CN102680462B - Method and device for on-line monitoring of contents of multiple heavy metals in water body - Google Patents
Method and device for on-line monitoring of contents of multiple heavy metals in water body Download PDFInfo
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Abstract
The invention relates to a method for the on-line monitoring of contents of multiple heavy metals in a water body. According to the method, a measuring light source which can provide a light source with a plurality of wavelengths or continuous wavelengths is adopted; a control system carries out sampling, reaction and coloration, an optical detection device carries out absorbance measurement on a colorimetric solution by adopting light with a specific wavelength of the measuring light source, and the optical detection device is an optical sensor or a spectrograph; after the control system measures the content of a heavy metal pollutant corresponding to the light with the specific wavelength in a water sample to be monitored, the determination of the content of a heavy metal corresponding to the light with the wavelength is finished; and the cyclic coloration measurement is carried out until the determination on the contents of all heavy metal pollutants is finished. With the adoption of the method, the sequential determination on the contents of multiple different heavy metal substances in water on one monitoring device can be realized, and the setting can be carried out through software, so that the measurement accuracy is improved, the cost is reduced, the monitoring efficiency is greatly increased, the space occupied by mounting a plurality of measurement equipment is reduced, and the kinds of monitored heavy metals can be automatically selected as required.
Description
Technical field
The invention belongs to by means of measure material chemistry or physical property is tested or the technical field of analysis of material, optical method is utilized in particular to one, by arranging the measurement light source of the light source that can provide multiple wavelength or the light source providing continuous wavelength, and circulatory monitoring flow process makes any multiple different heavy metal element in the method and monitoring device with various heavy content in the on-line monitoring water body comparing the content measuring this heavy metal contaminants in water sample in real time after suitable chromogenic reagent and component to be measured carry out reacting with the change of the maximum absorption wavelength light intensity set.
Background technology
Heavy metal refers to the metal that proportion is greater than 5, accumulate in human body and acquire a certain degree, slow poisoning can be caused, wherein to harm maximum have plumbous Pb, mercury Hg, cadmium Cd, chromium Cr, arsenic As etc., this five heavy metal species is defined as domestic the most seriously and in the urgent need to the heavy metal element of monitor closely at present.These heavy metals can not be decomposed in water, if there is no perfect monitoring mechanism, tight monitoring equipment, biological meeting absorb heavy metal from environment, and through the biological magnification of food chain, enrichment in higher organisms body, be converted into the metallic compound that toxicity is stronger, enter human body eventually through food, be detrimental to health.Well-known minamata disease (mercury pollution) and Itai-itai diseases (cadmium pollution) are exactly caused by heavy metal pollution.Therefore, the control of heavy metal is very urgent, and in water, heavy metal pollution is the most serious and the most in the urgent need to address problem of current all heavy metal pollution, and in water, the control of heavy metal again must with the monitoring of heavy metal for top priority.
Define the detection method of each Heavy Metallic Elements in water in national standard, domestic and foreign literature also has relevant statement to this.What extensively adopt in prior art mainly contains spectrophotometric method, atomic absorption spectrography (AAS), electrochemical process and atomic fluorescence method etc.Wherein spectrophotometric method can measure the content of heavy metal in various water, the method is due to simple to operate, qualitative, quantitatively accurate, and it is high with the degree of conformity of national standard and industry standard, therefore content of beary metal in experimental determination and on-line monitoring water is widely used in, but the method causes on-line monitoring equipment can only measure the content of a heavy metal species because each color of chromogenic reaction is different and can produce interference mutually between reagent, and efficiency is lower at every turn.For atomic absorption spectrography (AAS) and atomic fluorescence method, because the difference of the chemical property of heavy metal to be measured own and the pretreated complexity of water sample make these two kinds of methods inherently cannot be applied to on-line monitoring, and be only applicable to being applied to laboratory in hand sampling mode to measure content of beary metal in water.Electrochemical process is that except photometry, another kind is widely used in the important method of content of beary metal in on-line monitoring water at present, can most of heavy metal substance in on-line determination water separately, also can several specific heavy metal substance of Simultaneously test, as lead, cadmium, copper, but then can not realize for the demand of heavy metal in on-line determination multiple water while of thinking arbitrarily to combine.
