CN103837525A - Device and method for measuring total chromium of water body by flow-injection chemiluminiscence method by enriching and eluting - Google Patents

Device and method for measuring total chromium of water body by flow-injection chemiluminiscence method by enriching and eluting Download PDF

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CN103837525A
CN103837525A CN201410082137.6A CN201410082137A CN103837525A CN 103837525 A CN103837525 A CN 103837525A CN 201410082137 A CN201410082137 A CN 201410082137A CN 103837525 A CN103837525 A CN 103837525A
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enrichment
wash
chamber
pipeline
solution
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CN103837525B (en
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刘岩
褚东志
李洋
吴丙伟
张述伟
吴宁
马然
张颖颖
曹煊
刘东彦
郭翠莲
张颖
王茜
石小梅
王昭玉
范萍萍
张国华
吕靖
张婷
曹璐
任国兴
王洪亮
陈朝贵
杨小满
高杨
程岩
侯广利
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Oceanographic Instrumentation Research Institute Shandong Academy of Sciences
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Oceanographic Instrumentation Research Institute Shandong Academy of Sciences
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Abstract

The invention provides a device and a method for measuring total chromium of a water body by a flow-injection chemiluminiscence method by enriching and eluting. The method comprises the following steps: enriching total chromium based on a magnetic nano material, then eluting, forming a complex by eluted total chromium and dimethyl dimethoxy silicane, and oxidizing the complex and peroxided oxalate so as to generate chemiluminiscence, wherein the chemiluminiscence intensity has linear relationship with the concentration of the total chromium in the water body. A method for measuring total chromium of the water body by the flow-injection chemiluminiscence method by enriching and eluting of the magnetic nano material is established by utilizing an enriching-eluting-complexing-chemiluminiscence technique. The characteristics of rapidity, simplicity, convenience and high accuracy can be achieved in the determination of total chromium in the water body.

Description

Enrichment wash-out Flow Injection Chemiluminescence is measured the device and method of the total chromium of water body
Technical field
The present invention relates to environmental chemistry monitoring technical field, specifically, relate to measure the method for heavy metal in water.
Background technology
Chromium is one of important content in water body environment monitoring.At present, the common method of measuring total chromium in water body has diphenyl carbazide spectrophotometry, flameless atomic absorption spectrometry etc., these method general character are that the duration is long, analytic process is numerous and diverse, condition harshness, reagent consumption are large, and some method also introducing in various degree harmful organic solvent, cause the waste of a large amount of reagent, produce secondary pollution.Simultaneously most methods need expensive large-scale instrument, method is all the pattern to lab analysis after employing on-site sampling in addition, can not realize scene, the real-time mode of measuring, sample transportation and processing procedure are easily introduced other interfering materials, the accuracy of impact analysis.Therefore this process is for trace level ultimate analysis, can not guarantee the possibility that there will not be secondary to get dirty, and for example, for water body environment complicated and changeable: element morphology is affected greatly by space-time; Majority is again in interrelated, interactional state; In environment, temperature, pressure changes greatly, and accuracy and the reliability of its result are under suspicion, thereby can not definitely grasp water quality present situation and ANOMALOUS VARIATIONS thereof.
In recent years, along with the development of electronic technology, new material, new technology, new optical device, especially making rapid progress of computer technology, carry out the corresponding appearance of method of the total chromium of analyzing water body by automatic analyzer, although these technology have been broken away from some shortcomings of lab analysis, as long in the duration, analytic process is numerous and diverse, condition harshness etc., but the defect that it also exists, and poor stability, sensitivity and resolution are low, ion interference etc. is difficult to overcome, make it range of application and be restricted, could not be widely used.
Existing enrichment method and device exist bioaccumulation efficiency low in addition, and system selectivity is bad, easily introduce and disturb, and organic solvent use amount is large, has secondary pollution problems.The chemiluminescence detection chamber using is now owing to being used flow through structure, and the sample residence time is short, the low defect of chemical reflective detection efficiency.
Summary of the invention
The invention provides a kind of enrichment wash-out Flow Injection Chemiluminescence and measure the device and method of the total chromium of water body, what it can solve that prior art exists can not work on the spot, analyzes the duration long, and analytic process is numerous and diverse, condition harshness, energy consumption are large, especially produce secondary pollution problems.Design enrichment-wash-out chamber and chemiluminescence detection chamber by novelty, solved existing enrichment method and existed bioaccumulation efficiency low, system selectivity is bad, easily introduces and disturbs, and organic solvent use amount is large, has secondary pollution problems; Solved the chemiluminescence detection chamber of present use owing to using flow through structure, the sample residence time is short, and the low defect of chemical reflective detection efficiency has realized efficiently concentrating-wash-out, the total chromium of rapid flow injected chemical luminescence method measurement water body.
