WO2017065395A1 - Appareil d'analyse de métaux lourds d'articles multiples en temps réel, procédé d'analyse de métaux lourds d'articles multiples en temps réel, et procédé de fabrication de capteur d'appareil d'analyse de métaux lourds - Google Patents

Appareil d'analyse de métaux lourds d'articles multiples en temps réel, procédé d'analyse de métaux lourds d'articles multiples en temps réel, et procédé de fabrication de capteur d'appareil d'analyse de métaux lourds Download PDF

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WO2017065395A1
WO2017065395A1 PCT/KR2016/008179 KR2016008179W WO2017065395A1 WO 2017065395 A1 WO2017065395 A1 WO 2017065395A1 KR 2016008179 W KR2016008179 W KR 2016008179W WO 2017065395 A1 WO2017065395 A1 WO 2017065395A1
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Prior art keywords
sample
unit
redox
heavy metal
measurement
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PCT/KR2016/008179
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English (en)
Korean (ko)
Inventor
손창식
황경엽
김유정
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(주)썬텍엔지니어링
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Priority claimed from KR1020150142823A external-priority patent/KR101631186B1/ko
Priority claimed from KR1020150142824A external-priority patent/KR101652086B1/ko
Application filed by (주)썬텍엔지니어링 filed Critical (주)썬텍엔지니어링
Publication of WO2017065395A1 publication Critical patent/WO2017065395A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water

Definitions

  • the present invention relates to a heavy metal analysis device, a method and a method for manufacturing a sensor of the heavy metal analysis device, and more particularly, after stabilization to an optimal state for measuring the sample to be measured, at least one heavy metal is detected simultaneously, but included in the sample After determining the type of heavy metal, the real-time multi-item heavy metal analysis device, real-time multi-item heavy metal analysis method and the heavy metal analysis to measure the content of the heavy metal by selectively driving the sensor capable of measuring the determined at least one heavy metal A method for manufacturing a sensor of a device.
  • water environmental standards or water
  • water facilities such as river water, lake water, water supply, reservoir, groundwater, water purification facilities, and swimming pools
  • water Use water and perform water quality control to meet the purpose of using the “sample” water.
  • trace amount of substances contained in water should be detected and the amount of detected substances should be measured.
  • the detection of heavy metals in water is performed by taking a sample rather than an on-site analysis, and performing a pre-treatment process in several steps according to the characteristics of the measured sample in a laboratory. It is measured using.
  • the spectroscopic methods include chromatography (Gel Permeation Chromatography (GPC), Gas Chromatography (GC), High Performance Liquid Chromatography (HPLC), etc.), Inductive Plasma Spectroscopy (ICP-MS), Atomic Emission Spectroscopy (AES), etc. .
  • GPC Gel Permeation Chromatography
  • GC Gas Chromatography
  • HPLC High Performance Liquid Chromatography
  • ICP-MS Inductive Plasma Spectroscopy
  • AES Atomic Emission Spectroscopy
  • these spectroscopic methods can analyze multiple heavy metals at once, but require expensive external analysis equipment.
  • the accuracy is reduced due to the interference error caused by the change of the measurement environment, it is impossible to quickly respond to heavy metal contamination because a long analysis time is required.
  • Electrochemical analytical methods are used in various fields due to economical efficiency, relatively short analysis time, and high accuracy.
  • blood glucose sensors, biomarkers, and the detection of a specific substance such as a specific substance is widely used, but most of the measuring sensors used for electrochemical analysis is used as a one-time equipment.
  • the electrochemical sensor may modify the electrode modifications on the surface of the measuring electrode according to the species to be detected to increase the sensitivity of the electrode and increase the selectivity of detection.
  • the life of the sensor is determined by the material electrodeposition on the sensor electrode, the modification method, and the electrochemical measurement method, there is a demand for a method of maximizing the life of the sensor.
  • an object of the present invention is to stabilize at the optimum state for measuring a sample to be measured, and then to simultaneously detect one or more heavy metals, and to first determine the type of heavy metals included in the sample, and then to measure at least one or more heavy metals determined.
  • the present invention provides a real-time multi-item heavy metal analysis device, a real-time multi-item heavy metal analysis method, and a sensor manufacturing method of the heavy metal analysis device to selectively drive the sensor to measure the content of the heavy metal.
  • a sample measuring unit including a water pollutant measuring module configured to output a pollution degree value for a pollutant; And the oxidation supplied to the reaction sensor when the redox current value having the change is measured when a change in the oxidation reduction current value measured by the reaction sensor occurs in the sample flowing into the water flow path.
  • It includes a control module including a heavy metal detection control unit for detecting and classifying pollutants by a reducing supply power value, and activating a selective measurement sensor corresponding to the classified pollutants and receiving and outputting a pollutant value for the pollutants. Characterized in that.
  • the measuring cell may include: a main body including a water inlet through which a sample to be measured is introduced, a sensor coupler, and a water outlet through which the sample is discharged; And the water flow path connected to the water inlet of the main body and connected to the water outlet via the sensor coupler to form the pattern.
  • the water pollutant measuring module includes a reaction sensor at an inlet of an incoming sample and applies a redox supply power to the sample through the reaction sensor immersed in the incoming sample to generate a redox, and by the redox phenomenon Measures the generated redox current value, calculates the redox current change due to the difference from the redox current value measured by the previous redox supply, and calculates the redox current change outside the preset normal range.
  • a reaction sensor unit for outputting a corresponding redox supply power value causing the change in the redox current;
  • a plurality of pollution measurement to measure and output the contamination level of the detected pollutants with a pollution measurement sensor for detecting different pollutants at the rear end of the reaction sensor for the inflow direction of the sample and the pollution degree of the detected pollutants
  • a pollution measurement unit including a control unit, selected by at least one pollution measurement unit of the pollution measurement unit under control, and driving the selected pollution measurement unit to measure and output the pollution level of the corresponding pollutant and the pollutant;
  • a storage unit storing a pollutant DB by a range of redox power supplies defining a pollutant by a range of redox supply power and a pollution measurement unit by a pollutant; And determining a pollutant corresponding to the redox supply power value input from the reaction sensor unit by referring to the pollutant DB for each range of the redox power source, and controlling the pollution measurement sensor unit corresponding to the pollutant to determine the pollution
  • the reaction sensor is installed at a vertex on the water flow path closest to the inlet, and the measuring sensor is installed at each of the other vertices on the water flow path.
  • the pattern of the water flow path is characterized in that it is configured in a sawtooth shape.
  • the reaction sensor unit measures a redox current value of a sample introduced with a reaction sensor, and measures at least two redox currents that output the redox supply power value when the amount of change in the redox current is outside the normal range. part; And receiving a redox supply power, which is connected to the redox current measuring units and is a measurement voltage to be supplied to the redox current measuring unit, and selectively supplies the redox supply power to the redox current measuring unit under the control of the controller. And a sensor selector.
  • the pollution measurement sensor unit a plurality of the pollution measurement unit; And a measurement sensor selection unit connected to the plurality of pollution measurement units and selectively supplying the measurement voltage supplied from the measurement voltage supply unit to the pollution measurement unit under the control of the controller.
  • the apparatus may further include: a sample stabilization unit receiving water from a field water supply pipe as a sample, measuring and outputting electrical conductivity and pH of the sample to be supplied, and stabilizing the sample and providing the sample to the sample supply unit. It is done.
  • the sample stabilization unit includes an electrical conductivity sensor and a pH sensor unit for measuring the electrical conductivity and pH of the water; a sample state measuring unit for measuring and outputting electrical conductivity and pH; and the control corresponding to the measured electrical conductivity and pH.
  • a first stabilization unit including a measurement auxiliary solution supply unit supplying a measurement auxiliary solution to the sample to be measured under the control of a module; And a second stabilization unit under the control of the control module to submerge the sample stabilized in the first stabilization unit by applying a rotational force to the sample to remove bubbles from the sample, wherein the control module is configured to remove from the sample stabilization unit.
