KR101256414B1 - water pollution measurement system by using gas sensor - Google Patents

Abstract

The present invention relates to a water pollution measurement system using a gas concentration sensor, by measuring the concentration of the polluting gas generated from the sample polluted water by evaporating the polluted gas dissolved in the sample polluted water, the type and odor of the polluted gas The present invention relates to a water pollution measurement system using a gas concentration sensor that can determine the degree.

Description

Water pollution measurement system by using gas sensor

The present invention relates to a water pollution measurement system using a gas concentration sensor, by measuring the concentration of the polluting gas generated from the sample polluted water by evaporating the polluted gas dissolved in the sample polluted water, the type and odor of the polluted gas The present invention relates to a water pollution measurement system using a gas concentration sensor that can determine the degree.

When the sample contaminated water is introduced into the conventional water quality measurement tank to measure the multi-item contaminant of the sample contaminated water, there is a problem that green algae and microorganisms are introduced from the source of the sample contaminated water through the inflow pipe.

On the other hand, when the water quality sensor array is exposed to a material to be measured (lead, cadmium, mercury, copper, chlorine ions, nitrate nitrogen), the sensor-specific voltage change as well as the sensor for measuring the exposed items are mutually changed. Is generated. The general ISE sensor is widely known as a device for detecting a small amount of a measurement substance even in a low concentration range. However, when ions with similar electrical properties are mixed, it is difficult to selectively detect a measurement substance and mistake a similar substance as a measurement substance to determine a quantitative value. It is also known as an inevitable pretreatment equipment.

On the other hand, since the water quality measuring sensor to measure the pollution component and the degree of contamination in the dissolved state in water, there was a disadvantage in that it is limited to measure the type and degree of odor that can be detected by the human sense of smell.

On the other hand, various semiconductor type gas concentration measuring sensors for detecting and preventing harmful gases including polluting gas generated by contaminated water in advance have been improved to cope with various factors. In addition, a performance evaluation method for the developed gas concentration sensor and a method for estimating the gas concentration (C) from the sensed output signal data have been presented.

The performance evaluation of a semiconductor gas concentration sensor that is commonly used includes voltage (Vair) or resistance (Rair), which is an output value before gas is injected into the gas concentration measurement sensor, and output voltage (Vgas) and resistance (after gas is injected). Rgas) or the resistance change (Rx) is a proportional formula, and is made up of the following relational formula.

[Equation 1]

S = Vair / Vgas, S = Vgas / Vair, S = Rair / Rgas, S = Rgas / Rair

&Quot; (2) "

S = (Vair-Vgas) / Vair, S = (Vair-Vgas) / Vgas, S = (Rair-Rgas) / Rair, S = (Rair-Rgas) / Rgas

&Quot; (3) "

S = Rgas / Rx

However, the conventional evaluation method evaluates the performance of the gas concentration measuring sensor by a simple proportional expression of the output values Vair and Rair before the gas is injected into the gas concentration measuring sensor and the output values Vgas, Rgas and Rx after the gas is injected. As a result, the performance of the gas concentration sensor could not be objectively evaluated due to the initial output value that generally varies depending on the measurement environment. In addition, in the manufacturing process of the gas concentration measurement sensor, as all the gas concentration measurement sensor does not have a constant resistance value, there was a problem that the output characteristics are different for each gas concentration measurement sensor. That is, the output value proportional expressions before and after gas injection were expressed with various values, and thus a unified performance evaluation method could not be applied. In addition, when the measurement gas is repeatedly injected at regular intervals, the output value of the gas concentration measurement sensor is expressed differently every moment, and thus there is a problem that the sensitivity reproducibility, which is a main requirement of the gas concentration measurement sensor, is significantly reduced.

The output characteristics of the semiconductor gas concentration measurement sensor are determined based on the initial resistance value RS and the injected gas concentration C of the gas concentration measurement sensor as main factors. , C) is not clearly explained. Since the initial resistance value RS is a known value at the manufacturing stage, although the injected gas concentration C can be estimated by analyzing the electrical output signal of the gas concentration measuring sensor, there is no clear definition of the output characteristic. Many difficulties have also occurred in estimating the gas concentration (C).

The present invention is to provide a water pollution measurement system that can measure the type and degree of odor that can be detected by the human sense of smell by measuring the pollution component and the degree of contamination of the polluting gas generated from the sample contaminated water.

The present invention is to provide a water pollution measurement system that can more accurately measure the concentration of the polluting gas generated from the sample contaminated water.

The present invention provides a gas concentration measuring chamber 20 in which sample contaminated water is stored; Evaporation means (30) for evaporating contaminated gas dissolved in sample contaminated water stored in the gas concentration measuring chamber (20); A gas concentration measuring apparatus (1000) having a gas concentration measuring sensor (313) for measuring the concentration of the polluting gas generated from the gas concentration measuring chamber (20); It relates to a water pollution measurement system using a gas concentration measurement sensor comprising a.

In the present invention, the evaporation means 30 may include a hot water chamber 31 for indirectly heating the gas concentration measuring chamber 20, the evaporation means 30 for the gas concentration measurement Vibration means 35 for applying vibration to the chamber 20, the vibration means 35 is stored in the bath chamber 31 to indirectly heat the gas concentration measurement chamber 20 It may include an ultrasonic vibrator provided in the bath chamber 31 to generate a vibration in the gas concentration measurement chamber 20 by applying a movement to the bath liquid.

