 110. In other words, as described above, the second material 230 may react with the oxidizing electrode 151 to produce the precipitate 235.

Generally, in the conventional electrolysis using an oxidizing electrode and a reducing electrode, the free electrons (e ^- ) emitted from the oxidizing electrode move to the reducing electrode and are recombined with the positive (+) ion of the oxidizing electrode . As a result, foreign matter has been deposited on the surface of the conventional reduction electrode.

However, in the boron concentration system according to the embodiment of the present invention, the second material 230 is injected into the reaction vessel 110 by the sub-measurement unit 2100 so that the free electrons e ^- It is possible to prevent recombination with metal cations. Therefore, since the total amount of the free electrons e ^- participates in the reduction reaction of the reducing electrode 155, the number of the free electrons e ^{- -} ) can be derived.

According to an embodiment, when the oxidation electrode 151 is silver (Ag), the second material 230 may be sodium bromide (NaBr). The sodium bromide (NaBr) can be decomposed into sodium ion (Na ⁺ ) and bromine ion (Br ^- ) on the second mixed sample.

The bromine ion (Br < "& gt ^; ) which is an anion can be combined with the silver ion (Ag ⁺ ). Thus, the precipitate, silver bromide (AgBr), can be produced (see Chemical Formula 3 below).

On the other hand, the cationic sodium ion (Na < ^{+ &} gt ^; ) can be stabilized in the second mixed sample. In other words, the sodium ion (Na ⁺ ) may not react with other ions in the second mixed sample while maintaining the ionic state.

As described above, the second material 230 may combine with the oxidizing electrode 151 to produce the precipitate 235. Accordingly, the type of the second material 230 may vary depending on the type of the oxidizing electrode 151.

The second material 230 may include at least one selected from the group consisting of NaBr, NaCl, KCl, CaCl ₂ , , Sodium sulphate (Na ₂ S), potassium sulphate (K ₂ S), calcium sulphate (CaS), sodium sulphate (Na ₂ SO ₄ ), potassium sulphate (K ₂ SO ₄ ), calcium sulphate (CaSO ₄ ) ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), or calcium carbonate (CaCO ₃ ).

According to another embodiment, when the oxidizing electrode 151 is copper (Cu), the second material 230 is sodium sulfide (Na ₂ S), sulfide, potassium (K ₂ S), sodium carbonate (Na ₂ CO ₃ ), Potassium carbonate (K ₂ CO ₃ ), or ammonium carbonate ((NH ₄ ) ₂ CO ₃ ).

According to another embodiment, when the oxidation electrode 151 is zinc (Zn), the second material 230 may include at least one selected from the group consisting of sodium sulfide (Na ₂ S), potassium sulfide (K ₂ S), ammonium sulfide ₄₎ may be at least any one of the ₂ S), magnesium sulfide (MgS), barium sulfide (BaS), or calcium sulfide (CaS).

The third material 250 may be a material for eliminating ion imbalance generated in the second mixed sample.

More specifically, the third material 250 may be an electrolyte. Accordingly, when the third material 250 is injected into the reaction vessel 110, it can be completely ionized in the second mixed sample.

The ionized third material 250 may be in a stable state in the second mixed sample. Accordingly, when the anion (-) present in the second mixed sample is reduced by the combination of the positive (+) of the oxidizing electrode 151 and the negative (-) of the second material 230, The ionic imbalance can be solved by the anions of the third material 250, Thus, abrupt interruption of electrolysis can be prevented.

As a conventional technique for preventing the ion imbalance from occurring, there is a method using a solt bridge. However, since the ion exchange method using the solt bridge requires a plurality of reaction vessels each accommodating an oxidizing electrode and a reducing electrode, there is a disadvantage that the size of equipment is increased and the cost is increased.

Above all, when the ions pass through the solt bridge, the traveling speed of the ions may be lowered. Accordingly, it takes a long time to measure the concentration of boron (B), and measurement of the real time boron (B) concentration in the reactor may be unsuitable.

