CN103076381A - Anodic stripping voltammetric mechanism-based online automatic monitoring system for heavy metal ions in water - Google Patents
Anodic stripping voltammetric mechanism-based online automatic monitoring system for heavy metal ions in water Download PDFInfo
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Abstract
An anodic stripping voltammetric mechanism-based online automatic monitoring system for heavy metal ions in water takes electrochemical anodic stripping square wave method as a detecting mechanism and mainly comprises a system control molecule, a water sample filtering molecule, a water sample pretreating molecule, a sensor molecule and an analyzing molecule. The online automatic monitoring system for the heavy metal ions in water can continuously monitor multiple heavy metal ions in water on the spot in real time and perform pre-warning process according to whether the heavy metal content exceeds a standard or not. The online automatic monitoring system for the heavy metal ions in water is relatively low in cost, convenient to carry and easy to operate, can achieve remote control and data networking, and has a wide application prospect in routine water quality detection, real-time monitoring, pre-warning and prevention and emergency processing.
Description
Technical field
The present invention relates to a kind of is the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry.This heavy metal ion online auto monitoring system is mainly by system control module, water sample filtering module, water sample pretreatment module, sensor assembly, analysis module forms, and can detect simultaneously contents of many kinds of heavy metal ion, and cost is lower, easy operating can be realized unattended operation, accomplishes in real time, continuous monitoring and remote monitoring, reach timely grasp main river water quality situation, the great basin-wide water pollution accident of early-warning and predicting accomplishes to take precautions against, solve the purpose of burst water pollution accident.
Background technology
Along with the expansion in city and the development of large-scale industry, all there is heavy metal pollution in atmosphere, soil, the water environment.Heavy metal pollution is one of maximum water pollution problems of harm, and heavy metal element is long-term accumulation non-degradable in vivo often, even also can produce adverse consequences, the human and hydrobiological existence of serious threat in the situation of trace extremely.
At present, the trace metal ion monitoring method that is generally used in the environmental water sample has atomic absorption spectrum (AAS), inductivity coupled plasma mass spectrometry analytic approach (ICP-MS), inductively coupled plasma atomic emission spectrum (ICP-AES), high performance liquid chromatography, immunoassay etc.Based on the analytic system of atomic emission spectrum technology, such as AAS, ICP-MS, ICP-AES, use comparatively extensive, have highly sensitive, detectability is low, disturb the advantages such as little.Yet these instruments are comparatively expensive, heaviness, and power consumption is large, and sample detection occurs to pollute and loss easily, is not suitable for the real time monitoring field.
Compare with the inductivity coupled plasma mass spectrometry analytic approach with the atomic emission spectrum technology, but based on the heavy metal in water ion monitoring instrument of Electrochemical Detection mechanism have that equipment is simple, analysis cost is low, detection time fast field monitoring advantage, in the trace heavy metal ion analysis field, obtain a wide range of applications.Heavy metal in water ion online auto monitoring system of the present invention is as the basis take the Electrochemical Stripping voltammetry, realized robotization online, real-time, the continuous monitoring heavy metal in water, that native system has is low in energy consumption, miniaturization, integrated advantage, be fit to very much heavy metal in water real time monitoring field, have broad application prospects.
Summary of the invention
The purpose of this invention is to provide a kind of heavy metal in water ion online auto monitoring system take the Anodic stripping voltammetry as mechanism, it is characterized in that this online auto monitoring system is microminiaturized with each independent process of heavy metal ion monitoring, form functional module, mainly by filtering module, the water sample pretreatment module, sensor assembly, control module, analysis module forms.Each functional module is separate, and by computer software control, but automation mechanized operation realizes the automatic monitoring of Heavy Metals in Waters ion.
To achieve these goals, the present invention adopts following operation steps:
1) by small pump, water sample to be measured is extracted;
2) after water sample to be measured filtered, degrades through filtering module and pretreatment module, it was to be measured to enter test pool etc.;
2) sensor surface carries out plated film modification processing;
3) sensor after the modification is tested the water sample after standard solution test, the processing successively;
4) sensor was deposited in the storage pool after test finished;
5) successively pickling and washing of system pipeline and measuring cell;
6) the more above-mentioned water sample test result of analysis module analysis, do qualitative, quantitative calculating after, the result is issued remote terminal, a sample test end cycle.
Among the present invention, a full test cycle of heavy metal in water ion online auto monitoring system mainly comprises the sensor plated film, water sample pre-service, standard solution test, sample liquid test, discharging of waste liquid and cleaning.
Among the present invention, the sensor of heavy metal in water ion online auto monitoring system is to be made of galvanochemistry three electrodes.