  • the sample supply unit After stabilizing the sample by controlling the sample stabilization unit according to the electrical conductivity and pH input, the sample supply unit is controlled to supply the stabilized sample to the sample measuring unit, and in response to receiving heavy metal detection information from the sample measuring unit, It further comprises a sample stabilization control unit for obtaining and outputting the measurement information including the heavy metal detection amount.
  • the water supply pipe is characterized in that any one of the water supply pipe for supplying sea water, ground water supply pipe for supplying ground water, wastewater treatment discharge pipe, water supply pipe and residential area network.
  • the apparatus includes: an auxiliary solution input DB defining a measurement auxiliary solution supply amount according to electrical conductivity and pH value, and a storage unit storing a heavy metal classification DB defining heavy metal and heavy metal contamination measurement sensor unit information by redox power supply value range ; An interface unit connected to the sample state measurement unit, a measurement auxiliary solution supply unit, a reaction sensor unit, and a plurality of pollution measurement sensor units to transmit and receive data; And a display unit which displays information on the selected heavy metal and the amount of heavy metal included in the sample, wherein the sample stabilization control unit receives an electrical conductivity and a pH value from a sample state measurement unit through the interface unit, and the auxiliary The measurement auxiliary solution input amount corresponding to the input conductivity and pH value is determined by referring to the solution input DB, and the measurement auxiliary solution supply part is controlled by the determined measurement auxiliary solution input amount to stabilize the measurement auxiliary solution by adding it to the sample.
  • the second stabilizing unit is characterized in that the rotating impeller.
  • the terthiophene monomer is characterized in that 3- (2-aminopyrimidyl) -2,2: 5,2-terthiophene (APT).
  • Real-time multi-item heavy metal analysis method for achieving the above object: the redox current value by the redox generated by applying a redox supply power of the sample supplied through the reaction sensor unit when the sample to be measured is supplied Measure the redox supply power value by comparing the measured redox current value with the previous redox current value and measuring the redox supply power value when the change exceeds the preset normal range.
  • a pollutant classification process of identifying and classifying a pollutant corresponding to the measured redox supply power value by referring to a pollutant DB for each redox supply power source of a storage unit;
  • a pollution measuring unit selecting process of identifying a pollution measuring unit capable of measuring the identified and classified pollutants, and controlling a measuring sensor selecting unit to supply a measurement voltage to the identified pollution measuring unit;
  • a pollution measurement process of measuring a pollution degree of the identified and classified pollutants through a pollution measurement unit supplied with the measurement voltage.
  • the method may further include a sample stabilization process configured to stabilize and supply a sample to be supplied to the water flow path of the measurement cell, which is configured at the front of the measurement cell having the water flow path including the reaction sensor and the measurement sensors. It characterized in that the process after the redox power value measurement process is performed for the sample that is stabilized through the stabilization process.
  • the pollutant classification process may include: setting a normal idle state to set the pollution measuring unit to an idle state when the amount of change in the redox current is within a normal range; And when the amount of change in the redox current falls outside the normal range, identifying and classifying a contaminant corresponding to the redox supply power range to which the measured redox supply power value belongs by referring to the pollutant DB for each redox supply power in a storage unit. It characterized in that it comprises a pollutant classification step.
  • the sample stabilization process may include a first stabilization process in which a control module measures electrical conductivity and pH, determines an input amount of a measurement auxiliary solution corresponding to the measured electrical conductivity and pH, and inputs the sample to the sample; And a second stabilizing process of driving a second stabilizing unit configured to be immersed in the sample under control of a control module to apply bubbles to the sample to remove bubbles of the sample.
  • Method for manufacturing a measuring sensor of a real-time multi-item heavy metal analysis device for achieving the above object:
  • gold, nickel and APT on the electrode An electrodeposition process that is electrically electrodeposited on; And a nickel removal process for selectively removing nickel on the electrodeposited electrode.
  • the electrodeposition process is carried out on the electrode, 1 x 10 -2 M gold chloride trihydrate (HAuCl 4 ⁇ 3H 2 O), 1.5 x 10 -2 M nickel sulfide hexahydrate (NiSO 4 6 H 2 O), and dimetalsulfoxide (Dimethylsulfoxide: Sulfuric acid solution production step of producing 10 M L of 1 x 10 -2 M APT dissolved in DMSO) to 1.5 M sulfuric acid solution; And it is characterized in that it comprises a plating step of plating a gold, nickel and APT at a time by putting a constant current in the sulfuric acid solution.
  • the nickel removal process is characterized in that to form a porous gold-APT composite structure by selectively removing nickel electrochemically on the electrode plated with gold, nickel and APT.
  • the method further includes a pH control step of adjusting the pH of the sample solution to 1 to 2, wherein the electrodeposition step further comprises a current control step of adjusting the current to 1 to 5 ⁇ A, wherein the current is adjusted It characterized in that the sulfuric acid solution generation step and the plating step in the state.
  • the method further includes a pH adjustment step of adjusting the pH of the sample solution to 1.5, wherein the electrodeposition step further includes a current adjustment step of adjusting the current to 2 ⁇ A, wherein the current is adjusted. It characterized in that the sulfuric acid solution generation step and the plating step.
  • the present invention is provided with a reaction sensor in the water inlet portion of the water flow path of the measuring cell to determine whether the incoming water satisfies the conditions of the water quality of the water quality management area, and when the conditions are satisfied by keeping the pollution measuring sensors idle It has the effect of maximizing the reproducibility and life of the measuring sensors.
  • the present invention has the effect of preventing unnecessary power consumption because the measurement sensor is not driven when the water quality of the sample is good.
  • the present invention is equipped with a reaction sensor in the water inlet portion of the water flow path of the sample measuring unit, and after determining the type of contamination to be measured first through the reaction sensor, it is unnecessary to drive the pollution measuring sensors according to the analysis results By keeping the pollution measuring sensor idle, the reproducibility and life of the measuring sensors can be maximized, and the power consumption can be minimized.
  • the present invention measures the electrical conductivity and pH of the water supplied from the field in the sample stabilization unit, and stabilizes the water to be measured, that is, the sample to be supplied by supplying the measurement auxiliary solution corresponding to the measured electrical conductivity and pH to the water It has the effect of supplying a sample optimized for measurement, and has the effect of detecting heavy metals more accurately.
  • the present invention has the effect of reducing the measurement error by stabilizing the sample by removing the air bubbles generated in the sample having a rotary impeller introduced.
  • the present invention automatically stabilizes the sample as described above, there is no need for the administrator to perform the pretreatment process one by one. As it can be seen, there is no need to take extra time to test whether the sample is stabilized.
  • the senor for detecting Cr (VI) according to the present invention is capable of selective detection without the interference effect of other active species, and also does not require additional electrodeposition time, thereby quickly reducing the Cr (VI) present in industrial or ground water. As it can be detected, it has an effect that can be used for real-time field analysis.
  • an electrode modified with a polymer as the heavy metal detection sensor according to the present invention, it has the effect of stably detecting a plurality of heavy metals at the same time without deterioration of performance, that is, a decrease in sensitivity even when used for a long time.
  • FIG. 1 is a view showing the configuration of a real-time multi-item heavy metal analysis device according to the present invention.
  • FIG. 2 is a view showing the configuration of the sample measuring unit of the real-time multi-item heavy metal analysis device according to the present invention.
  • FIG. 3 is a view showing a detailed configuration of the water pollutant measurement module of the sample measuring unit according to the present invention.
  • FIG. 4 is a conceptual diagram of a measurement sensor for detecting heavy metals according to an embodiment of the present invention.
  • FIG. 5 is an SEM image of an electrode surface electrochemically electrodeposited with an aminopyrimidyl terthiophene monomer and graphene on a glassy carbon electrode.
  • HMI 6 is a SWV analysis result according to the synthesis conditions of the electrodeposited material of the solution containing 500 ppb of heavy metal ions (HMI).
  • Figure 7 is a result of confirming the optimum conditions
  • Figure 7 (A) is a result according to the type of the supporting electrolyte containing 500 ppb of heavy metal ions (HMI)
  • Figure 7 (B) is a result of the pH change of the solution 7 (C) shows the result of the deposition time change.
