KR101723883B1 - Apparatus and method for measuring total organic carbon with integrated oxidation reactor - Google Patents

Abstract

The present invention relates to an apparatus to measure total organic carbon having an integrated oxidation reactor and a measuring method thereof and, more specifically, relates to an apparatus to measure the total organic carbon having an integrated oxidation reactor, comprising: a first multi-channel valve which selectively injects an analysis sample, reagent, and high-purity gas into an oxidation reaction unit; the oxidation reaction unit including an agitator which mixes the analysis sample and the reagent injected from the first multi-channel valve; and an oxidation lamp mounted on the outside of the reactor which oxidizes organic carbon in the analysis sample; a switching valve; a second multi-channel valve connected to the switching valve and a syringe pump capable of changing a flow path to allow CO_2, which is generated by allowing the organic carbon be oxidized in the oxidation reaction unit, be transferred to the syringe pump; and the syringe pump connected to the second multi-channel valve, which controls the pressure of the oxidation reaction unit through the switching valve and the second multi-channel valve, which injects the analysis sample and the reagent from the first multi-channel valve into the oxidation reaction unit, which collects CO_2 generated by allowing the organic carbon be oxidized in the oxidation reaction unit, and which supplies the collected CO_2 to a detection unit. The present invention aims to provide an apparatus to measure the total organic carbon having an integrated oxidation reactor and a measuring method thereof, capable of oxidizing a sample in the same reactor without transferring the sample into an oxidation chamber after removing inorganic carbon.

Description

TECHNICAL FIELD The present invention relates to an apparatus and a method for measuring total organic carbon with an integrated oxidation reaction tank,

The present invention relates to an apparatus and a method for measuring total organic carbon having an integral type oxidation reaction tank for measuring total organic carbon.

The need for on-line measurement systems that directly measure samples in the field rather than off-line measurement methods that collect samples and analyze them in the laboratory has increased the accuracy of measurement equipment and the economical cost of maintenance It is becoming a very important determinant in product selection.

The total organic carbon measuring device is classified into ultraviolet wet oxidation and burning oxidation according to an oxidation method. The measurement step generally includes 1) a step of injecting a sample and a reagent; 2) removing the inorganic carbon in the sample; 3) organic carbon oxidation step; 4) a step of recovering carbon dioxide (CO ₂ ) gas which is a by-product of oxidation; 5) measuring the total organic carbon after transferring the recovered carbon dioxide to a NDIR (Non-Dispersive Infra-Red) detector; 6) Sample discharging and washing steps.

Conventional on-line total organic carbon continuous automatic measuring apparatus comprises a sample and reagent injecting unit, an inorganic carbon removing unit, an oxidation reaction unit, a detecting unit, and an operation control unit (FIG. 1). In the case of the oxidation reaction part, it is divided into the ultraviolet oxidation reaction part and the high temperature combustion oxidation reaction part depending on the oxidation method. In this process, it is very important to precisely take a certain amount of sample from the sample from which the inorganic carbon has been removed and transfer it to the oxidation reaction tank.

In general, the inorganic carbon decontamination and the oxidation reaction unit are independently constructed. In order to transfer the sample from which the inorganic carbon has been removed to the oxidation reaction unit, the sample is transferred through various pumps such as a peristaltic pump and a syringe pump and a transfer pipe. However, in such a process, there is a problem that the sample is lost during the transfer process or the sample can not be transferred quantitatively to the oxidation reaction unit due to the cause of the accuracy and performance degradation of the pump. In particular, in the case of a continuous automatic measuring apparatus, if a sample can not be quantitatively transferred due to such a problem, a significant measurement error may occur. Such a measurement error frequently occurs, which is a major cause of obstructing accurate TOC measurement.

Recently, Korean Patent No. 1576603 (total organic carbon measuring apparatus using total amount of carbon dioxide equipped with sample loop for quantitative injection and total organic carbon measuring method using the same) improved the conventional technique, To solve these problems by improving the function (Fig. 2). In addition, research has been carried out to improve the accuracy by using the mean value of three times repeated measurements in the processing unit by shortening the analysis time about 3 times as compared with the existing equipment. However, even in this case, the technical limitations caused by the sample transfer can not be fundamentally solved.