In the present invention, the evaporation means 35 may evaporate the gas evaporated from the sample contaminated water temporarily stored in the gas concentration measuring chamber 20 in a non-atomized state.

In the present invention, the gas concentration measuring apparatus 1000 is a gas injection for injecting a measurement gas which is a contaminated gas generated from the gas concentration measuring chamber 20 in the space where the gas concentration measuring sensor 313 is disposed. Device 100; As the measurement gas is injected, an output voltage value V _L , which is a voltage between the load resistance R _L connected in series with the gas concentration measurement sensor 313, is measured, so that the measurement gas is measured. A gas adsorption amount calculator 411 for calculating a gas adsorption amount that is an amount adsorbed by the gas concentration sensor 313; A gas concentration calculation unit (420) for calculating a concentration of the measurement gas injected from the gas injection device (100) from the adsorption amount of the measurement gas calculated from the gas adsorption amount calculation unit (411); . ≪ / RTI >

In the present invention, the gas adsorption amount calculation unit 411 obtains a first output voltage which is the output voltage V _L according to the flow of the measurement gas injection time, and the measurement gas is output from the first output voltage. A first output voltage change rate, which is a change rate of the output voltage V _L according to the flow of the injection time, is obtained, and the first output voltage change rate is integrated from the first output voltage change rate according to the flow of the measurement gas injection time ( The gas output amount may be calculated from the first output voltage change rate integration value, which is the value of the first output voltage change rate integrated value.

The present invention provides an odorless air injector 200 that injects odorless air into a space where the gas concentration sensor 313 is disposed; The gas desorption amount calculating unit 412 which measures the output voltage V _L as the time of injecting the odorless air is calculated, and calculates a gas desorption amount which is the amount of the measurement gas separated from the gas concentration measuring sensor 313. ); The performance of the gas concentration measuring sensor 313 is determined by comparing the gas adsorption amount calculated by the gas adsorption amount calculating unit 411 with the gas desorption amount calculated by the gas desorption amount calculating unit 412. Sensor performance determination unit 430; . ≪ / RTI >

In the present invention, the gas desorption amount calculating unit 412 obtains a second output voltage which is the output voltage V _L according to the flow of the odorless air injection time, and the odorless air from the second output voltage. A second output voltage change rate, which is a change rate of the output voltage V _L according to the flow of the injection time, is obtained, and the second output voltage change rate is integrated as the odorless air injection time flows from the second output voltage change rate. The gas desorption amount may be calculated from the second output voltage change rate integrated value by obtaining the second output voltage change rate integrated value.

In the present invention, the odorless air injection device 200 may include an activated carbon filter 210 connected to the air flow path 220 for injecting odorless air into the space where the gas concentration sensor 313 is disposed. have.

According to the present invention, in order to selectively inject one of the measurement gas and the odorless air into the space where the gas concentration measurement sensor 313 is disposed, the gas injection device 100 and the odorless air injection device 200 may be used. It may include a selection valve (V) selectively connected to any one, the gas injection device 100 is connected to the gas concentration measurement chamber 20 to guide the measurement gas to the selection valve (V) Measuring gas guiding tube 120; A dust filter (130) installed on the measurement gas guide tube (120) to filter dust from the measurement gas; A water removal device (140) installed on the measurement gas guide tube (120) to filter moisture from the measurement gas; It may include.

In the present invention, the gas concentration calculating unit 420 may extract the concentration of the measurement gas from the characteristic relational expression between the gas adsorption amount and the concentration of the measurement gas, and the characteristic relational expression is a plurality of samples. It can be obtained from a regression analysis method between the sample gas adsorption amount, which is the gas adsorption amount measured for the measurement gas, and the concentration of the sample measurement gas.

The present invention has the advantage of measuring the type and degree of contamination of the contaminated gas generated from the sample contaminated water and the degree of contamination of the contaminated gas generated from the sample contaminated water that can be sensed by the human sense of smell.

According to the present invention, the method of estimating the concentration of the polluted gas from the adsorption amount of the polluted gas adsorbed on the gas concentration sensor shows the characteristics of low relative standard deviation even when the concentration is increased and the number of measurement repetitions is increased. have.

1 is a schematic configuration diagram of a main part of Embodiment 1;
FIG. 2 is a side view for explaining a connection state of some gas concentration measurement sensors in FIG. 1; FIG.
3 is a layout view of an electrochemical gas concentration measurement sensor in which a sensing surface is installed perpendicular to a sensor unit flow path, and a sensor chromatogram graph of the sensor.
4 is a layout view of an electrochemical gas concentration measurement sensor in which a sensing surface is installed horizontally in a sensor unit flow path and a sensor chromatogram graph of the sensor.
5 is a flowchart of Embodiment 2;
6 is a graph of a first output voltage and a graph of a second output voltage.
7 is a graph of a first output voltage change rate and a second output voltage change rate.
8 is a graph of a first output voltage change rate integration value and a second output voltage change rate integration value.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

However, in describing the present invention, a detailed description of known functions or configurations will be omitted in order not to disturb the gist of the present invention.

Example 1

Example 1 relates to a water pollution measurement system using a gas concentration sensor according to the present invention.

