KR101098960B1 - Pollutant detection method using liquid photoreactor and its device - Google Patents

Abstract

A contaminant detection device using a liquid phase photoreactor for gas phase sample detection is disclosed. The pollutant detection device using a liquid phase photoreactor for gas phase sample detection according to the present invention is for detecting and detecting specific pollutants contained in exhaust gas or air.
A sample supply unit for transporting a gaseous sample collected from exhaust gas or air using a carrier gas;
A reaction inducing material supply unit for supplying a liquid reaction inducing material for reacting with the gas phase sample to generate a photo reaction by using a peristaltic pump;
A gaseous sample carried by the sample supply unit and a liquid reaction inducer supplied by the reaction inducing material supply unit have a reaction chamber for causing a photoreaction, and the gaseous sample and liquid reaction inducer generated in the reaction chamber A liquid phase photoreactor having a photodetector for detecting a photoreaction; And
And a control unit for controlling the sample supply unit and the reaction inducing substance supply unit, and processing and storing data obtained from the photodetector.

Description

Method for detecting pollutant using liquid photoreactor and its device {METHOD FOR POLLUTANT DETECTING USING LIQUID PHOTOREACTOR AND SYSTEM THEREOF}

The present invention relates to a method for detecting a pollutant using a liquid phase photoreactor and a device thereof, and more particularly, to a reaction generation signal generated after inducing a chemical reaction with a liquid phase reactant to a specific substance included in a gaseous sample. The present invention relates to a method and apparatus for detecting pollutants using a liquid phase photoreactor capable of detecting a selective, stable, effective, and rapid process.

As a background art of the invention, a nitrogen oxide measuring apparatus using a colorimetric method for measuring nitrogen oxides in the atmosphere or exhaust gas is disclosed.

As shown in FIGS. 8 and 9, in order to measure the amount of nitrogen oxides (NOx), a filter paper sensor 111 coated with a reagent which is reacted with nitric oxide (NO 2) and coated, and the filter paper sensor 111 is centered. A sensor holder 110 supported to be positioned at the light source, a photodiode 121 for irradiating light of a predetermined wavelength to the filter paper sensor 111, and a photo for measuring light remaining after being absorbed by the filter paper sensor 111 The main body 120 includes a main body 120 including a supply pipe 123 for supplying gas to the internal space, a discharge pipe for removing gas from the internal space, and a space in which the diode 122 is diffused. For amplifying a signal related to the amount of nitrogen oxides (NOx) measured from the measurement unit 100 and the photodiode 122 of the measurement unit 100 is formed of a housing 130 having a lid with a built-in 120 Amplifier 210 and the amplifier 21 A display unit 200 including a display unit 220 for displaying a signal amplified by 0) and a gas containing nitrogen oxide (NOx) into the measurement unit 100 and discharged from the measurement unit 100. The discharge unit 300 is composed of a flow meter 310 and the pump 320.

However, in order to measure nitrogen oxides contained in the atmosphere or exhaust gas, such a measuring apparatus manufactures a filter paper sensor by depositing the filter paper in a reagent reacting with nitrogen oxide and discoloring and drying it, and collecting it into the space where the filter paper sensor is installed. After supplying the prepared sample, the light of the photodiode having a certain wavelength is projected, and the light absorbed by the filter paper sensor from the projected light is measured with a photodiode, and then the absorbance measured is compared with the prepared calibration curve and nitrogen oxide or nitrogen. Being configured to measure specific contaminants such as oxides, it was difficult to continuously measure specific contaminants, it took a lot of time to measure one type of sample, the task of measuring one sample was very complicated, and passive elements Has been applied in most cases, the accuracy of the measurement was poor.

Republic of Korea Patent Publication No. 10-2002-0094096 (2002.12.18)

The technical problem of the present invention is to provide a detection apparatus capable of quickly and efficiently detecting specific pollutants contained in exhaust gas or the atmosphere.

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

The technical problem is to detect specific pollutants in the gaseous phase contained in the exhaust gas or the atmosphere according to the present invention,

Carry a gaseous sample collected from the exhaust gas or the atmosphere using a carrier gas, and temporarily fill the sample loop with the amount of sample to be detected once, and then supply the carrier gas to the sample loop to transport the gaseous sample. A sample supply unit;

A reaction inducing material supply unit for supplying a liquid reaction inducing material for generating a photoreaction with the gas phase sample using a peristaltic pump;

A photodetector for detecting a photoreaction generated in the reaction chamber, the reaction chamber including a gaseous sample carried by the sample supply unit and a liquid reaction inducer supplied by the reaction inducing material supply unit causing a photoreaction; Liquid photoreactor equipped; And

It is achieved by providing a contaminant detection device using a liquid photoreactor characterized in that it comprises a control unit for controlling the sample supply unit and the reaction induction material supply unit, and processing and storing the data obtained from the photodetector.