Korean Patent No. 1576603 (published on December 21, 2015)

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a continuous total organic carbon automatic measuring apparatus capable of oxidizing a sample in the same reaction tank without removing the inorganic carbon after transferring the sample to the oxidation tank. And a method for measuring the total organic carbon.

It is another object of the present invention to provide a method and apparatus for solving the problem of error in continuous automatic measurement due to loss of sample generated in the process of transferring a sample to an oxidation tank after removal of inorganic carbon, A total organic carbon measuring device provided with an integral oxidation reaction tank which can be maintained at all times, and a measuring method thereof.

In order to accomplish the above object, a total organic carbon measuring apparatus having an integrated oxidation reaction tank according to a preferred embodiment of the present invention includes a first multi-channel valve for selectively introducing analytical sample, reagent and high purity gas into the oxidation reaction unit, ; The oxidation reaction unit mixing the analytical sample and the reagent and oxidizing organic carbon in the analytical sample with an oxidation lamp; The syringe pump and the detection unit are selectively connected to the oxidation reaction unit, the inorganic carbon present in the form of carbonate or carbon dioxide is discharged to the outside through the discharge port without passing through the syringe pump or the detection unit, or the carbon dioxide A switching valve for selectively controlling the supply to the syringe pump or the detection unit; A second multichannel valve communicating with the switching valve and the syringe pump, the second multichannel valve capable of changing a flow path through which the carbon dioxide produced by oxidizing organic carbon in the oxidation reaction unit is transferred; And a control unit for controlling the pressure of the oxidation reaction unit to flow the analytical sample and reagent from the first multi-channel valve to the oxidation reaction unit, or to capture carbon dioxide produced by oxidation of organic carbon in the oxidation reaction unit, And the syringe pump to supply the detection signal to the detection unit.

In one embodiment, the total organic carbon measuring apparatus having the integrated oxidation reaction tank may further include a high-purity gas detector connected to the first multi-channel valve for detecting the presence of the high-purity gas used for discharging the inorganic carbon existing in the form of carbonate or carbon dioxide A flow controller for removing inorganic carbon to regulate the supply; A flow rate controller for measuring organic carbon, which is connected to the first multi-channel valve and regulates supply of high purity gas used for collecting carbon dioxide produced by oxidation of organic carbon into a syringe pump; And a mass flow rate controller connected to the switching valve and the detection unit for monitoring whether or not high purity gas is supplied for transferring the carbon dioxide captured by the syringe pump to the detection unit and for maintaining the flow rate of the high purity gas supplied to the detection unit constant .

In one embodiment, in the total organic carbon measuring apparatus having the integrated oxidation reaction tank, the oxidation reaction unit may include an ultraviolet oxidation lamp for irradiating ultraviolet rays to oxidize the analytical sample to carbon dioxide and water; A photodiode sensor capable of detecting intensity of light of the ultraviolet oxidation lamp; A reaction tank made of quartz to enable ultraviolet irradiation; An agitator for mixing the analytical sample and the reagent, and a sample inlet sensor for detecting whether the analytical sample is normally introduced into the reaction tank.

In one embodiment, in the total organic carbon measuring apparatus having the integral oxidation reaction tank, the detection unit may include a non-dispersion infrared detector for detecting carbon dioxide, and the second multi-channel valve may be configured to detect whether the operation state of the syringe pump is normal And a pressure sensor capable of determining whether or not it is possible.

In one embodiment of the present invention, in the total organic carbon measuring apparatus having the integrated oxidation reaction tank, the switching valve may include a sample ring having a predetermined volume to inject a predetermined amount of carbon dioxide produced by oxidation of the organic carbon, And a moisture trap for removing moisture that lowers the sensitivity of the detection unit is connected.