FIG. 1 is a schematic configuration diagram of an essential part of Embodiment 1, FIG. 2 is a side view for explaining a connection state of some gas concentration measurement sensors in FIG. 1, and FIG. 3 is an electrical formula in which a sensing surface is installed perpendicular to a sensor part flow path. Fig. 4 shows a layout of the gas concentration measuring sensor and a sensor chromatogram graph of the sensor, and Fig. 4 shows a layout of the electrochemical gas concentration measuring sensor and a sensor chromatogram graph of the sensor in which the sensing surface is horizontally installed in the sensor unit flow path.

Referring to FIG. 1, Embodiment 1 includes a gas concentration measuring chamber 20, an evaporation means 30, a pressure maintaining odorless air injection device 40, and a gas concentration measuring device 1000.

Referring to FIG. 1, a sample contaminant inflow pipe 21 for introducing sample contaminant is connected to the gas concentration measuring chamber 20. Sample contaminated water inlet pipe 21 may be provided with a pump (not shown). The sample contaminated water is stored in the gas concentration measuring chamber 20 through the sample contaminated water inflow pipe 21. Meanwhile, a sample contaminant discharge pipe 23 for discharging the sample contaminated water stored in the gas concentration measurement chamber 20 is connected to the gas concentration measurement chamber 20.

Referring to FIG. 1, the evaporation means 30 includes a vibration chamber 35 for applying vibration to the bath chamber 31 for indirectly heating the gas concentration measurement chamber 20 and the gas concentration measurement chamber 20. Include. The evaporation means 30 is for evaporating the contaminated gas dissolved in the sample contaminated water stored in the gas concentration measuring chamber 20.

Referring to FIG. 1, a bath liquid is stored in a bath 31 for a bath, and a gas concentration measuring chamber 20 is locked from the bottom to an upper predetermined portion in the bath. Therefore, when the bath liquid is heated, the sample contaminated water stored in the gas concentration measuring chamber 20 is indirectly heated. The sample contaminated water stored in the gas concentration measuring chamber 20 is indirectly heated by the bath liquid, and is gradually heated to an even temperature. A hot wire 33 for heating the bath liquid may be installed in the bath chamber 31.

Referring to Figure 1, the vibration means 35 is to generate a vibration in the gas concentration measurement chamber 20 by applying a motion to the bath liquid. Therefore, the gas concentration measuring chamber 20 is mounted to be shaken by the movement of the bath liquid. Since vibration is generated in the gas concentration measuring chamber 20, the contaminated gas dissolved in the sample contaminated water stored in the gas concentration measuring chamber 20 is more easily evaporated. On the other hand, the vibrating means 35 may be an ultrasonic vibrator installed in the chamber for water bath 31. The ultrasonic vibrator not only generates motion in the bath liquid but also serves to increase the temperature of the bath liquid by applying energy to the bath liquid. On the other hand, the evaporation means 30 preferably evaporates the gas evaporated from the sample contaminated water stored in the gas concentration measuring chamber 20 in a non-atomized state. Therefore, the evaporation means 30 can maintain the temperature of the bath liquid at 30 ° C ~ 40 ° C.

Referring to FIG. 1, the pressure maintaining odorless air supply device 40 may include an activated carbon filter 41. One end of the pressure maintaining odorless air inlet pipe 43 is connected to the pressure maintaining odorless air supply device 40. The other end of the pressure maintaining odorless air inlet pipe 43 is introduced into the gas concentration measuring chamber 20 whose upper end is sealed. The pressure maintaining odorless air supply device 40 is for supplying the pressure maintaining odorless air to the gas concentration measuring chamber 20. The pressure in the gas concentration measuring chamber 20 is maintained above a predetermined pressure by the odorless air supplied from the pressure maintaining odorless air supply device 40.

Referring to FIG. 1, the gas concentration measuring apparatus 1000 includes a gas injecting apparatus 100, an odorless air injecting apparatus 200, a gas concentration measuring sensor 310, a gas amount calculating unit 410, and a gas concentration calculating unit 420. ). The gas concentration measuring apparatus 1000 is for measuring the concentration of the polluted gas generated from the gas concentration measuring chamber 20. Since the gas concentration measuring apparatus 1000 measures the concentration of a plurality of gases that can be sensed by the human sense of smell, it is possible to determine the type of odor generated by the sample contaminated water and the degree of odor.

Referring to FIG. 1, the gas concentration measuring sensor 310 includes a gas concentration measuring sensor 313 and a sensor unit flow path 311 in which the gas concentration measuring sensor 313 is disposed. The gas concentration measuring sensor 313 may be a plurality of gas concentration measuring sensors 313-1, 313-2,..., 313-8, and 313-9 which are arranged in series on the sensor unit flow path 310P. have. The gas concentration measuring sensor 313 may include a semiconductor gas concentration measuring sensor, an electrochemical gas concentration measuring sensor, a photoionization gas concentration measuring sensor, or the like.

 1, 2 and 3, the gas concentration measuring sensors 313-2, 313-7, 313-8, and 313-9 of the gas concentration measuring sensors 313 measure the electrochemical gas concentration. As the sensor portion flow path 311 is disposed at the bending point, the sensing surface 313a of the gas concentration measuring sensor 313 is positioned perpendicular to the flow of the fluid.

3 and 4, the gas concentration measurement sensors 313-2, 313-7, 313-8, and 313-9, which are electrochemical gas concentration measurement sensors, have a sensing surface 313a flowing in the fluid. It shows higher sensing efficiency when placed perpendicular to the flow of fluid than when positioned parallel to. This can be confirmed by the graphs of FIGS. 3 and 4.