The sample supply unit,

A sample pump for supplying a gas phase sample to the sample loop;

A sample flow meter configured to control a supply amount of a gaseous sample supplied to the sample loop;

A transport gas flow meter for controlling a flow of a transport gas for transporting the gaseous sample filled in the sample loop to the reaction chamber;

A separation column for separating and removing photoreactive substances other than specific contaminants to be detected from a gaseous sample supplied to the reaction chamber by a carrier gas flowing through the carrier gas flow meter; And

The controller is connected to the sample pump, the sample flow meter, the sample loop, the transport gas flow meter, and the separation column, respectively, to temporarily fill a gas phase sample in the sample loop, and to supply the transport gas flowing through the transport gas flow meter to the separation column. It can be made by including a multi-directional switch valve controlled by.

The multi-directional switch valve,

A first port connected to the sample pump;

A second port connected to the sample flow meter;

Third and fourth ports respectively connected to both ends of the sample loop;

A fifth port connected to the transport gas flow meter;

A sixth port connected to the separation column; And

When filling a sample in the sample loop, the third and fourth ports are connected to the first and second ports, and the fifth and sixth ports are connected to each other, and a sample temporarily filled in the sample loop is supplied to the reaction chamber. In this case, the third and fourth ports may be connected to the fifth and sixth ports, respectively, and a plurality of connection ports connecting the first and second ports to each other may include a rotary controlled by the controller. .

The control unit,

The rotary control of the multi-directional switch valve may be controlled to transfer the gas phase sample filled in the sample loop to the separation column every 2-3 minutes.

The liquid phase photoreactor,

A sample inlet connected to the sample supply unit and an induction material inlet connected to the reaction inducing material supply unit are provided at one side of the reaction chamber, and the other side of the reaction chamber is provided with an outlet for discharging the reactant having completed the photoreaction. A reaction block having a membrane installed in the reaction chamber to induce an optical reaction between the gaseous sample passing through the chamber and the liquid reaction inducing material;

A detection block having a through hole for passing light in a region facing the reaction chamber, coupled to the reaction block, and a detector induction tube having a photodetector coupled to an opposite side of the through hole; And

It may include a transparent partition wall disposed between the reaction block and the detection block to separate the reaction chamber from the through hole.

The membrane,

It is made of hydrophilic nylon material and may be white.

Between the reaction block and the detection block,

An auxiliary transparent partition wall for isolating the reaction chamber in duplicate may be disposed by a partition block to maintain a distance from the transparent partition wall.

Between the reaction block, the partition block and the detection block,

An airtight holding member may be provided to prevent leakage of the reactant material passing through the reaction chamber.

The inner interval of the reaction chamber,

It can consist of 1mm-5mm.

The photodetector may further include an optical amplifier.

The control unit,

When the program starts, it initializes all interfaces, sets the execution conditions, switches the rotary position of the multi-directional switch valves, so that the gaseous sample filled in the sample loop is transferred to the reaction chamber through the separation column by the carrier gas, By controlling the peristaltic pump to supply the reaction inducing material to the reaction chamber, and receives the data of the photodetector detecting the light reaction generated in the reaction chamber and outputs to the display device, the predetermined time elapses the multi-directional switch The valve may be configured to switch the rotary position so that a certain amount of gaseous sample is filled in the sample loop and store the data of the photodetector.

On the other hand, the present invention, as a method for detecting a specific pollutant in the gas phase contained in the exhaust gas or the atmosphere using the pollutant detection device according to claim 12,

a) preparing a gas flow sample of a predetermined flow rate by controlling the multi-directional switch valve to be transferred from the sample flowmeter to the sample loop by a sample pump to temporarily fill the sample loop;

b) driving and controlling the multi-directional switch valve in a state in which the gas phase sample is filled in the sample loop, so that the gaseous sample filled in the sample loop is continuously transported through the gas flow meter to the separation column. A conveying step for conveying;

c) separating and removing photoreactive materials except for specific contaminants from the gaseous sample transferred to the separation column and supplying them to the reaction chamber and controlling the reaction inducing material supply unit to generate a photoreaction with the gaseous sample. Supplying a liquid reaction inducing substance for the reaction chamber;

d) a photoreaction step such that the gaseous sample and the reaction inducing material supplied to the reaction chamber cause a photoreaction at the surface of the membrane; And

e) a contaminant detection method using a liquid phase photoreactor, characterized in that the detection step of detecting the photoreaction generated in the membrane with the photo detector.

Step e),

The method may further include analyzing the photo response data detected by the photo detector and storing the analyzed chromatogram.

According to the present invention, the specific material contained in the exhaust gas or the atmosphere is configured to be introduced into the reaction chamber through which the light is blocked through the sample inlet at a predetermined time (for example, 2-3 minutes) after filling the sample tube. Rapid reaction of gaseous samples enables the detection of specific substances.

In addition, the membrane in the reaction chamber is made of a hydrophilic nylon material for amplifying the surface area reaction, the liquid reaction inducing material and the gas phase sample that is continuously introduced on the even surface of the membrane to photoreact to emit photons, This can be detected with a photodetector. Therefore, the reaction generation signal can be detected stably and effectively, thereby providing the effect of accurately measuring a specific substance from the gas phase sample.