In order to reach the object solving the problems of the technologies described above, technical scheme of the present invention is, a kind of enrichment wash-out Flow Injection Chemiluminescence is measured the device of the total chromium of water body, and described device comprises enrichment-wash-out chamber, sensing chamber, Electro-Optical Sensor Set, control device, data processing equipment, water sample pump, buffer solution pump, oxidant pump, enrichment liquid pump, wash-out liquid pump, water sample pump after wash-out, complexing agent pump, luminescence reagent pump, described enrichment-wash-out chamber is by pipeline and water sample pipeline, damping fluid pipeline, oxygenant pipeline, pregnant solution pipeline, eluent pipeline connects, and sensing chamber is by pipeline and luminescence reagent pipeline, complexing agent pipeline, eluent pipeline connects, described enrichment-wash-out chamber comprises enrichment-wash-out chamber on top and the air chamber of bottom, described enrichment-wash-out chamber top is provided with water sample entrance and eluent entrance, described enrichment-wash-out chamber bottom is provided with eluent escape hole and pregnant solution escape hole, in described enrichment-wash-out chamber, be interval with multiple tracks sieve plate, on sieve plate, be filled with graininess magnetic Nano material at least partly, between described enrichment-wash-out chamber and described air chamber, be provided with micropore electromagnet, described air chamber is provided with nitrogen inlet.
Described graininess magnetic Nano material is parcel dimethyl silicone polymer coating take tri-iron tetroxide as carrier, utilizes sodium humate load to modify the magnetic Nano material of dimethyl silicone polymer coating.
Described sieve plate is to be made up of polytetrafluoroethylmaterial material, except the superiors' sieve plate, is filled with described graininess magnetic Nano material on all the other sieve plates.
Described sensing chamber sidewall is provided with cotton-shaped glass wool.
Enrichment wash-out Flow Injection Chemiluminescence is measured a method for the total chromium of water body, and described method is carried out in the steps below by said apparatus:
(1), chemical illuminating reagent-peroxyoxalate under luminescence reagent pumping action as current-carrying;
(2), water sample and buffer solution under the effect of water sample pump and buffer solution pump, make water sample mix with the acetic acid-ammonium acetate solution in buffer solution-acetic acid-ammonium acetate pipeline respectively;
(3), mix rear continuation flows in pipeline, mix with the potassium persulfate solution in oxygenant-potassium persulfate pipeline again, under pH4.5~5.5 condition providing at acetic acid-ammonium acetate buffer solution, in flow process, in potassium persulfate oxidation water, trivalent chromium is sexavalent chrome;
(4), after oxidation reaction, mixed solution together flows into enrichment-wash-out chamber, inlet time is 10-15s, then stops flowing into.Top, enrichment-wash-out chamber mainly completes the work of enrichment-wash-out, be provided with POLYTETRAFLUOROETHYLSIFTER SIFTER, on sieve plate, be filled with graininess magnetic Nano material, bottom, enrichment chamber is provided with air chamber, between air chamber and top, enrichment-wash-out chamber, micropore electromagnet is installed, air chamber is provided with nitrogen and passes into valve, stops passing into nitrogen after passing into nitrogen bubble 30-50s, graininess magnetic Nano material and water body are mixed, complete enrichment process;
(5), micropore electromagnet is powered up, make electromagnet produce magnetic, electromagnet attracts magnetic Nano material to be deposited on every layer of sieve plate, and enrichment liquid pump stops after opening 20-30s, siphons away pregnant solution;
(6), stop after opening eluent-perchloric acid potassium pump 10-15s, the power-off of micropore electromagnet, loses magnetism electromagnet, passes into nitrogen graininess magnetic Nano material and water body are mixed, and stops passing into nitrogen after bubbling 30-50s;
(7), micropore electromagnet powers up, and makes electromagnet produce magnetic, electromagnet attracts magnetic Nano material to be deposited on every layer of sieve plate, after wash-out, water sample pump is opened, and siphons away eluent;
(8), mix with the dimethyldimethoxysil,ne solution in complexing agent-dimethyldimethoxysil,ne pipeline under the effect of eluent water sample pump after wash-out, in dimethyldimethoxysil,ne and eluent, total chromium forms complex compound;
(9), complex solution and current-carrying mix after together with the sensing chamber of circulating, sensing chamber's sidewall is provided with cotton-shaped glass wool, solution is by the mode infiltrating, flow down from top, cotton-shaped glass wool is flocculent structure, and micropore is many, surface area is large, has very strong adsorptive power, strengthened chemical reflector efficiency, pattern of invasion provides the photomultiplier in Electro-Optical Sensor Set to detect the efficiency of the chemiluminescence signal in solution;
(10) light signal that the solution that, photomultiplier convection current is passed through sends gathers amplification, and convert electric signal to and send into microcomputer data processing equipment, data processing equipment calculates the blank signal obtaining and sample signal, again according to the signal level difference data corresponding relation of signal level difference data and standard model, calculate in water body the concentration of total chromium, and show, printout.