Referring to FIG. 1, the gas injection device 100 is a device for injecting a measurement gas, which is a pollutant gas generated from the gas concentration measurement chamber 20, into the sensor unit flow path 311, and the odorless air injection device 200 is It is a device for injecting odorless air into the sensor portion flow path (311).

 Referring to FIG. 1, the gas amount calculator 410 includes a gas adsorption amount calculator 411 and a gas desorption amount calculator 412. The gas adsorption amount calculator 411 and the gas desorption amount calculator 412 may be one and the same apparatus.

The gas adsorption amount calculating unit 411 has a load resistance (R) connected in series with the internal resistance of the gas concentration measuring sensor 313 as time for the measurement gas is injected into the sensor unit flow path 311 (see FIG. 3). _L , see FIG. 3) The output voltage (V _L , see FIG. 3), which is the voltage between both ends, is measured. The gas adsorption amount calculation unit 411 uses the output voltage (V _L , see FIG. 3) measured according to the passage of time when the measurement gas is injected, and the measurement gas is gas concentration during the injection time of the measurement gas. It is an apparatus which calculates the gas adsorption amount which is the quantity adsorb | sucked to the measurement sensor 313. The method for calculating the gas adsorption amount by the gas adsorption amount calculation unit 411 will be described in detail with reference to the second embodiment.

The gas desorption amount calculating unit 412 has an output voltage V that is a voltage between both ends of the load resistance R _L (see FIG. 3) as the time when the odorless air is injected into the sensor unit flow path 311 (see FIG. 3). _L , see Fig. 3). The gas desorption amount calculating unit 412 measures the output voltage V _L (see FIG. 3) measured as the time when the odorless air is injected flows, and the measurement gas is measured by the gas concentration measuring sensor ( A device for calculating a gas desorption amount which is an amount away from 313. The method for calculating the gas desorption amount by the gas desorption amount calculating unit 412 will be described in detail in the second embodiment.

Referring to FIG. 1, the gas concentration calculating unit 420 calculates the concentration of the measurement gas from the characteristic relational expression between the gas adsorption amount and the concentration of the measurement gas. The method for calculating the concentration of the measurement gas by the gas concentration calculating unit 420 will be described in detail with reference to the second embodiment.

Referring to FIG. 1, the sensor performance determining unit 430 compares the gas adsorption amount calculated by the gas adsorption amount calculating unit 411 with the gas desorption amount calculated by the gas desorption amount calculating unit 412, and compares the gas. The performance of the concentration measuring sensor 313 is determined. A method of determining the performance of the gas concentration measuring sensor 313 will be described in detail with reference to the second embodiment.

Referring to FIG. 1, Embodiment 1 has a selector valve V selectively connected to either the gas injection device 100 or the odorless air injection device 200. By the operation of the selection valve V, either one of the measurement gas and the odorless air is selectively injected into the sensor portion flow path 311. Therefore, the gas concentration measurement sensor 313 can be cleaned and stabilized by operating the selection valve V and injecting odorless air after calculating the concentration of the measurement gas. As a result, the measurement accuracy of the gas concentration measurement sensor 313 can be maintained, and the life of the gas concentration measurement sensor 313 can be increased. The selector valve V may be formed of Teflon and sus materials, which are non-polluting materials, to enhance resistance to contamination and durability. Because of this, even long time use does not cause problems such as adsorption, corrosion and contamination.

Referring to FIG. 2, the odorless air injector 200 includes an activated carbon filter 210 installed in an air flow path 220 through which atmospheric air is sucked to remove odors of inhaled atmospheric air. Therefore, the smell of atmospheric air can be removed. In addition, the odorless air injector 200 may be configured as a separate tank to directly supply odorless air. However, in this case, there is a problem in that the cost increases in use.

Referring to FIG. 1, the gas injection device 100 includes a measurement gas guide tube 120 for sucking the measurement gas. The measuring gas guide tube 120 is introduced into the gas concentration measuring chamber 210 whose one end is closed. The other end of the measurement gas guide tube 120 is connected to the selection valve V (see FIG. 1).

Referring to FIG. 1, the measurement gas guide tube 120 may be provided with a dust filter 130 that filters dust contained in the measurement gas and a water removal device 140 that filters moisture contained in the measurement gas. The dust filter 130 may include a first dust filter 130-1 and a second dust filter 130-2 installed before and after the water removing device 140. Moisture treated in the water removal device 140 is discharged to the outside by the solenoid valve.

Referring to FIG. 1, the measurement gas guide tube 120 may be provided with a flow meter 150 capable of measuring a flow rate. Meanwhile, the flow rate meter 150 may be installed on the sensor unit flow path 311 instead of the measurement gas guide tube 120.

Example 2

Example 2 relates to a gas concentration measuring method using the gas concentration measuring apparatus of Example 1.

5 is a flowchart of Embodiment 2, FIG. 6 is a graph of the first output voltage and a second output voltage, FIG. 7 is a graph of the first output voltage variation rate and a graph of the second output voltage variation rate, FIG. Represents a graph of the first output voltage change rate integration value and a graph of the second output voltage change rate integration value.