Since the gaseous sample can be measured continuously, it is possible to accurately detect and measure specific contaminants from the atmosphere using a mobile vehicle or an aircraft.

1 is a schematic block diagram illustrating a contaminant detection device using a liquid phase photoreactor according to an embodiment of the present invention.
2a and 2b are schematic diagrams for explaining the operation of the multi-directional switch valve of the pollutant detection device shown in FIG.
3 is a front view of the liquid phase photoreactor shown in FIG. 1.
4 is a cross-sectional view of the bonding state of the liquid phase photoreactor shown in FIG.
FIG. 5 is a diagram illustrating analysis data of pollutants detected and analyzed by the pollutant detection device shown in FIG. 1.
6 is a graph showing a standardized analysis result for verifying the performance of the contaminant detection device using a liquid phase photoreactor according to the present invention.
7 is a flow chart for explaining the operation of the control unit according to the present invention.
8 is a schematic configuration diagram showing a pollutant measuring device according to the prior art.
FIG. 9 is a cross-sectional view of the pollutant measuring apparatus shown in FIG. 8.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, descriptions of already known functions or configurations will be omitted to clarify the gist of the present invention. And, as used herein, the singular forms may include the plural forms as well, unless the context clearly indicates otherwise. Also, as used herein, "comprise" and / or "comprising" specifies the presence of the mentioned shapes, numbers, steps, actions, members, elements and / or groups of these. It is not intended to exclude the presence or the addition of one or more other shapes, numbers, acts, members, elements and / or groups.

In the accompanying drawings, FIG. 1 is a schematic configuration diagram illustrating a contaminant detection apparatus using a liquid photoreactor according to an embodiment of the present invention, FIG. 2 is a front view of the liquid photoreactor shown in FIG. 1 is a cross-sectional view of the combined state of the liquid phase photoreactor shown in FIG. 1, and FIG. 4 is a diagram showing analysis data of contaminants detected and analyzed by the pollutant detection device shown in FIG.

Contaminant detection apparatus using a liquid photoreactor according to the present invention can detect a photoreaction material, for example, a variety of substances that photoreact with a luminol solution, in the present embodiment environmentally acetyl nitrate peroxide ( PAN: Peroxyacetyl nitrate) will be described based on the detection.

As shown in Figures 1 and 3, the contaminant detection device is a device for detecting a specific substance, for example, acetyl nitrate peroxide in the gas phase using the liquid phase photoreactor 10 for gas phase sample detection As a 200, a gaseous sample collected from exhaust gas or air is transported using a carrier gas, and the sample loop 170 is temporarily filled with a sample amount to be detected once and then the carrier is supplied to the sample loop 170. Sample supply unit 100 for supplying the gas to convey the gas phase sample to the reaction chamber 28 of the liquid photoreactor 10 to be described later, and a liquid reaction inducing substance for generating a photoreaction with the gas phase sample, for example For example, the reaction inducing substance supply unit 300 for supplying the luminol solution showing the luminol reaction to the reaction chamber 28 using the peristaltic pump 320, and the reaction with the gaseous sample carried by the sample supply unit 100 are induced. To the material supply unit 300 And a liquid photoreactor 10 having a reaction chamber 28 in which the supplied liquid reaction inducing substance causes a photoreaction, and a photodetector 34 for detecting the photoreaction generated in the reaction chamber 28; The controller 400 is configured to control the sample supply unit 100 and the reaction inducing substance supply unit 300, process, store, and display data obtained from the liquid phase photoreactor 10.

This will be described in more detail as follows.

The sample supply unit 100 includes a sample pump 110 for supplying a gas phase sample to the sample loop 170, a sample flow meter 150 configured to control a supply amount of the gas phase sample supplied to the sample loop 170. By the transport gas flow meter 140 for controlling the flow of the transport gas for transporting the gaseous sample filled in the sample loop 170 to the reaction chamber 28 and the transport gas flowing through the transport gas flow meter 140 Separation column 190, a sample pump 170, a sample flow meter 150, a sample loop for separating and removing photoreactive substances other than specific contaminants to be detected from a gaseous sample supplied to the reaction chamber 28 (170), the transport gas flow meter 140, the separation column 190 is connected to each of the separation column using a transport gas flowing through the transport gas flow meter 140 after temporarily filling the gas phase sample in the sample loop 170 To feed 190 It is composed of a multi-directional switch valve 120 is controlled by the control unit 400, the gas phase indicator passing through the separation column 190 is supplied to the reaction chamber 28 every set time.

At this time, the volume of the sample loop 170 is about 1ml. This volume can vary depending on various conditions. That is, the gaseous sample having a volume of 1 ml is configured to be supplied to the reaction chamber 28 through the separation column 190 at a predetermined time after filling the sample loop 170. This means that gaseous samples can react quickly to detect certain substances.