The present invention also has following additional technical feature:
Described water sample liquid inventory is 5.0-10ml/min.
Described acetic acid-ammonium acetate buffer solution flow is 0.1--0.5ml/min, and concentration is (1.0-1.5) × 10 -2mol/L.
Described potassium persulfate solution flow is 0.1-0.5ml/min, and concentration is (0.5-1.0) × 10 -2mol/L.
Described graininess magnetic Nano material is parcel dimethyl silicone polymer coating take tri-iron tetroxide as carrier, utilizes sodium humate load to modify the functional magnetic nano material of preparation.
Described enrichment-wash-out chamber adopts polytetrafluoro material; structure is divided into top enrichment-wash-out chamber and bottom air chamber; top mainly completes the work of enrichment-wash-out; be provided with POLYTETRAFLUOROETHYLSIFTER SIFTER; totally 5 layers; on every layer of sieve plate, be filled with graininess magnetic Nano material, the superiors' sieve plate is empty, mainly prevents from stopping up injection port in particle mixed process.Bottom, enrichment chamber is provided with air chamber, between air chamber and enrichment-wash-out chamber, micropore electromagnet is installed, and air chamber is provided with nitrogen and passes into valve.When in enrichment-elution process, pass into nitrogen bubble, guarantee that particle evenly mixes with solution, after enrichment-elution process completes, micropore electromagnet powers up, and attraction magnetic Nano material is deposited on every layer of sieve plate, completes pregnant solution and eluent is discharged smoothly.Multiple sieve plate is set, has guaranteed that on every layer of sieve plate, graininess magnetic Nano material mixes with the even of water body, increased enrichment and elution efficiency.
The nitrogen flow that described bubbling enters enrichment-wash-out chamber is 20-50ml/min.
Described eluent-potassium perchlorate flow is 0.5-1.0ml/min.
Described complexing agent is 0.5-1.0ml/min in pumping action down-off, and concentration is 0.1-0.3mol/L.
Described peroxyoxalate is as current-carrying under pumping action, and flow is 0.1-0.3ml/min, and concentration is 0.01-0.03mol/L.
Described sensing chamber adopts stainless steel material, chamber sidewall is provided with cotton-shaped glass wool, solution is by the mode infiltrating, flow down from top, cotton-shaped glass wool is flocculent structure, and micropore is many, surface area is large, has very strong adsorptive power, strengthened chemical reflector efficiency, pattern of invasion provides the efficiency of the chemiluminescence signal in photomultiplier detection solution in Electro-Optical Sensor Set.
Described photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
Described pump is peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
Utilize microcomputer data processing equipment, realize the calculating to total chromium concn in described data processing equipment control, signal processing and water body by software programming.
Nano material is because specific surface area is large, and high adsorption capacity, adsorption capacity to many heavy metal ion are large, and can reach adsorption equilibrium within a short period of time, is a kind of ideal Solid-Phase Extraction sorbing material.Particularly magnetic Nano material, because having superparamagnetism, by means of externally-applied magnetic field, can shorten enrichment time greatly.Silicon coating material can strengthen absorption property through modifying, simplifies enrichment operation, improve the recovery etc., a kind of macromolecule ionic liquid of sodium humate, by utilize sodium humate load modify tri-iron tetroxide-wrap up in dimethyl silicone polymer core-shell structure magnetic nano material extracting and enriching water total chromium there is very large application prospect, be a kind of ideal heavy metal ion extracting and enriching mode.Utilize in addition the high sensitivity of chemiluminescence reaction to become the desirable means that present analysis is measured, in water body, chromium and dimethyldimethoxysil,ne solution are mixed to form complex compound; This complex compound mixes with peroxyoxalate and has specificity chemiluminescence phenomenon; In the strong degree of chemiluminescence and water body, the concentration of total chromium element has linear relationship simultaneously, therefore have fast by the method for utilizing total chromium in magnetic Nano material enrichment-wash-out flow-injection chemiluminescence method water body that enrichment-wash-out-complexing-chemiluminescence sets up, the feature easy, accuracy is high.