  • FIG. 8 is a graph (A) and a calibration curve (B) for detecting heavy metal ions (HMI) analyzed by square wave voltammetry (SWV) within each heavy metal concentration range at 1 ppb to 10 ppm under optimal conditions. Is the result.
  • HMI heavy metal ions
  • SWV square wave voltammetry
  • FIG. 9 is a graph showing a graph (A) and a calibration curve (B) for detecting heavy metal ions (HMI) analyzed by chronocoulmetry (CC) within each heavy metal concentration range at 1 ppb to 10 ppm under optimal conditions. .
  • Figure 10 shows a schematic diagram of a measuring sensor for detecting the Cr (VI) according to an embodiment of the present invention.
  • FIG. 11 compares the sensitivity after detecting 1 ppm of Cr (VI) with each modified electrode after reforming the measuring sensor step by step.
  • Figure 12 shows the surface image of the electrode completed in the present invention.
  • FIG. 13 shows the effects of (A) pH and (B) electrolyte on 1 ppm of Cr (VI) on the electrode.
  • FIG. 14 shows signal changes for each concentration (A) and corresponding calibration curves obtained by linear scanning voltammetry with electrodes modified with a composite plating layer of porous gold and APT in the range of 10 ppm to 5 ppm under optimal conditions. (B) is shown.
  • 15 is a view showing the detailed configuration of the sample stabilization unit of the real-time multi-item heavy metal analysis device according to the present invention.
  • 16 is a view showing an example of the actual configuration of the sample stabilization unit, the sample supply unit and the sample measuring unit of the real-time multi-item heavy metal analysis device according to the present invention.
  • 17 is a view showing the configuration of the sample stabilization control unit of the control module of the real-time multi-item heavy metal analysis apparatus according to the present invention.
  • FIG. 18 is a flowchart illustrating a real-time multi-item heavy metal detection method through selective electrode activation according to the present invention.
  • 19 is a flowchart illustrating an electrode activation method of a real-time multi-item heavy metal detection method according to an embodiment of the present invention.
  • 20 is a flowchart illustrating a sample stabilization method of the real-time multi-item heavy metal detection method according to the present invention.
  • FIG. 1 is a view showing the configuration of a real-time multi-item heavy metal analysis device according to the present invention.
  • the real-time multi-item heavy metal analyzing apparatus of the present invention includes a sample measuring unit 200, a sample supplying unit 300, a control module 400, and a storage unit 430 according to the first embodiment.
  • the sample stabilization unit 100, the input unit 440, the output unit 450, and the interface unit 460 may be further included.
  • the real-time multi-item heavy metal analysis device is connected to the water supply pipe of the site detects heavy water, which is a contaminant contained in the water of the site supplied through the water supply pipe, that is, the sample, and outputs the detected heavy metal information and detection amount.
  • the site may be a river, a lake, a water supply source, a reservoir, groundwater, seawater, deep water such as deep seawater, a water purification plant, a swimming pool, a pipe network for supplying water to a city premises.
  • the sample supply unit 300 is connected to the water supply pipe receiving the water from the site according to an embodiment receives the water in the field in real time as a sample to supply to the sample measuring unit 200.
  • the sample measuring unit 200 receives the sample supplied from the sample supply unit 300, detects the type of heavy metal and the amount of each heavy metal included in the sample, and outputs the sample to the control module 400.
  • the storage unit 430 may include a program area for storing a control program for controlling the operation of the water pollutant measuring module 100 according to the present invention, a temporary area for temporarily storing data generated during the execution of the control program, and It includes a data area for storing data.
  • the data area of the storage unit 430 defines pollutants by range of redox supply power (potential), and pollutant measurement capable of measuring the pollution degree of the corresponding pollutant by pollutant.
  • the redox supply power is a potential supplied to the reaction sensor 62 of the reaction sensor unit 60 to be described later with reference to FIGS. 2 and 3.
  • the contaminant definition according to the redox supply power range may be defined as -1.3V ⁇ -0.9V for the contaminant zinc, the cadmium (Cd) For the lead (Pb) and copper (Cu), the redox supply range is -0.3 to 0.2V, and the redox supply range is defined as -0.3V to 0.2V.
  • 0.2V to 0.5V may be defined for (Hg).
  • the measured product contains zinc. it means.
  • the storage unit 430 may be stored in the auxiliary solution input DB for defining the measurement auxiliary solution input amount to at least one of the conductivity value and the pH value according to the present invention.
  • the input unit 440 may be an input device 441 such as a keyboard or a mouse as a means for receiving a command and information from the outside and outputting the command and information to the control module 400, or from a remote manager to a communication network such as an internet network or a mobile communication network. It may be a receiver 442 of a remote communication unit that receives information and commands through communication (not shown) and outputs it to the control module 400.
  • the output unit 450 is a configuration for outputting the water pollution degree measurement result to the user and the administrator to output the information output from the control module 400, the display unit 451 for outputting the water pollution degree measurement results in text, graphics and the like and the measurement result It may be a transmitter 452, such as a remote communication unit for transmitting to a computer terminal or the like outside of a remote place through a communication network (not shown).
  • the communication unit means that both the receiver and the transmitter are included.
  • the telecommunication units 442 and 452 may be a wired / wireless local area network (LAN) communication means for connecting to a wired or wireless internet network or a code division multiple access (CDMA) communication means for connecting to a mobile communication network.
  • LAN local area network
  • CDMA code division multiple access
  • the interface unit 460 interfaces signals transmitted and received between the two components in order to facilitate signal transmission and reception between the control module 400 and other components such as impedance matching.
  • the interface unit 460 may interface signals transmitted and received between the sample stabilization unit 100 and the control module 400 performing mechanical control according to the present invention.
  • the interface unit 460 may be configured between the sample measuring unit 200 and the control module 400, or may be configured between the sample supply unit 300 and the control module 400.
  • the interface unit 460 may be configured between the sample measuring unit 200, the pump, the valve.
  • Sample stabilization unit 100 is configured according to the second embodiment of the present invention is connected to the water supply pipe receiving the water from the site receives the water of the site in real time as a sample, the electrical conductivity and pH of the sample supplied Detects at least one or more and outputs them to the control module 400, stabilizes the sample under the control of the control module 400 in response to the output electrical conductivity and pH, and provides the sample to the sample supply unit 300. do.
  • the sample measuring unit 200 is supplied with the stabilized sample, detects the type of heavy metal and the amount of each heavy metal contained in the sample and outputs to the control module 400.
  • sample supply unit 300 is configured between the sample stabilization unit 100 and the sample measurement unit 200, under the control of the control module 400 in the sample stabilization unit 100 The stabilized sample is supplied to the sample measuring unit 200.
  • the control module 400 includes a heavy metal detection control unit 420 according to the first embodiment, and further includes a sample stabilization control unit 410 according to the second embodiment. Control the operation.
  • the sample stabilization control unit 410 stabilizes the sample by controlling the sample stabilization unit 100 in response to the electrical conductivity and pH input from the sample stabilization unit 100 as described above.
  • the heavy metal detection control unit 420 controls the sample measuring unit 200 to analyze the heavy metal type included in the sample, and receives the heavy metal (detection) amount of the analyzed heavy metal from the sample measuring unit 200 and outputs the received heavy metal. Output through the unit 450.
  • FIG. 2 is a view showing the configuration of the sample measuring unit of the real-time multi-item heavy metal analysis device according to the present invention.
  • the sample measuring unit 200 of the present invention includes a water pollutant measuring module 500 including a measuring cell 210, a reaction sensor 62, and a measuring sensor 72.
  • the measuring cell 210 is configured such that the water to be measured is introduced and discharged after detecting the pollutants in the water and measuring the degree of contamination.
  • Measuring cell 210 of the present invention includes a body 220 and the water flow path (230).
  • the main body 220 includes a water inlet 221, a plurality of sensor couplers 222, and a water outlet 223, and a water flow path 220 is formed inward.