A method for measuring total organic carbon having an integrated oxidation reactor according to a preferred embodiment of the present invention includes the steps of introducing an analyte and a reagent into an oxidation reaction unit communicating with a first multi-channel valve; A high purity gas is supplied to transfer the inorganic carbon present in the form of carbonate or carbon dioxide into the analysis sample to a switching valve communicating with the oxidation reaction unit and discharged to the outside through the outlet of the switching valve without passing through the syringe pump and the detection unit step; Irradiating ultraviolet rays to the analytical sample in the oxidation reaction unit from which the inorganic carbon has been removed to oxidize organic carbon in the analytical sample to generate carbon dioxide; Collecting carbon dioxide produced by oxidizing the organic carbon in the oxidation reaction unit with a syringe pump communicating with the switching valve; Transferring the collected carbon dioxide to a detecting portion communicating with the switching valve; And measuring an amount of carbon dioxide generated by oxidizing the organic carbon transferred to the detection unit.

In one embodiment, in the method for measuring total organic carbon having the integrated oxidation reaction tank, the step of discharging the inorganic carbon containing carbonates and carbon dioxide to the outside may include the steps of discharging the inorganic carbon to a high purity gas Operating the valve of the flow rate controller for removing inorganic carbon to control the supply of the high-purity gas to the oxidation reaction unit at a preset flow rate; Removing the inorganic carbon in the analytical sample by discharging the gasified carbon dioxide, which is volatilized together with the high-purity gas in the oxidation reaction tank, to the outlet of the switching valve by operating the switching valve; And closing the valve of the flow rate controller for removing the inorganic carbon when the removal of the inorganic carbon is completed, to block the inflow of the high purity gas.

In one embodiment, the step of collecting carbon dioxide produced by oxidizing the organic carbon in the oxidation reaction unit with a syringe pump, which is in communication with the switching valve, in the method of measuring total organic carbon with the integrated oxidation reaction tank, The valve of the flow rate controller for measuring the organic carbon for controlling the supply of the high purity gas used for collecting the carbon dioxide produced by the oxidation of the organic carbon to the syringe pump is turned ON and the high purity gas is supplied to the oxidation reactor ; Operating the switching valve and the second multi-channel valve to allow the oxidation reaction tank and the syringe pump to communicate with each other; operating the syringe pump to collect gasified carbon dioxide volatilized with high purity gas into a syringe; And stopping the flow of the high-purity gas by operating the valve of the flow rate controller for measuring organic carbon to OFF when the collection is completed.

In one embodiment of the present invention, the step of transferring the collected carbon dioxide to the measuring unit communicating with the switching valve may include the step of controlling the mass flow rate controller connected to the switching valve and the detecting unit, Monitoring whether or not high-purity gas is supplied to transfer the carbon dioxide captured by the syringe pump to the detection unit, and maintaining a constant flow rate of the high-purity gas supplied to the detection unit; And removing the water trap which is connected to the switching valve to reduce the sensitivity of the detection unit.

In one embodiment, the total organic carbon measurement method including the integral oxidation reaction tank may include a screen or an abnormality code so that the user can detect whether the analyte and the reagent are abnormal when the analyte and the reagent are not introduced using the sample introduction sensor. ; Monitoring the performance of the syringe pump by measuring the internal pressure of the syringe with a pressure sensor and automatically generating an anomaly code in advance when the syringe pump performance begins to fall below a certain level; Monitoring the performance of an ultraviolet oxidation lamp used for oxidizing an analytical sample using a photodiode sensor and automatically generating an anomaly code in advance when the performance begins to drop below a predetermined standard; The amount of high purity gas is calculated by using a flow rate controller for removal of inorganic carbon, a flow rate controller for measuring organic carbon, and a mass flow rate controller. If the remaining amount of the high purity gas is less than a predetermined standard, Automatically; Monitoring the flow rate of the high purity gas that transfers carbon dioxide to the non-dispersive infrared detector using a mass flow rate controller, and automatically generating an abnormal code if the flow rate deviates from a predetermined reference range.

According to the total organic carbon measuring instrument and the measuring method of the present invention, it is possible to carry out the removal of inorganic carbon and the oxidation step of the total organic carbon continuous automatic measuring apparatus in the same reaction tank, thereby improving the reproducibility and accuracy Can be solved and the system can be simplified so that the user can more easily maintain the measuring apparatus.

