CN203688493U - On-line multi-parameter heavy metal analyzer - Google Patents

On-line multi-parameter heavy metal analyzer Download PDF

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Publication number
CN203688493U
CN203688493U CN201320835330.3U CN201320835330U CN203688493U CN 203688493 U CN203688493 U CN 203688493U CN 201320835330 U CN201320835330 U CN 201320835330U CN 203688493 U CN203688493 U CN 203688493U
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module
water sample
electrode
valve
transfer valve
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乐文志
李艳丽
文新江
王勇平
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Bixing Iot Technology Shenzhen Co ltd
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ZHONGXING INSTRUMENT (SHENZHEN) Co Ltd
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Abstract

The utility model discloses an on-line multi-parameter heavy metal analyzer which is used for detecting the content of heavy metals in water. The analyzer is characterized by comprising a control module, a water sample acquisition pretreatment module, a quantification module, a detection module and a waste liquid emptying module, wherein the water sample acquisition pretreatment module, the quantification module, the detection module and the waste liquid emptying module are respectively communicated with the control module; the control module is used for controlling the water sample acquisition pretreatment module to lead a water sample to be tested into the quantification module; the water sample to be tested, which is in the quantification module, is pressed into the detection module through a pressure pump and a liquid conveying pipeline; the content of the heavy metals in the water sample to be tested is detected through the detection module; the water sample to be tested, which is detected, is led into the waste liquid emptying module and discharged into a waste liquid bucket through the waste liquid emptying module. According to the analyzer, reagent flowing paths are independent according to testing requirements, so that the cross contamination of the flowing paths is avoided; the accuracy of a testing result is ensured by virtue of precise quantification modes; different quantification modes are adopted according to different quantitative precision requirements, so that the cost is lowered and the maintenance quantity is reduced; mercury liquid is recycled and a bismuth film is plated, so that the secondary contamination of an environment is reduced.

Description

Multiparameter heavy metal online analyzer
Technical field
The utility model relates to the in-line analyzer of heavy metal monitoring in water quality, in particular multiparameter heavy metal analyser.
Background technology
Heavy metal online analyzer device mainly adopts two kinds of analytical approachs at present, is respectively ultraviolet light-visible spectrophotometry and electrochemical process.Ultraviolet light-visible spectrophotometry heavy metal online analyzer device is applied at most on current heavy metal online analyzer market, have advantages of that cost is low, but detectability can only reach tens ppb levels, major part can only be used for the on-line monitoring of industrial waste water, cannot meet the heavy metal on-line monitoring requirement in potable water, surface water and groundwater, and reagent consumption is large, the test duration is long, and maintenance cost is high.On market, the method for another heavy metal online analyzer is electrochemical process, the sensitivity of the method method is very high, selectivity good, detectability is low, measured matter concentration can reach ppb magnitude, in simple, easy to operate, the applicable surface water of instrument stream and underground water on-line analysis and Chemical Manufacture, automatically controls.Electrochemical process heavy metal online analyzer have detectability low, can be less than a ppb level, but at present domestic electrochemical heavy metals in-line analyzer is in by the status of external instrument monopolization, instrument purchase cost is high, promotes and is difficult at home.
Electrochemical process is in the market measured heavy metal online analyzer device and is mainly external instrument, adopt electrode to be mainly dropping-mercury electrode, consume a large amount of mercury, require very high to dripping mercury control assembly, and can not be subject to any vibrations in operational process, the oxide of mercury and mercury has very strong toxicity in addition, can cause secondary pollution to water body.The application, for above requirement, has designed a kind of multiparameter heavy metal online analyzer, meets the requirement of on-line monitoring instrument.
Summary of the invention
The purpose of this utility model is, a low detectability is provided, high selectivity, high stability, non-secondary pollution, operating cost low for detect the heavy metal online analyzer of multiple element simultaneously.