5, Embodiment 2 has a first odorless air injection step (S10). In the first odorless air injection step S10, the first odorless air is injected into the sensor unit flow path 311, which is a space in which the gas concentration measurement sensor 313 is disposed by the odorless air injection device 200. Therefore, in the first odorless air injection step S10, the selection valve V is selectively connected to the odorless air injection device 200. On the other hand, when the contaminated gas is adsorbed on the surface of the gas concentration measuring sensor 313 before the injection of the measuring gas which is the polluting gas generated from the gas concentration measuring chamber 20 (see FIG. 1), the gas concentration measuring sensor 313 There is a problem that it is difficult to accurately measure the concentration of the measurement gas because the sensitivity of. Therefore, by injecting the first odorless air before the injection of the measurement gas, it is possible to remove the polluted gas adsorbed to the gas concentration measurement sensor 313 to accurately measure the concentration of the measurement gas.

Referring to Fig. 5, the second embodiment has a gas injection step S20. In the gas injection step S20, the measurement gas is injected into the sensor unit flow path 311 by the gas injection device 100. Therefore, in the gas injection step S20, the selection valve V is selectively connected to the gas injection device 100. As the gas injection step S20 is performed, the measurement gas is adsorbed onto the sensing surface 313a of the gas concentration measurement sensor 313.

Referring to FIG. 5, Embodiment 2 has a first output voltage obtaining step S30. In the first output voltage acquiring step (S30), the output voltage V _L of the gas concentration measuring sensor 313 is measured as the time for which the measurement gas is injected flows, and corresponds to the flow of time for which the measurement gas is injected. A first output voltage which is an output voltage V _L is obtained. The curve between the points P1 and P2 in Fig. 7 is a graph of the first output voltage obtained in the first output voltage acquisition step. The first output voltage acquired in the first output voltage obtaining step is the sum of the output voltages V _L for the respective gas concentration measuring sensors 313-1, 313-2,..., 313-8, and 313-9. This may be the mean of these sums. Hereinafter, the first output voltage obtained in the first output voltage acquiring step is the output voltage V _L of each of the gas concentration measuring sensors 313-1, 313-2,..., 313-8, and 313-9. The case of sum is demonstrated.

5, Example 2 has a gas adsorption amount calculating step S40. In the gas adsorption amount calculating step (S40), the gas adsorption amount, which is the amount of the measurement gas adsorbed to the gas concentration measuring sensor 313, is calculated from the first output voltage. The gas adsorption amount is the sum of the amounts of the measurement gases adsorbed to the respective gas concentration measurement sensors 313-1, 313-2, ..., 313-8, and 313-9.

Referring to FIG. 5, the gas adsorption amount calculating step S40 includes a first output voltage fluctuation rate obtaining step S42 and a first output voltage fluctuation rate integration value obtaining step S44.

In the first output voltage change rate obtaining step (S42), a first output voltage change rate, which is a change rate of the output voltage V _L according to the passage of time, when the measurement gas is injected, is obtained. The curve between the points Q1 and Q2 in Fig. 7 is a graph of the first output voltage change rate obtained in the first output voltage change rate obtaining step. That is, the first output voltage change rate may be represented by a slope graph of a curve between P1 and P2 points shown in FIG. 6.

In the first output voltage change rate integration value obtaining step (S44), the first output voltage change rate integrated value, which is a value obtained by integrating the first output voltage change rate with the passage of time from which the measurement gas is injected, from the first output voltage change rate. Will be obtained. The area S1 in FIG. 8 is an area formed by the curve and the time axis between the points Q1 and Q2 in FIG. 7 and represents an integrated value of the first output voltage variation rate during the time that the measurement gas is injected. The first output voltage change rate integrated value thus obtained is measured by the gas concentration measuring sensors 313-1, 313-2,..., 313-8, and 313-9 as the gas injection step S20 is performed. The gas adsorption amount, which is the sum of the amounts adsorbed on the substrate, is shown. The gas adsorption amount calculation method by this method is called a sensor chromatogram area extraction method.

Referring to FIG. 5, Example 2 has a gas concentration calculating step S50. In the gas concentration calculating step S50, the concentration of the measured gas injected in the gas injection step S20 is calculated using the gas adsorption amount obtained in the gas adsorption amount calculating step S40. The concentration of the measurement gas is obtained by using a characteristic relationship between the gas adsorption amount obtained in the gas adsorption amount calculation step S40 and the concentration of the measurement gas. The characteristic relation can be obtained by a regression analysis method between the sample gas adsorption amount, which is the gas adsorption amount obtained for a plurality of sample measurement gases, and the concentration of the sample measurement gas. Since this method is a method that is frequently used statistically, detailed description thereof will be omitted.

5, Embodiment 2 has a second odorless air injection step (S60). The second odorless air injection step S60 is performed after the gas adsorption amount calculation step S40 or after the gas concentration calculation step S50 is performed. In the second odorless air injection step (S60), the second odorless air is injected into the sensor unit flow path 311, which is a space in which the gas concentration measurement sensor 313 is disposed by the odorless air injection device 200. The second odorless air can be the same odorless air as the first odorless air. Meanwhile, in the second odorless air injection step S60, the selection valve V is selectively connected to the odorless air injection device 200.