Summary of the invention
The technical matters that the present invention solves is, the live effect cannot taking into account monitoring cost and monitoring due to prior art is reliable, and the user one caused cannot choose at random the quantity of the heavy metal factor of needs monitoring according to the feature of self water quality, two when need, monitoring is multiple to be measuredly needs multiple stage monitoring instrument because of the period of the day from 11 p.m. to 1 a.m, high expensive, and need a large amount of spaces to put, even if the three disposable content monitoring various heavy, its monitoring accuracy also cannot meet the problem of the detection requirement of the pollution source water quality heavy metal concentration that State Bureau of Environmental Protection proposes, and then provide method and the monitoring device of various heavy content in a kind of on-line monitoring water body.
The technical solution adopted in the present invention is, a kind of method of various heavy content in on-line monitoring water body, and method adopts the measurement light source of the light source that can provide the light source of multiple wavelength or provide continuous wavelength; Control system sets the heavy metal number of N number of measurement content as required, N >=1; Setting temperature of reaction T, reaction time t1, colorimetric time t2; Determine water sample to be measured, reaction solution and chromophoric solution; Determine the number selecting solenoid valve in solenoid valve group; Control system is got N volume water sample A to be measured by sampling system and is inserted reaction unit, controls temperature of reaction to setting value T; Stop after reaction time t1 the control of temperature of reaction T and make temperature of reaction T be reduced to environment temperature, obtaining reactant liquor B; Control system control sampling system gets a volume reactant liquor B and quantitative chromophoric solution inserts colorimetric device, is obtained by reacting color solution C, the colour developing t2 time; The light contrast colors liquid C of specific wavelength in measurement light source is adopted to carry out absorbance measuring, according to the intensity variation produced, changed by optical detection apparatus measured light intensity, described optical detection apparatus is the optical sensor of the intensity of N kind incident light that can measure described measurement light source and provide or the spectrometer with light splitting function; After control system records the content of heavy metal contaminants corresponding to the light of specific wavelength in water sample to be measured, the content of beary metal that the light of this wavelength is corresponding measures and terminates; Control system controls colorimetric device and discharges color solution C; A volume reactant liquor B and suitable quantitative chromogenic solution is repeated to insert colorimetric device and carry out the absorbance measuring of the light of other wavelength, until the assay of all heavy metal contaminants terminates.
Preferably, if the course of reaction of reaction time t1 needs oxygenant, then quantitative oxygenant is inserted reaction unit and is entered the stage of reaction by control system control sampling system together with sample A, controls temperature of reaction to setting value T; After reaction certain hour t1, stop the control to temperature of reaction T, and make temperature of reaction T be reduced to environment temperature; Control system control sampling system gets quantitative reductive agent and above-mentioned solution reaction obtains reactant liquor B.
Preferably, described measurement light source is multi-wavelength measurement light source or continuous wavelength measurement light source, and described measurement light source comprises optical splitter or described measurement light source is rotating light source apparatus; Described measurement light source often can be opened or just be opened when needs use.
Preferably, described chromophoric solution comprises buffer solution, screening agent and characteristic developer.
Preferably, 0 DEG C≤T≤200 DEG C.
Preferably, 0s≤t1≤3600s.
Preferably, 0s≤t2≤3600s.
Preferably, a kind of monitoring device adopting the method for various heavy content in on-line monitoring water body, described monitoring device comprises control system, sampling system, reaction unit and colorimetric device, described control system is connected with sampling system, described sampling system is connected with reaction unit and colorimetric device by solenoid valve group, described colorimetric device is provided with entrance aperture and perforation hole, and described entrance aperture is connected with measurement light source, and described perforation hole is connected with optical detection apparatus.
Preferably, described sampling system comprises quantitative system, and described quantitative system comprises proportioning device, reaction unit sample intake passage and colorimetric device sample intake passage.
Preferably, described reaction unit is reaction tank, and colorimetric device is colorimetric pool.