The utility model provides a kind of multiparameter heavy metal online analyzer, for detection of the content of beary metal in water quality, it comprises: control module and the water sampling pretreatment module being communicated with it respectively, quantitatively module, the emptying module of detection module and waste liquid, wherein, control module control water sampling pretreatment module will be tested water sample and be introduced in quantitative module, through forcing pump and liquid-transport pipe-line, the test water sample in quantitative module is pressed in detection module, by detection module, the content of beary metal in test water sample is detected, test water sample after detection imports the emptying module of waste liquid, be discharged in waste liquid barrel by the emptying module of waste liquid.
Preferably, described multiparameter heavy metal online analyzer also comprises dilution module, and described dilution module is communicated between quantitative module and detection module, carries out dilution process with the test water sample to deriving in quantitative module.
Preferably, described water sampling pretreatment module comprises several many qis valves, air and alkali lye transfer valve and dilution transfer valve, described many qis valve is connected with water sample bucket, deionization water bucker and digestion solution bucket respectively, import corresponding test water sample or reagent to quantitative module respectively, described air and alkali lye transfer valve are communicated with the valve of qi more than wherein, in air and alkali lye transfer valve, air transfer valve and air communication, alkali lye transfer valve is communicated with alkali lye, the Chang Kaiduan of dilution transfer valve is communicated with many qis valve and diluting tank respectively, and common port is communicated with peristaltic pump.Many qis valve connects respectively common port, water sample, digestion solution, acid solution, the deionized water of air transfer valve and realizes stream switching.Air and alkali lye transfer valve are realized the function conversion of sample introduction and stirring.Dilution transfer valve is realized the switching of water sample and dilution.
Described quantitative module comprises digestion pool, six logical proportional valve and fixed displacement pumps, wherein, between digestion pool and many qis of reagent valve, be communicated with by digestion pool transfer valve, six logical proportional valves are communicated between dilution module and detection module, and fixed displacement pump is communicated with reaction tank by a flow channel switching valve.Digestion pool realize water sample to be measured clear up obtain total heavy metal ion, six logical proportional valves realize by switching quantitative ring the quantitative effect of clearing up water sample, fixed displacement pump is realized extracting and will be treated that quantitative liquid is full of quantitative ring.Described detection module comprises reaction tank, is built in electrode and stirrer in reaction tank, and described stirrer is electrically connected with control module, and described reaction tank is communicated with plated film liquid pump and diluting tank, and the test water sample after coating liquid and dilution is imported in reaction tank.
Wherein, described electrode comprises working electrode, auxiliary electrode and contrast electrode, wherein, working electrode forms current return with auxiliary electrode and contrast electrode respectively, described working electrode is selected from glassy carbon electrode or gold electrode, described auxiliary electrode is selected from platinum electrode or platinum plate electrode, and described contrast electrode is selected from silver/silver chloride electrode or saturated calomel electrode.
Between described digestion pool and digestion pool transfer valve, and be provided with photoelectric detection system between described peristaltic pump and dilution transfer valve.Between digestion pool transfer valve and dilution transfer valve, be provided with peristaltic pump.Compared with prior art, the liquid flow path of the utility model multiparameter heavy metal online analyzer adopts the principle of independent separate, select multiple quantitative manner according to the requirement of different basis weights degree of accuracy, due to quantitative be the prescribed volume in proportional valve, avoid the impact on measuring accuracy of dead volume between wearing and tearing and the pump line of peristaltic pump, sample introduction uses air as carrier, has avoided the mutual pollution between reagent simultaneously, also guarantees the accurate of sample introduction reagent.The utility model adopts accurate proportional valve, and the low peristaltic pump of cost, has not only guaranteed quantitative precision, and has reduced the cost, and greatly guaranteed and extend the serviceable life of system, has reduced maintenance.Key reagents of the present utility model, adopts part reagent stream independent, fully avoids the cross pollution of reagent.Meanwhile, the working electrode that the utility model adopts is solid electrode, comprises glass-carbon electrode, and gold electrode etc., effectively avoid the secondary pollution of traditional dropping-mercury electrode in test, and the potential window of glass-carbon electrode is wide in addition, can test many kinds of substance.Coating liquid of the present utility model adopts recycle and reuse or the coating liquid without pollution remission in addition, there is no secondary pollution completely, and the linearity and the repeatability of electrode are better than dropping-mercury electrode.In reactor, adopt inert gas deoxygenation, played the effect stirring and also effectively removed the oxygen of clearing up in water sample to the impact of measuring, an other plated film can be measured more than 200 times, has reduced maintenance, the preferred bismuth film of plated film or mercury film, wherein bismuth film non-environmental-pollution.