  • the sensor coupling hole 222 is coupled to the reaction sensor 62 and the measurement sensor 72 so as to contact the water flowing through the water flow path 230.
  • the water flow path 230 is a water supply pipe through which water to be measured is a pipe passing through the water inlet 221, the water outlet 223, and the plurality of sensor coupling holes 222.
  • the water flow path 230 is a sawtooth pattern so that the water flowing into the measuring cell 210 is in contact with the surface of the reaction sensor 62 and the measuring sensor 72 in an optimal path to increase the sensitivity of the electrochemical detection reaction It may be configured in the form of.
  • the reaction sensor 62 and the measurement sensor 72 may be disposed at the vertices of the top and bottom of the pattern of the water flow path 220.
  • the reaction sensor 62 and the measurement sensor 72 may be configured such that the vertices of the water flow path 230 is connected to the sensor coupler 222 of the body 220.
  • the sample measuring unit 200 includes at least one or more reaction sensors 62 and at least one or more measuring sensors 72 coupled to the sensor coupler 222 of the measuring cell 210 through the water flow path 230.
  • the type of pollutant contained in the flowing water is detected, and the contamination (concentration) caused by the detected pollutant is measured and output.
  • the reaction sensor 62 will be coupled to the sensor coupler 222-1 at the very front of the water flow path 230 as shown in FIG. Detailed configuration and operation of the water pollutant measurement module 500 will be described with reference to FIG. 3.
  • FIG. 3 is a view showing a detailed configuration of the water pollutant measurement module of the sample measuring unit according to the present invention.
  • the water pollutant measurement module 500 includes a measurement voltage supply unit 40 and a sensor module 50.
  • the measurement voltage supply unit 40 receives the source power and generates and outputs a measurement voltage to supply the source power to the reaction sensor unit 60 and the pollution measurement sensor unit 70 to measure the pollutants contained in the water.
  • the measurement voltage may be a redox supply power supplied to the reaction sensor 62, or may be a measurement supply power supplied to the measurement sensor 72.
  • the measured power supply may also vary depending on the type of pollution, that is, the type of heavy metal. Therefore, the range of the measurement voltage supplied to the reaction sensor 62 and the measurement sensor 72 may be different, and the range of the measurement voltage supplied to the measurement sensor 72 may also vary according to the type of pollutant.
  • the sensor module 50 includes a reaction sensor unit 60 and a pollution measurement sensor unit 70 to detect the type of pollutant contained in the water flowing in the water flow path 230 of the measurement cell 210.
  • the pollution degree of the detected pollutant is measured and output to the heavy metal detection control unit 420 of the control module 400.
  • the reaction sensor unit 60 includes a reaction sensor 62 at the inlet of the inflowing water to apply a redox supply power to the inflowing water to generate a redox, and measure a redox current according to the amount of redox generated. The amount of change in the redox current is measured in comparison with the previously measured redox current, and the redox supply power range value in which the change in the redox current is generated is output to the heavy metal detection controller 420.
  • the reaction sensor unit 60 may be configured to have a pollutant DB for each of the redox supply power range of the storage unit 430, in which case the pollutant information corresponding to the calculated redox supply power range value is obtained.
  • the reaction sensor unit 60 determines the presence or absence of water pollutants such as heavy metals, trace organic toxic substances, general inorganic substances (nitrogen, phosphorus, etc.), and receives information corresponding to the detected water pollutants. It may be configured to output to the detection control unit 420. In addition, the reaction sensor unit 60 receives the redox supply power of the redox supply power range directly from the measurement voltage supply unit 40 under the control of the heavy metal detection control unit 420, and supplies the reaction sensor 62 to the reaction sensor 62.
  • water pollutants such as heavy metals, trace organic toxic substances, general inorganic substances (nitrogen, phosphorus, etc.
  • the redox current value measured according to the heavy metal detection control unit 420 is output to determine whether the redox current changes and the redox supply power range generated by the heavy metal detection control unit 420, and redox supply Contaminants corresponding to the power range may be configured to be classified.
  • the reaction sensor unit 60 may be constituted by one redox current measuring unit 61, and the plurality of oxidation voltages supplied from the plurality of redox current measuring units 61 and the measured voltage supply unit 40 may be oxidized. It may be configured to include a reaction sensor selection unit 63 for outputting only to the redox current measurement unit 61 selected by the heavy metal detection control unit 420 of the reduction current measurement unit 61.
  • the redox current measuring unit 61 includes a reaction sensor 62, and supplies the measurement voltage, that is, a redox supply power, to a predetermined range to the reaction sensor 62, and the reaction sensor 62 measures the measurement. Due to the redox reaction corresponding to the voltage change, the amount of redox current change according to the type and presence of pollutants contained in the water can be measured, and the redox supply power range value (or contamination) that has changed the redox current. Material information) will be output to the heavy metal detection control unit 420.
  • the Coulomb method determines the presence of contaminants in a sample by measuring the amount of charge over time.
  • the reaction sensor 62 should monitor the measurement object flowing along the water flow path 220 in real time, the reaction sensor 62 should be made of platinum because it must be strong against external stimuli, excellent in durability, and high in electrical reflection.
  • the pollution measuring sensor unit 70 selects the measured voltages supplied from the plurality of pollution measuring units 71 and the measurement voltage supply unit 40 by the heavy metal detection control unit 420 of the plurality of pollution measuring units 71. It is configured to include a measurement sensor selection unit 73 for outputting only to the pollution measurement unit (71).
  • the pollution measuring unit 71 includes measurement sensors 72 disposed at the rear end of the reaction sensor 62 on the water flow path 230, and measures the pollution degree of each pollutant to detect the heavy metals. Will output
  • the electrochemical method applied to the pollution measuring unit 71 the above-described chronocoulomb method, square wave voltammetry (SWV), or the like may be applied. Since the chronocoulomb method and the square wave voltammetry method described above are well known to those skilled in the art, detailed description thereof will be omitted.
  • the measuring sensor 72 preferably uses a carbon electrode that is stable and economical to a variety of materials, and in order to increase sensitivity, graphene and graphene are exposed on a carbon electrode exposed surface according to a detection species. It is preferable to use the conductive polymer mixture electrodeposited, and it may be preferable to use one of the plurality of measurement sensors 72 as a nanoporous gold plated electrode capable of detecting chromium.
  • Electrodepositing the surface of carbon electrode with graphene and conductive polymer mixture increases the surface area of the electrode and enhances the electron transfer reaction with the sample, providing excellent selectivity, stability and detection sensitivity for heavy metal detection. do.
  • the surface electrodeposition material and its shape differ depending on the pollutant species.
  • the heavy metal adsorbed on the surface of the electrode is removed by applying an oxidation potential to the electrode of the measuring sensor 72 after the injection of the cleaning solution according to a user-set cycle, and the mixture of graphene and the conductive polymer By re-depositing, the life of the electrode can be extended and the sensitivity of the sensor can be improved.
  • FIG. 4 is a conceptual diagram of a measurement sensor for detecting heavy metals according to an embodiment of the present invention
  • FIG. 5 is a scanning electron microscope of an electrode surface electrochemically electrodeposited with an aminopyrimidyl terthiophene monomer and graphene on a glassy carbon electrode ( SEM)
  • FIG. 6 is a SWV analysis result according to sensor denaturation conditions of a solution containing 500 ppb of heavy metal ions (HMI)
  • FIG. 7 is a result of checking an optimum condition.
  • FIG. 7 Is the result according to the type of supporting electrolyte containing 500 ppb of heavy metal ions (HMI)
  • Figure 7 (B) is the result of the pH change of the solution
  • Figure 7 (C) is the result of the deposition time change
  • 8 is a graph (A) and a calibration curve (B) for detecting heavy metal ions (HMI) analyzed by square wave voltammetry (SWV) within each heavy metal concentration range at 1 ppb to 10 ppm under optimal conditions.
  • SWV square wave voltammetry
  • 9 shows 1 ppb under optimal conditions. It is a result which shows the graph (A) and the calibration curve (B) for detecting heavy metal ion (HMI) analyzed by chronocoulmetry (CC) within each heavy metal concentration range from -10 ppm.