The invention provides method and the monitoring device of various heavy content in a kind of on-line monitoring water body, utilize optical method, employing can provide the light source of multiple wavelength or provide the measurement light source of the light source of continuous wavelength to discharge incident light, after water sample to be measured and reaction reagent control sampling system quantitative sampling by control system, enter reaction unit react, enter colorimetric device after solution dosing section after reaction and successively with include buffer solution, screening agent, the chromophoric solution effect colour developing of the reagent such as characteristic developer, the optical detection apparatus that chromogenic reaction stablizes the rear optical sensor passing through the intensity measuring the multiple incident light that described measurement light source provides or the spectrometer with light splitting function receives measurement, the content of certain heavy metal species in water sample to be measured can be measured with the change comparison of the maximum absorption wavelength light intensity set in advance, after recording the content of a heavy metal contaminants, discharge all solution in colorimetric device, solution enters colorimetric device and repeats observation process and measures the content of next heavy metal species until all measure end after dosing section reaction more immediately, method of the present invention can realize the content of heavy metal substance in the multiple different water of sequentially determining on a monitoring device, and all arrange in advance by software, improve the precision of measurement, reduce costs, substantially increase monitoring efficiency, decrease the space of installing and taking needed for multiple stage measuring equipment, and can need according to client the heavy metal kind selecting monitoring voluntarily.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to this.
As shown in the figure, the present invention relates to the method for various heavy content in a kind of on-line monitoring water body, method adopts the measurement light source 1 of the light source that can provide the light source of multiple wavelength or provide continuous wavelength; Control system sets the heavy metal number of N number of measurement content as required, N >=1; Setting temperature of reaction T, reaction time t1, colorimetric time t2; Determine water sample to be measured, reaction solution and chromophoric solution; Determine the number selecting solenoid valve in solenoid valve group 8; Control system is got N volume water sample A to be measured by sampling system and is inserted reaction unit, controls temperature of reaction to setting value T; Stop after reaction time t1 the control of temperature of reaction T and make temperature of reaction T be reduced to environment temperature, obtaining reactant liquor B; Control system control sampling system gets a volume reactant liquor B and quantitative chromophoric solution inserts colorimetric device, is obtained by reacting color solution C, the colour developing t2 time; The light contrast colors liquid C of specific wavelength in measurement light source 1 is adopted to carry out absorbance measuring, according to the intensity variation produced, changed by optical detection apparatus 2 measured light intensity, described optical detection apparatus 2 is the optical sensor of the intensity of N kind incident light that can measure described measurement light source 1 and provide or the spectrometer with light splitting function; After control system records the content of heavy metal contaminants corresponding to the light of specific wavelength in water sample to be measured, the content of beary metal that the light of this wavelength is corresponding measures and terminates; Control system controls colorimetric device and discharges color solution C; A volume reactant liquor B and suitable quantitative chromogenic solution is repeated to insert colorimetric device and carry out the absorbance measuring of the light of other wavelength, until the assay of all heavy metal contaminants terminates.
If the course of reaction of reaction time t1 needs oxygenant, then quantitative oxygenant is inserted reaction unit and is entered the stage of reaction by control system control sampling system together with sample A, controls temperature of reaction to setting value T; After reaction certain hour t1, stop the control to temperature of reaction T, and make temperature of reaction T be reduced to environment temperature; Control system control sampling system gets quantitative reductive agent and above-mentioned solution reaction obtains reactant liquor B.
Described measurement light source 1 is multi-wavelength measurement light source or continuous wavelength measurement light source, and described measurement light source 1 comprises optical splitter or described measurement light source 1 is rotating light source apparatus; Described measurement light source 1 often can be opened or just be opened when needs use.
The actual proterties of light source in actual mechanical process is depended in the opening and closing of measurement light source 1.
Described chromophoric solution comprises buffer solution, screening agent and characteristic developer.
0℃≤T≤200℃。
0s≤t1≤3600s。
0s≤t2≤3600s。
A kind of monitoring device adopting the method for various heavy content in on-line monitoring water body, described monitoring device comprises control system, sampling system, reaction unit and colorimetric device, described control system is connected with sampling system, described sampling system is connected with reaction unit and colorimetric device by solenoid valve group 8, described colorimetric device is provided with entrance aperture 3 and perforation hole 4, described entrance aperture 3 is connected with measurement light source 1, and described perforation hole 4 is connected with optical detection apparatus 2.
In the present invention, sampling system comprises titer, reaction reagent and water sample to be measured, and described titer passage 5, reagent passage 6 and water sample passage 7 to be measured carry out quantitative sampling by the conversion of solenoid valve group 8 and be pushed in reaction unit and reaction tank 9 or colorimetric device and colorimetric pool 10 carrying out reacting or developing the color.
Described sampling system comprises quantitative system, and described quantitative system comprises proportioning device, reaction unit sample intake passage 12 and colorimetric device sample intake passage 13.