Referring to Fig. 5, Embodiment 2 has a second output voltage acquisition step S70. In the second output voltage acquiring step S70, the output voltage V _L of the gas concentration sensor 313 is measured as the time when the second odorless air is injected flows, and corresponds to the flow of the second odorless air injection time. A second output voltage which is an output voltage V _L is obtained. The curve between the points P2 and P3 in Fig. 6 is a graph of the second output voltage obtained in the second output voltage acquisition step. The second output voltage acquired in the second output voltage obtaining step S70 is an output voltage V _L for each of the gas concentration measuring sensors 313-1, 313-2,..., 313-8, and 313-9. Sum of

5, Example 2 has a gas desorption amount calculating step S80. In the gas desorption amount calculating step (S80), the gas desorption amount, which is a quantity away from the gas concentration measuring sensor 313, is calculated from the second output voltage. The gas desorption amount is measured by each of the gas concentration measuring sensors 313-1, 313-2 that the measured gas adsorbed to the respective gas concentration measuring sensors 313-1, 313-2,..., 313-8, 313-9. ,…, 313-8, 313-9).

Referring to FIG. 5, the gas desorption amount calculating step S80 includes a second output voltage fluctuation rate obtaining step S82 and a second output voltage fluctuation rate integration value obtaining step S84.

In the second output voltage change rate obtaining step (S82), a second output voltage change rate, which is a change rate of the output voltage V _L according to the flow of the second odorless air injection time, is obtained from the second output voltage. The curve between the Q2 and Q3 points in Fig. 7 is a graph of the second output voltage change rate obtained in the second output voltage change rate obtaining step. That is, the second output voltage change rate may be represented by a slope graph of a curve between P2 and P3 points shown in FIG. 6.

In the second output voltage change rate integration value obtaining step (S84), the second output voltage change rate integrated value, which is a value obtained by integrating the second output voltage change rate according to the flow of the injection time of the second odorless air, from the second output voltage change rate. Will be obtained. The area S2 of FIG. 8 is an area formed by the curve and the time axis between the points Q2 and Q3 in FIG. 7 and represents the second output voltage change rate integration value during the second odorless air injection time. The second output voltage change rate integrated value thus obtained is measured by the respective gas concentration measuring sensors 313-1, 313-2, ..., 313-8, 313 as the second odorless air injection step S20 is performed. The amount of gas desorption which is the sum of the amounts away from -9) is shown. The gas desorption amount calculation method by this method is called a sensor chromatogram area extraction method.

Referring to FIG. 5, Embodiment 2 includes a sensor performance determination step S90 of determining the performance of the gas concentration measurement sensor 313. In the sensor performance determination step (S90), the gas adsorption amount calculated in the gas adsorption amount calculation step (S40) and the gas desorption amount calculated in the gas desorption amount calculation step (S80) are compared with each other. You will judge performance. For example, when the difference between the gas adsorption amount and the gas desorption amount for the gas concentration measurement sensor 313 is managed within 3%, the adsorption and desorption of the measurement gas to the gas concentration measurement sensor 313 sensing surface 313a is performed. Since this is reversible, it can be judged that the performance of the gas concentration measuring sensor 313 is good. On the other hand, if the difference between the gas adsorption amount and the gas desorption amount for the gas concentration measurement sensor 313 is greater than 3 to 5%, the measurement gas is adsorbed to the gas concentration measurement sensor 313 and then desorption is performed. It is determined that the performance of the gas concentration measuring sensor 313 is poor. The performance of the gas concentration sensor 313 may be used as an indicator of whether the activated carbon filter 210 of the odorless air injector 200 is replaced and whether the pipe of the gas concentration measuring apparatus is contaminated.

Although not shown in FIG. 5, in Embodiment 2, the pollutant gas adsorbed by the gas concentration measuring sensor 313 falls off from the gas concentration measuring sensor 313 as the first odorless air injection step S10 is performed. Quantity calculation step can be performed. The polluted gas desorption amount calculating step may be performed by a method similar to the gas desorption amount calculating step S80. As a result, the amount of polluting gas falling from the sensing surface 313a of the gas concentration measuring sensor 313 can be measured, and thus, there is an advantage in that the pollution degree of air can be reversed.

Although not shown in FIG. 5, Embodiment 2 may be repeatedly performed from S20 to S80. In this case, the time for injecting the second odorless air in the second odorless air injection step S60 may be longer than the time for injecting the measurement gas in the gas injection step S20. Since the time for injecting the second odorless air is longer than the time for injecting the measurement gas in the gas injection step S20, the sensitivity of the gas concentration measuring sensor 313 to the measurement gas may be increased. When the measuring gas is injected into the sensor unit flow path 311 for a long time, the amount of the measuring gas attached to the sensing surface 313a of the gas concentration measuring sensor 313 is increased, so that the characteristic of the gas concentration measuring sensor 313 is increased. Is changed. Therefore, when the second odorless air is injected for a long time and there is no change in the gas desorption amount with respect to the sensing surface 313a of the gas concentration measuring sensor 313, a more precise measurement value can be obtained by injecting the measurement gas. There is this.

Tables below show hydrogen sulfide (H ₂ S) of various concentrations measured by a conventional voltage comparison method and the value measured by the sensor chromatogram area extraction method of Example 2.