As described above, the sub-measurement unit 2100 of the boron concentration system according to the embodiment of the present invention may be configured such that the complete ionization is performed in a stable state in the second mixed sample, By introducing the third material 250, it is possible to prevent ion unbalance in the second mixed sample, thereby preventing unintentional interruption of electrolysis.

In addition, cations and anions ionized from the third material 250 are freely moved in the reaction vessel 110 in which the electrode unit 150 is commonly accommodated, so that current flow is smooth and suitable for real-time boron (B) concentration measurement can do.

The power supply unit 300 may be a device that supplies current to the second mixed sample through the circuit C. In other words, the second mixed sample can be electrolyzed by the power supply unit 300.

More specifically, when power is supplied to the oxidation electrode 151 by the power supply unit 300, an oxidation reaction may occur in the oxidation electrode 151 which is a negative electrode.

When power is supplied to the reduction electrode 155 by the power supply unit 300, a reduction reaction may occur at the reduction electrode 155, which is an anode. At this time, the oxidation reaction and the reduction reaction may proceed at the same time.

The power supply unit 300 may include an electric isolation function. Accordingly, when power is supplied to the power supply unit 300, the interference of the electric field generated between the oxidation electrode 151 and the reduction electrode 155 can be minimized.

The power supply unit 300 may be at least one of a power supply, a battery, or a battery-powered pH meter coupled to the pH meter 500, which will be described later. According to an embodiment, the power source unit 300 may be a battery.

The current measurer 400 can measure the amount of current (i) supplied from the power supply unit 300 in real time. The current data measured from the current meter 400 may be transmitted to the analyzer 600.

The current meter 400 may be a device for determining the amount of charge Q at a proper time t, which is a neutralization point of the second mixed sample. The method of calculating the amount of charge Q will be described more specifically in the analyzer 600 described later.

The current measurement range of the current measuring device 400 may be less than 50 mA from 10 mA or more. The type of the pH meter 500 to be described later may be changed according to a current measurement range of the current meter 400. This will be described in more detail in the description of the pH meter 500.

At least a portion of the second mixed sample may be immersed in the pH meter 500. Accordingly, the pH meter 500 can measure the pH concentration change in the second mixed sample in real time. At this time, the concentration data measured from the pH meter 500 may be transmitted to the analyzer 600, similarly to the current meter 400 described above.

The pH meter 500 may be used to derive an appropriate time t, which is a neutralization point of the second mixed sample. The method of deriving the appropriate time point (t) will be described more specifically in the analysis unit 600, which will be described later.

As described above, the type of the pH meter 500 may be determined according to the current measurement range of the current meter 400.

According to one embodiment, when the current measuring range is less than 50 mA from 10 mA or more, the pH meter 500 may use a pH meter.

According to another embodiment, when the current measurement range is 50 mA or more, the indicator may be used with the pH meter 500. For example, the indicator may be at least one of bromothymol blue, methyl red, phenol red, or o-cresol red.

When the indicator is used in the pH meter 500, the pH meter 500 may further include a spectroscope for analyzing a color change of the indicator. For example, the spectrometer may be capable of real-time monitoring and measurement by a UV-vis spectrophotometer or Raman spectroscopic method.

The pH meter 500 may include an electric isolation function, such as the power supply unit 300 described above. Accordingly, it is possible to prevent the data from being corrected by the interference of the electric field generated from the oxidation electrode 151 and the reduction electrode 155 when measuring the data of the pH meter 500.

The analyzer 600 may perform a coulometric titration analysis at the neutralization point of the second mixed sample based on the data transmitted from the current meter 400 and the pH meter 500 .

In other words, the analyzer 600 calculates the amount of charge (Q) generated by electrolysis at the appropriate time (t) at which the second mixed sample is completely neutralized, so that the amount of boron (B) can be calculated.

The analysis unit 600 may include a first calculation unit 610, a second calculation unit 630, a third calculation unit 650, and a fourth calculation unit 670.

The first calculator 610 may graph the current data transmitted from the current meter 400 and the concentration data transmitted from the pH meter 500. In other words, the first calculation unit 610 may transform the current data and the concentration data into a pH graph and a current graph, respectively.