The reagent stream of this multiparameter heavy metal online analyzer is independent according to test request, and stream is without cross pollution; Accurate quantitative manner, guarantees test result accuracy; According to the requirement of different basis weights precision, take different basis weights mode, reduce costs, reduce maintenance; Mercury solution reclaims and plating bismuth film reduces secondary environmental pollution.
Accompanying drawing explanation
Fig. 1 is the module diagram of multiparameter heavy metal online analyzer of the present utility model;
Fig. 2 is the pipeline schematic diagram of multiparameter heavy metal online analyzer of the present utility model.
Embodiment
Below in conjunction with accompanying drawing, embodiment of the present utility model is further detailed.
The utility model provides a kind of multiparameter heavy metal online analyzer, for detection of the content of beary metal in water quality, it comprises: control module 10 and the water sampling pretreatment module 20 being communicated with it respectively, quantitative module 30, detection module 40 and the emptying module 50 of waste liquid, control module 10 is carried out integrated control to each functional module.Wherein, control module 10 is controlled water sampling pretreatment module 20 and will be tested water sample and introduce in quantitative module 30, through forcing pump and liquid-transport pipe-line, the test water sample in quantitative module 30 is pressed in detection module 40, by detection module 40, the content of beary metal in test water sample is detected, test water sample after detection imports the emptying module 50 of waste liquid, is discharged in waste liquid barrel by the emptying module 50 of waste liquid.
In preferred embodiment of the present utility model, described heavy metal online analyzer also further comprises dilution module 60, described dilution module 60 is communicated between quantitative module 30 and detection module 40, so that the test water sample of deriving in quantitative module 30 is carried out to dilution process, by dilution process, obtain the test water sample of low concentration.
Water sampling pretreatment module 20 comprises several many qis valves 1,2, air and alkali lye transfer valve 22 and dilution transfer valve 13, wherein, described many qis valve is connected with water sample bucket, deionization water bucker and digestion solution bucket respectively, realize the switching between variety classes liquid, for example: the switching between water sample and digestion solution.Import corresponding test water sample or reagent to quantitative module 30 respectively.In Fig. 2, many qis valve 1-1 is communicated with water sample bucket, many qis valve 1-2, many qis valve 1-3 are communicated with digestion solution bucket, many qis valve 1-4 is communicated with deionization water bucker, many qis valve 1-5 is connected with the common port 12-3 of air and alkali lye transfer valve 22, in air and alkali lye transfer valve 22, air transfer valve 12-1 and air communication, alkali lye transfer valve 12-2 is communicated with alkali lye, the common port 1-8 of many qis valve is communicated with the Chang Kaiduan 13-2 of dilution transfer valve 13, the common port 13-3 of dilution transfer valve 13 is communicated with peristaltic pump 8, and the Chang Kaiduan 13-1 of dilution transfer valve 13 is communicated with diluting tank.The preferred two-position three-way valve of described many qis valve.Many qis valve 1 connects respectively common port, water sample, digestion solution, acid solution, the deionized water of air transfer valve and realizes stream switching.Air and alkali lye transfer valve are realized the function conversion of sample introduction and stirring.Dilution transfer valve is realized the switching of water sample and dilution.