Measuring gas: H ₂ S 1 ppm, sensor model: MICS 5521 (manufacturer E2V, Switzerland) Base (Vair) Max (Vgas) Vgas / Vair Sout area 1st 1.57 2.10 1.34 50.4 2nd 1.59 2.09 1.31 49.6 3rd 1.62 2.08 1.28 50.5 Average 1.59 2.09 1.31 50.17 Standard Deviation (S.D) 0.03 0.01 0.03 0.49 Relative standard deviation (% RSD) 1.58 0.48 2.05 0.98

In the table above Vair is exposure to odorless air indicates the output voltage (V _L) in the gas concentration measuring sensor 313, Vgas the output voltage (V _L in the gas concentration measuring sensor 313 when exposed to the measurement gas ), And Sout_area represents the first output voltage change rate integration value to the gas adsorption amount obtained by the sensor chromatogram area extraction method.

Measuring gas: H ₂ S 5 ppm, gas concentration measuring sensor: MICS 5521 (manufacturer E2V, Switzerland) Base (Vair) Max (Vgas) Vgas / Vair Sout area 1st 1.53 2.69 1.76 103.9 2nd 1.60 2.55 1.59 106.7 3rd 1.65 2.41 1.46 103.0 Average 1.59 2.55 1.60 104.53 Standard Deviation (S.D) 0.06 0.14 0.15 1.93 Relative standard deviation (% RSD) 3.78 5.49 9.29 1.85

Measuring gas: H ₂ S 10 ppm, gas concentration measuring sensor: MICS 5521 (manufacturer E2V, Switzerland) Base (Vair) Max (Vgas) Vgas / Vair Sout area 1st 1.54 2.81 1.82 133.8 2nd 1.67 2.71 1.62 129.8 3rd 1.76 2.67 1.52 129.4 Average 1.66 2.73 1.65 131.00 Standard Deviation (S.D) 0.11 0.07 0.16 2.43 Relative standard deviation (% RSD) 6.68 2.64 9.45 1.86

Measuring gas: H ₂ S 1ppm, gas concentration measuring sensor: TGS 2602 (manufactured by Figaro Research Institute, Japan) Base (Vair) Max (Vgas) Vgas / Vair Sout area 1st 1.42 2.19 1.54 65.2 2nd 1.44 2.10 1.46 68.4 3rd 1.44 2.07 1.44 64.1 Average 1.43 2.12 1.48 65.90 Standard Deviation (S.D) 0.01 0.06 0.06 2.23 Relative standard deviation (% RSD) 0.81 2.95 3.75 3.39

Measuring gas: H ₂ S 5ppm, gas concentration measuring sensor: TGS2602 (manufactured by Figaro Research Institute, Japan) Base (Vair) Max (Vgas) Vgas / Vair Sout area 1st 1.43 2.95 2.06 152.7 2nd 1.48 2.94 1.99 150.5 3rd 1.59 2.92 1.84 144.4 Average 1.50 2.94 1.96 149.20 Standard Deviation (S.D) 0.08 0.02 0.12 4.30 Relative standard deviation (% RSD) 5.46 0.52 5.87 2.88

Measuring gas: H ₂ S 10ppm, gas concentration measuring sensor: TGS2602 (manufactured by Figaro Research Institute, Japan) Base (Vair) Max (Vgas) Vgas / Vair Sout area 1st 1.55 3.48 2.25 206.9 2nd 1.65 3.55 2.15 204.6 3rd 1.76 3.40 1.93 201.7 Average 1.65 3.48 2.11 204.40 Standard Deviation (S.D) 0.11 0.08 0.16 2.61 Relative standard deviation (% RSD) 6.35 2.16 7.62 1.27

As can be seen from the results of Tables 1 to 6 above, in the conventional voltage measurement method, the variation of the Vair value occurs as the number of measurements is repeated, and the relative standard deviation of the Vair value increases as the concentration of the measurement gas increases. It can be seen that the larger.

In contrast, the sensor chromatogram area extraction method exhibits a low relative standard deviation even when the concentration of the measurement gas is increased and the number of times of measurement is increased.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

20: chamber for measuring gas concentration
30: Evaporation means 31: Chamber for hot water
35: vibration means
100: gas injection device 120: measuring gas guide tube
130: dust filter 140: moisture removal device
200: odorless air injector 210: activated carbon filter
220: Air flow path
313: gas concentration measuring sensor
411: gas adsorption amount calculation unit 412: gas desorption amount calculation unit
420: gas concentration calculation unit 430: sensor performance determination unit
1000: gas concentration measuring device

Claims (14)