In addition, in the conventional method, the inorganic carbon in the sample is continuously removed so that the high purity gas must be continuously injected, thereby increasing the consumption amount of the expensive high purity gas. However, According to the total organic carbon measuring device and the measuring method thereof, when the organic carbon is oxidized after the inorganic carbon is removed from the integrated oxidation tank, the use of high purity gas for removing inorganic carbon is blocked, It is effective.

In addition, according to the total organic carbon measuring method of the present invention, it is possible to diagnose the state of the measuring apparatus in real time, to inform the user of the normal operation of the component and the replacement cycle, The accuracy can be maintained.

1 is a configuration diagram of a conventional total organic carbon measuring apparatus.
2 is a configuration diagram of a total organic carbon measuring apparatus using a conventional sample loop.
3 is a schematic diagram of a total organic carbon continuous automatic measuring apparatus according to an embodiment of the present invention.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Terms including ordinals, such as first, second, etc., may be used to describe various elements, but the elements are not limited to these terms. The terms are used only for the purpose of distinguishing one component from another.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . 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 this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

In the following description of the present invention with reference to the accompanying drawings, the same components are denoted by the same reference numerals regardless of the reference numerals, and redundant explanations thereof will be omitted. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

3 is a configuration diagram of a total organic carbon continuous automatic measuring apparatus according to an embodiment of the present invention. As shown in the figure, the apparatus for measuring total organic carbon with integrated oxidation reaction tank according to the present invention comprises a first multi-channel valve for selectively introducing analytical sample, reagent and high purity gas into an oxidation reaction unit, The oxidation reaction unit oxidizing the inorganic carbon and oxidizing the organic carbon in the analysis sample with an oxidation lamp; The syringe pump and the detection unit are selectively connected to the oxidation reaction unit, the inorganic carbon containing carbonate and carbon dioxide is discharged to the outside without passing through the syringe pump or the detection unit, or the carbon dioxide generated by oxidation of the organic carbon is supplied to the syringe pump Or a switching valve for selectively controlling the supply to the detection unit; A second multichannel valve communicating with the switching valve and the syringe pump, the second multichannel valve capable of changing a flow path through which the carbon dioxide produced by oxidizing organic carbon in the oxidation reaction unit is transferred; And a control unit for controlling the pressure of the oxidation reaction unit to flow the analytical sample and reagent from the first multi-channel valve to the oxidation reaction unit, or to capture carbon dioxide produced by oxidation of organic carbon in the oxidation reaction unit, And the syringe pump to supply the detection signal to the detection unit.

Each of these components can be connected to a teflon or stainless steel tube.

In one embodiment, the oxidation reaction unit includes an ultraviolet oxidation lamp for irradiating ultraviolet rays to oxidize the analytical sample to carbon dioxide and water; A photodiode sensor capable of detecting intensity of light of the ultraviolet oxidation lamp; A reaction tank made of quartz to enable ultraviolet irradiation; An agitator for mixing the analytical sample and the reagent, and a sample inlet sensor for detecting whether the analytical sample is normally introduced into the reaction tank.

The oxidation reaction unit 50 according to the present invention mixes an analytical sample with a reagent, removes inorganic carbon, or oxidizes the analytical sample to an organic material.

In order to measure total organic carbon as mentioned above, 1) the steps of injecting analytes and reagents; 2) an inorganic carbon removal step in the analytical sample; 3) organic carbon oxidation step; 4) a step of recovering carbon dioxide (CO ₂ ) gas which is a by-product of oxidation; 5) a measurement step of calculating the total organic carbon after transferring the recovered carbon dioxide to a non-dispersive infrared detector and detecting it; 6) Analytical sample discharge and cleaning steps should be performed.