Among the present invention, three electrodes of the sensor of heavy metal in water ion online auto monitoring system are that the thin polystyrene sheet of 5x5cm makes by silk screen print method at area, working electrode is graphite electrode, and contrast electrode is the Ag/AgCl electrode, is the Ag electrode to electrode.
Among the present invention, the modification film of the sensor of heavy metal in water ion online auto monitoring system is bismuth, gold or mercury film.
Among the present invention, the water sample filtering module of heavy metal in water ion online auto monitoring system forms (water sample sample introduction direction and filtering direction are orthogonal) by the tangential flow filtration system, and the flow velocity ratio of sample introduction liquid and filtered fluid is 10: 1.
Among the present invention, the water sample pretreatment module of heavy metal in water ion online auto monitoring system is comprised of ultraviolet lamp tube, and the organism in the water sample is carried out degradation treatment, and the wave band of ultraviolet light is 300-400nm.
Among the present invention, but the water sample of heavy metal in water ion online auto monitoring system through filtration, direct-detection after the degradation treatment, need not to add again other electrolyte or damping fluid.
Among the present invention, the movement of the sensor of heavy metal in water ion online auto monitoring system is assisted to finish by two dimension (XZ) mechanical arm, installation of sensors is in mechanical arm tail end, control module control two-dimentional machinery arm is realized sensor mobile and detection between different test pools, prevents cross pollution between the sample.
Among the present invention, the analysis module of heavy metal in water ion online auto monitoring system is comprised of the micro electric chem workstation, uses galvanochemistry square wave leaching method, realizes that the scene of copper, lead, zinc, cadmium, mercury, arsenic heavy metal ion is detected real-time.
Among the present invention, the control module of heavy metal in water ion online auto monitoring system is comprised of microcomputer, single-chip microcomputer and control software, can realize sample introduction, sample pretreatment, detection analysis, discharging of waste liquid and electrode, pipeline, electrolytic cell, pipeline cleaning.
Among the present invention, the sensor of heavy metal in water ion online auto monitoring system before each test all the old film of auto-erasing, electroplate new film, guaranteed that the RSD of each measurement result is not more than 3%.
Among the present invention, the test of the titer of heavy metal in water ion online auto monitoring system is in order to evaluate and test sensor along with the increase of test period, the detection signal of the heavy metal ion of same concentration known is had undamped, is used for improving measuring accuracy, revise test error, in time change electrode.Detection frequency for titer can be inserted into test period one time according to the detection demand at any time by control module.
Among the present invention, heavy metal in water ion online auto monitoring system is realized cycle detection under control module control, and a cycle detection cycle is 20min.
Among the present invention, the water sample minimum detectable quantity of heavy metal in water ion online auto monitoring system is 1mL/ time, and the fastest detection frequency is 20min/ time.
Among the present invention, the data of the analysis module of heavy metal in water ion online auto monitoring system record can directly be read by remote terminal, realize network remote control.
Among the present invention, heavy metal in water ion online auto monitoring system can be connected with remote control center, realizes that remote control center is to data processing and the Real Time Monitoring of a plurality of monitoring fields.
Description of drawings
Fig. 1 is the structural representation of heavy metal in water ion online auto monitoring system.
Among the figure 1, the water sample pond, 2, pickling tube, 3, the distillation pond, 4, filter liquid pool, 5, clear up sample cell, 6, the standard model liquid storage tank, 7, sensor is electroplated the decorating liquid pond, 8, electroplate to modify the pond, 9, test pool, 10, storage pool, 11, waste liquid pool, 12, stirrer (2), 13, digestion device, 14, solenoid valve (10).
Fig. 2 is the workflow diagram of heavy metal in water ion online auto monitoring system.
Specific embodiments
Embodiment 1:
Control module control small pump extracts water sample to be measured to the water sample pond also; Water sample carries out the ultraviolet degradation treatment and deposits to clearing up sample cell etc. to be tested after filtering; Control module control application of sample pipeline makes sensor electrical plating bath (0.002M gold chloride) inject electroplating pool, therein to taking the gold-plated film modified processing of galvanochemistry in the electrode table; Standard model liquid (1ppm mercuric nitrate) injects test pool; Sensor is transferred to test pool after modifying, and enables mercury tenor in the electrochemical workstation measurement standard sample liquid as standard value and record; Waste liquid in the emptying test pool and pickling, washing pipeline and test pool; The control module pilot piping extracts and filters, degrades water sample to test pool, and measurement mercury tenor wherein is as measured value and record, and analysis module calculates water sample mercury concentration of metal ions according to the data of measured value and standard value, and the result is issued remote terminal; Waste liquid and carry out pickling, washing pipeline and test pool in the emptying test pool; Sensor moves to store in the storage pool waits for test next time; Finish a measuring period.