The multi-directional switch valve 120 has six ports as shown in FIGS. 2A and 2B, and includes a first port 121 connected to a sample pump and a second port connected to a sample flowmeter 150. A third port 123 and a fourth port 124 connected to both ends of the sample loop 170, a fifth port 125 connected to the transport gas flow meter 140, and a separation column The sixth port 126 connected to the 190 and the third and fourth ports 123 and 124 are connected to the first and second ports 121 and 122 while filling the sample loop 170 with the fifth and sixth ports. When the ports 125 and 126 are connected and the sample temporarily filled in the sample loop 170 is supplied to the reaction chamber 280, the third and fourth ports 123 and 124 are connected to the fifth and sixth ports 125 and 126, respectively. The first and second ports 121 and 122 include a plurality of connection ports 127 that are connected to each other and are configured as a rotary drive 128 controlled by the controller 400.

This multi-directional switch valve 120 is connected to the sample pump 110 and the sample flow meter 150 through the sample loop 170 when the gas phase sample is not supplied to the reaction chamber 28 as shown in FIG. In this case, the sample pump 110 sucks the gaseous sample at a constant flow rate through the sample flowmeter 150 to fill the sample loop 170 at all times. Then, the transport gas flow meter 140 and the separation column 190 are connected so that the transport gas flows to the separation column 190 through the transport gas flow meter 140. As shown in FIG. 2B, when the gas phase sample is supplied to the reaction chamber 28, the sample pump 110 and the sample flow meter 150 are disconnected from the sample loop 170 to block the sample pump 110 and the sample flow meter ( 150 is connected, and the sample loop 170 is connected to the transport gas flow meter 140 and the separation column 190, respectively, so that the gaseous sample filled therein is transported to the separation column 190 by the transport gas. Will be.

Separation column 190 is a gas column (GC) separation column commonly used in analytical chemistry, and consists of a thin tube coated on the inner circumferential surface. The separation column 190 has a function of allowing a wide variety of compounds contained in the environment to pass through a thin tube with a special coating, thereby separating according to the chemical properties (nonpolarity, molecular weight, volatility, etc.) of the material inside the tube. Have

For example, in order to detect the concentration of acetyl nitrate peroxide (PAN) in the air, the concentration of acetyl nitrate peroxide (PAN) can be known only by separating and removing the material which reacts with luminol in the air in advance. At this time, in addition to acetyl nitrate peroxide (PAN), NO ₂ (nitrogen dioxide), O ₃ , H ₂ O _2, etc. are included. The separation column 190 is disposed in front of the liquid photoreactor 10 as in the present embodiment. By separating the acetyl nitrate peroxide (PAN) and NO ₂ before the gaseous sample (air in the air) to the liquid photoreactor 10, the photoreaction with the reactants in the reaction chamber 28 and then the light It is necessary to measure the concentration of acetyl nitrate peroxide (PAN) alone. At this time, since O ₃ (ozone) and H ₂ O ₂ (hydrogen peroxide) are decomposed in the separation tube and do not flow into the reaction chamber 28, there is no need to separate them.

The sample supply unit 100 described above is controlled by the control unit 400 to supply the sample to the reaction chamber 28 at a predetermined time interval for a predetermined amount of the sample. That is, the gaseous sample is supplied to the reaction chamber 28 at a predetermined amount every time set by the multi-directional switch valve 120 controlled by the controller 400.

For example, the control unit 400 is to transport the gas phase sample filled in the sample loop 170 to the separation column 190 every two to three minutes intervals to be supplied to the reaction chamber 28 and the transport gas flow meter 140 and The sample flow meter 150, the sample pump 110, and the multidirectional switch valve 120 are controlled.

On the other hand, the reaction induction material supply unit 300 is configured to supply the liquid reaction induction material stored in the storage container to the induction material inlet 22 using the peristaltic pump 320. The peristaltic pump 320 is also controlled by the controller 400.

And, the outlet 26 is connected to the discharge vessel for storing the discharged material is discharged.

The control unit 400 is configured to control the sample supply unit 100 and the reaction induction material supply unit 300 to process, store, and display data obtained from the liquid phase photoreactor 100. To this end, the control unit 400 incorporates real-time chromatogram peak software. The optical signal detected through such software can be calculated and displayed. In addition, the controller 400 may include a serial interface for driving each driving device, and further includes display means for displaying data.

That is, the controller 400 controls the transport gas flow meter 140, the sample flow meter 150, and the sample pump 110, and separates the gas phase sample filled in the sample loop 170 every two to three minutes. The multi-directional switch valve 120 is driven and controlled to be transferred, and the concentration of a specific substance (acetyl peroxide in this embodiment) is calculated by processing chromatogram data detected by the photodetector 34. will be.

To this end, the controller 400 may be configured as follows.