Magnetic Nano material enrichment-wash-out Flow Injection Chemiluminescence is measured the method for the total chromium of water body by the integrated portable injection chemiluminescence Photodetection system light, mechanical, electrical, computing machine forms.Can be divided into five parts by operational module:
Part I is enrichment-elution system; enrichment-wash-out cell structure is divided into top, enrichment-wash-out chamber and air chamber; top mainly completes the work of enrichment-wash-out; be provided with POLYTETRAFLUOROETHYLSIFTER SIFTER; totally 5 layers; on every layer of sieve plate, be filled with graininess magnetic Nano material; graininess magnetic Nano material is parcel dimethyl silicone polymer coating take tri-iron tetroxide as carrier; utilize sodium humate load to modify the functional magnetic nano material of preparation; the superiors' sieve plate is empty, mainly prevents from stopping up injection port in particle mixed process.Bottom, enrichment chamber is provided with air chamber, between air chamber and top, enrichment-wash-out chamber, micropore electromagnet is installed, and air chamber is provided with nitrogen and passes into valve.When in enrichment-elution process, pass into nitrogen bubble, guarantee that particle evenly mixes with solution, after enrichment-elution process completes, micropore electromagnet powers up, and attraction magnetic Nano material is deposited on every layer of sieve plate, completes pregnant solution and eluent is discharged smoothly.Multiple sieve plate is set, has guaranteed that on every layer of sieve plate, graininess magnetic Nano material mixes with the even of water body, increased enrichment and elution efficiency.
Part II is flow injection part, be mainly in water body total chromium and complexing agent-dimethyldimethoxysil,ne as one moving, without the continuous flow of airspace, there is complex reaction, form complex compound, this complex compound again with chemical illuminating reagent-peroxyoxalate generation chemical reaction, finally produce can be detected chemiluminescence signal, by carrier band in sensing chamber.
Part III is opto-electronic conversion and amplifier section, the main low-light photomultiplier that adopts is as detecting element, carrier fluid circulation sensing chamber, sensing chamber's sidewall is provided with cotton-shaped glass wool, and solution is by the mode infiltrating, flow down from top, cotton-shaped glass wool is flocculent structure, and micropore is many, surface area is large, has very strong adsorptive power, strengthened chemical reflector efficiency, pattern of invasion provides the efficiency of the chemiluminescence signal in photomultiplier detection solution in Electro-Optical Sensor Set; The light signal producing is transformed into electric signal immediately, and by continuous recording.
Part IV is data acquisition, recording section, and this part completes collection, A/D conversion, transmission and the storage of electric signal.
Part V is microcomputer data handling system, main being responsible for calculated the blank signal obtaining and sample signal, strengthen again the signal enhancing degree difference data corresponding relation of degree difference data and standard model according to signal, calculate in water body the concentration of total chromium element, and show, printout.
Because chemiluminescence reaction speed is very fast conventionally; so must guarantee sample and mixing that luminescence reagent can fast, effectively, highly reappear; Flow Injection Technique has met this requirement; therefore it is not only highly sensitive that the portable injection chemiluminescence mode that produces of combining with chemiluminescence analysis by enrichment-wash-out-complexing-Flow Injection Technique is measured in water body the method for total chromium; the range of linearity is wide; and fast, favorable reproducibility, automaticity be high, can be developed rapidly in fields such as environmental analyses.
The present invention processes the method for measuring to total chromium in water body by integrated enrichment-wash-out-complexing technology, Flow Injection Technique, chemiluminescence, electrooptical device, data acquisition, software.By enrichment-wash-out-complexing-integrated design, can realize the total chromium efficiently concentrating of trace in water body-quick wash-out and complexing and there is automatic injection in conjunction with Flow Injection Technique, controlled dispersion and accurately feature fast, adopt again sensitive chemical luminescence detection method, therefore utilize integrated enrichment-wash-out-complexing-technology, in the flow-injection chemiluminescence method water body that the complex compound forming by detection is again set up chemiluminescence degree value, the method for total chromium has scene, fast, easy, sensitive feature, what it can solve that prior art exists can not work on the spot, analyze the duration long, analytic process is numerous and diverse, condition harshness, energy consumption is large, especially produce secondary pollution problems, current very effective express-analysis means, it is desirable environmental analysis detection method, belong to environmental protection method.The advantage that this method has can make this method developed and popularization in fields such as environmental analyses.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, method of the present invention is described in detail.
Fig. 1 is the inventive method principle of work process flow diagram;
Fig. 2 is the structure of the detecting device schematic diagram that the inventive method adopts.