In the present invention, sampling system comprises quantitative system, carries out quantitative liquid bulk product controlled by the light source for quantitative some pairing uses that quantity tube is arranged and optical receiver by quantitative system.Changed by the light intensity making light source be transmitted into optical receiver when volumetric soiutions flows in quantity tube and determine whether solution continues flowing or static, thus determines the volume of solution.
Described reaction unit is reaction tank 9, and colorimetric device is colorimetric pool 10.
In the present invention, solenoid valve group 8 comprises several solenoid valves, and different solenoid valves is connected with titer passage 5, reagent passage 6, water sample passage 7 to be measured, reaction unit sample intake passage 12, colorimetric device sample intake passage 13, reaction tank 9 and colorimetric pool 10 respectively.
In the present invention, measurement light source 1, optical detection apparatus 2 can be connected with the entrance aperture 3 of colorimetric pool 10 and perforation hole 4 respectively by optical fiber 11, also can not pass through optical fiber 11, directly be located at entrance aperture 3 and perforation hole 4 place respectively.
In the present invention, in colorimetric pool 10, pumping equipment is set, after the measurement of content having carried out a heavy metal species, the solution in colorimetric pool 10 can be discharged rapidly to facilitate the colorimetric measurement of carrying out next heavy metal species.
In the present invention, in on-line monitoring water body, the principle of work of the method for various heavy content is: utilize optical method, employing can provide the light source of multiple wavelength or provide the measurement light source 1 of light source of continuous wavelength to transmitting illuminant on colorimetric device, enter after the quantitative system dosing section that solution controls in sampling system by control system after water sample to be measured and reaction reagent being reacted colorimetric device also successively with include buffer solution, screening agent, the chromophoric solution effect colour developing of characteristic developer etc., chromogenic reaction stablize after by receiving measurement by the optical sensor of intensity or the optical detection apparatus 2 of the spectrometer with light splitting function that can measure the multiple incident light that described measurement light source 1 provides, the content of certain heavy metal species in water sample to be measured can be measured with the change comparison of the maximum absorption wavelength light intensity set in advance, discharge all solution in colorimetric device, separately get quantitative reaction liquid circulation development step subsequently, measure the content of next heavy metal species until all measure end.
In the present invention, except the method for various heavy content in aforesaid on-line monitoring water body, if the standard value of heavy metal free content, then also need the content of each heavy metal in bioassay standard liquid, flow process is as follows:
Step one: reset: control system measures the heavy metal number N of content as required, N >=1; Setting temperature of reaction T, setting reaction time t1, setting colorimetric time t2; Confirmed standard liquid and the reagent in reacting; Determine the number selecting solenoid valve in solenoid valve group 8.
Step 2: sampling: the solenoid valve group 8 valve road of titer passage 5 is opened, it is to be measured that the control system quantitative system controlled in sampling system gets N dimension criteria liquid A by titer passage 5.
Step 3: reaction: control system controls that titer A is inserted reaction unit and enters the stage of reaction, controls temperature of reaction to setting value T; After reaction certain hour t1, stop the control to temperature of reaction T, and make temperature of reaction T be reduced to environment temperature, obtain reactant liquor B; When measuring process needs oxygenant together to react, by reagent passage 6, control system controls sampling system, and sampling system adds reaction unit after getting quantitative oxygenant by quantitative system; After reaction certain hour t1, terminate temperature control and make reaction unit temperature be reduced to environment temperature, if added a certain amount of oxygenant in course of reaction, by reagent passage 6, control system controls sampling system, sampling system adds reaction unit after getting a certain amount of reductive agent by quantitative system, finally obtains reactant liquor B.
Step 4: colour developing: control system controls sampling system and gets a volume reactant liquor B, insert colorimetric device, by reagent passage 6, control system controls that sampling system gets quantitative buffer solution, colorimetric device inserted by screening agent, characteristic developer, makes reactant liquor B carry out being obtained by reacting color solution C with quantitative buffer solution, screening agent, characteristic developer successively.