That is, as shown in FIG. 7, when the program is started, all interfaces are initialized, execution conditions are set, and rotary 128 positions of the multi-directional switch valve 120 are switched to fill the sample loop 170. The gaseous sample is transferred to the reaction chamber 28 through the separation column 190 by the transport gas, and the peristaltic pump 320 is controlled so that the reaction inducing substance is supplied to the reaction chamber 280 and the reaction chamber ( Receiving data of the photodetector 340 that senses the light response generated in the 280, and outputs to the display device (for example, a computer monitor, etc.), when a predetermined time elapses, the rotary of the multi-directional switch valve 120 (128) The position is switched so that a certain amount of gaseous sample is filled in the sample loop 170, and the data of the photodetector 34 is stored.

On the other hand, the liquid-phase photoreactor 10 for detecting a gas phase sample is to react a gas phase sample and a liquid reaction inducing material to detect a specific substance contained in the gas phase sample, the sample inlet (Ga) 24) and a reaction block 20 having a reaction chamber 28 in communication with the induction material inlet 22 and connected to an outlet 26 through which the reaction liquid and gas are discharged, and one side of the reaction block 20; A detection block 30 having a photodetector 34 for detecting light generated in the photoreaction in the reaction chamber 28 and coupled to the reaction block 20 and the detection block 30. The chamber 28 is composed of a transparent partition wall 40 that separates and separates from the through hole 32.

This will be described in more detail as follows.

First, the liquid phase photoreactor for gas phase sample detection according to the present invention may be formed in a circle or a square, and the like, but is not limited to any one shape.

The reaction block 20 is configured to react the gaseous material with the liquid reaction inducing material, and an induction material inlet 22 through which the liquid reaction inducing material is introduced is formed on one surface consisting of a square or a circle, and the induction material inlet 22 After the gas phase sample and the liquid reaction inducer reacts at a position spaced by), an outlet 26 through which the reactant is discharged is formed. In addition, a sample inlet 24 through which the gaseous sample is introduced is formed at the induction material inlet 22. That is, the sample inlet 24 is formed to communicate with the reaction chamber 28 side of the induction material inlet 22. Thus, the liquid induction material is introduced into the reaction chamber 28 together with the gaseous sample while passing through the induction material inlet 22.

On the other hand, in the center of the reaction block 20, one side is connected to the induction material inlet 22 and the sample inlet 24, the other side is formed with a reaction chamber 28 is connected to the outlet (26). The reaction chamber 28 is a space in which light is blocked in order to create a condition for causing a gaseous sample and a reaction inducing material to cause a photoreaction (luminol reaction). As shown in this embodiment, the partition wall block is formed in an open state. The reaction chamber 28 sealed by the transparent partition 40 while being combined with 50 may be formed, or may be formed in the reaction block 20 by itself.

The reaction chamber 28 is a space for the photoreaction (photon generation reaction, so-called luminol reaction) on the surface of the membrane 27, which is to be described later, the membrane 27 is a hydrophilic gas phase sample and the reaction inducing material.

As such, the membrane 27 for inducing the photoreaction between the gas phase sample and the reaction inducing substance in the reaction chamber 28 is preferably made of a hydrophilic nylon material.

This is because the surface of the membrane 27 made of hydrophilic nylon is even, and the surface is even and the hydrophilicity is good, so that the reaction liquid (reaction inducing substance) can be uniformly diffused on the surface, thereby spreading and moving along the even surface. This is because the reaction inducing substance and the gas phase sample can be stably reacted while moving. In addition, since the membrane 27 made of hydrophilic nylon is formed white, the loss of photons generated by photoreaction at the surface of the membrane 27 can be minimized.

Thus, the membrane 27 is made of a hydrophilic nylon material it is possible to measure the low concentration of a specific material.

Such a membrane 27 is installed in close contact with one side of the reaction chamber 28 (the surface facing the transparent partition wall) without being lifted up. To this end, one surface of the reaction chamber 28 should be processed evenly. At this time, the membrane 27 is fixed to each of the reaction chamber 28 (inlet side and outlet side) by fixing means (bonding, fitting, various other fixing means) can be installed in a flat unfolded state, transparent It may be attached to the partition 40, but is most preferably installed in close contact with one side wall of the reaction chamber (28).

On the other hand, the transparent partition 40 forming the reaction chamber 28 is made of glass or quartz. An airtight packing may be installed between the transparent partition 40 and the reaction block 20.

An interval between the reaction chamber 28 (between the transparent partition wall and one surface of the reaction chamber facing the transparent partition wall) may be 1 mm to 5 mm. In this case, the internal spacing of the reaction chamber 28 may vary depending on the material to be detected, but is approximately 2 mm. This is because when the interval is less than 1mm, the flow of the reactant is too fast to cause sufficient photoreaction, and when it is 5mm or more, bubble phenomenon occurs due to the liquid reaction inducing substance and gas. Therefore, it is preferably made of 2 mm.

In addition, when the detection block 30 is coupled to the reaction block 20, the transparent partition 40 may be disposed between the reaction block 20 and the detection block 30 to form the reaction chamber 28. As shown in FIG. 3, the partition block 50 is disposed between the reaction block 20 and the partition block 50 to form the reaction chamber 28. At this time, the airtight holding member 70 is disposed between the transparent partition 40 and the partition block 50. At this time, a through hole 54 for passing photons generated in the reaction chamber 28 is formed at the center of the partition block 50.