Then, the first calculator 610 can derive the appropriate time t from which the second mixed sample is completely neutralized from the pH graph. More specifically, the appropriate time point t may coincide with a time point at which the pH graph fluctuates. Accordingly, the first calculating unit 610 can extract the inflection point through the second derivative of the pH graph to derive the appropriate time t.

The second calculator 630 may calculate the amount of charge Q generated during the appropriate time t based on the current graph and the appropriate time t.

The charge amount Q can be calculated by multiplying or integrating the amount of current i generated during the appropriate time t on the basis of the current graph (see Equation 1 below)

Q; Charge amount (C)

i; Current Amount (A)

t; The appropriate time (t)

According to the embodiment, in the sub-measuring unit 2100, the substance to be precipitated on the surface of the reducing electrode 155 is non-existent in the reducing reaction, and the stabilized ion distribution in the second mixed sample The graph can be in the form of a constant graph. Accordingly, the second calculator 630 may calculate the charge quantity Q by multiplying the optimum time t and the current amount i.

The third calculator 650 may calculate the number of moles of the free electrons e ^- based on the amount of charge Q. [ More specifically, the number of moles of the free electrons e ^- can be calculated by dividing the amount of charge Q by a Faraday constant F (see Equation 2 below).

[e ^- ]; Free electron (mole)

Q; Charge quantity

F; Faraday constant

The fourth calculator 670 can derive the concentration of the boron (B) in the measurement sample based on the calculated number of moles of the free electrons (e ^- ).

More precisely, the optimum time t is determined by the hydrogen ion (H ⁺ ) and the reducing electrode 155, which are completely dissociated by the reaction of the measurement sample and the first material 210, of the hydroxyl ion (OH ^-) generated during the reduction reaction may be a point that is completely neutralized. Therefore, the number of moles of the free electrons (e ^- ) generated during the appropriate time (t) can be controlled by controlling the number of moles of the free electrons (e-) generated during the reduction reaction of the reducing electrode 155 may correspond to the concentration of the hydrogen ions and to complete the reaction (H ⁺⁾ hydroxyl ions (OH ^{- -)} concentration, and the hydroxide ion (OH) a.

At this time, the hydrogen ion (H ⁺ ) can be completely dissociated at the same coefficient ratio as the reaction ratio of the measurement sample. Consequently, as a result, the number of moles of the free electrons e ^- can be converted to the concentration of boron (B).

Referring again to FIG. 1, the filter 2500 may be connected in series with the sub-measurement unit 2100. Accordingly, the discharged sample, which is the product of the sub-measuring unit 2100, can be filtered.

More specifically, the filter 2500 may remove unreacted ions and the precipitates 235 in the second mixed sample.

According to the embodiment, the discharge sample filtered through the first to third materials 210, 230, 250 and the sediments 235 in the second mixed sample flows along the bypass channel 2000, (1000). ≪ / RTI > At this time, a pump or the like may be further included to facilitate the inflow of the discharged sample.

In the case of the conventional Voronometer, the discharged sample, from which the base component has not been removed, is discharged to the outside of the system, and a separate radioactive waste treatment has to be carried out.

However, in the case of the error-correcting boron concentration measuring system according to the embodiment of the present invention, the discharged sample filtered by the filter 2500 is again injected into the main channel 1000, It is possible to provide the above-mentioned error-correcting boron concentration measuring system which is environmentally friendly and highly safe.

The valve unit 3000 can adjust the inflow amount of the measurement sample introduced into specific configurations. The opening and closing of the valve unit 3000 can be automatically controlled by the operation control unit (not shown).

More specifically, the valve unit 3000 may include a first valve 3100, a second valve 3300, and a third valve 3500. The first valve 3100 may be disposed on the bypass passage 2000 having one end connected to the first branch point A and the other end connected to the sub measurement unit 2100. Accordingly, the measurement period of the sub-measurement unit 2100 can be adjusted by the operation control unit (not shown).