1, pregnant solution gatherer; 2, enrichment liquid pump; 3, oxygenant; 4, oxidant pump; 5, damping fluid; 6, buffer solution pump; 7, water sample; 8, blank solution-distilled water; 9, water sample pump; 10, enrichment-wash-out chamber; 11, wash-out liquid pump; 12, eluent; 13, complexing agent pump; 14, complexing agent; 15, luminous agent pump; 16, luminous agent; 17, sensing chamber; 18, control device; 19, data processing equipment; 20, liquid waste collector; 21, Electro-Optical Sensor Set; 22, water sample pump after wash-out; 23, nitrogen cylinder.
Fig. 3 is enrichment-wash-out cell structure schematic diagram that the inventive method adopts.
10, enrichment-wash-out chamber; 10-1, water sample entrance; 10-2, nitrogen exhaust valve; 10-3, sieve plate; 10-4, graininess magnetic Nano material; 10-5, enrichment-wash-out chamber; 10-6, eluent escape hole; 10-7, pregnant solution escape hole; 10-8, micropore electromagnet; 10-9, air chamber; 10-10, nitrogen inlet; 10-11, eluent entrance.
Fig. 4 is sensing chamber's structural representation that the inventive method adopts.
17, sensing chamber; 17-1, photomultiplier; 17-2, cotton-shaped glass wool; 17-3, entrance; 17-4, outlet.
Embodiment
Referring to Fig. 3, enrichment-wash-out chamber 10 comprises enrichment-wash-out chamber 10-5 on top and the air chamber 10-9 of bottom, and enrichment-wash-out chamber 10-5 on top is cylindrical shape, and the air chamber of bottom is that 10-9 is conical.Enrichment-wash-out chamber 10-5 top is provided with water sample entrance 10-1 and eluent entrance 10-11, enrichment-wash-out chamber 10-5 bottom is provided with eluent escape hole 10-6 and pregnant solution escape hole 10-7, in enrichment-wash-out chamber 10-5, be interval with 5 road sieve plate 10-3, sieve plate 10-3 is made up of polytetrafluoroethylmaterial material.Except the sieve plate 10-3 of the superiors, on remaining sieve plate 10-3, be filled with graininess magnetic Nano material 10-4, described graininess magnetic Nano material 10-4 is parcel dimethyl silicone polymer coating take tri-iron tetroxide as carrier, utilizes sodium humate load to modify the magnetic Nano material of dimethyl silicone polymer coating.Between enrichment-wash-out chamber 10-5 and air chamber 10-9, be provided with micropore electromagnet 10-8, described air chamber 10-9 is provided with nitrogen inlet 10-10.
Referring to Fig. 4, sensing chamber's 17 sidewalls are provided with cotton-shaped glass wool 17-2 from top to bottom, solution is by the mode infiltrating, flow down from top, cotton-shaped glass wool is flocculent structure, and micropore is many, surface area is large, has very strong adsorptive power, strengthened chemical reflector efficiency, pattern of invasion provides the photomultiplier in Electro-Optical Sensor Set to detect the efficiency of the chemiluminescence signal in solution.
Referring to Fig. 1 and Fig. 2, the inventive method comprises following step:
(1) chemical illuminating reagent-peroxyoxalate 16 under luminescence reagent pump 15 effect as current-carrying;
(2) water sample mixes with the acetic acid-ammonium acetate solution in buffer solution 5-acetic acid-ammonium acetate pipeline under the effect of water sample pump 9;
(3) mix rear continuation flows in pipeline, mix with the potassium persulfate solution in oxygenant 3-potassium persulfate pipeline again, under pH4.5~5.5 condition providing at acetic acid-ammonium acetate buffer solution, in flow process, in potassium persulfate oxidation water, trivalent chromium is sexavalent chrome.
(4) after oxidation reaction, mixed solution together flows into enrichment-wash-out chamber 10, and inlet time is 10-15s, then stops flowing into.Enrichment-wash-out chamber 10-5 mainly completes the work of enrichment-wash-out, be provided with POLYTETRAFLUOROETHYLSIFTER SIFTER 10-3, on sieve plate 10-3, be filled with graininess magnetic Nano material 10-4, bottom, enrichment chamber is provided with air chamber 10-9, between air chamber 10-9 and enrichment wash-out chamber 10-5, micropore electromagnet 10-8 is installed, air chamber 10-9 is provided with nitrogen inlet 10-10 place and is provided with nitrogen gas admittance valve, after passing into nitrogen bubble 30-50s, stop passing into nitrogen, graininess magnetic Nano material 10-4 and water body are mixed, complete enrichment process.
(5) the micropore electromagnet 10-8 between air chamber 10-9 and enrichment-wash-out chamber 10-5 powers up, make micropore electromagnet 10-8 produce magnetic, it is upper that micropore electromagnet 10-8 attracts magnetic Nano material to be deposited to every layer of sieve plate 10-3, and enrichment liquid pump stops after opening 20-30s, siphons away pregnant solution.