On the other hand, the auxiliary transparent partition wall 52 is disposed on one surface of the partition block 50. The auxiliary transparent partition wall 52 blocks the reaction chamber 28 in a double manner so that the reactant material (gas and liquid) passing through the reaction chamber 28 together with the transparent partition wall 40 does not leak to the detection block 30. It is for. The auxiliary transparent partition wall 52 is also made of quartz or the like similar to the transparent partition wall 40.

In the detection block 30, a through hole 32 coincident with the through hole 54 of the partition block 50 is formed in an area in contact with the partition block 50. This through hole 32 is for causing photons emitted from the reaction chamber 28 to reach the photodetector 34.

The detector guide tube 36 having the photodetector 34 is coupled to the other end region of the detection block 30. In this case, the photodetector 34 includes an optical amplifier.

On the other hand, the areas in which the reaction block 20, the transparent block 50 and the detection block 30 abut each other are formed in multiple stages, and the above-described airtight holding member 70 is disposed therebetween. As described above, since the reaction chamber 28 is isolated by the transparent partition 40 and the auxiliary transparent partition 52, a phenomenon in which the reactant flows out to the detector induction tube 36 is prevented.

Since the above-described reaction block 20, the transparent block 50, and the detection block 30 are each composed of a single piece and are mutually coupled, maintenance of parts, such as replacement of parts, can be easily performed.

The process of detecting pollutants from the atmosphere or the exhaust gas using the pollutant detection device configured as described above is as follows.

Prior to explaining the action, the gas phase sample may be variously applied, but as described above, the process of detecting peroxyacetyl nitrate (PAN) in the air pollutant will be described.

As shown in FIGS. 1 to 7, first, a gas flow sample of a predetermined flow rate (approximately 1 ml) collected by the sample pump 110 is operated by the control operation of the controller 400 through the sample flow meter 150. The sample loop 170 mounted on the directional switch valve 120 is filled. In this case, as illustrated in FIG. 2A, the first port 121 connected to the sample pump 110, the 3.4 ports 123 and 124 connected to both ends of the sample loop 170, and the second port connected to the sample flow meter 150 ( 122 is connected by the rotary 128. This step is a preparation step for supplying the collected gaseous sample to the reaction chamber 28.

Subsequently, the gas phase sample filled in the sample loop 170 is controlled by driving the multi-directional switch valve 120 while the gas phase sample is filled in the sample loop 170 in the preparation step. It is to be transferred to the separation column 190 by the transport gas continuously flowing through. That is, the multi-directional switch valve 120 is operated by the controller 400 at predetermined time intervals, for example, every two to three minutes, and the third port 123 connected to the sample loop 170 is transferred to a transport gas flow meter ( A gaseous sample filled in the sample loop 170 by connecting the fifth port 125 connected to the 140 and the fourth port 124 connected to the sixth port 126 connected to the separation column 190. By the transfer to the separation column 190 by. Herein, the multi-directional switch valve 120 is operated by the control unit 400 at intervals of 2 to 3 minutes, and the gaseous sample is transferred to the separation column 190. Not only does it mean that it can be quickly transported and analyzed, but it also means that many samples can be analyzed quickly. As such, the process of transferring the sample filled in the sample loop 170 to the separation column 190 using a transport gas is a transfer step.

In this process, when the gaseous sample transferred to the separation column 190 passes through the separation column 190, a specific material included in the sample, for example, a specific material causing a photoreaction with the reaction inducing material (for example, For example, NO ₂ ) is separated.

That is, the separation column 190 serves to pre-separate other materials except for nitrate peroxide (PAN) contained in the sample. In the absence of the separation column 190, the light from the liquid phase reactor 10 It is not possible to tell whether it comes from acetyl nitrate peroxide or from another substance (other than acetyl nitrate permeate may be present in the sample), so the gaseous sample that is passed excludes certain substances, namely acetyl nitrate peroxide. To separate and remove matter.

Subsequently, the photoreactive material except for a particular contaminant is separated and removed from the gaseous sample transferred to the separation column 190 and then supplied to the reaction chamber 28 and the reaction inducing material supply unit 300 is controlled to control the gaseous sample. And a liquid reaction inducing substance for generating a photoreaction to the reaction chamber 28. That is, when the gas phase sample is supplied to the reaction chamber 28, the peristaltic pump 320 is operated to supply a reaction inducing material, for example, a luminol solution, to the inducing material inlet 22. As described above, the sample and the reaction inducing substance are supplied to the reaction chamber 28.

When the luminol solution is supplied to the induction material inlet 22 and the gaseous sample is supplied to the sample inlet 24, the liquid reaction inducer (luminol solution) introduced into the reaction chamber 28 is made of a hydrophilic nylon material. While uniformly diffused on the surface of the membrane 27 is made to move toward the outlet 26, at the same time the gaseous sample is subjected to a photoreaction (luminol reaction) with the liquid reaction inducer uniformly diffused on the surface of the membrane 27 do.