  • a measuring sensor 72 is formed on an electrode and the electrode, and includes an aminopyrimidyl terthiophene monomer and graphene oxide. It includes a polymerized polymer coating layer.
  • aminopyrimidyl terthiophene monomer is 3,2-aminopyrimidyl-2: 2,5: 2-terthiophene [3 '-(2-aminopyrimidyl) -2,2': 5 ', 2' '- terthiophene].
  • the sensor can detect Zn (II), Cd (II), Pb (II), Cu (II) and Hg (II) simultaneously.
  • Method for producing a heavy metal detection sensor 72 comprises the steps of dissolving aminopyrimidyl terthiophene and graphene oxide in a solvent to prepare a mixed solution (first step); And electrolytically polymerizing the mixed solution of the first step on the electrode by an electrochemical method to form a polymer coating layer consisting of an aminopyrimidyl terthiophene monomer and graphene oxide (second step).
  • the mixed solution of the first step may dissolve 50 to 70% by weight of aminopyrimidyl terthiophene and 30 to 50% by weight of graphene oxide in a solvent, the solvent may be acetonitrile, dichloromethane, tetrahydrofuran, It may be selected from the group consisting of dimethylformamide and dimethyl sulfoxide, but is not limited thereto.
  • the detection sensitivity of heavy metals was 1.2 times for Zn (II), 2.4 times for Cd (II), 3 times for Pb (II), 4.6 times for Cu (II) and Hg ( II) increased 2.2 times.
  • the present invention is to stabilize the sample by adjusting the pH of the sample solution to 3 to 7 in the sample stabilization unit 100; And it may provide a method for detecting the heavy metal at the same time in real time comprising the step of depositing the sample solution in the measurement sensor 72 for heavy metal detection according to the present invention. More specifically, as an experimental parameter for detecting heavy metal ions, it is important to optimize the type of supporting electrolyte, sample solution pH, and sample deposition time of the heavy metal sample solution. As the supporting electrolyte of the sample solution, acetate buffer may be used. The optimal pH of the solution can be 4.7. In addition, the sample solution may be deposited on the heavy metal detection sensor 72 for 300 seconds, but is not limited thereto. A method of stabilizing the sample in an optimal state to detect heavy metals from the sample will be described in detail with reference to FIG. 20 to be described later.
  • the sample measuring unit 200 may simultaneously detect Zn (II), Cd (II), Pb (II), Cu (II), Hg (II), and the like.
  • the square wave voltammetry (SWV) and chronocoulmetry (CC) under the optimized conditions using the measurement sensor 72 for detecting heavy metals according to the present invention Quantitatively analyzed the concentration of heavy metal ions.
  • the dynamic range of the sensor is 10 ppb to 10 ppm, and the detection limit is 11.3 ppb for Zn (II), 4.4 ppb for Pb (II), respectively. It was found that Cd (II) was 5.3 ppb, Hg (II) was 13.1 ppb, and Cu (II) was 9.2 ppb.
  • the detection limit of each metal ion within the 10 ppb -10 ppm dynamic range is 3.8 ppb for Zn (II), 1.2 ppb for Pb (II), respectively. Cd (II) was found to be 1.2 ppb, Hg (II) was 3.0 ppb, and Cu (II) was 2.0 ppb.
  • the senor according to the present invention is coated with a polymer film formed by electropolymerization using aminopyrimidyl terthiophene and graphene oxide, stability can be maintained for a long time.
  • aminopyrimidyl terthiophene [3 '-(2-aminopyrimidyl) -2,2': 5 ', 2' '-terthiophene; APT] and graphene oxide (GO) were dissolved in an acetonitrile solvent containing 0.1 M TBAP [tetrabutylammonium perchlorate] as a supporting electrolyte in a 2: 1 weight ratio.
  • the APT used was synthesized according to previously known methods (D.M. Kim, K.-B. Shim, J. I. Son, S. S. Reddy, Y. B. Shim, Electochimica Acta 104, (2013), 332-329).
  • the solution was electropolymerized by cyclic voltammetry to form an APT / graphene oxide (GO) polymer film on the electrode surface.
  • the glassy carbon electrode was performed three times at a scanning speed of 100 mV / s in a range of 0.0 V to + 1.5 V potential.
  • APT / graphene oxide (GO) polymer film on the surface of the sensor fabricated in Example 1 was confirmed by a scanning electron microscope (SEM) image. SEM images were obtained using Tescan Model Vega3 SB.
  • APT / GO was electrochemically electrodeposited on the smooth surface of the glassy carbon electrode before modification of the polymer film as shown in FIG. 5 (A).
  • FIG. 5 (B) the polymer was formed around the graphene oxide on the electrode surface. It was confirmed that it was evenly distributed.
  • SWV analysis was performed by using square wave voltammetry (SWV).
  • the working electrode was a glassy carbon electrode with APT / graphene oxide polymer modified as a trielectrode method
  • silver / silver chloride was used as a reference electrode
  • a platinum wire was used as an auxiliary electrode.
  • SWV analysis was performed by scanning the potential from -1.5V to + 0.5V, pulse amplitude was 25.0 mV, potential step was 4.0 mV, frequency was 15.0 Hz.
  • Heavy metal samples were prepared by diluting a solution containing Zn (II), Cd (II), Pb (II), Cu (II) and Hg (II) ions to a concentration of 500 ppb with 0.05 M acetate buffer (pH 4.7). It was.
  • the heavy metal detection performance was excellent in the order of the glassy carbon electrodes ⁇ APT ⁇ rGO ⁇ GO ⁇ APT / GO before the modification.
  • the detection sensitivity of APT / GO is 1.2 times for Zn (II), 2.4 times for Cd (II), 3 times for Pb (II), 4.6 times for Cd (II) and Hg compared to pre-modified glassy carbon electrodes. (II) confirmed a 2.2-fold increase.
  • the type of electrolyte, pH and adsorption time of heavy metal ions were determined at a concentration of 500 ppb heavy metal ions.
  • the change of the current according to the kind of supporting electrolyte (sodium acetate, sodium chloride, sodium nitrate, sodium phosphate) treated in the sample was confirmed.
  • the electrolyte of the heavy metal sample was confirmed that the sodium acetate solution is suitable, and the pH is optimal condition when pH 4.7, the experiments were then carried out under the above conditions.
  • the optimum time for depositing heavy metal ions on the sensor was selected as 300 seconds.
  • the linear range of heavy metal ions (HMI) calibration curves is 10 ppb to 10 ppm, and the correlation coefficients are 0.994 for Zn (II), 0.940 for Pb (II), and Cd ( II) was 0.996, Hg (II) was 0.964, and Cu (II) was 0.887.
  • the detection limit of each metal ion is 11.3 ppb for Zn (II), 4.4 ppb for Pb (II), 5.3 ppb for Cd (II), 13.1 ppb for Hg (II) and Cu (II) ) was found to be 9.2 ppb.
  • the linear range of the HMI calibration curve is 10 ppb to 10 ppm, and the correlation coefficients are 0.986 for Zn (II), 0.998 for Pb (II), 0.947 for Cd (II), and Hg ( II) was 0.978 and Cu (II) was 0.981, and the detection limits of heavy metal ions were 3.8 ppb for Zn (II), 1.2 ppb for Pb (II), 1.2 ppb for Cd (II), and Hg (II) for 3.0 ppb and Cu (II) were 2.0 ppb.
  • the detection limit of heavy metal ions is lower than that of the SWV quantitative analysis, and according to the present invention, the chronoculon method using a sensor modified with APT / graphene oxide (GO) under optimization conditions according to the present invention (The chronocoulmetry (CC) method was able to effectively detect the low concentration of heavy metal ions.
  • the electrode modified with APT / graphene oxide (GO) simultaneously showed heavy metal ions (HMI) and was identified as a stable sensor that can be analyzed in a short time and can be used for a long time.