In the present invention, the first multi-channel valve 20 is adjusted to be connected to the analytical sample 25 in order to inject the analytical sample and the reagent, and the analytical sample is supplied to the oxidation reaction tank 52 by a predetermined amount using the syringe pump 10 . At this time, the analytical sample supplied to the oxidation reaction tank 52 may exist as an inorganic carbon compound such as carbonate (CO ₃ ^-2 ) and bicarbonate (HCO ₃ ^- ). If such an inorganic carbon compound is not removed, it is present in a state of carbon dioxide after oxidation, which causes an error in the measurement of the total organic carbon. Since the carbonic acid (CO ₃ ^-2 ) and bicarbonate (HCO ₃ ^- ) are present as carbon dioxide in the acidic condition (pH <4), the phosphoric acid reagent 24 is introduced into the oxidation reaction tank 52 When the mixture is injected and mixed with the agitator 51, the inorganic carbon in the analytical sample is present in the form of carbon dioxide.

In order to remove the inorganic carbon existing in the carbon dioxide form from the analytical sample, the valve of the flow rate controller 21 for removing the inorganic carbon, which is connected to the high purity gas in the state where the stirrer 51 is formed, And a high purity gas is injected into the oxidation reaction tank 52 at a predetermined flow rate. The switching valve 40 is operated to volatilize the high purity gas in the oxidation reaction tank 52 and discharge the gasified carbon dioxide to the outlet of the switching valve 40 to remove the inorganic carbon in the analytical sample. When the removal of the inorganic carbon is completed, the valve of the flow rate controller 21 for removing the inorganic carbon is turned off to block the flow of the high purity gas.

In the prior art, the module for removing inorganic carbon is configured separately from the oxidizing tank, and is configured to continuously remove the inorganic carbon in the analytical sample, and it is common to continuously inject the high purity gas. Due to this device configuration, the consumption of high purity gas has technical limitations that occur at all times during operation of the device.

In the prior art, it is common practice to transfer the analytical sample from which the inorganic carbon has been removed to the oxidation reaction tank to oxidize the analytical sample. However, in the present invention, by constituting the apparatus as described above so as to be oxidizable in the same reaction tank, So that the technical limit of the analytical sample remaining in the transfer tube can be improved.

After the inorganic carbon is removed, the syringe pump 10, the first multi-channel valve 20 and the switching valve 40 are operated to inject the oxidizing agent of the potassium persulfate 23 into the analytical sample, . In addition, ultraviolet rays are irradiated to the organic substances present in the analytical sample mixed with the oxidizing agent by operating the ultraviolet oxidation lamp 55, and the organic substances are oxidized to CO ₂ and H ₂ O by the ultraviolet rays in the regions of 185 nm and 254 nm.

In order to recover the CO2 generated by the oxidation of the organic substance in the gaseous state, the valve of the flow rate controller 22 for measuring organic carbon connected to the high purity gas in the state where the stirrer 51 is formed is turned on, Purity gas is injected into the oxidation reaction tank 52 at a flow rate. At this time, the switching valve 40 and the second multi-channel valve 30 are operated to communicate the syringe pump 10 with the oxidation reaction tank 52, and the syringe pump 10 is operated to volatilize together with the high- The carbon dioxide is collected by the syringe 12. When the carbon dioxide gas collection is completed, the valve of the flow rate controller 22 for measuring organic carbon is turned off to block the flow of high purity gas. At this time, the syringe 12 is maintained at a constant temperature by the heater 11. [

The second multi-channel valve may include a pressure sensor 32 for checking whether the gas of the syringe 12 for capturing the carbon dioxide gas is sealed, and the syringe pump May include a heater 11 to maintain the temperature inside the syringe 12 at a constant temperature.

The captured carbon dioxide must be transferred to a non-dispersive infrared detector 60 for measurement. And is conveyed to the sample ring pipe 44 mounted on the switching valve 40 for injecting a certain amount of the carbon dioxide gas collected in the non-dispersion infrared ray detector 60 for accurate measurement. At this time, the carbon dioxide transferred to the sample ring pipe (44) can be transferred to the non-dispersion infrared detector (60) at a constant flow rate. When carbon dioxide is injected into the non-dispersive infrared detector 60, the non-dispersive infrared detector 60 converts the carbon dioxide into an electric signal, and converts the electric signal generated in the operation program into a total organic carbon concentration.