Step 5: colorimetric: after step 4 stablizes t2, by providing the light source of multiple wavelength or provide the measurement light source 1 of the light source of continuous wavelength to send incident light, the light contrast colors liquid C of specific wavelength is adopted to carry out absorbance measuring, produce intensity variation, optical detection apparatus 2 measured light intensity changes, and described optical detection apparatus 2 is the optical sensor of the intensity of N kind incident light that can measure described measurement light source 1 and provide or the spectrometer with light splitting function; After control system records the content of the heavy metal that the light of specific wavelength is corresponding in titer, the content of beary metal that the light of this wavelength is corresponding measures end;
Step 6: discharge opeing: control system controls colorimetric device and discharges color solution C;
Step 7: judge: when also having other content of beary metal to measure, repeat following steps by step 4, until terminate.
The embodiment of the present invention 1:
Adopt the content of total chromium and total nickel in water in the method for various heavy content in on-line monitoring water body of the present invention and monitoring device Simultaneously test Electroplate Factory Sewage outlet.Colorimetric measurement wavelength is chosen as total chromium respectively and measures at 540nm, total nickel measures at 520nm, measurement light source 1 send have continuous wavelength can through optical splitter light splitting produce respectively 540nm and 520nm incident light source or send respectively 540nm and 520nm monochromatic source and by rotating light source apparatus to realize the switching of light source; The monochromatic light that measurement light source 1 produces passes through optical fiber 11 from entrance aperture 3 vertical irradiation to colorimetric pool 10, be irradiated to via optical fiber 11 change that optical detection apparatus 2 measures light intensity from perforation hole 4 by the outgoing light source of colorimetric pool 10, temperature of reaction is set as 60 degrees Celsius, reaction time is set as 4 minutes, the colorimetric time is set to 1 minute, reagent type number on reaction unit sample intake passage 12 is set as 3 kinds, and the reagent type on colorimetric device sample intake passage 13 is set as 4 kinds.
Be provided with rear startup to measure, by water sample passage 7 to be measured, control system controls sampling system sampling, sampling pump 14 controls to get two volumes water sample to be measured by the first light source 16 used for quantitative pairing that the first quantity tube 15 in quantitative system is arranged and the first optical receiver 17, and the solenoid valve group 8 valve road of water sample again by reaction unit sample intake passage 12 after quantitatively switches and pushed reaction tank 9 by sampling pump 14 by buffering pipeline 18; then sampling system with the mode same with getting water sample to be measured by reagent passage 6 by liquor potassic permanganate (oxygenant) quantitatively after be taken into reaction tank 9, start temperature control program and controlled the temperature of reaction of reaction tank 9 by heating arrangement 19 to 60 degree, react after 4 minutes, terminate temperature control and make reaction tank 9 temperature be reduced to environment temperature, then sampling system with the mode same with getting water sample to be measured by reagent passage 6 respectively by sodium nitrite solution and urea liquid (reductive agent) successively by the first quantity tube 15 quantitatively after be taken into reaction tank 9, reactant liquor in reaction tank 9 after reaction terminates by control system is divided into two parts, sampling system is got a wherein volume in the mode same with getting water sample to be measured and to be switched the second quantity tube 20 of the colorimetric device sample intake passage 13 entered in quantitative system through the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 and controlled to be taken into colorimetric pool 10 quantitatively for the quantitative some secondary light source 21 that uses and the second optical receivers 22 of matching by what the second quantity tube 20 was arranged, then sampling system with the mode same with getting water sample to be measured by reagent passage 6 through the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 switch by developer diphenylcarbazide solution by the second quantity tube 20 quantitatively after be taken into colorimetric pool 10 and carry out chromogenic reaction, developing time adopts the light of 540nm wavelength to carry out absorbance measuring after within 1 minute, terminating, just the content of total chromium in water sample can be measured according to the change of light intensity before and after colour developing, now total chrome content measures and terminates, control system controls to discharge all solution in colorimetric pool 10.
Perform same program subsequently, first sampling system will react the solenoid valve group 8 valve road of another volumetric reaction liquid in the reaction tank 9 after terminating through colorimetric device sample intake passage 13 and switch the second quantity tube 20 of the colorimetric device sample intake passage 13 entered in quantitative system in the mode same with getting water sample to be measured, and controlled to be taken into colorimetric pool 10 quantitatively by the secondary light source 21 for quantitative some pairing uses that the second quantity tube 20 is arranged and the second optical receiver 22, then sampling system switches successively by ammonium citrate solution (buffer solution) by reagent passage 6 through the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 in the mode same with getting water sample to be measured, colorimetric pool 10 is taken into after iodine solution (screening agent) is quantitative by the second quantity tube 20, last sampling system is taken into colorimetric pool 10 by reagent passage 6 and carries out chromogenic reaction after the switching of the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 is quantitative by the second quantity tube 20 by developer dimethylglyoxime solution, developing time adopts the light of 520nm wavelength to carry out absorbance measuring after within 1 minute, terminating, just the content of total nickel in water sample can be measured according to the change of light intensity before and after colour developing, now total nickel assay terminates, control system controls to discharge all solution in colorimetric pool 10.