  • HMI heavy metal ions
  • FIG. 10 shows a schematic diagram of a measuring sensor for detecting the Cr (VI) according to an embodiment of the present invention
  • Figure 11 shows the modification of the measuring sensor step by step to 1 ppm of Cr (VI) with each modified electrode
  • FIG. 12 shows the surface image of the electrode completed in the present invention
  • FIG. 13 shows (A) pH, (B) for 1 ppm of Cr (VI) for the electrode.
  • FIG. 14 is a signal change of concentration (A) obtained by using a linear scanning voltammetry as an electrode for modifying a composite plating layer of porous gold and APT in the range of 10 ppm to 5 ppm under optimal conditions.
  • a calibration curve for detection (B) corresponding thereto.
  • a glassy carbon electrode may be used as the electrode, but is not limited thereto.
  • the terthiophene monomer is preferably a 3- (2-aminopyrimidyl) -2,2: 5,2-terthiophene (APT) monomer.
  • a terthiophene monomer solution in which Aminopyrimidine Terthiophene (APT) was dissolved in dimethyl sulfoxide (DMSO), a terthiophene monomer solution was mixed with a sulfuric acid solution containing gold and nickel. By applying a constant current, the plating layer can be formed electrochemically on the electrode surface.
  • APT Aminopyrimidine Terthiophene
  • DMSO dimethyl sulfoxide
  • the composite layer of porous gold and APT may be formed by selectively removing nickel on the glassy carbon electrode on which the plating layer of gold, nickel, and monomer is formed by using an electrochemical method.
  • porous gold-APT modified electrode thus obtained can be used to develop an electrochemical hexavalent chromium detection sensor capable of selectively analyzing trace amounts of Cr (VI) without disturbing other active species.
  • the dynamic range of the heavy metal detection measurement sensor 72 manufactured under the optimized conditions is 10 ppb to 100 ppb and 100 ppb to 1 ppm, and the detection limit is 1.6 ppb. It is possible to measure Cr (VI) even in a sample, namely tap water.
  • the present invention comprises the steps of adjusting the pH of the sample solution to 1 to 2; And it provides a Cr (VI) detection method comprising the step of adjusting the current applied in the manufacturing of the measurement sensor for detecting the Cr (VI) to 1 to 5 ⁇ A, more preferably, the pH of the sample solution Adjusting to 1.5; And it provides a Cr (VI) detection method comprising the step of adjusting the current applied when manufacturing the sensor to + 2 ⁇ A.
  • Adjusting the current is a condition for forming a nanoporous membrane for chromium detection in the sensor.
  • the detection method can selectively detect trace amounts of Cr (VI).
  • APT monomers were synthesized according to known methods (Electrochim. Acta. 2013, 104, 322). 1.0 x 10 -3 M gold chloride trihydrate (HAuCl 4 ⁇ 3H 2 O) and 1.5 x 10 -2 M nickel sulfide hexahydrate (NiSO 4 ⁇ 6 H 2 O) to modify the glassy carbon electrode (GCE) surface ) And 1.5 M sulfuric acid solution in which 10.0 ⁇ L of DMSO dissolved in 1.0 x 10 -2 M APT was dissolved. HAuCl 4 3H 2 O ( ⁇ 99.9% trace metals basis) and NiSO 4 ⁇ 6H 2 O ( ⁇ 99.99% trace metals basis) were purchased from Sigma-Aldrich (USA). A standard Cr (VI) solution for atomic absorption spectrometer was purchased from NIST (USA). Other chemicals were used purified to ACS reagent grade. Distilled water (18 M ⁇ / cm) was obtained using a Millipore system.
  • the glassy carbon electrode (GCE) is passed a constant current of +2 ⁇ A in the prepared solution for 60 seconds to form a composite plating layer of gold, nickel and APT.
  • the plated electrode was selectively removed from nickel by scanning at a rate of 200 mV / s from 0 V to +1.5 V using cyclic voltammetry in a 1.5 M sulfuric acid solution to form a porous gold-APT composite layer.
  • the conceptual diagram of the manufacturing of the sensor is shown in FIG.
  • Cyclic voltammetry (CV) and linear scanning voltammetry (LSV) analysis were performed using potentiostat / galvanostat (Kosentech Model KST-P2, South Korea). In this case, a three-electrode system was used in which the modified GCE (diameter: 3.0 mm), Ag / AgCl, and platinum wires prepared as the working electrode, the reference electrode, and the auxiliary electrode were used.
  • LSV analysis was performed by scanning the potential from +0.8 V to +0.3 V compared to Ag / AgCl, with a scanning speed of 50 mV / s.
  • a stock solution containing 1000 ppm of Cr (VI) ions was prepared.
  • the solution used for the experiment was prepared by diluting in a standard solution. Nitrogen gas was purged in the diluted solution for 20 minutes to remove dissolved oxygen. The voltammetric analysis was performed after the porous gold-APT modified electrode was transferred to a conduit containing only the supporting electrolyte solution.
  • the surface of the porous gold-APT modified electrode was observed in a field emission scanning electron microscope (SEM, Zeiss Supra40 VP, Germany) and is shown in FIG. 12. As can be seen in Figure 12 it can be confirmed that the porous structure, the size of the porous structure was about 200 nanometers. Therefore, it was confirmed that nanoporous gold-APT composite layer was successfully formed on the surface of GCE.
  • the pH of the sample solution was set to 1.5 in the following experiment.
  • the supporting electrolyte was changed to 0.1 M nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and perchloric acid, and the optimum electrolyte was found by detecting Cr (VI).
  • the use of nitric acid as an electrolyte showed a larger peak current than when using another electrolyte. Therefore, the electrolyte to be used in subsequent experiments may be acetic acid, nitric acid solution, and the like.
  • the concentration of other metal ions to see the interference effect was 10 ppm.
  • the peak current of Cr (VI) also showed a difference of about 1.1%, which is within the error range.
  • no additional peaks were observed for Cd (II), Pb (II), Cu (II), Hg (II) and Zn (II), and the peak current of Cr (VI) was also within the margin of error. The difference was about%. Therefore, it was confirmed that the present electrode can selectively detect Cr (VI) without interfering with other active species.
  • a calibration curve for detecting Cr (VI) was obtained under the optimum experimental conditions selected above. Detection experiments were performed using LSV with increasing concentrations from 10 ppb to 5 ppm, and the peak currents indicated at this time were shown as calibration curves. The correlation coefficient of the calibration curve was 0.96, and the dynamic range of the calibration curve was 10 ppb to 100 ppb and 100 ppb to 1 ppm. The detection limit calculated using the slope of the calibration curve was 1.6 ppb.
  • Figure 15 is a view showing a detailed configuration of the sample stabilization unit of the real-time multi-item heavy metal analysis device according to the present invention
  • Figure 16 is a real configuration of a sample stabilization unit, a sample supply unit and a sample measuring unit of the real-time multi-item heavy metal analysis device according to the present invention An example is shown.
  • the sample stabilization unit 100 is controlled by the sample stabilization control unit 410 of the control module 400 so that the sample measuring unit 200 can more accurately detect heavy metals contained in the sample. Stabilize.
  • the sample stabilization unit 100 includes a first stabilization unit 110 and a second stabilization unit 140.
  • the first stabilization unit 110 may adjust the measurement auxiliary solution to store and input the sample state measurement unit 120 and the measurement auxiliary solution to measure and output the electrical conductivity and pH of the sample to be supplied, the control module ( Under the control of 400, the measurement auxiliary solution supply unit 130 for inputting the measurement auxiliary solution to the sample.
  • the measurement auxiliary solution is a solution for adjusting the electrical conductivity and pH, acetate buffer solution, etc. may be used.
  • the first stabilization unit 110 includes a sample state measurement unit 120 and a measurement auxiliary solution supply unit 130 as described above.
  • the sample state measuring unit 120 includes an electric conductivity sensor 121 for measuring and outputting an electric conductivity of a sample supplied with an electric conductivity sensor, and a pH sensor unit for measuring and outputting a pH of a sample, including a pH sensor. (122).