As an embodiment of the present invention, it is possible to monitor the supply of the high-purity gas that carries the carbon dioxide to the non-dispersive infrared detector 60 and to maintain the flow rate of the high-purity gas constant to ensure measurement stability such as measurement accuracy and reproducibility And may further include a moisture trap (42) for removing moisture that affects the measurement sensitivity of the non-dispersive infrared detector (60) in the gas being transferred to the MFC (41). At this time, in order to enable long-term use by removing the water trapped in the water trap 42, a valve of the flow rate controller 42 and a flow meter are operated while the carbon dioxide is injected into the non-dispersion infrared detector 60, So that moisture remaining in the moisture trap 42 is removed.

As described in detail above, according to the apparatus for measuring total organic carbon and the method for measuring the total organic carbon having the integrated oxidation reaction tank of the present invention, the inorganic carbon removal and oxidation steps of the total organic carbon continuous automatic measuring apparatus are performed in the same reaction tank , The problem of reproducibility and accuracy due to sample loss can be solved, and the system can be simplified, so that the user can more easily maintain the measuring apparatus.

Table 1 shows the measurement uncertainty values indicating the reproducibility and accuracy of the measuring apparatus according to the present invention. As shown in Table 1, the total organic carbon measuring apparatus equipped with the integrated oxidation reaction tank according to the present invention and the conventional separating type organic carbon measuring apparatus in which inorganic carbon decontamination and oxidation tank were separated from each other, The uncertainty values for the factors were estimated.

Among the main factors influencing the measurement, the sample injection is divided into a pump injection, an inorganic carbon removal sample injection, an oxidation injection sample injection, and a sample loop injection. The conventional separation type total organic carbon measurement device has an uncertainty The uncertainty of the sample injection of the oxidized part with the highest contribution rate is 0.050.

However, the apparatus for measuring total organic carbon having the integrated oxidation reaction tank according to the present invention eliminates the step of injecting the sample in the oxidation part by simplifying the apparatus by the integral structure, and thus has an influence on the total uncertainty due to injection of the sample in the oxidized part And the total uncertainty sum is reduced. Therefore, according to the apparatus and method for measuring total organic carbon with integrated oxidation reaction tank according to the present invention, reproducibility and accuracy of measurement can be improved.

Uncertainty classification Total Organic Carbon Analyzer with Integrated Oxidation Reactor Conventional detachable total organic carbon measuring device Relative standard uncertainty (ur (x)) Contribution Rate (%) Relative standard uncertainty (ur (x)) Contribution Rate (%) Pump sample injection 0.003 2.56 0.003 1.64 Injection of Inorganic Carbon Decontamination 0.018 14.88 0.022 10.91 Sample injection of oxidized part X X 0.050 24.76 Sample injection of sample loop 0.015 12.40 X X Variability of transport gas flow rate 0.029 23.97 0.046 23.06 Inorganic carbon removal rate 0.034 28.11 0.044 21.84 Oxidation rate 0.021 17.36 0.035 17.37 Standard material uncertainty 0.001 0.72 0.001 0.43  Sum 0.121 100 0.202 100

In addition, in the conventional method, the inorganic carbon in the sample is continuously removed so that the high purity gas must be continuously injected, thereby increasing the consumption amount of the expensive high purity gas. However, According to the total organic carbon measuring device and the measuring method thereof, when the organic carbon is oxidized after the inorganic carbon is removed from the integrated oxidation tank, the use of high purity gas for removing inorganic carbon is blocked, It is effective.

In addition, according to the total organic carbon measuring method of the present invention, it is possible to diagnose the state of the measuring apparatus in real time, to inform the user of the normal operation of the component and the replacement cycle, The accuracy can be maintained.

In the above description, each component and / or function described in the embodiments may be combined and combined. If a person skilled in the art is familiar with the technical idea of the present invention, 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.

