CN103344692A - Method for detecting heavy metal ions in sewage - Google Patents
Method for detecting heavy metal ions in sewage Download PDFInfo
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- CN103344692A CN103344692A CN2013102629348A CN201310262934A CN103344692A CN 103344692 A CN103344692 A CN 103344692A CN 2013102629348 A CN2013102629348 A CN 2013102629348A CN 201310262934 A CN201310262934 A CN 201310262934A CN 103344692 A CN103344692 A CN 103344692A
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Abstract
The invention relates to a method for detecting heavy metal ions in sewage. A glassy carbon electrode decorated by a carbon nano tube is used as a working electrode, a platinum/titanium (Pt/Ti) electrode is used as an auxiliary electrode, and a saturated magnesium/magnesium chloride (Ag/AgCl) electrode is used as a reference electrode. An anodic stripping voltammetry is used for detecting the content of heavy metal ions such as plumbum ions (Pb2+) in the sewage produced after a neodymium iron boron product is electroplated. Compared with the traditional spectrophotometric method and mass spectrum coupling method, the method for detecting the heavy metal ions in the sewage provided by the invention is simple in detection operation, high in detection efficiency, free from causing secondary pollution to the environment, and environment-friendly.
Description
Technical field
The present invention relates to the sewage detection field that the neodymium iron boron product electroplating technology produces, particularly the neodymium iron boron product electroplating technology produces the detection range of heavy metal ion in the sewage.
Background technology
Sintered NdFeB NdFeB system (typical case's representative of rare-earth-iron-boron based permanent magnet) permanent magnet is the best permanent magnetic material of present magnetic property, has been widely used in numerous areas such as motor, automobile, wind-power electricity generation.But this class magnet has one than significant disadvantages, i.e. magnet corrosion-resistant (magnet weightlessness is bigger), thus need electroplate one deck resistant material at the neodymium iron boron finished product, to delay the corrosion of neodymium iron boron magnetic body.For example, coating such as electrogalvanizing, nickel, ambrose alloy nickel on neodymium iron boron magnetic body.But electroplating technology can produce the sewage that contains the plurality of heavy metal ion, and these sewage must be through handling, and just can be discharged in the environment after making wherein heavy metal ion be reduced to state specified standards.Therefore, the heavy metal ion that detects in these sewage becomes requisite key link.
The heavy metal ion detection method that is produced in the sewage after at present domestic neodymium iron boron product commonly used is electroplated has spectrophotometric method, atomic emission spectrometry (AES), atomic absorption spectrography (AAS) (AAS), inductively coupled plasma mass spectrometry coupling method (ICP-MS) etc.These detection methods are difficult to realize field quick detection owing to complicated operation, instrument costliness, sample analysis are consuming time long and carry reason such as inconvenience.
Stripping voltammetry is that the twenties in 20th century is by a kind of electrochemical analysis method that detects heavy metal ion of Jaroslav Heyrovsky invention.This method is that heavy metal ion to be measured is enriched to earlier on the working electrode, and current potential is just scanned by negative sense, makes this heavy metal ion from the electrode stripping, records the electric current-potential curve of this process in leaching.In certain scope, the peak height of electric current-potential curve and the concentration of heavy metal ion are linear, and different heavy metal ion has different spike potentials in identical electrolytic solution.Heavy metal ion comprises electrolysis enrichment and two processes of electrolysis stripping in anodic stripping voltammetry (ASV) the detection water.The first step, it is enrichment process, reduction potential is added on the working electrode, when the electromotive force of electrode surpasses the evolution or deposition potential of certain heavy metal ion, this metal ion species will be reduced to metal and electroplate on the surface of working electrode in the solution, and reduction potential is applied on the working electrode to such an extent that more long this metal that is plated on the electrode surface that restores of time is more many.Second step then was the electrolysis process in leaching, when enough metal levels are plated on the working electrode surface, increased electromotive force with constant speed to working electrode, and this metal will stripping on working electrode (being oxidation).The researcher can identify the kind of metal according to the position of oxidation potential, and can carry out the detection of contents of many kinds of heavy metal ion by the difference of oxidation potential simultaneously.Compare concentration of heavy metal ion in the calculation sample by calculating standard solution under electric current peak height or peak area and the same terms.So stripping peak current and spike potential can be used as quantitatively and the basis of qualitative analysis concentration of heavy metal ion.Up to the present, the ASV method can be measured the heavy metal element more than 40 kinds, it can the fast detecting sample in trace (10
-6Advantages such as that heavy metal ion mol/L), this method have is highly sensitive, apparatus is simple, and detection speed is fast, easily be automated.And so far stripping voltammetry all to adopt traditional working electrode be hanging mercury electrode (HME) and mercury film electrode (MFE), because mercury contains severe toxicity is arranged, can environment be polluted, so the non-mercury type electrode anode stripping voltammetry of the friendly type of research environment detects heavy metal ion and expands its bioanalysis purposes and environmental monitoring is the important topic that will study of electrochemical analysis worker in recent years.