In this process, the luminol solution and the gas phase sample react with the luminol on the membrane 27 to generate light.

That is, when the gaseous sample is introduced into the light-reacting reaction chamber 28, the surface of the hydrophilic nylon membrane 27 configured to amplify the surface area reaction and photoreacts with the liquid luminol solution continuously introduced as in the following formula It will emit photons. As such, the reaction between the sample and the reactant on the surface of the membrane 27 is a photoreaction step.

In this process, the light generated in the reaction chamber 28 reaches the photodetector 34 through the transparent partition 40 and the auxiliary transparent partition 52, and the optical amplifier of the photodetector 34 amplifies the light. After detecting and converting the signal into an electrical signal, the control unit 400 transmits the signal. In this case, the controller 400 analyzes the photo response data detected by the photo detector 34 and stores the analyzed chromatogram. This process is a detection step of detecting a specific substance through the light generated by the photoreaction of the sample.

That is, the controller 400 operates as shown in FIGS. 4 and 7 to process data using built-in software. In addition, the controller 400 stores the data, and detects and analyzes acetyl nitrate peroxide contained in the air pollutant by a separate command.

On the other hand, the reaction material completed the reaction while passing through the membrane 27 is discharged to the discharge vessel through the outlet (26).

As such, the sample loop 170 is provided in the multi-directional switch valve 120, and the gas phase sample is filled in the sample loop 170, and the filled gaseous sample is transferred to the separation column 190 by a transport gas. After the supply to the reaction chamber 28, the detection of the sample can be made in a short time. That is, by setting the gaseous sample to be filled in the sample loop 170 every 2-3 minutes, the sample filled in the sample loop 170 every 2-3 minutes to the reaction chamber 28 through the separation column 190. Because of the transfer, one sample can be detected in a short time of 2-3 minutes.

In addition, the multi-barrier structure of the liquid phase photoreactor 10 for detecting the gas phase sample enables the gas phase sample and the liquid reactant to be stably reacted without leaking, thereby enabling low concentration detection of the material. The analysis results can be obtained.

Experimental Example

In order to verify the performance of the liquid-phase photoreactor according to the present invention, only a standard material, for example, nitric acid peroxide (PAN) was supplied to detect the number of photons by the luminol reaction, and the result was Same as the graph shown in FIG.

As shown in FIG. 6, when a standard material corresponding to 8,6,5,4,2,1 ppbv (part per billion by volume) of nitric acid peroxide (PAN) is injected, the photodetector (PMT) of the liquid phase photoreactor is used. The number of photons measured is represented by the peak height. In other words, the results show a fairly linear (r ² = 0.996374) result, which means that stable detection and analysis is possible. Considering that the peak height is about 350 at 1 ppbv, the minimum detection concentration is very small. It can be seen from the graph that the level is 0.03-0.05 ppbv.

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

10: liquid phase photoreactor 20: reaction block
22: induction material inlet 24: sample inlet
26 outlet 27
28: reaction chamber
30: detection block 32: through hole
34: photodetector 36: detector guide tube
40: transparent partition 50: partition block
52: auxiliary transparent partition 70: airtight member
100: sample supply unit 110: sample pump
120: multi-directional switch valve 121: first port
122: second port 123: third port
124: fourth port 125: fifth port
126: 6th port 127: connection port
128: rotary 140: gas flow meter for transport
150: sample flow meter 170: sample loop
190: separation column 200: pollutant detection device
300: induction material supply unit 320: peristaltic pump
400:

Claims (14)