10: syringe pump 32: pressure sensor
11: heater 33: plug (clogged port)
12: Syringe 40: Switching valve
20: first multi-channel valve 41: mass flow controller (MFC)
21: Flow rate controller for removing inorganic carbon 42: Flow rate controller
22: Flow rate controller for measuring organic carbon 43: Moisture trap
23: reagent (potassium persulfate) 44: sample ring tube
24: reagent (phosphoric acid) 50: integral oxidation reaction unit (inorganic carbon removal / oxidation reaction)
25: Analytical sample 51: Stirrer
26: Standard solution 52: Oxidation reaction tank
27: distilled water (diluted water) 53: photodiode sensor
28: distilled water (washing water) 54: analytical sample introduction sensor
29: discharge (waste liquid line) 55: ultraviolet oxidation lamp
30: second multi-channel valve 60: non-dispersive infrared (NDIR) detector
31: High purity gas

Claims (10)

A first multi-channel valve for selectively introducing the analysis sample, the reagent, and the high-purity gas into the oxidation reaction unit;
And a second multi-channel valve An oxidation reaction unit including an agitator for mixing the analytical sample and the reagent, and an oxidation lamp mounted outside the reaction tank for oxidizing organic carbon in the analytical sample;
Wherein the oxidation reaction unit, the syringe pump, and the detection unit are selectively connected to discharge the inorganic carbon present in the form of carbonate or carbon dioxide through the discharge port without passing through the syringe pump or the detection unit, A switching valve for controlling the supply of carbon dioxide to the syringe pump and the detection unit;
A second multichannel valve communicating with the switching valve and the syringe pump to change a flow path of the carbon dioxide generated by oxidation of organic carbon in the oxidation reaction unit to the syringe pump; And
Channel valve, the analytical sample and the reagent are introduced into the oxidation reaction unit from the first multi-channel valve by controlling the pressure of the oxidation reaction unit through the switching valve and the second multi-channel valve, A syringe pump for collecting carbon dioxide produced by oxidation of organic carbon in the oxidation reaction unit and supplying the collected carbon dioxide to the detection unit;
And an integrated oxidation reaction tank.
The method according to claim 1,
A flow controller for removing inorganic carbon, which is connected to the first multi-channel valve and regulates the supply of high-purity gas used for discharging the carbon dioxide generated by oxidation of the inorganic carbon to the outside;
A flow rate controller for measuring organic carbon, which is connected to the first multi-channel valve and regulates supply of high purity gas used for collecting carbon dioxide produced by oxidation of organic carbon into a syringe pump; And
A mass flow rate controller connected to the switching valve and the detection unit for monitoring whether or not high purity gas is supplied for transferring the carbon dioxide captured by the syringe pump to the detection unit and for maintaining a flow rate of the high purity gas supplied to the detection unit constant;
Further comprising an integrated oxidation reaction tank (10).
The apparatus of claim 1, wherein the oxidation reaction unit comprises:
An ultraviolet oxidation lamp for irradiating ultraviolet rays to oxidize the analytical sample to carbon dioxide and water; A photodiode sensor capable of detecting intensity of light of the ultraviolet oxidation lamp; A reaction tank made of quartz to enable ultraviolet irradiation; And an analytical sample inlet sensor capable of detecting whether the analytical sample is normally introduced into the reaction tank.
The method according to claim 1,
Wherein the detector includes a non-dispersive infrared detector for detecting carbon dioxide,
Wherein the second multi-channel valve includes a pressure sensor capable of determining whether the operation state of the syringe pump is normal or not.
The apparatus according to claim 1,
And an analysis sample ring pipe having a predetermined volume to inject a predetermined amount of carbon dioxide produced by oxidation of the organic carbon into the detection unit,
And a moisture trap for removing moisture that lowers the sensitivity of the detection unit is connected to the oxygen sensor.
Introducing the analytical sample and the reagent into an oxidation reaction part communicating with the first multi-channel valve;
A high purity gas is supplied to transfer the inorganic carbon present in the form of carbonate or carbon dioxide into the analysis sample to a switching valve communicating with the oxidation reaction unit and discharged to the outside through the outlet of the switching valve without passing through the syringe pump and the detection unit step;
Irradiating ultraviolet rays to the analytical sample in the oxidation reaction unit from which the inorganic carbon has been removed to oxidize organic carbon in the analytical sample to generate carbon dioxide;