The second valve 3300 may be disposed on the bypass passage 2000 having one end connected to the filter 2500 and the other end connected to the second branch point B. [ Accordingly, the amount of the discharged sample flowing into the main channel 1000 can be controlled.

The third valve 3500 may be disposed on a connection rod connecting the reaction vessel 110 and the injection unit 200. Accordingly, the amount of the first to third materials 210, 230, and 250 injected into the reaction tank 110 can be controlled.

The setting conversion unit 4000 may adjust the scale of the main measurement unit 1100. More specifically, the setting conversion unit 4000 can calculate the correction data by comparing the boron concentration data measured by the main measurement unit 1100 and the sub measurement unit 2100. At this time, the correction data can be calculated by the data interpolation method.

Thereafter, the setting conversion unit 4000 may adjust the scale of the main measurement unit 1100 by the calculated correction data.

The scale-adjusted result data can be transmitted to the reactor operating unit. Accordingly, the reactor operation part can control the output of the reactor by adjusting the amount of the sample to be charged to the reactor based on the corrected boron concentration measurement data.

In the case of the conventional Voronometer using the neutron measurement method, a measurement error is accumulated during long-term use, so that the measurement data of the boron concentration is distorted, and it is difficult to measure the boron concentration with high reliability.

However, in the error-correcting boron concentration measurement system according to the embodiment of the present invention, the data conversion unit 4000 can correct the data scale of the boron concentration measured from the main measurement unit 1100 at regular intervals have. Accordingly, by preventing the measurement data from being distorted due to the cumulative error, it is possible to provide the above-mentioned error-correcting boron concentration measuring system with high accuracy.

The operation control unit (not shown) may control the operations of the sub-measurement unit 2100, the valve unit 3000, and the setting conversion unit 4000 at predetermined intervals as described above.

At all times, the valve unit 3000 of the error-correcting boron concentration measuring system is closed, and the sub-measuring unit 2100 and the setting conversion unit 4000 may be in a stopped state. Accordingly, the measurement sample may be introduced into the main measurement unit 1100 along the main flow path 1000. Accordingly, in the error-correcting boron concentration measuring system, only the boron concentration measurement by the main measuring unit 1100 can be performed in real time at all times.

On the other hand, in the case of a specific period, the valve unit 3000 of the boron concentration system is opened by the operation control unit (not shown), and the sub measurement unit 2100 and the setting conversion unit 4000 are operated have. Accordingly, at least a part of the measurement specimen may flow into the bypass flow path 2000 at the first branch point (A). Accordingly, in the error-correcting boron concentration measuring system, the boron concentration measurement by the main measuring unit 1100 and the sub-measuring unit 2100 can be simultaneously performed in a specific period.

The structures of the error-correcting boron concentration measuring system according to the embodiment of the present invention have been described above. The error correction type boron concentration measuring system includes a main flow path, a bypass flow path, a main measuring part, a sub measuring part, a filter, a valve part, an error correcting part, a setting converting part and an operation controlling part, (Chemical & Volume Control System), it is possible to measure the concentration of boron (B) precisely in the sample.

Hereinafter, a boron concentration measurement method according to the above-described embodiment of the present invention will be described with reference to Figs. 3 to 5. Fig.

3 is a flowchart illustrating a method for measuring a boron concentration in a specific period according to an embodiment of the present invention.

1 to 3, the measurement sample may be injected into the main channel 1000 (S1000).

In the normal case (S2000), the boron concentration of the measurement sample passing through the main channel 1000 can be measured by the neutron measurement method in the main measurement unit 1100 (S3000). The measured boron concentration data in the measurement sample may be transmitted to the reactor operation unit (S3500). Accordingly, in the reactor operation part, the output of the reactor can be controlled by adjusting the amount of the sample to be measured.

In the case of a specific period (S2000), at least the part of the sample to be measured may flow into the bypass flow path 2000 at the first branch point (A) of the measurement sample passing through the main flow path 1000 S4000).

