CN102998358B - Method and device for sequentially injecting lead in online detection of water quality - Google Patents
Method and device for sequentially injecting lead in online detection of water quality Download PDFInfo
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- CN102998358B CN102998358B CN201210582086.4A CN201210582086A CN102998358B CN 102998358 B CN102998358 B CN 102998358B CN 201210582086 A CN201210582086 A CN 201210582086A CN 102998358 B CN102998358 B CN 102998358B
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Abstract
The invention relates to a method for sequentially injecting lead in online detection of water quality, wherein each step for detecting lead in stripping voltammetry and quantitative dose delivery of required solvent or solution are finished in sequence with sequential injection method; the method comprises the following steps: plating mercury on the surface of a working electrode by using mercury plating liquid HgSO4 solution or Hg(NO3)2 solution; absorbing lead ions in a raw water sample by using polystyrene-dithizone nanofiber; then eluting and condensing into sample water for detection; respectively injecting the sample water and carrier liquid in a electrolytic bath at fixed quantities, wherein the deposition potential is -1.0 to -1.2V, the deposition time is 140-160s, the cleaning potential is -0.3V, and the time is 15s; carrying out anode stripping voltammetry detection on the sample water so as to obtain a sample water stripping voltammetry curve, wherein the stripping peak area is combined with the stripping peak area of a guide sample; and calculating to obtain the lead concentration of sample water. The invention provides a special detection device, which is accurate in fixed quantity and high in sensitivity and can realize online and quick detection of lead content in various water sources.
Description
Technical field
The present invention relates to method and device thereof that a kind of sequential injection detects water quality lead online, for the automatic on-line monitoring to water quality lead content, belong to chemical analysis and monitoring water environment analysis field.
Background technology
Lead is the toxic metals that can accumulate in human body and animal tissue, its main poisonous effect is to cause anemia, nervous function imbalance and injury of kidney, lead contamination in water system is mainly derived from waste water discharges such as accumulator, smelting, five metals, machinery, coating or electroplating industry, therefore, the on-line monitoring of the lead content of industrial water drainage is very necessary.Stripping voltammetry is considered to detect the efficacious prescriptions method that a kind of trace heavy metal ion has.Stripping voltammetry is by the measured matter electrolysis regular hour under suitable condition, then change the current potential of electrode, make to be enriched in the material stripping again on this electrode, the concentration that belongs to ion according to the volt-ampere curve peak height obtaining in process in leaching and GOLD FROM PLATING SOLUTION is proportional, reaches the object of quantitative test.The testing process of current stripping voltammetry adopts manual operations more, and operation is many, troublesome poeration, and poor reproducibility, accuracy of detection is not high, can not adapt to the real time on-line monitoring to industrial waste water lead tolerance.
Summary of the invention
The object of this invention is to provide a kind of method that sequential injection detects water quality lead online, this law is introduced sequential injection technology, realizes online, fast detecting to lead content in the various water sources such as the day water, sewage and industrial waste water.The present invention also provides a kind of device of implementing the method.
The inventive method following steps:
(1). will plate mercury solution HgSO by peristaltic pump
4solution or Hg (NO
3)
2solution is quantitatively input in electrolytic cell by kapillary, at working electrode surface plating mercury; Sedimentation potential is-1.0 V, and sedimentation time is 180 s; Plating mercury solution HgSO
4solution or Hg (NO
3)
2solution concentration is 200 mg/L;
(2). suck former water sample by syringe pump, more former water sample is injected to adsorption column, water flows out from adsorption column, and in water, lead ion is adsorbed material absorption and holds back; Described sorbing material is polystyrene-dithizone nanofiber;
(3). inject deionized water to adsorption column, the lead ion that wash-out has adsorbed, is collected into eluting water in sample storage bottle, and this is detection sample water;
(4). by peristaltic pump by quantitative sample water through kapillary and be injected in electrolytic cell;
(5). carry by peristaltic pump, current-carrying liquid is injected in electrolytic cell through kapillary, current-carrying liquid injection rate IR is 4 times of detection sample water volume that step (4) is injected; Described current-carrying liquid is NaAc-HAc, NaCl-HCl, KNO
3or KCl solution, solution concentration is 0.2 mol/L;
(6). it is-1.0 ~-1.2 V that sedimentation potential is set, sedimentation time is 140 s ~ 160 s, and cleaning current potential is-0.3 V, and the time is 15s, by anodic stripping voltammetry, the lead content of sample water in electrolytic cell is measured, obtained sample water Stripping Voltammetry curve and corresponding stripping peak area; To the mark liquid that adds the known lead concentration of certain volume in electrolytic cell, obtain volt-ampere curve and corresponding stripping peak area after a mark by micro pump; Again to the mark liquid that adds same amount in electrolytic cell, obtain volt-ampere curve and corresponding stripping peak area after secondary mark; Obtain concentration plumbous in sample water by above three stripping calculated by peak area.