So far, the online Simultaneously test of total chromium, total nickel terminates, and sampling system discharges all solution in reaction tank 9.
Above-mentioned optical method measurement needs to demarcate in advance with standard solution, calibration process is identical with measuring process, the titer passage 5 of monitoring device comprises the first titer passage and the second titer passage, then calibrating procedure is started, its implementation is identical with measuring process, calibration process can be realized by the measurement titer in titer passage 5 being carried out to each content of beary metal, total chromium and total nickel two groups of calibration factors can be produced respectively after demarcation completes, these two groups of calibration factors are used for calculating the actual content of total chromium and total nickel in water sample to be measured respectively in measuring process after chromogenic reaction terminates and measures absorbance.
The embodiment of the present invention 2:
Adopt the content of total lead, total mercury, total cadmium in water in the method for various heavy content in on-line monitoring water body of the present invention and monitoring device Simultaneously test metal smelting factory sewage floss hole.Colorimetric measurement wavelength is chosen as total mercury respectively and measures at 485nm, total lead measures at 510nm, total cadmium measures at 518nm, measurement light source 1 is for having xenon lamp or the mercury lamp of continuous wavelength, optical monitoring device 2 is spectrometer, the light that measurement light source 1 produces passes through optical fiber 11 from entrance aperture 3 vertical irradiation to colorimetric pool 10, be irradiated to via optical fiber 11 change that light intensity measured by the spectrometer with light splitting function and light intensity measuring ability from perforation hole 4 by the outgoing light source of colorimetric pool 10, temperature of reaction is set as 100 degrees Celsius, reaction time is set as 10 minutes, the colorimetric time is set to 5 minutes, reagent type number on reaction unit sample intake passage 12 is set as 2 kinds, reagent type on colorimetric device sample intake passage 13 is set as 5 kinds.
Be provided with rear startup to measure, by water sample passage 7 to be measured, the sampling pump 14 in sampling system is controlled by control system, sampling pump 14 controls to get three volumes water sample to be measured by the first light source 16 used for quantitative some pairings that the first quantity tube 15 in quantitative system is arranged and the first optical receiver 17, extracted by buffering pipeline 18 by the sampling pump 14 in sampling system, the solenoid valve group 8 valve road switching of water sample again by reaction unit sample intake passage 12 after quantitative system is quantitative is pushed reaction tank 9 by sampling pump 14 by buffering pipeline 18, then sampling system with the mode same with getting water sample to be measured by reagent passage 6 by acid potassium permanganate-potassium persulfate mixed solution (oxygenant) quantitatively after be taken into reaction tank 9, control system is started temperature control program and is controlled the temperature of reaction of reaction tank 9 by heating arrangement 19 to 100 degree, react after 10 minutes, terminate temperature control and make reaction tank 9 temperature be reduced to environment temperature, then sampling system with the mode same with getting water sample to be measured by reagent passage 6 by oxammonium hydrochloride solution (reductive agent) by the first quantity tube 15 quantitatively after be taken into reaction tank 9, reactant liquor in reaction tank 9 after reaction terminates by control system is divided into three parts, sampling system is got a wherein volume in the mode same with getting water sample to be measured and to be switched the second quantity tube 20 of the colorimetric device sample intake passage 13 entered in quantitative system through the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 and controlled to be taken into colorimetric pool 10 quantitatively for the quantitative some secondary light source 21 that uses and the second optical receivers 22 of matching by what the second quantity tube 20 was arranged, then sampling system with the mode same with getting water sample to be measured by reagent passage 6 through the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 switch by buffering agent sodium sulfite solution by the second quantity tube 20 quantitatively after be taken into colorimetric pool 10, last sampling system is taken into colorimetric pool 10 by reagent passage 6 and carries out chromogenic reaction after the switching of the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 is quantitative by the second quantity tube 20 by developer dithizone solution, developing time selects the light of 485nm wavelength to carry out absorbance measuring after within 5 minutes, terminating, just the content of total mercury in water sample can be measured according to the change of light intensity before and after colour developing, now total mercury content measures and terminates, control system controls to discharge all solution in colorimetric pool 10.