  • the conductivity sensor of the conductivity sensor unit 121 and the pH sensor of the pH sensor unit 122 may be installed in the water (sample) supply pipe, but the water tank 141 containing water stabilized by the measurement auxiliary solution. It would be desirable to be installed in.
  • the water tank 141 will be preferably configured to maintain a certain amount.
  • the auxiliary solution supply unit 130 includes a measurement auxiliary solution container 131 and a measurement auxiliary solution including a multi-path automatic valve 132 for introducing the measurement auxiliary solution contained in the measurement auxiliary solution container 131 into the supplied water.
  • Supply unit 130 is included.
  • the multi-path automatic valve 132 is connected to the auxiliary solution supply pipe connected to the water supply pipe receiving the sample and the measurement auxiliary solution container 131 as shown in Figure 3 and connected to the sample supply unit 300 by the auxiliary solution It is connected to the sample supply pipe for supplying the stabilized sample to the sample supply unit 300.
  • the second stabilization unit 140 is configured to flow into the lower end of the sample for the stabilization of the sample and to flow in the bottom surface of the water tank 141 and the water tank 141 configured to overflow when a predetermined amount or more of the sample flows in It may include a rotary impeller 142 to remove the bubbles contained in the sample.
  • the pH and electrical conductivity of the first stabilizer 140 is adjusted and the sample from which the bubbles are removed from the second stabilizer will be supplied to the sample measuring unit 200 through the sample supply unit 300.
  • 17 is a view showing the configuration of the sample stabilization control unit of the control module of the real-time multi-item heavy metal analysis apparatus according to the present invention.
  • the sample stabilization control unit 410 includes a pretreatment sample inspection unit 411, a sample supply control unit 412, a stabilization control unit 413, a real-time heavy metal monitoring unit 414, and a water state notification unit 415.
  • the pretreatment sample inspecting unit 411 measures the state of the sample before heavy metal detection through the sample state measuring unit 120 of the first stabilization unit 110. That is, the pretreatment sample inspecting unit 411 measures the electrical conductivity and pH of the sample supplied to the water tank 141 through the electrical conductivity sensor unit 121 and the pH sensor unit 122 of the sample state measuring unit 120, It is determined whether the electrical conductivity value and the pH value measured with reference to the auxiliary solution input amount DB of the storage unit 430 require the addition of the auxiliary solution, and when the auxiliary solution is required, the electrical conductivity value and the pH value are required. The auxiliary solution input amount corresponding to the output is determined and output to the stabilization controller 413.
  • the pretreatment sample inspecting unit 411 determines whether or not the sample is stabilized according to the auxiliary solution input amount, and displays it on the display unit 451, and notifies the sample supply control unit 412 that the sample is stabilized.
  • the sample supply control unit 412 controls the sample supply unit 300 when the sample supply event occurs to supply the sample contained in the water tank 141 to the sample measurement unit 200.
  • the sample supply event may be generated at a predetermined time period, may be generated when the sample supply command through the input unit 440, may be generated when the sample stabilization is completed from the pre-process sample inspection unit 411, complex depending on whether or not to stabilize the sample It may be generated as
  • the stabilization control unit 413 stabilizes the sample by removing the bubbles of the sample contained in the water tank 141 by driving the rotating impeller 142 during the operation of the heavy metal analysis device, and inputs the auxiliary solution input amount from the pretreatment sample inspection unit 411.
  • the multi-path automatic valve 132 of the measurement auxiliary solution supply unit 130 By controlling the multi-path automatic valve 132 of the measurement auxiliary solution supply unit 130 to supply the auxiliary solution to the sample contained in the water tank 141 to stabilize the sample.
  • the real-time heavy metal monitoring unit 414 drives the sample measuring unit 200 when the sample supply event occurs to be supplied through the sample supply unit 300 and included in the sample flowing through the water flow path 230 of the main body 220.
  • the sorted heavy metals are classified, and the content of the classified heavy metals is received and stored and displayed on the display unit 451.
  • the water state notification unit 415 is a telecommunication unit for receiving water state information including information measured and determined by the preprocessing sample inspecting unit 411, heavy metal type information detected by the real-time heavy metal monitoring unit 414, and a detection amount for each heavy metal. (442, 452) to remote water quality testing centers.
  • FIG. 18 is a flowchart illustrating a real-time multi-item heavy metal detection method through selective electrode activation according to the present invention.
  • the heavy metal detection control unit 420 of the control module 400 measures water (water), that is, a sample, through a water supply device (not shown) such as the sample supply unit 300. And supplying the redox current measuring unit 61 (S111), supplying the redox supply power to the reaction sensor 62, and checking whether the redox current value is input by the redox supply power supply. By measuring the redox current value (S113).
  • the heavy metal detection control unit 420 compares the input redox current value with the previously input redox current value and calculates a redox current change amount (S114). It is determined whether the amount of change exceeds the normal range (S115).
  • the heavy metal detection control unit 420 refers to the pollutant DB for each redox supply power range to the redox current. Analyze and classify pollutants corresponding to the redox supply power range to which the redox supply power value that caused the change belongs, and refer to the pollutant DB by redox power supply value range and at least one corresponding to the classified pollutants.
  • the contamination measurement unit 71 is searched and the measurement sensor selection unit 73 is controlled to select the retrieved contamination measurement unit 71 (S116).
  • the heavy metal detection control unit 420 controls the measurement voltage supply unit 40 to supply the measurement voltage to the selected pollution measurement unit 71 (S117). At this time, according to the pollution measuring unit 71 may supply a measurement voltage having each measurement specific voltage.
  • the heavy metal detection control unit 420 monitors whether the pollution measurement (current) value is input from the pollution measurement unit 71 (S119).
  • the contamination measurement value may be a current change amount value.
  • the pollution measurement unit 71 When the measurement voltage value is input, the pollution measurement unit 71 outputs a pollution measurement (current) value according to the pollution degree. At this time, the heavy metal detection control unit 420 determines whether the contamination measurement value is input from all the pollution measurement units 71 when the selected pollution measurement unit 71 is two or more (S121).
  • the heavy metal detection control unit 420 converts the measured pollution measurement values into pollution levels for the corresponding pollutants, and displays pollutant information and information indicating how much of the pollutants are included in the water. It will output (S123).
  • the output of the information may be made through the display unit 451 of the output unit 450, or is transmitted to a server (not shown) of a remote water quality control center (not shown) through the remote communication unit 452 to the manager terminal. It could be done through
  • the heavy metal detection control unit 420 checks whether a measurement cancellation event occurs (S125).
  • the measurement cancellation event may be generated when the pollution measurement value is not input from any one of the selected pollution measurement unit 71 for a predetermined time or may be generated through the input unit 30 by an administrator.
  • the heavy metal detection control unit 420 When the measurement cancellation event occurs, the heavy metal detection control unit 420 outputs the input pollutant contamination level, and outputs the related information related to the unmeasured pollutant (S127).
  • the related information may be, for example, pollutant information and information of the pollution measuring unit 71 measuring the pollution level of the pollutant.
  • the heavy metal detection control unit 420 may request the inspection of the pollution measurement unit 71, the reaction sensor 62 and the redox current measuring unit 61.
  • 19 is a flowchart illustrating an electrode activation method of a real-time multi-item heavy metal detection method according to an embodiment of the present invention.
  • the heavy metal detection control unit 420 refers to the pollutant DB for each of the redox power values to generate the redox current change. A value is obtained (S211).
  • the heavy metal detection control unit 420 determines whether the redox supply power supply (above) is in the range of -1.3V to -0.9V (S215) or in the range of -0.9V to -0.3V. It is determined whether the value is in the range (S217), -0.3V to 0.2V (S219), or in the range of 0.2V to 0.5V (S221).
  • the heavy metal detection control unit 420 detects and outputs a concentration of zinc (Zn) that is a pollutant when the redox supply power supply (above) is in the range of -1.3 V to -0.9 V. -1) and the second pollution measuring unit detects and outputs the concentration of cadmium (Cd), which is a pollutant, when the redox supply power supply (above) is in the range of -0.9V to -0.3V.