The described plating mercury solution of step (1) is HgSO
4, Hg (NO
3)
2, HgSO
4-NaAc or Hg (NO
3)
2-NaAc solution, HgSO
4or Hg (NO
3)
2concentration is 200 mg/L, and NaAc concentration is 0.01 mol/L.
After step (6) completes, with 30 mmol/L HNO
3-0.1 mol/L KNO
3for cleaning fluid, cleaning fluid to be carried and is injected in electrolytic cell by peristaltic pump, selected cleaning current potential is-1.5 V, scavenging period is 60 s, washes the mercury film of electrode surface.
The invention provides automatic on-line and detect plumbous device, comprise electrolytic cell (T), syringe pump (P1), peristaltic pump (P2), micro-sampling pump (P3), the first solenoid valve (V1), the second solenoid valve (V2), the 3rd solenoid valve (V3), the 4th solenoid valve (V4), hyperchannel sequence valve (V5), T-valve (V6), electrochemical workstation (H) and panel computer (G), each parts are linked to be system by high molecule plastic flexible pipe, and its annexation is as follows:
In electrolytic cell (T), be inserted with working electrode (B1), contrast electrode (B2) and auxiliary electrode (B3), described each electrode is connected with the corresponding interface of electrochemical workstation (H) respectively; Electrochemical workstation (H) is connected with panel computer (G);
The first solenoid valve (V1) the 1st interface connect water sample source, the first solenoid valve the 2nd interface be connected with the 1st interface of the second solenoid valve (V2), the interface 3 of the first solenoid valve (V1) be eluent export;
The 2nd interface of the second solenoid valve (V2) is connected with syringe pump, and the interface 3 of the second solenoid valve (V2) connects adsorption column (D), is filled with sorbing material polystyrene-dithizone nanofiber in the interior adsorption column of adsorption column (D);
The 1st interface of the 3rd solenoid valve (V3) is waste liquid outlet, and the 2nd interface connects adsorption column (D) outlet, and interface 3 connects sample water storage bottle (E);
The 4th solenoid valve (V4) the 1st interface be waste liquid outlet, the 4th solenoid valve V4 the 2nd interface be connected with the 1st interface of T-valve (V6) through peristaltic pump (P2), the interface 3 of the 4th solenoid valve V4 is distilled water import;
Hyperchannel sequence valve (V5) comprises a hub-interface and selects with it the 1st ~ 5th interface communicating; Between the 2nd interface of described hub-interface and T-valve (V6), be connected quantitatively to encircle (L); The annexation of other each interface of hyperchannel sequence valve (V5) is as follows: the 1st interface connects electrolytic cell (T), the 2nd interface connects sample water storage bottle, interface 3 connects current-carrying liquid storage bottle (F), the 4th interface connects cleaning fluid storage bottle (J), and the 5th interface connects plating mercury solution storage bottle (K); The outlet of micro-sampling pump (P3) is connected with electrolytic cell.
Described high molecule plastic flexible pipe is internal diameter 1.1 ~ 1.3 mm, the polyfluortetraethylene pipe of external diameter 2.5 ~ 3.0 mm.
Described quantitative ring (L) for internal diameter be 2.0 mm, external diameter is 3.75 mm, length is the polyfluortetraethylene pipe of 2 m.
The internal diameter that connects the polyfluortetraethylene pipe of micro-sampling pump (P3) is 0.8 mm, and external diameter is 1.6 mm.
Method and device that the present invention detects water quality lead have the following advantages:
(1) the present invention detects lead concentration by sequential injection for stripping voltammetry, realizing detection order controls continuously and automatically, can carry out online lead content in the various water sources such as the day water, sewage and industrial waste water, fast detecting, the polyfluortetraethylene pipe that adopts fixed length is quantitatively to encircle, water sample is quantitatively accurate, has height reappearance.
(2) the present invention adopts adsorption column that the lead in former water sample is adsorbed in polystyrene-dithizone nanofiber, then lead is eluted in eluent, plumbous enrichment in former water sample is become to the sample water of high concentration, thereby can detect the water sample that lead tolerance is very little, get rid of the interference of other metallic ion, improved the sensitivity detecting.
(3) structure of the detecting device is simple, and the failure rate of stream is very low.
(4) can react at normal temperatures, without heating, make instrument system simpler.
Accompanying drawing explanation
Fig. 1 is that plumbous automatic on-line detects plumbous apparatus structure schematic diagram.