Perform same program subsequently, first sampling system switches the second quantity tube 20 of the colorimetric device sample intake passage 13 entered in quantitative system in the mode same with getting water sample to be measured by reacting the solenoid valve group 8 valve road of second part of one volume reactant liquor in the reaction tank 9 after terminating through colorimetric device sample intake passage 13 and matches the secondary light source 21 that uses and the second optical receiver 22 by being used for that the second quantity tube 20 is arranged quantitative some and control to be taken into colorimetric pool 10 quantitatively, then sampling system switches dibasic ammonium citrate-sodium sulphite-oxammonium hydrochloride-potassium cyanide mixed solution (buffering agent by reagent passage 6 through the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 in the mode same with getting water sample to be measured, smoke agent for shielding) by the second quantity tube 20 quantitatively after be taken into colorimetric pool 10, last sampling system is taken into colorimetric pool 10 by reagent passage 6 and carries out chromogenic reaction after the switching of the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 is quantitative by the second quantity tube 20 by developer dithizone solution, developing time selects the light of 510nm wavelength to carry out absorbance measuring after within 5 minutes, terminating, just total plumbous content in water sample can be measured according to the change of light intensity before and after colour developing, now total Determination of Pb terminates, control system controls to discharge all solution in colorimetric pool 10.
Perform same program subsequently, first sampling system switches the second quantity tube 20 of the colorimetric device sample intake passage 13 entered in quantitative system in the mode same with getting water sample to be measured by reacting the solenoid valve group 8 valve road of last volumetric reaction liquid in the reaction tank 9 after terminating through colorimetric device sample intake passage 13 and matches the secondary light source 21 that uses and the second optical receiver 22 by being used for that the second quantity tube 20 is arranged quantitative some and control to be taken into colorimetric pool 10 quantitatively, then sampling system switches successively by potassium sodium tartrate solution (buffer solution) by reagent passage 6 through the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 in the mode same with getting water sample to be measured, colorimetric pool 10 is taken into after NaOH-potassium cyanide mixed solution (smoke agent for shielding) is quantitative by the second quantity tube 20, last sampling system is taken into colorimetric pool 10 by reagent passage 6 and carries out chromogenic reaction after the switching of the solenoid valve group 8 valve road of colorimetric device sample intake passage 13 is quantitative by the second quantity tube 20 by developer dithizone solution, developing time selects the light of 518nm wavelength to carry out absorbance measuring after within 5 minutes, terminating, just the content of total cadmium in water sample can be measured according to the change of light intensity before and after colour developing, now total cadmium content measures and terminates, control system controls to discharge all solution in colorimetric pool 10.
So far, the online Simultaneously test of total mercury, total plumbous, total cadmium terminates, and sampling system discharges all solution in reaction tank 9.
Above-mentioned optical method is measured all to be needed to demarcate in advance with standard solution, calibration process is identical with measuring process, the titer passage 5 of monitoring device comprises the first titer passage, second titer passage and the 3rd titer passage, then calibrating procedure is started, its implementation is identical with measuring process, calibration process can be realized by the measurement titer in titer passage 5 being carried out to each content of beary metal, total mercury can be produced respectively after demarcation completes, total lead and total cadmium three groups of calibration factors, these three groups of calibration factors are used for calculating the actual content of total chromium and total nickel in water sample to be measured respectively in measuring process after chromogenic reaction terminates and measures absorbance.
The invention solves prior art and cannot take into account the reliable and user one that is that cause of the live effect of monitoring cost and monitoring cannot choose at random the heavy metal factor that needs are monitored quantity according to the feature of self water quality, two when need, monitoring is multiple to be measuredly needs multiple stage monitoring instrument because of the period of the day from 11 p.m. to 1 a.m, high expensive, and need a large amount of spaces to put, even if the three disposable content monitoring various heavy, its monitoring accuracy also cannot meet the problem of the detection requirement of the pollution source water quality heavy metal concentration that State Bureau of Environmental Protection proposes.