Summary of the invention
The purpose of this invention is to provide a kind of heavy metal ion such as Pb that can the fast detecting neodymium iron boron product electroplates in the sewage that the back produces
2+Deng, and can not cause to second environmental pollution the environmentally friendly method with heavy metal ion in the non-mercury type electrode anode stripping voltammetry detection sewage.
The method of heavy metal ion in the detection sewage of the present invention comprises step: (1) is gathered sewage sample and is transferred PH2-5; (2) logical inert gas is removed the dissolved oxygen DO in the sewage sample; (3) with anodic stripping voltammetry, employing comprises the three-electrode system of working electrode, auxiliary electrode and contrast electrode, by regulating electrochemical workstation, with heavy metal ion enrichment, leave standstill stripping again, electric current-the potential curve that records this process in leaching records the stripping peak point current of this process in leaching, and scans resulting linear fit formula according to the standard solution anode stripping under the same terms and calculate concentration of heavy metal ion in the sample; In the described three-electrode system of step (3), as working electrode, the Pt/Ti electrode is as auxiliary electrode with carbon nano tube modified glass-carbon electrode, and saturated Ag/AgCl electrode is as contrast electrode.
It is good that step (1) is transferred PH4-5 with the HAc-NaAc damping fluid.
The enrichment process work potential of step (3) heavy metal ion is-1.2-0.9V, and the time of setting is 30-500s, makes heavy metal ion enrichment in the solution under stirring condition to working electrode.
The process in leaching working electrode electromotive force of step (3) heavy metal ion makes the heavy metal particle stripping that is enriched on the working electrode by-0.8-0.2V forward scan.
The present invention adopts the CHI660C electrochemical workstation of Shanghai occasion China Instr Ltd., described carbon nano tube modified glass carbon working electrode adopts carbon nano-tube and double hexadecyl phosphoric acid is joined in the ultrapure water, obtain the suspending liquid of black after the ultrasonic dispersion, glass-carbon electrode adopts alumina powder and chamois leather to be polished to minute surface, behind the ultrapure water cleaning, drying, above-mentioned black suspension is added drop-wise to the glass-carbon electrode surface, namely makes carbon nano tube modified glass-carbon electrode with infrared lamp after with solvent evaporates wherein.
The present invention adopts carbon nano tube modified glass-carbon electrode as working electrode, and the Pt/Ti electrode is as auxiliary electrode, and saturated Ag/AgCl electrode is electroplated the back heavy metal ion Pb that produced in sewage with anodic stripping voltammetry to neodymium iron boron product as contrast electrode
2+, Cu
2+Isoionic content detects.Than traditional spectrophotometric method, mass spectrum coupling method etc. adopt method of the present invention to carry out that the detection of heavy metal ion in the sewage is easy and simple to handle, detection efficiency is high and can not cause to second environmental pollution environmental friendliness.
Description of drawings
Fig. 1 is pick-up unit synoptic diagram of the present invention;
Fig. 2 is the volt-ampere curve figure that the progressively dripping method of lead ion solution obtains;
Fig. 3 is the linear fit figure of plumbum ion concentration and peak current;
Among the figure: 1, electrochemical workstation; 2, carbon nano tube modified glass-carbon electrode; 3, contrast electrode; 4, platinum titanium electrode; 5, magnetic stirring apparatus.
Embodiment
Embodiment 1
Neodymium iron boron is electroplated the used water of factory and generally need just can be discharged in the physical environment through handling.After the institute sewage effluent is handled, need measure the content of heavy metal ion wherein whether below state specified standards.The sewage sample 10ml that obtains after treatment is placed in the beaker, the HAc-NaAc buffer solution of 1 mol/L of adding and sample equal volume in beaker, measuring the solution pH value is 4.3.Beaker is put on the magnetic stirring apparatus, adopt anodic stripping voltammetry, with carbon nano tube modified glass-carbon electrode as working electrode, the Pt/Ti electrode is as auxiliary electrode, saturated Ag/AgCl electrode is as contrast electrode, each electrode is wired to the CHI660C electrochemical workstation respectively, feeds 10min nitrogen in beaker, to remove the dissolved oxygen DO in the water.Then magnetic stirring apparatus is opened, adopted the electric current-time curve operation on the electrochemical workstation, make work potential be-1.2V, enrichment time is 3min, makes heavy metal ion enrichment in the solution under stirring condition to working electrode; After the enrichment operation is finished, close magnetic stirring apparatus, with solution left standstill 3mim.Adopt the anodic stripping voltammetry in the electrochemical workstation to carry out the stripping operation to being enriched to heavy metal particles on the working electrode then, with the working electrode electromotive force by-0.8-0.2V forward scan, sweep speed 10mV/s, record heavy metal ion Pb
2+The stripping peak current is 22.31 μ A.