Collecting carbon dioxide produced by oxidizing the organic carbon in the oxidation reaction unit with a syringe pump communicating with the switching valve;
Transferring the collected carbon dioxide to a detecting portion communicating with the switching valve; And
Measuring an amount of carbon dioxide produced by oxidizing the organic carbon transferred to the detection unit;
Lt; / RTI &gt;
The oxidation reaction unit includes an agitator for mixing the analytical sample and the reagent introduced from the first multi-channel valve, and an oxidation lamp mounted on the outside of the reaction tank to oxidize organic carbon in the analytical sample,
A second multichannel valve communicating with the switching valve and the syringe pump to change the flow path so that the carbon dioxide generated by oxidation of organic carbon in the oxidation reaction unit is transferred to the syringe pump; The syringe pump is operated to control the pressure of the oxidation reaction unit to flow the analytical sample and the reagent from the first multi-channel valve to the oxidation reaction unit, Collecting carbon dioxide produced by oxidation of organic carbon in the oxidation reaction tank, and supplying the collected carbon dioxide to the detection unit.
The method of claim 6, wherein the step of discharging carbon dioxide produced by oxidizing the inorganic carbon to the outside comprises:
The valve of the flow rate controller for removing the inorganic carbon which controls the supply of the high purity gas used for discharging the carbon dioxide generated by the oxidation of the inorganic carbon to the outside is operated to the ON state and the high purity gas is subjected to the oxidation reaction ;
Removing the inorganic carbon in the analytical sample by discharging the gasified carbon dioxide, which is volatilized together with the high-purity gas in the oxidation reaction tank, to the outlet of the switching valve by operating the switching valve; And
Closing the valve of the flow rate controller for removing the inorganic carbon when the removal of the inorganic carbon is completed, to block the inflow of the high purity gas;
And measuring the total organic carbon content of the integrated oxidation reaction tank.
7. The method of claim 6, wherein the step of collecting the carbon dioxide produced by oxidizing the organic carbon in the oxidation reaction unit with a syringe pump,
Before the syringe pump is used for collecting the organic carbon, the valve of the flow rate controller for measuring organic carbon, which controls the supply of the high purity gas used for collecting the carbon dioxide produced by the oxidation of the organic carbon into the syringe pump, is turned ON, Injecting a high purity gas into the oxidation reaction tank at a flow rate;
Blocking the flow of the high-purity gas by operating the valve of the flow rate controller for measuring organic carbon when the collection is completed;
Further comprising the step of measuring the total organic carbon concentration.
The method according to claim 6, wherein the step of transferring the collected carbon dioxide to a measuring unit communicating with the switching valve comprises:
Monitoring a mass flow rate controller connected to the switching valve and the detector to monitor whether high purity gas is supplied to the detector for transferring the carbon dioxide collected in the syringe pump to the detector and to maintain a constant flow rate of the high purity gas supplied to the detector; And
Removing moisture that lowers the sensitivity of the detection portion, the moisture trap connected to the switching valve;
Further comprising the step of measuring the total organic carbon concentration.
The method according to claim 6,
A step of automatically generating a screen or an anomaly code so that the user can detect whether the analytical sample and the reagent are not introduced by using the analytical sample introduction sensor;
Monitoring the performance of the syringe pump by measuring the internal pressure of the syringe with a pressure sensor and automatically generating an anomaly code in advance when the syringe pump performance begins to fall below a certain level;
Monitoring the performance of an ultraviolet oxidation lamp used for oxidizing an analytical sample using a photodiode sensor and automatically generating an anomaly code in advance when the performance begins to drop below a predetermined standard;
The amount of high purity gas is calculated by using a flow rate controller for removal of inorganic carbon, a flow rate controller for measuring organic carbon, and a mass flow rate controller. If the remaining amount of the high purity gas is less than a predetermined standard, Automatically; And
Monitoring the flow rate of the high purity gas that transfers carbon dioxide to the non-dispersive infrared detector using a mass flow rate controller, and automatically generating an anomaly code when the flow rate deviates from a predetermined reference range. A method for measuring total organic carbon having a reaction tank.

Images