The present invention arranges the measurement light source 1 of the light source that can provide the light source of multiple wavelength or provide continuous wavelength by utilizing optical method to pass through, the light contrast colors liquid of specific wavelength is adopted to carry out absorbance measuring, produce intensity variation, use the change of optical detection device 2 measured light intensity of the optical sensor measuring the intensity of the N kind incident light that described measurement light source provides or the spectrometer with light splitting function to measure the content of a few heavy metal species pollutant in water sample in real time; Method of the present invention can realize the content of heavy metal substance in the multiple different water of sequentially determining on a monitoring device, and all arrange in advance by software, improve the precision of measurement, reduce costs, substantially increase monitoring efficiency, decrease the space of installing and taking needed for multiple stage measuring equipment, and can need according to client the heavy metal kind selecting monitoring voluntarily.
Claims (8)
1. the method for various heavy content in on-line monitoring water body, is characterized in that: method adopts the measurement light source of the light source that can provide the light source of multiple wavelength or provide continuous wavelength; Control system sets the heavy metal number of N number of measurement content as required, N >=1; Setting temperature of reaction T, reaction time t1, colorimetric time t2; Determine water sample to be measured, reaction solution and chromophoric solution; Determine the number selecting solenoid valve in solenoid valve group; Control system is got N volume water sample A to be measured by sampling system and is inserted reaction unit, controls temperature of reaction to setting value T; Stop after reaction time t1 the control of temperature of reaction T and make temperature of reaction T be reduced to environment temperature, obtaining reactant liquor B; Control system control sampling system gets a volume reactant liquor B and quantitative chromophoric solution inserts colorimetric device, is obtained by reacting color solution C, the colour developing t2 time; The light contrast colors liquid C of specific wavelength in measurement light source is adopted to carry out absorbance measuring, according to the intensity variation produced, changed by optical detection apparatus measured light intensity, described optical detection apparatus is the optical sensor of the intensity of N kind incident light that can measure described measurement light source and provide or the spectrometer with light splitting function; After control system records the content of heavy metal contaminants corresponding to the light of specific wavelength in water sample to be measured, the content of beary metal that the light of this wavelength is corresponding measures and terminates; Control system controls colorimetric device and discharges color solution C; A volume reactant liquor B and suitable quantitative chromogenic solution is repeated to insert colorimetric device and carry out the absorbance measuring of the light of other wavelength, until the assay of all heavy metal contaminants terminates; If the course of reaction of reaction time t1 needs oxygenant, then quantitative oxygenant is inserted reaction unit and is entered the stage of reaction by control system control sampling system together with water sample A to be measured, controls temperature of reaction to setting value T; After reaction certain hour t1, stop the control to temperature of reaction T, and make temperature of reaction T be reduced to environment temperature; Control system control sampling system gets quantitative reductive agent and above-mentioned solution reaction obtains reactant liquor B.
2. the method for various heavy content in a kind of on-line monitoring water body according to claim 1, it is characterized in that: described measurement light source is multi-wavelength measurement light source or continuous wavelength measurement light source, described measurement light source comprises optical splitter or described measurement light source is rotating light source apparatus; Described measurement light source often can be opened or just be opened when needs use.
3. the method for various heavy content in a kind of on-line monitoring water body according to claim 1, is characterized in that: described chromophoric solution comprises buffer solution, screening agent and characteristic developer.
4. the method for various heavy content in a kind of on-line monitoring water body according to claim 1, is characterized in that: 0 DEG C≤T≤200 DEG C.
5. the method for various heavy content in a kind of on-line monitoring water body according to claim 1, is characterized in that: 0s≤t1≤3600s.
6. the method for various heavy content in a kind of on-line monitoring water body according to claim 1, is characterized in that: 0s≤t2≤3600s.
7. the monitoring device of the method for various heavy content in the on-line monitoring water body adopting one of claim 1 ~ 6 described, it is characterized in that: described monitoring device comprises control system, sampling system, reaction unit and colorimetric device, described control system is connected with sampling system, described sampling system is connected with reaction unit and colorimetric device by solenoid valve group, described colorimetric device is provided with entrance aperture and perforation hole, described entrance aperture is connected with measurement light source, and described perforation hole is connected with optical detection apparatus; Described sampling system comprises quantitative system, and described quantitative system comprises proportioning device, reaction unit sample intake passage and colorimetric device sample intake passage.
8. a kind of monitoring device adopting the method for various heavy content in on-line monitoring water body according to claim 7, it is characterized in that: described reaction unit is reaction tank, colorimetric device is colorimetric pool.
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