  • Select (71-2) (S225) and if the value of the redox power supply (above) is in the range of -0.3V to 0.2V, the concentration of lead (Pb) and copper (Cu), which are pollutants, is detected and output.
  • the concentration of mercury (Hg), which is a pollutant is detected and output.
  • the fourth pollution measurement unit 71-4 is selected (S229). If the measured redox power supply (top) value is 0.2V, the heavy metal detection control unit 420 may also include 0.2V in the range of -0.3V to 0.2V where redox potential ranges for lead and copper, and to oxidize mercury. Since it is also included in the reduction potential value range of 0.2V to 0.5V, the third pollution measuring unit 71-4 and the fourth pollution measuring unit 71-5 are selected.
  • a dedicated contamination measurement unit 71-m for detecting chromium may be assigned to continuously check whether the sample contains chromium, and is supplied through the reaction sensor 62. If the redox supply power supply (above) is in the range of +0.5 V to +0.6 V, the m-th pollution measurement unit 71-m that detects and outputs the allocated chromium (Cr) concentration may be driven.
  • 20 is a flowchart illustrating a sample stabilization method of the real-time multi-item heavy metal detection method according to the present invention.
  • the sample stabilization control unit 410 of the control module 400 controls the multipath automatic valve 132 when power is supplied to the heavy metal analyzing apparatus and starts supplying the sample to the water tank 141 (S311).
  • the rotary impeller 142 By driving the rotary impeller 142 through the stabilization control unit 413, stabilization is performed by removing bubbles of the sample supplied to the water tank 141 (S312).
  • the sample stabilization control unit 410 drives the sample state measurement unit 120 through the pretreatment sample inspection unit 411 to perform electrical conductivity and The measurement of the pH is started (S313).
  • the sample stabilization control unit 410 checks whether the conductivity value and the pH value, which are the sample state values, are input through the pretreatment sample inspection unit 411 (S315).
  • the sample stabilization control unit 410 determines whether the conductivity and pH value measured by referring to the auxiliary solution input amount DB through the pretreatment sample inspection unit 411 require the input of the auxiliary solution. It is determined whether or not (S317).
  • the sample stabilization control unit 410 determines whether the sample is currently being supplied through the sample supply control unit 412 (S319), and if the sample is being supplied, the sample supply control unit.
  • the sample supply unit 300 is controlled through the block 412 to block the sample supply to the sample measuring unit 200 (S321).
  • the sample stabilization control unit 410 is the auxiliary solution input amount of the storage unit 430 through the pretreatment sample inspection unit 411
  • the auxiliary solution input amount corresponding to the measured electric conductivity value and pH value is determined by referring to the DB (S323).
  • the auxiliary solution input amount may be calculated in real time by reflecting the electrical conductivity value and the pH value every time the auxiliary solution is added.
  • the sample stabilization control unit 410 controls the multi-path automatic valve 132 of the measurement auxiliary solution supply unit 130 through the stabilization control unit 413 to adjust the auxiliary solution by the amount of the auxiliary solution input tank 141.
  • the auxiliary solution input amount may be measured with an input amount measuring means for measuring the input amount from the measurement auxiliary solution container 131 to the pipe supplied to the multi-path automatic valve 132, and the electrical conductivity value measured in the water tank 141. And it may be measured indirectly by adding the auxiliary solution until the pH value satisfies the sample measurement stabilization conditions.
  • the sample stabilization control unit 410 controls the sample supply unit 300 to supply the sample of the water tank 141 to the sample measuring unit 200 (S127).
  • the present invention is not limited to the above-described typical preferred embodiment, but can be carried out in various ways without departing from the gist of the present invention, various modifications, alterations, substitutions or additions in the art réelle who has this can easily understand it. If the implementation by such improvement, change, replacement or addition falls within the scope of the appended claims, the technical idea should also be regarded as belonging to the present invention.
  • reaction sensor 61 redox current measuring unit
  • reaction sensor 63 reaction sensor selection unit
  • sample stabilization unit 110 first stabilization unit
  • sample state measurement unit 120 sample state measurement unit 121: electrical conductivity sensor unit
  • measuring auxiliary solution container 132 multi-path automatic valve
  • measuring cell 220 main body
  • sample supply unit 400 control module
  • sample stabilization control unit 411 pretreatment sample inspection unit

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  • Food Science & Technology (AREA)
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Abstract

La présente invention concerne un appareil et un procédé d'analyse de métaux lourds, et un procédé de fabrication d'un capteur d'un appareil d'analyse de métaux lourds et, plus particulièrement, un appareil d'analyse de métaux lourds d'articles multiples en temps réel, un procédé d'analyse de métaux lourds d'articles multiples en temps réel, et un procédé de production d'un capteur de l'appareil d'analyse de métaux lourds qui détecte simultanément au moins un métal lourd après stabilisation d'un échantillon à mesurer dans un état optimal pour la mesure, et qui, de préférence, détermine le type du métal lourd contenu dans l'échantillon, et mesure ensuite la teneur en métal lourd en actionnant sélectivement un capteur apte à mesurer au moins un métal lourd déterminé.
PCT/KR2016/008179 2015-10-13 2016-07-27 Appareil d'analyse de métaux lourds d'articles multiples en temps réel, procédé d'analyse de métaux lourds d'articles multiples en temps réel, et procédé de fabrication de capteur d'appareil d'analyse de métaux lourds WO2017065395A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR1020150142823A KR101631186B1 (ko) 2015-10-13 2015-10-13 선택적 전극 활성화를 통한 수질오염물질 동시 검출 장치 및 방법
KR10-2015-0142823 2015-10-13
KR10-2015-0142824 2015-10-13
KR1020150142824A KR101652086B1 (ko) 2015-10-13 2015-10-13 시료 안정화 기능을 가지는 실시간 중금속 분석 장치 및 방법
KR10-2015-0143795 2015-10-15
KR20150143795 2015-10-15

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CN110967334A (zh) * 2019-12-18 2020-04-07 成都理工大学 一种地下水重金属监测方法及其装置
CN111257316A (zh) * 2020-02-11 2020-06-09 军事科学院系统工程研究院卫勤保障技术研究所 一种便携式纳米检测仪
CN112557380A (zh) * 2020-07-16 2021-03-26 虞乐 一种环保的自动化重金属残留物检测方法
CN115308284A (zh) * 2022-08-10 2022-11-08 江苏省农业科学院 基于电致化学发光的镉离子检测电极、制备方法及其应用
CN117401869A (zh) * 2023-12-11 2024-01-16 广东车海洋环保科技有限公司 一种自助洗车机的废水回收智能检测系统及其控制方法
CN118125674A (zh) * 2024-05-07 2024-06-04 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) 一种重金属污染水域的治理设备及方法

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CN107247083A (zh) * 2017-06-08 2017-10-13 北京农业信息技术研究中心 一种农田重金属污染在线监测预警与实时处理系统及方法
CN107247083B (zh) * 2017-06-08 2023-08-04 北京农业信息技术研究中心 一种农田重金属污染在线监测预警与实时处理系统及方法
CN110967334A (zh) * 2019-12-18 2020-04-07 成都理工大学 一种地下水重金属监测方法及其装置
CN111257316A (zh) * 2020-02-11 2020-06-09 军事科学院系统工程研究院卫勤保障技术研究所 一种便携式纳米检测仪
CN112557380A (zh) * 2020-07-16 2021-03-26 虞乐 一种环保的自动化重金属残留物检测方法
CN115308284A (zh) * 2022-08-10 2022-11-08 江苏省农业科学院 基于电致化学发光的镉离子检测电极、制备方法及其应用
CN115308284B (zh) * 2022-08-10 2024-05-24 江苏省农业科学院 基于电致化学发光的镉离子检测电极、制备方法及其应用
CN117401869A (zh) * 2023-12-11 2024-01-16 广东车海洋环保科技有限公司 一种自助洗车机的废水回收智能检测系统及其控制方法
CN118125674A (zh) * 2024-05-07 2024-06-04 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) 一种重金属污染水域的治理设备及方法

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