(6) after unlatching eluent-perchloric acid potassium pump 10-15s, stop 11s, micropore electromagnet 10-8 power-off, loses magnetism electromagnet, passes into nitrogen graininess magnetic Nano material 10-4 and water body are mixed, and stops passing into nitrogen after bubbling 30-50s.
(7) micropore electromagnet powers up 10-8, makes micropore electromagnet 10-8 produce magnetic, and it is upper that micropore electromagnet 10-8 attracts magnetic Nano material to be deposited to every layer of sieve plate 10-3, and after wash-out, water sample pump 22 is opened, and siphons away eluent.
(8) under the effect of eluent water sample pump 22 after wash-out, mix with the dimethyldimethoxysil,ne solution in complexing agent 14-dimethyldimethoxysil,ne pipeline, in dimethyldimethoxysil,ne and eluent, total chromium forms complex compound;
(9) complex solution flows into sensing chamber 17 together with after current-carrying mixing, sensing chamber's 17 sidewalls are provided with cotton-shaped glass wool 17-2, solution is by the mode infiltrating, flow down from top, cotton-shaped glass wool 17-2 is flocculent structure, and micropore is many, surface area is large, has very strong adsorptive power, strengthened chemical reflector efficiency, pattern of invasion provides the photomultiplier in Electro-Optical Sensor Set 21 to detect the efficiency of the chemiluminescence signal in solution;
(10) light signal that the solution that photomultiplier convection current is passed through sends gathers amplification, and convert electric signal to and send into microcomputer data processing equipment, data processing equipment 19 calculates the blank signal obtaining and sample signal, again according to the signal level difference data corresponding relation of signal level difference data and standard model, calculate in water body the concentration of total chromium, and show, printout.
In the above-described embodiments:
Described water sample liquid inventory is 5.0-10ml/min.
Described acetic acid-ammonium acetate buffer solution flow is 0.1-0.5ml/min, and concentration is (1.0-1.5) × 10 -2mol/L.
Described potassium persulfate solution flow is 0.1-0.5ml/min, and concentration is (0.5-1.0) × 10 -2mol/L.
Described graininess magnetic Nano material is parcel dimethyl silicone polymer coating take tri-iron tetroxide as carrier, utilizes sodium humate load to modify the functional magnetic nano material of preparation.
Described enrichment-wash-out chamber adopts polytetrafluoro material; structure is divided into top enrichment-wash-out chamber 10-5 and bottom air chamber 10-9; top mainly completes the work of enrichment-wash-out; be provided with POLYTETRAFLUOROETHYLSIFTER SIFTER 10-3; totally 5 layers; on every layer of sieve plate 10-3, be filled with graininess magnetic Nano material 10-4, the sieve plate 10-3 of the superiors does not place graininess magnetic Nano material 10-4, mainly prevents from stopping up injection port in particle mixed process.Bottom, enrichment chamber is provided with air chamber 10-9, between air chamber 10-9 and enrichment-wash-out chamber, micropore electromagnet 10-8 is installed, and the air chamber entrance 10-10 place of air chamber 10-9 is provided with nitrogen and passes into valve.When in enrichment-elution process, pass into nitrogen bubble, guarantee that particle evenly mixes with solution, after enrichment-elution process completes, micropore electromagnet powers up, and attracts magnetic Nano material to be deposited to every layer of sieve plate 10-3 and goes up, and completes pregnant solution and eluent is discharged smoothly.Multiple sieve plate 10-3 is set, has guaranteed that the upper graininess magnetic Nano material 10-4 of every layer of sieve plate 10-3 mixes with the even of water body, has increased enrichment and elution efficiency.
The nitrogen flow that described bubbling enters enrichment chamber is 20-50ml/min.
Described eluent-potassium perchlorate flow is 0.5-1.0ml/min.
Described complexing agent is 0.5-1.0ml/min in pumping action down-off, and concentration is 0.1-0.3mol/L.
Described peroxyoxalate is as current-carrying under pumping action, and flow is 0.1-0.3ml/min, and concentration is 0.01-0.03mol/L.
Described sensing chamber adopts stainless steel material, chamber sidewall is provided with cotton-shaped glass wool, solution is by the mode infiltrating, flow down from top, cotton-shaped glass wool is flocculent structure, and micropore is many, surface area is large, has very strong adsorptive power, strengthened chemical reflector efficiency, pattern of invasion provides the efficiency of the chemiluminescence signal in photomultiplier detection solution in Electro-Optical Sensor Set.
Described photomultiplier adopts Japanese shore pine Photosensor Modules H5784 Series.
Described pump is peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
Utilize microcomputer data processing equipment, realize the calculating to total chromium concn in described data processing equipment control, signal processing and water body by software programming.