Embodiment 2:
Control module control small pump extracts water sample to be measured to the water sample pond also; Water sample carries out the ultraviolet degradation treatment and deposits to clearing up sample cell etc. to be tested after filtering; Control module control application of sample pipeline makes sensor electrical plating bath (0.002M bismuth nitrate) inject electroplating pool, therein to taking the film modified processing of galvanochemistry plating bismuth in the electrode table; Standard model liquid (1ppm copper, lead, zinc, cadmium, arsenic salt) injects test pool; Sensor is transferred to test pool after modifying, and enables each content of beary metal in the electrochemical workstation measurement standard sample liquid as standard value and record; Waste liquid in the emptying test pool and pickling, washing pipeline and test pool; The control module pilot piping extracts and filters, degrades water sample to test pool, measure wherein each tenor as measured value and record, analysis module calculates Copper in Water Samples, lead, zinc, cadmium, arsenic salt concentration of metal ions according to the data of measured value and standard value, and the result is issued remote terminal; Waste liquid and carry out pickling, washing pipeline and test pool in the emptying test pool; Sensor moves to store in the storage pool waits for test next time; Finish a measuring period.
Claims (10)
1. one kind is the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that this monitoring system is detection mechanism based on Anodic stripping square wave method, by system control module, the water sample filtering module, the water sample pretreatment module, sensor assembly, analysis module forms.But contents of many kinds of heavy metal ion in this monitoring system real-time continuous field monitoring water body, and whether exceed standard according to content of beary metal and to make early warning and process.
By claimed in claim 1 be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, its characterization step is as follows successively:
1) by small pump, water sample to be measured is extracted;
2) after water sample to be measured filtered, degrades through filtering module and pretreatment module, it was to be measured to enter test pool etc.;
2) sensor surface carries out plated film modification processing;
3) sensor after the modification is tested the water sample after standard solution test, the processing successively;
4) sensor was deposited in the storage pool after test finished;
5) successively pickling and washing of system pipeline and measuring cell;
6) the more above-mentioned water sample test result of analysis module analysis, do qualitative, quantitative calculating after, the result is issued remote terminal, a sample test end cycle.
By claim 1 or 2 described be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that, should be that a full test cycle of the heavy metal in water ion online auto monitoring system of mechanism is 20min based on anodic stripping voltammetry, comprise the sensor plated film, water sample filters, the water sample pre-service, the standard solution test, sample liquid test, discharging of waste liquid and system are cleaned.
By claim 1 or 2 described be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that sensor is comprised of galvanochemistry three electrodes, electrode is made by silk screen print method, cheap, good reproducibility is easy to produce in enormous quantities.
By claim 1 or 2 described be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that, the sample introduction module is comprised of the tangential flow filtration system, water sample sample introduction direction and filtering direction are orthogonal, can effectively filter impurity in the water sample to be measured, prevent that impurity stops up the test macro pipeline in the water sample.
By claim 1 or 2 described be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that, sample pretreatment module utilizes the organic substance in the ultraviolet irradiation degraded water body, prevents that organism is to the interference of sensor.
By claim 1 or 2 described be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that, control module control two-dimentional machinery arm is realized sensor mobile and detection between different test pools, prevents cross pollution between the sample.
By claim 1 or 2 described be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that, analysis module is comprised of the micro electric chem workstation, need not to add electrolyte or damping fluid in the water sample, through can directly detecting real-time contents of many kinds of heavy metal ion after filtration, the degradation treatment.
By claim 1 or 2 described be the heavy metal in water ion online auto monitoring system of mechanism based on anodic stripping voltammetry, it is characterized in that sensor assembly old film of auto-erasing all before each test is electroplated new film, guarantee the reappearance of each measurement result, can realize cycle detection.