When the measurement sample is injected into the main measurement part 1100 along the main flow path 1000 in step S5000, the main measurement part 1100 can measure the concentration in the measurement sample by the neutron measurement method (S5100).

When the measurement sample is injected into the sub-measurement unit 2100 along the bypass flow path 2000 (S5000), the sub-measurement unit 2100 measures the concentration of boron in the measurement sample by the electricity quantity titration method (S5500).

4 is a flowchart for explaining a method of measuring the boron concentration in the sub-measuring unit of the error-correcting boron concentration measuring system according to the embodiment of the present invention.

Referring to FIGS. 1 to 4, the measurement sample may be input to the reaction tank 110 in the sub-measurement unit 2000 (S5510). At this time, the measurement sample may be put into the oxidation electrode 151 and the reducing electrode 155 until at least some of the oxidation electrode 151 and the reducing electrode 155 are immersed.

Thereafter, the first material 210 may be injected into the reaction vessel 110 containing the measurement sample to produce a first mixed sample (S5520). The first material 210 may react with the measurement sample in the first mixed sample to dissociate the hydrogen ions (H ⁺ ).

At this time, the first material 210 may be excessively injected into the reaction tank 110. More specifically, the molar concentration (M) of the first material 210 injected into the reaction tank 110 may be at least one of values from 2 to 10 times the molar concentration (M) of the measurement sample Can be one value. Accordingly, the hydrogen ion (H ⁺ ) can be completely dissociated during the reaction of the measurement sample and the first material 210.

Thereafter, the second material 230 and the third materials 250 are injected into the first mixed sample to produce a second mixed sample (S5530). The second material 230 and the third material 250 may be dissociated in the first mixed sample.

A current may be supplied from the power supply unit 300 to the circuit C. When a current is supplied from the power source unit 300, the second mixed sample may be electrolyzed (S5540).

During the electrolysis, the pH meter 500 may be operated to measure the concentration of the hydrogen ion (H ⁺ ) in the second mixed sample in step S5550.

At the same time as the measurement of the pH meter 500, the current meter 400 may be operated to measure the current amount i of the second mixed sample with respect to time (S5560).

After a predetermined time has elapsed, the power source of the power source unit 300 may be cut off. The measured data from the current meter 400 and the pH meter 500 may then be transmitted to the analyzer 600 (S5570).

The analyzer 600 may calculate the concentration of boron based on the received concentration data and the current data (S5580).

5 is a flowchart for explaining a boron concentration calculation method by the analyzer in the boron concentration measurement method according to the embodiment of the present invention.

1 to 5, the analyzer 600 analyzes the time-series current data measured from the current meter 400 and the concentration data of the hydrogen ions (H ⁺ ) measured by the pH meter 500 over time (S5581). At this time, the pH graph may represent a neutralized titration graph in which the pH concentration changes from acidic to neutral to basic.

Then, the appropriate time point t may be extracted from the pH graph (S5582). As described with reference to FIG. 1, the appropriate time point t may be extracted through the second derivative of the pH graph as a point at which an inflection occurs.

When the appropriate time point t is extracted, the charge amount Q may be calculated by multiplying or integrating the current amount i measured during the appropriate time point t from the current graph S5583.

The calculated amount of charge (Q) is again divided into the Faraday constant (F) the free electrons (e ^-) can be calculated on the molar number (mole) of (S5584).

The number of moles of the free electrons e ^- corresponds to the concentration of the hydroxide ion (OH ^- ), the hydrogen ion (H ⁺ ) and the concentration of the measurement sample as described with reference to FIG. 1 . Therefore, the number of moles of the free electrons e ^- can be converted to the concentration of the boron (B) in the measurement sample (S5585).

1 to 3, the boron concentration data measured by the main measuring unit 1100 and the sub-measuring unit 2100 may be compared with each other to calculate correction data (S6000).

The scale of the main measuring unit can be corrected by the calculated correction data (S7000).

The scale-corrected boron concentration data can be transmitted to the reactor operation unit (S8000).

Thereafter, the discharged sample discharged from the sub-measuring unit flows into the filter 2500, and unreacted ions and the precipitate 235 can be filtered (S9000).