Described quantitative module 30 comprises digestion pool 7, six logical proportional valve 3 and fixed displacement pumps 10, wherein, between digestion pool 7 and many qis valve 1,2, digestion pool transfer valve 14 is set, the Chang Kaiduan 14-1 of digestion pool transfer valve 14 is connected with peristaltic pump 8, the Chang Kaiduan 14-2 of digestion pool transfer valve 14 is connected with many qis valve 1,2, and the common port 14-3 of digestion pool transfer valve 14 is communicated with digestion pool 7.Import test water sample, deionized water and digestion solution by many qis valve 1,2 to digestion pool 7, be provided with photoelectric level detection module at the water inlet of digestion pool 7, to measure the mixed liquor importing in digestion pool 7.Six logical proportional valves 3 are connected with many qis valve 1,2, be communicated with diluting tank 6 by pump 15, switching controls is cleared up the test water sample that water sample imports clearing up and diluting from diluting tank 6, or import water sample, deionized water and digestion solution by many qis valve 1,2, water side at six logical proportional valves 3 is provided with photoelectric level detection module, mixes with the test water sample that imports reaction tank 5 to being measured by six logical proportional valves 3.Fixed displacement pump 10 is communicated with reaction tank 5 by flow channel switching valve 18, between flow switch valve 18 and fixed displacement pump 10, photoelectric level detection module is set, and imports quantitatively test water sample to measure.
Described detection module 40 comprises reaction tank 5, is built in electrode and stirrer in reaction tank 5, and described stirrer is electrically connected with control module 10, and described reaction tank is communicated with plated film liquid pump and diluting tank, and the test water sample after coating liquid and dilution is imported in reaction tank.Described electrode comprises working electrode, auxiliary electrode and contrast electrode, wherein, working electrode forms current return with auxiliary electrode and contrast electrode respectively, described working electrode is selected from glassy carbon electrode or gold electrode, described auxiliary electrode is selected from platinum electrode or platinum plate electrode, and described contrast electrode is selected from silver/silver chloride electrode or saturated calomel electrode.In reaction tank 5, use cloth compression ring to mix test water sample, adopt nitrogen or machinery to stir test water sample.
The test process of content of beary metal is as follows: control nitrogen break-make and carry out deoxygenation, control module 10 is in the time of stirring and deoxygenation, apply constant current potential to working electrode, in test water sample, the tested heavy metal of part reverts on working electrode, then, stop stirring or air-blowing, then to working electrode certain potentials, apply again the scanning current potential of certain Changing Pattern with working electrode, at this moment, be enriched in heavy metal on working electrode again oxidized and be dissolved in test water sample, acquisition stream is through the electric current of working electrode and auxiliary electrode and the current potential of working electrode simultaneously, the current potential collecting and electric current are delivered to control module and carry out data processing, thereby obtain kind and the concentration information of tested heavy metal in unknown water sample.Finally, the emptying module of control module control waste liquid start pump by the discharging of waste liquid in reaction tank 5 in waste liquid barrel.
Described dilution module 60 is communicated between quantitative module 30 and detection module 40, so that the test water sample of deriving in quantitative module 30 is carried out to dilution process.Dilution module 60 comprises diluting tank 6, deionized water 2-5 is connected with many qis valve 2, many qis valve common port is connected with six logical proportional valves 3, fixed displacement pump 10 is connected with the common port 16-3 of flow channel switching valve 16, the Chang Kaiduan 16-1 of flow channel switching valve 16 is connected with six logical proportional valves 3, six logical proportional valves 3 are connected with diluting tank 6, and diluting tank 6 is connected with dilution transfer valve Chang Kaiduan 13-1.By dilution module 60, the test water sample of quantitatively introducing is diluted, be then directed into reaction tank 5 and carry out the concentration detection of heavy metal.By test water sample is diluted, avoid highly concentrated solution to produce corrosion to instrument.
Between described digestion pool 7 and digestion pool transfer valve 14, there is photoelectric detection system, between digestion pool transfer valve 14 and dilution transfer valve 13, be provided with peristaltic pump 8, between described peristaltic pump 8 and dilution transfer valve 13, be also provided with photoelectric detection system, digestion pool transfer valve realize the suction of liquid to be cleared up and discharge, dilution transfer valve realize switching, the peristaltic pump of water sample and dilution realize in quantitative ring, treat quantitative liquid quantitatively and discharge, photoelectric detection system is realized and is judged that quantitative ring quantitatively completes and emptying.