10. by water quality heavy metal on-line monitoring system claimed in claim 1, it is characterized in that, this system can accomplish in real time, continuous monitoring and remote monitoring, reach timely grasp main river water quality situation, the great basin-wide water pollution accident of early-warning and predicting accomplishes to take precautions against, solve the purpose of burst water pollution accident.Water quality heavy metal on-line monitoring system cost of the present invention is lower, and easy operating has broad application prospects.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103411930A (en) * | 2013-07-26 | 2013-11-27 | 中国科学院安徽光学精密机械研究所 | Laser-induced breakdown spectrometry continuous detection device and method for heavy metal of water body |
| CN103558282A (en) * | 2013-10-30 | 2014-02-05 | 湖南科技大学 | Detection method for heavy metal elements in soil-water interface pollution flow of nonferrous metal mining area |
| CN103808788A (en) * | 2013-12-18 | 2014-05-21 | 上海仪电科学仪器股份有限公司 | Online water quality heavy-metal total amount monitor |
| CN105628770A (en) * | 2014-11-04 | 2016-06-01 | 长沙绿智电子科技有限公司 | Low concentration soluble metal thallium on-line detection apparatus and method |
| CN106125619A (en) * | 2016-08-03 | 2016-11-16 | 昆明理工大学 | The embedded equipment that in a kind of sewage, arsenic ion concentration over-standard processes in real time |
| CN106706732A (en) * | 2016-12-26 | 2017-05-24 | 安徽省碧水电子技术有限公司 | Water quality detection system based on bi-polar system |
| CN106770533A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with voice broadcast based on the two poles of the earth system water quality detection system |
| CN106770534A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with temperature sensor based on the two poles of the earth system water quality detection system |
| CN106770593A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with purging system based on the two poles of the earth system water quality detection system |
| CN106841334A (en) * | 2017-03-13 | 2017-06-13 | 宝鸡文理学院 | It is a kind of can real time on-line monitoring contents of many kinds of heavy metal ion detecting system and method |
| CN111537590A (en) * | 2020-04-15 | 2020-08-14 | 力合科技（湖南）股份有限公司 | Automatic on-line repairing method for mercury membrane modified electrode |
| CN113466010A (en) * | 2021-07-09 | 2021-10-01 | 利晟（杭州）科技有限公司 | Water pollution detection system based on electrochemical sensor |
| CN116879360A (en) * | 2023-06-27 | 2023-10-13 | 安徽环境科技集团股份有限公司 | Bioelectrochemistry in-situ monitoring method and device for groundwater pollution |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103411930A (en) * | 2013-07-26 | 2013-11-27 | 中国科学院安徽光学精密机械研究所 | Laser-induced breakdown spectrometry continuous detection device and method for heavy metal of water body |
| CN103411930B (en) * | 2013-07-26 | 2015-06-03 | 中国科学院安徽光学精密机械研究所 | Laser-induced breakdown spectrometry continuous detection device and method for heavy metal of water body |
| CN103558282A (en) * | 2013-10-30 | 2014-02-05 | 湖南科技大学 | Detection method for heavy metal elements in soil-water interface pollution flow of nonferrous metal mining area |
| CN103808788A (en) * | 2013-12-18 | 2014-05-21 | 上海仪电科学仪器股份有限公司 | Online water quality heavy-metal total amount monitor |
| CN103808788B (en) * | 2013-12-18 | 2016-08-17 | 上海仪电科学仪器股份有限公司 | Water quality online total metals monitor |
| CN105628770A (en) * | 2014-11-04 | 2016-06-01 | 长沙绿智电子科技有限公司 | Low concentration soluble metal thallium on-line detection apparatus and method |
| CN106125619B (en) * | 2016-08-03 | 2018-10-02 | 昆明理工大学 | The embedded equipment that arsenic ion concentration over-standard is handled in real time in a kind of sewage |
| CN106125619A (en) * | 2016-08-03 | 2016-11-16 | 昆明理工大学 | The embedded equipment that in a kind of sewage, arsenic ion concentration over-standard processes in real time |
| CN106706732A (en) * | 2016-12-26 | 2017-05-24 | 安徽省碧水电子技术有限公司 | Water quality detection system based on bi-polar system |
| CN106770533A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with voice broadcast based on the two poles of the earth system water quality detection system |
| CN106770534A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with temperature sensor based on the two poles of the earth system water quality detection system |
| CN106770593A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with purging system based on the two poles of the earth system water quality detection system |
| CN106841334A (en) * | 2017-03-13 | 2017-06-13 | 宝鸡文理学院 | It is a kind of can real time on-line monitoring contents of many kinds of heavy metal ion detecting system and method |
| CN106841334B (en) * | 2017-03-13 | 2023-05-05 | 宝鸡文理学院 | Detection system and method capable of monitoring various heavy metal ions on line in real time |
| CN111537590A (en) * | 2020-04-15 | 2020-08-14 | 力合科技（湖南）股份有限公司 | Automatic on-line repairing method for mercury membrane modified electrode |
| CN111537590B (en) * | 2020-04-15 | 2022-06-14 | 力合科技（湖南）股份有限公司 | Automatic on-line repairing method for mercury membrane modified electrode |
| CN113466010A (en) * | 2021-07-09 | 2021-10-01 | 利晟（杭州）科技有限公司 | Water pollution detection system based on electrochemical sensor |
| CN116879360A (en) * | 2023-06-27 | 2023-10-13 | 安徽环境科技集团股份有限公司 | Bioelectrochemistry in-situ monitoring method and device for groundwater pollution |
| CN116879360B (en) * | 2023-06-27 | 2024-06-11 | 安徽环境科技集团股份有限公司 | Bioelectrochemistry in-situ monitoring method and device for groundwater pollution |
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Application publication date: 20130501 |