The error correction type boron concentration measurement system and the boron concentration measurement method using the same according to the embodiments of the present invention have been described above. The error correction type boron concentration measurement system and the boron concentration measurement method using the same according to the embodiment of the present invention include a main flow path, a bypass flow path, a main measurement part, a sub measurement part, a filter, a valve part, a setting conversion part and an operation control part And the scale of the boron concentration measurement data of the main measurement unit can be corrected at regular intervals by the correction data calculated by the setting conversion unit. Accordingly, the measurement data is prevented from being distorted due to the cumulative error, thereby providing a high-accuracy and high-reliability error-correcting boron concentration measuring system and a boron concentration measuring method using the same.

While the present invention has been described in connection with what is presently considered to be practical and exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1000; Main Euro
1100; The main measuring part
2000; Bypass Euro
2100; Sub-
100; The reaction part
110; Reactor
150; The electrode portion
151; Oxidized electrode
155; Reduction electrode
200; Injection part
210; The first substance
230; The second substance
235; precipitate
250; Third substance
300; Power supply
400; Current meter
500; pH meter
600; Analysis section
610; The first calculation unit
630; The second calculation unit
650; The third calculation unit
670; The fourth calculation unit
2500; filter
3000; The valve portion
3100; The first valve
3300; The second valve
3500; The third valve
4000; Setting conversion unit

Claims (16)