The utility model also provides the method that adopts multiparameter heavy metal online analyzer to detect, and it comprises the following steps:
Step 1) gathers pretreatment module and from water sample bucket, deionization water bucker and digestion solution bucket, extracts water sample, deionized water and digestion solution respectively, and the digestion pool that imports quantitative module mixes in test water sample;
Step 2) adopt peristaltic pump that coating liquid is quantitatively transferred in reaction tank, simultaneously, through peristaltic pump, test water sample in digestion solution bucket is imported in diluting tank, after dilution, quantitatively imported in reaction tank by six logical proportional valves, will test water sample and coating liquid mixes in reaction tank;
Solution in step 3) control module control stirrer agitating reaction pond, control nitrogen break-make and carry out deoxygenation, stirring and removing under oxygen condition, apply constant potential to working electrode, tested heavy metal in test water sample is restored on working electrode, stop stirring and air-blowing, then apply the scanning current potential of certain Changing Pattern with working electrode, make to be enriched in heavy metal on working electrode again oxidized and be dissolved in test water sample;
Step 4) is delivered to control module by the current potential of the electric current of gathered working electrode, auxiliary electrode and working electrode and is carried out data processing, obtains kind and the concentration information of tested heavy metal in test water sample;
The waste liquid in reaction tank is discharged to waste liquid barrel by the emptying module of step 5) control module control waste liquid.
In step 1) in, in diluting tank, by the water sample in the abundant agitation and dilution of stirrer pond, reach the object mixing, draw water sample 1-1 and digestion solution 1-2 by peristaltic pump 8,1-3 enters in digestion pool 7 and clears up reaction, in digestion pool 7, blast air, improve and clear up effect simultaneously.
Then, control many qis valve 1,2, six by control module 10 and lead to proportional valve 3, flow channel switching valve 17,18 and fixed displacement pumps 10, make to clear up the water sample 2-2 six logical proportional valves 3 of flowing through, after being full of quantitative ring, flow channel switching valve 16 is switched to corresponding six logical proportional valves 3, Pneumatic creeping pump 11, pumps into air dielectric the water sample of clearing up in quantitative ring is entered in reaction tank 5.Adopt identical method, respectively the quantitative sample injections such as other electrolyte 2-3, correcting fluid 2-4 are introduced in reaction tank 5.Then, test water sample after clearing up is quantitatively introduced in diluting tank 6, after dilution, to test respectively the logical proportional valve of the employing such as water sample, deionized water six detects through photoelectric level, and introduce and in reaction tank 5, carry out redox reaction, first reduce rear oxidation, again oxidized and be dissolved in test water sample by being enriched in heavy metal on working electrode, carry out data processing in conjunction with the electric current of working electrode, auxiliary electrode and the current potential of working electrode, obtain kind and the concentration information of tested heavy metal in test water sample.Carry out concentration conversion according to dilution gfactor again, obtain actual concentration value.Finally, control discharging of waste liquid module startup pump the waste liquid in reaction tank is discharged to waste liquid barrel.
Liquid flow path of the present utility model adopts the principle of independent separate, select multiple quantitative manner according to the requirement of different basis weights degree of accuracy, adopt the quantitative water sample of peristaltic pump 8 to enter digestion pool 7, adopt the quantitative coating liquid 9-1 of peristaltic pump 9 to reaction tank 5, adopt photoelectric level detection module quantitatively to extract digestion solution, adopt fixed displacement pump 10, peristaltic pump 11, flow channel switching valve 16,17,18, six to lead to the mode that proportional valves 3 organically combine, realize accurate quantification, from 20 microlitres to 10 milliliter.Preferably 2 milliliters, this instrument, due to quantitative be the prescribed volume in proportional valve, avoid the impact on measuring accuracy of dead volume between wearing and tearing and the pump line of peristaltic pump, sample introduction uses air as carrier, avoid the mutual pollution between reagent simultaneously, avoided the phase between reagent simultaneously.The utility model adopts accurate proportional valve, and the low peristaltic pump of cost, has not only guaranteed quantitative precision, and has reduced the cost, and greatly guaranteed and extend the serviceable life of system, has reduced maintenance.Key reagents of the present utility model, adopts part reagent stream independent, fully avoids the cross pollution of reagent.