The light signal that reaction is sent is faint chemiluminescence signal, faint optical signal is through optical lens cumulative, import photomultiplier, light signal is converted to electric signal output through photomultiplier processing, output electrical signals is changed through feeble signal amplifying circuit, is amplified to certain voltage amplitude and send the A/D ALT-CH alternate channel of data processing equipment to carry out quantification treatment.
The above, be only preferred embodiment of the present invention, is not the restriction of the present invention being made to other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.All technical solution of the present invention contents that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.

Claims (10)

1. enrichment wash-out Flow Injection Chemiluminescence is measured a device for the total chromium of water body, and described device comprises enrichment-wash-out chamber, sensing chamber, Electro-Optical Sensor Set, control device, data processing equipment, water sample pump, buffer solution pump, oxidant pump, enrichment liquid pump, wash-out liquid pump, water sample pump after wash-out, complexing agent pump, luminescence reagent pump, described enrichment-wash-out chamber is by pipeline and water sample pipeline, damping fluid pipeline, oxygenant pipeline, pregnant solution pipeline, eluent pipeline connects, and sensing chamber is by pipeline and luminescence reagent pipeline, complexing agent pipeline, eluent pipeline connects, it is characterized in that, described enrichment-wash-out chamber comprises enrichment-wash-out chamber on top and the air chamber of bottom, described enrichment-wash-out chamber top is provided with water sample entrance and eluent entrance, described enrichment-wash-out chamber bottom is provided with eluent escape hole and pregnant solution escape hole, in described enrichment-wash-out chamber, be interval with multiple tracks sieve plate, on sieve plate, be filled with graininess magnetic Nano material at least partly, between described enrichment-wash-out chamber and described air chamber, be provided with micropore electromagnet, described air chamber is provided with nitrogen inlet.
2. a kind of enrichment wash-out Flow Injection Chemiluminescence according to claim 1 is measured the device of the total chromium of water body, it is characterized in that, described graininess magnetic Nano material is parcel dimethyl silicone polymer coating take tri-iron tetroxide as carrier, utilizes sodium humate load to modify the magnetic Nano material of dimethyl silicone polymer coating.
3. a kind of enrichment wash-out Flow Injection Chemiluminescence according to claim 1 is measured the device of the total chromium of water body, it is characterized in that, described sieve plate is to be made up of polytetrafluoroethylmaterial material, except the superiors' sieve plate, is filled with described graininess magnetic Nano material on all the other sieve plates.
4. a kind of enrichment wash-out Flow Injection Chemiluminescence according to claim 1 is measured the device of the total chromium of water body, it is characterized in that, described sensing chamber sidewall is provided with cotton-shaped glass wool.
5. utilize a method for the total chromium of measurement device water body described in claim 1 or 2 or 3 or 4, its spy
Levy and be, described method is carried out in the steps below by described device:
(1), chemical illuminating reagent-peroxyoxalate under luminescence reagent pumping action as current-carrying;
(2), water sample and buffer solution under the effect of water sample pump and buffer solution pump, make water sample mix with the acetic acid-ammonium acetate solution in buffer solution-acetic acid-ammonium acetate pipeline respectively;
(3), mix rear continuation flows in pipeline, mix with the potassium persulfate solution in oxygenant-potassium persulfate pipeline again, under pH4.5~5.5 condition providing at acetic acid-ammonium acetate buffer solution, in flow process, in potassium persulfate oxidation water, trivalent chromium is sexavalent chrome;
(4), after oxidation reaction, mixed solution together flows into enrichment-wash-out chamber, inlet time is 10-15s, then stop flowing into, the air chamber of enrichment-wash-out chamber stops passing into nitrogen after passing into nitrogen bubble 30-50s, and graininess magnetic Nano material and water body are mixed, and completes enrichment process;
(5), micropore electromagnet is powered up, make electromagnet produce magnetic, electromagnet attracts magnetic Nano material to be deposited on every layer of sieve plate, and enrichment liquid pump stops after opening 20-30s, siphons away pregnant solution;
(6), stop after opening eluent-perchloric acid potassium pump 10-15s, the power-off of micropore electromagnet, loses magnetism electromagnet, passes into nitrogen graininess magnetic Nano material and water body are mixed, and stops passing into nitrogen after bubbling 30-50s;
(7), micropore electromagnet powers up, and makes electromagnet produce magnetic, electromagnet attracts magnetic Nano material to be deposited on every layer of sieve plate, after wash-out, water sample pump is opened, and siphons away eluent;
(8), mix with the dimethyldimethoxysil,ne solution in complexing agent-dimethyldimethoxysil,ne pipeline under the effect of eluent water sample pump after wash-out, in dimethyldimethoxysil,ne and eluent, total chromium forms complex compound;
(9), complex solution and current-carrying mix after together with flow into sensing chamber, sensing chamber's sidewall is provided with cotton-shaped glass wool, solution is by the mode infiltrating, from the top of cotton-shaped glass wool to dirty;
(10) light signal that the solution that, photomultiplier convection current is passed through sends gathers amplification, and convert electric signal to and send into microcomputer data processing equipment, data processing equipment calculates the blank signal obtaining and sample signal, again according to the signal level difference data corresponding relation of signal level difference data and standard model, calculate in water body the concentration of total chromium, and show, printout.