The lead ion standard solution uses the plumbi nitras preparation, obtains by progressively dripping, and drips test from the per 5 μ g of 0-60 μ g/L.5 μ g/L (a), 10 μ g/L (b), 15 μ g/L (c), 17 μ g/L (d) are chosen in experiment, 19 μ g/L (e), and 22 μ g/L (f), 50 μ g/L (g) and 60 μ g/L (h) carry out the making of stripping volt-ampere canonical plotting respectively, as Fig. 2.Fig. 3 is plumbum ion concentration linear fit figure in the sewage that obtains through dripping method progressively, can know by linear fit, in 5-60 μ g/L scope, the proportional example relation of plumbum ion concentration and peak current, the linear dependence degree is 0.999427, and its equation of linear regression is I (μ A)=6.7455+1.0952 C (μ g/l).It is 14.7 μ g/L that sample lead ion peak point current 22.31 μ A are brought into the plumbum ion concentration that can obtain in the equation in the test solution.
Adopt method of the present invention to carry out the detection of heavy metal ion in the neodymium iron boron plant effuent, than traditional spectrophotometric, methods such as mass spectrum coupling, it is strong, highly sensitive to have ability simple to operate, as to detect rapid and anti-other ion interference, and can not cause to second environmental pollution environmental friendliness.
Claims (4)
1. method that detects heavy metal ion in the sewage comprises step: (1) is gathered sewage sample and is transferred PH in the 2-5 scope; (2) logical inert gas is removed the dissolved oxygen DO in the sewage sample; (3) with anodic stripping voltammetry, employing comprises the three-electrode system of working electrode, auxiliary electrode and contrast electrode, by regulating electrochemical workstation, with heavy metal ion enrichment, leave standstill stripping again, record the stripping peak point current of this process in leaching, and scan resulting linear fit formula according to the standard solution anode stripping under the same terms and calculate concentration of heavy metal ion in the sample; It is characterized in that in the described three-electrode system of step (3), as working electrode, the Pt/Ti electrode is as auxiliary electrode with carbon nano tube modified glass-carbon electrode, saturated Ag/AgCl electrode is as contrast electrode.
2. detect the method that heavily belongs to ion in the sewage according to claim 1, it is characterized in that, step (1) is transferred PH4-5 with the HAc-NaAc damping fluid.
3. detect the method for heavy metal ion in the sewage as claimed in claim 1 or 2, it is characterized in that, the enrichment process work potential of step (3) heavy metal ion is-1.2-0.9V, and enrichment time is 30-500s, makes heavy metal ion enrichment in the solution under stirring condition to working electrode.
4. detect the method for heavy metal ion in the sewage as claimed in claim 1 or 2, it is characterized in that, the process in leaching working electrode electromotive force of step (3) heavy metal ion makes the heavy metal particle stripping that is enriched on the working electrode by-0.8-0.2V forward scan.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103969320A (en) * | 2014-05-07 | 2014-08-06 | 深圳市宇驰检测技术有限公司 | Anodic stripping voltammetric detection method for cadmium in rice |
| CN104076083A (en) * | 2014-06-25 | 2014-10-01 | 施世英 | Heavy metal ion concentration test method adopting secondary sample injection |
| CN112161969A (en) * | 2020-10-23 | 2021-01-01 | 中国科学院合肥物质科学研究院 | Method and system for detecting content of metal ions in different forms |
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| CN102262112A (en) * | 2011-04-02 | 2011-11-30 | 中国科学院烟台海岸带研究所 | Alloy electrode electrochemical sensor for detecting trace heavy metals |
| CN102445488A (en) * | 2011-09-20 | 2012-05-09 | 青岛佳明测控仪器有限公司 | Multiparameter water quality heavy metal automatic online monitor based on anodic stripping voltammetry |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102262112A (en) * | 2011-04-02 | 2011-11-30 | 中国科学院烟台海岸带研究所 | Alloy electrode electrochemical sensor for detecting trace heavy metals |
| CN102445488A (en) * | 2011-09-20 | 2012-05-09 | 青岛佳明测控仪器有限公司 | Multiparameter water quality heavy metal automatic online monitor based on anodic stripping voltammetry |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103969320A (en) * | 2014-05-07 | 2014-08-06 | 深圳市宇驰检测技术有限公司 | Anodic stripping voltammetric detection method for cadmium in rice |
| CN104076083A (en) * | 2014-06-25 | 2014-10-01 | 施世英 | Heavy metal ion concentration test method adopting secondary sample injection |
| CN112161969A (en) * | 2020-10-23 | 2021-01-01 | 中国科学院合肥物质科学研究院 | Method and system for detecting content of metal ions in different forms |
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Application publication date: 20131009 |