A main measuring unit positioned on the main flow passage through which the measurement sample passes and measuring the concentration of boron in the measurement sample in real time using a neutron measurement method;
A sub-measurement unit located on the bypass flow path branched from the main flow path and measuring the concentration of boron in the measurement sample passing through the bypass flow path at regular intervals by an electricity quantity titration method; And
A setting conversion unit for comparing the boron concentration data measured from the main measurement unit and the sub measurement unit to adjust a scale of the main measurement unit;
Wherein the boron concentration measuring system comprises:
The method according to claim 1,
A filter disposed in series with the sub-measurement unit on the bypass flow path to filter an exhausted sample that is a product of the sub-measurement unit; And
And a valve unit for controlling an injection amount of the measurement sample.
3. The method of claim 2,
And an operation control unit for controlling operations of the sub-measurement unit, the valve unit, and the setting conversion unit.
The method according to claim 1,
The sub-
A reaction unit for receiving the measurement sample injected through the bypass flow path at regular intervals; and an electrode unit including at least a part of the electrode unit including an oxidizing electrode and a reducing electrode in the reaction vessel;
A first substance which is an electrolyte for controlling dissociation of hydrogen ions, a second substance which is an electrolyte which has a standard oxidation potential of 0.8 V or lower and which reacts with the oxidation electrode to produce a precipitate, and an electrolyte which does not participate in chemical reaction in the reaction tank 3 material into the reaction vessel;
A power supply unit for supplying an electric current to the electrode unit to control electrolysis of the measurement sample and the second mixed sample in which the first to third materials are mixed;
A current meter for measuring an amount of current during electrolysis of the second mixed sample; And
A pH meter for measuring a concentration of hydrogen ions in the second measurement sample accommodated in the reaction tank;
An analyzer for analyzing data measured from the current meter and the pH meter to derive the concentration of boron in the second mixed sample;
Wherein the boron concentration measuring system comprises:
The method according to claim 1,
Wherein the amount of the sample to be measured injected into the main channel is 50 ml or less.
5. The method of claim 4,
Wherein the oxidation electrode is at least one of silver (Ag), copper (Cu), and zinc (Zn).
The method according to claim 6,
When the oxidation electrode is silver (Ag), the second material may be selected from the group consisting of sodium bromide (NaBr), sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl ₂ ), sodium sulfide (Na ₂ S) K ₂ S), calcium sulfide (CaS), sodium sulfate (Na ₂ SO _4), potassium sulfate (K ₂ SO _4), calcium sulfate (CaSO _4), sodium carbonate (Na ₂ CO _3), potassium carbonate (K ₂ CO ₃ ), Or calcium carbonate (CaCO ₃ )
When the oxidizing electrode is copper (Cu), the second material may be sodium sulfide (Na ₂ S), potassium sulfide (K ₂ S), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ) Ammonium ((NH ₄ ) ₂ CO ₃ ), and
When the oxidation electrode is zinc (Zn), the second material is selected from the group consisting of sodium sulfide (Na ₂ S), potassium sulfide (K ₂ S), ammonium sulfide ((NH ₄ ) ₂ S), magnesium sulfide Wherein the boron concentration is at least one of barium (BaS) and calcium sulfide (CaS).
5. The method of claim 4,
Wherein the first material comprises at least one of d-mannitol, sorbitol, xylitol, erythritol, or isomalt. Boron concentration measurement system.
5. The method of claim 4,
Wherein the cathode of the power unit is connected to the oxidation electrode and the anode of the power unit is connected to the current meter.
5. The method of claim 4,
Wherein the pH meter is at least one of a pH meter and an indicator.
11. The method of claim 10,
Wherein the pH meter is used as the pH meter when the current measurement range by the current meter is less than 50 mA from 10 mA or more.
11. The method of claim 10,
When the current measurement range by the current meter is 50 mA or more, the indicator is used as the pH meter,
Further comprising a spectroscope for analyzing a color change of the indicator according to a concentration of hydrogen ions in the measurement sample.
Injecting a measurement sample into the main flow path;
At least a part of the sample to be measured flows into the bypass flow path in a specific cycle;
Measuring the concentration of boron in the measurement specimen passing through the main flow path in the main measurement unit by a neutron measurement method;
Measuring a concentration of boron in the sample to be measured which passes through the bypass passage in a sub-measuring unit by an electricity quantity titration method;
Comparing the boron concentration data measured from the main measurement unit and the sub measurement unit to calculate correction data; And
Correcting the scale of the main measurement unit by the calculated correction data;
Wherein the boron concentration is in a range of from 1 to 10 ppm.
14. The method of claim 13,
In the step of calculating the correction data,
Wherein the correction data is calculated by a data interpolation method.
14. The method of claim 13,
In the step of measuring the concentration of boron in the measurement sample by the electrovalve titration method in the sub-
Injecting the measurement sample introduced from the bypass flow path into a reaction tank containing at least a portion of an electrode portion including an oxidation electrode and a reduction electrode in the sub-measurement portion;
Injecting a first substance, which is an electrolyte for dissociating hydrogen ions, from the injection unit into the reaction tank into which the measurement sample flows, to produce the first mixed sample;
A second substance which is an electrolyte which forms a precipitate by reacting with the oxidation electrode at a standard electrode potential of 0.8 V or lower and a third substance which is an electrolyte not participating in a chemical reaction in the reaction tank, To prepare a second mixed sample;
A current is supplied by a power supply unit to electrolyze the second mixed sample;
Measuring a hydrogen ion concentration of the second mixed sample with respect to time by a pH meter during the electrolysis;
Measuring a current amount of the second mixed sample with respect to time with a current meter at the time of electrolysis;
Measuring the concentration of the hydrogen ions, and transmitting the concentration data and the current data measured in the measuring the amount of current to the analyzer; And
Processing the transferred concentration data and current data to calculate a boron concentration in the analyzer;
Wherein the boron concentration is in a range of from 1 to 10 ppm.
16. The method of claim 15,
The step of calculating the concentration of boron in the measurement sample in the analysis unit may include:
Graphing the concentration data measured from the pH meter and extracting an appropriate time point at which the curve of the graph occurs;
Graphing the current data measured from the current meter and extracting the amounts of current measured up to the appropriate time point;
Calculating the amount of charge of the second mixed sample electrolyzed by integrating the extracted appropriate time and current amounts;
Dividing the charge amount by a Faraday constant to calculate the number of moles of free electrons; And
Mapping the number of moles of free electrons to the boron concentration;
Wherein the boron concentration is in a range of from 1 to 10 ppm.

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