To detect specific pollutants in gaseous gas contained in exhaust gas or atmosphere,
Carry a gaseous sample collected from the exhaust gas or the atmosphere using a carrier gas, and temporarily fill the sample loop with the amount of sample to be detected once, and then supply the carrier gas to the sample loop to transport the gaseous sample. A sample supply unit;
A reaction inducing material supply unit for supplying a liquid reaction inducing material for generating a photoreaction with the gas phase sample using a peristaltic pump;
A photodetector for detecting a photoreaction generated in the reaction chamber, the reaction chamber including a gaseous sample carried by the sample supply unit and a liquid reaction inducer supplied by the reaction inducing material supply unit causing a photoreaction; Liquid photoreactor equipped; And
And a control unit for controlling the sample supply unit and the reaction inducing substance supply unit, and processing and storing data obtained from the photodetector.
Pollutant detection device using a liquid photoreactor. The method of claim 1,
The sample supply unit,
A sample pump for supplying a gas phase sample to the sample loop;
A sample flow meter configured to control a supply amount of a gaseous sample supplied to the sample loop;
A transport gas flow meter for controlling a flow of a transport gas for transporting the gaseous sample filled in the sample loop to the reaction chamber;
A separation column for separating and removing photoreactive substances other than specific contaminants to be detected from a gaseous sample supplied to the reaction chamber by a carrier gas flowing through the carrier gas flow meter; And
The controller is connected to the sample pump, the sample flow meter, the sample loop, the transport gas flow meter, and the separation column, respectively, to temporarily fill a gas phase sample in the sample loop, and to supply the transport gas flowing through the transport gas flow meter to the separation column. It characterized in that it comprises a multi-directional switch valve controlled by,
Pollutant detection device using a liquid photoreactor. The method of claim 2,
The multi-directional switch valve,
A first port connected to the sample pump;
A second port connected to the sample flow meter;
Third and fourth ports respectively connected to both ends of the sample loop;
A fifth port connected to the transport gas flow meter;
A sixth port connected to the separation column; And
When filling a sample in the sample loop, the third and fourth ports are connected to the first and second ports, and the fifth and sixth ports are connected to each other, and a sample temporarily filled in the sample loop is supplied to the reaction chamber. And a rotary driven and controlled by the controller so as to have a plurality of connection ports connecting the third and fourth ports to the fifth and sixth ports, respectively and simultaneously connecting the first and second ports to each other. Made,
Pollutant detection device using a liquid photoreactor. The method of claim 3,
The control unit,
Characterized in that the driving control of the rotary of the multi-directional switch valve so that the gaseous sample filled in the sample loop is transferred to the separation column every 2-3 minutes,
Pollutant detection device using a liquid photoreactor. The method of claim 1,
The liquid phase photoreactor,
A sample inlet connected to the sample supply unit and an induction material inlet connected to the reaction inducing material supply unit are provided at one side of the reaction chamber, and the other side of the reaction chamber is provided with an outlet for discharging the reactant having completed the photoreaction. A reaction block having a membrane installed in the reaction chamber to induce an optical reaction between the gaseous sample passing through the chamber and the liquid reaction inducing material;
A detection block having a through hole for passing light in a region facing the reaction chamber, coupled to the reaction block, and a detector induction tube having a photodetector coupled to an opposite side of the through hole; And
And a transparent partition wall disposed between the reaction block and the detection block to separate and separate the reaction chamber from the through hole.
Pollutant detection device using a liquid photoreactor. The method of claim 5,
The membrane,
Characterized in that the hydrophilic nylon material,
Pollutant detection device using a liquid photoreactor. The method of claim 6,
The membrane,
Characterized in that it consists of white,
Pollutant detection device using a liquid photoreactor. The method of claim 6,
Between the reaction block and the detection block,
An auxiliary transparent partition wall for isolating the reaction chamber in a double, characterized in that arranged by the partition block to maintain a distance from the transparent partition wall,
Pollutant detection device using a liquid photoreactor. The method of claim 8,
Between the reaction block, the partition block and the detection block,
Characterized in that the airtight holding member for preventing the leakage of the reaction material passing through the reaction chamber,
Pollutant detection device using a liquid photoreactor. The method of claim 5,
The inner interval of the reaction chamber,
Characterized in that it is 1mm-5mm,
Pollutant detection device using a liquid photoreactor. The method of claim 5,
The photodetector further comprises an optical amplifier,
Pollutant detection device using a liquid photoreactor. The method according to any one of claims 1 to 11,
The control unit,
When the program starts, it initializes all interfaces, sets the execution conditions, switches the rotary position of the multi-directional switch valves, so that the gaseous sample filled in the sample loop is transferred to the reaction chamber through the separation column by the carrier gas, By controlling the peristaltic pump to supply the reaction inducing material to the reaction chamber, and receives the data of the photodetector detecting the light reaction generated in the reaction chamber and outputs to the display device, the predetermined time elapses the multi-directional switch And switching the rotary position of the valve so that a certain amount of gaseous sample is filled in the sample loop, and storing the data of the photodetector.
Pollutant detection device using a liquid photoreactor. A method for detecting a specific pollutant in the gas phase contained in the exhaust gas or the atmosphere by using the pollutant detection device according to claim 12,
a) preparing a gas flow sample of a predetermined flow rate by controlling the multi-directional switch valve to be transferred from the sample flowmeter to the sample loop by a sample pump to temporarily fill the sample loop;
b) driving and controlling the multi-directional switch valve in a state in which the gas phase sample is filled in the sample loop, so that the gaseous sample filled in the sample loop is continuously transported through the gas flow meter to the separation column. A conveying step for conveying;
c) separating and removing photoreactive materials except for specific contaminants from the gaseous sample transferred to the separation column and supplying them to the reaction chamber and controlling the reaction inducing material supply unit to generate a photoreaction with the gaseous sample. Supplying a liquid reaction inducing substance for the reaction chamber;
d) a photoreaction step such that the gaseous sample and the reaction inducing material supplied to the reaction chamber cause a photoreaction at the surface of the membrane; And
e) a detection step of detecting the photoreaction generated in the membrane with the photodetector,
Pollutant detection method using liquid photoreactor. The method of claim 13,
Step e),
And analyzing the photoreaction data detected by the photo detector and storing the analyzed chromatogram.
Pollutant detection method using liquid photoreactor.

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