6. method according to claim 5, is characterized in that, described water sample liquid inventory is 5.0-10ml/min; Described acetic acid-ammonium acetate buffer solution flow is 0.1-0.5ml/min, and concentration is (1.0-1.5) × 10 -2mol/L; Described potassium persulfate solution flow is 0.1-0.5ml/min, and concentration is (0.5-1.0) × 10 -2mol/L.
7. method according to claim 5, is characterized in that, the nitrogen flow that described bubbling enters enrichment-wash-out chamber is 20-50ml/min.
8. method according to claim 5, is characterized in that, described eluent-potassium perchlorate flow is 0.5-1.0ml/min.
9. method according to claim 5, is characterized in that, described complexing agent is 0.5-1.0ml/min in pumping action down-off, and concentration is 0.1-0.3mol/L.
10. method according to claim 5, is characterized in that, described peroxyoxalate is as current-carrying under pumping action, and flow is 0.1-0.3ml/min, and concentration is 0.01-0.03mol/L.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105301265A (en) * 2015-10-10 2016-02-03 山西师范大学 Automatic online magnetic solid-phase micro-extraction-desorption-detection apparatus and method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030193394A1 (en) * 1999-06-11 2003-10-16 Lamb George W. Apparatus and method for providing weather and other alerts
WO2004057312A1 (en) * 2002-12-20 2004-07-08 Research Institute Of Industrial Science & Technology Method and apparatus for analysing oxidation number 3 and 6 of chromium simultaneously
CN102788782A (en) * 2012-08-15 2012-11-21 山东省科学院海洋仪器仪表研究所 Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode
CN102809558A (en) * 2012-08-15 2012-12-05 山东省科学院海洋仪器仪表研究所 Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way
CN102841062A (en) * 2012-08-24 2012-12-26 渤海大学 Method for selectively and quantitatively collecting and measuring chromium (VI) in aquatic environment
CN102967574A (en) * 2012-12-11 2013-03-13 天津工业大学 Method for fast enriching and detecting trace amount of As (V) and Cr (VI) contained in water by filling microcolumn by utilizing fiber
CN103499570A (en) * 2013-10-14 2014-01-08 山东省科学院海洋仪器仪表研究所 Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030193394A1 (en) * 1999-06-11 2003-10-16 Lamb George W. Apparatus and method for providing weather and other alerts
WO2004057312A1 (en) * 2002-12-20 2004-07-08 Research Institute Of Industrial Science & Technology Method and apparatus for analysing oxidation number 3 and 6 of chromium simultaneously
CN102788782A (en) * 2012-08-15 2012-11-21 山东省科学院海洋仪器仪表研究所 Method for measuring dissolved oxygen of water body by flow-injection chemiluminiscence mode
CN102809558A (en) * 2012-08-15 2012-12-05 山东省科学院海洋仪器仪表研究所 Method for measuring polycyclic aromatic hydrocarbons (PAHs) of sea water in flow injection chemiluminescence way
CN102841062A (en) * 2012-08-24 2012-12-26 渤海大学 Method for selectively and quantitatively collecting and measuring chromium (VI) in aquatic environment
CN102967574A (en) * 2012-12-11 2013-03-13 天津工业大学 Method for fast enriching and detecting trace amount of As (V) and Cr (VI) contained in water by filling microcolumn by utilizing fiber
CN103499570A (en) * 2013-10-14 2014-01-08 山东省科学院海洋仪器仪表研究所 Detecting device and method for detecting flow injection chemiluminescence water inorganic mercury

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
付海曦等: "水体中重金属离子的检测方法研究进展", 《理化检验-化学分册》, vol. 48, no. 4, 30 April 2008 (2008-04-30) *
吴宏等: "流动注射在线富集分光光度法测定水样中痕量Cr", 《化工环保》, vol. 27, no. 6, 31 December 2007 (2007-12-31) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105301265A (en) * 2015-10-10 2016-02-03 山西师范大学 Automatic online magnetic solid-phase micro-extraction-desorption-detection apparatus and method thereof

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