The working electrode that the utility model adopts is solid electrode, comprises glass-carbon electrode, and gold electrode etc., effectively avoid the secondary pollution of traditional dropping-mercury electrode in test, and the potential window of glass-carbon electrode is wide in addition, can test many kinds of substance.Coating liquid of the present utility model adopts recycle and reuse or the coating liquid without pollution remission in addition, there is no secondary pollution completely, and the linearity and the repeatability of electrode are better than dropping-mercury electrode.In reactor, adopt inert gas deoxygenation, played the effect stirring and also effectively removed the oxygen of clearing up in water sample to the impact of measuring, an other plated film can be measured more than 200 times, has reduced maintenance, the preferred bismuth film of plated film or mercury film, wherein bismuth film non-environmental-pollution.

Claims (8)

1. a multiparameter heavy metal online analyzer, for detection of the content of beary metal in water quality, it is characterized in that comprising: control module and the water sampling pretreatment module being communicated with it respectively, quantitatively module, the emptying module of detection module and waste liquid, wherein, control module control water sampling pretreatment module will be tested water sample and be introduced in quantitative module, through forcing pump and liquid-transport pipe-line, the test water sample in quantitative module is pressed in detection module, by detection module, the content of beary metal in test water sample is detected, test water sample after detection imports the emptying module of waste liquid, be discharged in waste liquid barrel by the emptying module of waste liquid.
2. multiparameter heavy metal online analyzer according to claim 1, is characterized in that: further comprise dilution module, described dilution module is communicated between quantitative module and detection module, carries out dilution process with the test water sample to deriving in quantitative module.
3. multiparameter heavy metal online analyzer according to claim 2, it is characterized in that: described water sampling pretreatment module comprises several many qis valves, air and alkali lye transfer valve and dilution transfer valve, described many qis valve respectively with water sample bucket, deionization water bucker and digestion solution bucket are connected, import corresponding test water sample or reagent to quantitative module respectively, described air and alkali lye transfer valve are communicated with the valve of qi more than wherein, in air and alkali lye transfer valve, air transfer valve and air communication, alkali lye transfer valve is communicated with alkali lye, Chang Kaiduan and the normal-closed end of dilution transfer valve are communicated with many qis valve and diluting tank respectively, the common port of dilution transfer valve is communicated with peristaltic pump, many qis valve connects respectively the common port of air transfer valve, water sample, digestion solution, acid solution, deionized water is realized stream and is switched.
4. multiparameter heavy metal online analyzer according to claim 3, it is characterized in that: described quantitative module comprises digestion pool, six logical proportional valve and fixed displacement pumps, wherein, between digestion pool and many qis of reagent valve, be communicated with by digestion pool transfer valve, six logical proportional valves are communicated between dilution module and detection module, and fixed displacement pump is communicated with reaction tank by a flow channel switching valve.
5. multiparameter heavy metal online analyzer according to claim 4, it is characterized in that: described detection module comprises reaction tank, is built in electrode and stirrer in reaction tank, described stirrer is electrically connected with control module, described reaction tank is communicated with plated film liquid pump and diluting tank, and the test water sample after coating liquid and dilution is imported in reaction tank.
6. multiparameter heavy metal online analyzer according to claim 5, it is characterized in that: described electrode comprises working electrode, auxiliary electrode and contrast electrode, wherein, working electrode forms current return with auxiliary electrode and contrast electrode respectively, described working electrode is selected from glassy carbon electrode or gold electrode, described auxiliary electrode is selected from platinum electrode or platinum plate electrode, and described contrast electrode is selected from silver/silver chloride electrode or saturated calomel electrode.
7. multiparameter heavy metal online analyzer according to claim 3, is characterized in that: between described digestion pool and digestion pool transfer valve, and be provided with photoelectric detection system between described peristaltic pump and dilution transfer valve.
8. multiparameter heavy metal online analyzer according to claim 3, is characterized in that: between digestion pool transfer valve and dilution transfer valve, be provided with peristaltic pump.
CN201320835330.3U 2013-12-17 2013-12-17 On-line multi-parameter heavy metal analyzer Expired - Lifetime CN203688493U (en)

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