A gas concentration measuring chamber 20 in which sample contaminated water is stored;
Evaporation means (30) for evaporating contaminated gas dissolved in sample contaminated water stored in the gas concentration measuring chamber (20);
A gas concentration measuring apparatus (1000) having a gas concentration measuring sensor (313) for measuring the concentration of the polluting gas generated from the gas concentration measuring chamber (20);
Including but not limited to:
The evaporation means 35 is a water quality using a gas concentration measuring sensor, characterized in that to evaporate the gas evaporated from the sample contaminated water temporarily stored in the gas concentration measuring chamber 20 in a non-atomized state Pollution measurement system. A gas concentration measuring chamber 20 in which sample contaminated water is stored;
Evaporation means (30) for evaporating contaminated gas dissolved in sample contaminated water stored in the gas concentration measuring chamber (20);
A gas concentration measuring apparatus (1000) having a gas concentration measuring sensor (313) for measuring the concentration of the polluting gas generated from the gas concentration measuring chamber (20);
Including,
The evaporation means (30) is a water pollution measurement system using a gas concentration measuring sensor, characterized in that it comprises a chamber for heating indirectly heating the gas concentration measuring chamber (20). The method of claim 2,
The evaporation means (30) is a water pollution measurement system using a gas concentration measuring sensor, characterized in that it comprises a vibration means for applying a vibration to the gas concentration measuring chamber (20). The method of claim 3,
The vibration means 35 generates a vibration in the gas concentration measurement chamber 20 by applying a movement to the bath liquid stored in the bath chamber 31 to indirectly heat the gas concentration measurement chamber 20. The water pollution measurement system using a gas concentration measurement sensor, characterized in that it comprises an ultrasonic vibrator installed in the chamber for the bath. The method according to any one of claims 2 to 4 ,
The evaporation means 35 is a water pollution using a gas concentration measurement sensor, characterized in that to evaporate the gas evaporated from the sample contaminated water temporarily stored in the gas concentration measurement chamber 20 in a non-atomized state. Measuring system. A gas concentration measuring chamber 20 in which sample contaminated water is stored;
Evaporation means (30) for evaporating contaminated gas dissolved in sample contaminated water stored in the gas concentration measuring chamber (20);
A gas concentration measuring apparatus (1000) having a gas concentration measuring sensor (313) for measuring the concentration of the polluting gas generated from the gas concentration measuring chamber (20);
Including, but the gas concentration measuring apparatus 1000,
A gas injection device (100) for injecting a measurement gas which is a pollutant gas generated from the gas concentration measurement chamber (20) in a space where the gas concentration measurement sensor (313) is disposed;
As the measurement gas is injected, an output voltage value V _L , which is a voltage between the load resistance R _L connected in series with the gas concentration measurement sensor 313, is measured, so that the measurement gas is measured. A gas adsorption amount calculator 411 for calculating a gas adsorption amount that is an amount adsorbed by the gas concentration sensor 313;
A gas concentration calculation unit (420) for calculating a concentration of the measurement gas injected from the gas injection device (100) from the adsorption amount of the measurement gas calculated from the gas adsorption amount calculation unit (411);
Water pollution measurement system using a gas concentration measurement sensor comprising a. The method according to claim 6,
The gas adsorption amount calculation unit 411,
Obtain a first output voltage of the output voltage (V _L) in accordance with the flow of the measurement gas injection time and the rate of change of the output voltage (V _L) in accordance with the first flow of the measurement gas injection time from the output voltage Obtaining a first output voltage change rate, and obtaining a first output voltage change rate integrated value, which is a value obtained by integrating the first output voltage change rate according to the flow of the measurement gas injection time from the first output voltage change rate, The water pollution measurement system using the gas concentration measurement sensor, characterized in that for calculating the gas adsorption amount from the first output voltage change rate integration value. The method according to claim 6,
Odorless air injector 200 for injecting odorless air into the space where the gas concentration sensor 313 is disposed;
The gas desorption amount calculating unit 412 which measures the output voltage V _L as the time of injecting the odorless air is calculated, and calculates a gas desorption amount which is the amount of the measurement gas separated from the gas concentration measuring sensor 313. );
The performance of the gas concentration measuring sensor 313 is determined by comparing the gas adsorption amount calculated by the gas adsorption amount calculating unit 411 with the gas desorption amount calculated by the gas desorption amount calculating unit 412. Sensor performance determination unit 430;
Water pollution measurement system using a gas concentration measurement sensor comprising a. 9. The method of claim 8,
The gas desorption amount calculation unit 412,
Obtaining a second output voltage wherein the output voltage (V _L) in accordance with the odorless air flow injection time, and the rate of change of the output voltage (V _L) in accordance with from the second output voltage to the flow of the odorless air injection time Obtaining a second output voltage change rate, and obtaining a second output voltage change rate integration value, which is a value obtained by integrating the second output voltage change rate according to the flow of the odorless air injection time from the second output voltage change rate, And a gas desorption amount is calculated from a second output voltage change rate integration value. 10. The method of claim 9,
The odorless air injection device 200 includes an activated carbon filter 210 connected to an air flow path 220 for injecting odorless air into a space where the gas concentration sensor 313 is disposed. Water pollution measurement system using measurement sensor. 10. The method of claim 9,
In order to selectively inject either one of the measurement gas and the odorless air into the space where the gas concentration measurement sensor 313 is disposed, the gas injection device 100 and the odorless air injection device 200 may be Water pollution measurement system using a gas concentration measurement sensor, characterized in that it comprises a selection valve (V) which is selectively connected. The method of claim 9, wherein the gas injection device 100,
A measurement gas guide tube 120 connected to the gas concentration measurement chamber 20 to guide the measurement gas to a selection valve V;
A dust filter (130) installed on the measurement gas guide tube (120) to filter dust from the measurement gas;
A water removal device (140) installed on the measurement gas guide tube (120) to filter moisture from the measurement gas;
Water pollution measurement system using a gas concentration measurement sensor comprising a. 10. The method of claim 9,
The gas concentration calculator 420,
A water pollution measurement system using a gas concentration measurement sensor, characterized by extracting the concentration of the measurement gas from the characteristic relationship between the gas adsorption amount and the concentration of the measurement gas. The method of claim 13,
The characteristic relation is
A water pollution measurement system using a gas concentration measurement sensor, characterized in that obtained by a regression analysis method between the sample gas adsorption amount, which is the gas adsorption amount measured for a plurality of sample measurement gases, and the concentration of the sample measurement gas.

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