In figure: Vl---the first solenoid valve, V2-the second solenoid valve, V3-the 3rd solenoid valve, V4-the 4th solenoid valve, V5-hyperchannel sequence valve, V6-T-valve, Pl-syringe pump, P2-peristaltic pump, P3-micro-sampling pump, L-quantitatively encircles, I-liquid level detector, T-electrolytic cell, D-adsorption column, B1-working electrode, B2-contrast electrode, B3-auxiliary electrode, H-electrochemical workstation (buying from Institutes Of Technology Of Tianjin), G-panel computer, E-sample water storage bottle, F-current-carrying liquid storage bottle, J-cleaning fluid storage bottle, K-plating mercury solution storage bottle.
Embodiment
Detect plumbous method and process below in conjunction with accompanying drawing explanation with this device.
One. the preparation of reagent:
(1) the plumbous standard solution preparation of water quality
Accurately take 1.0000 g simple metal lead (purity >=99.9%) and be dissolved in 20 ml salpeter solutions (being made into by 10ml red fuming nitric acid (RFNA)+10ml water), 1000 ml that then add water, are diluted to the salpeter solution that concentration is 1000 mg/L, as mother liquor, stand-by.
Accurately pipette 12 ml mother liquors in 500 ml volumetric flasks, adding distil water, to scale, shakes up, and the mark-on liquid that is made into concentration and is 24 mg/L is stand-by.
(2) current-carrying liquid
Accurately take 11.69 g sodium chloride in 1000 ml volumetric flasks, adding distil water dissolves, then adds 16.66 ml concentrated hydrochloric acids, and adding distil water, to scale, shakes up, and this is current-carrying liquid, stand-by.
(3) plating mercury solution
Accurately take 0.1478g mercuric sulfate in 500 ml volumetric flasks, then add 0.82 g NaAc, adding distil water dissolves, and is settled to scale, shakes up, and this is for plating mercury solution, stand-by.
(4) cleaning fluid
Accurately take 10.11 g potassium nitrate in 1000 ml volumetric flasks, adding distil water dissolves, then adds 2 ml red fuming nitric acid (RFNA)s, and adding distil water, to scale, shakes up, and this is cleaning fluid, stand-by.
(5) eluent
Accurately pipette 31.25 ml red fuming nitric acid (RFNA)s in 1000 ml volumetric flasks, adding distil water, to scale, shakes up, and this is that eluent is stand-by.
Two. the testing process of lead concentration in water
1. working electrode B1 plating mercury film:
As Fig. 1, electrolytic cell T inserts working electrode B1, contrast electrode B2 and auxiliary electrode B3, and electrochemical workstation H is connected with three electrodes; T-valve V6 is adjusted to 1-2 position logical (the 1st interface communicates with the 2nd interface, lower same), and passage sequence valve V5 forwards 1 (meaning: 0, center interface communicates with the 1st interface, lower same) to; It is logical that the 4th solenoid valve V4 is adjusted to 1-2 position.Start peristaltic pump P2 forward (being clockwise direction) rotation, distilled water in electrolytic cell T discharged through following route: interface 2 → interface 1 of interface 2 → interface 1 → liquid level detector I → peristaltic pump P2 → four solenoid valve V4 of interface 1 → hub-interface → valve V6 of electrolytic cell T → valve V5, enters waste liquid bottle.
2. in electrolytic cell T, inject quantitatively plating mercury solution, order is as follows:
Keep the 1-2 position of T-valve V6 logical, the positive hour hands rotation of peristaltic pump P2, hyperchannel sequence valve V5 forwards 8 to, plating mercury solution is through following route: plate interface 8 → hub-interface of mercury solution → valve V5 → quantitatively encircle interface 2 → interface 1 of L → valve V6, in the time that liquid level detector I has detected liquid level, illustrate that quantitatively ring L has been full of mercury solution, stop peristaltic pump P2.Forward hyperchannel sequence valve V5 to 1, start the rotation of peristaltic pump P2 inhour, the plating mercury solution quantitatively encircling in L is injected in electrolytic cell T through hub-interface and the interface 1 of valve V5; This step repeats 4 times, adds 4 times of quantitatively amounts of ring L, completes plating mercury solution injecting program.
3. plating mercury film
In galvanochemistry working software in panel computer G, select " time m-current method ", carry out electrochemical deposition under constant potential, sedimentation potential be-1.0 V, and sedimentation time is 180 s, completes to the plating mercury film of working electrode B1 sequentially.
4. reclaim plating mercury solution
Hyperchannel sequence valve V5 first forwards 1 to, and peristaltic pump P2 forward is injected quantitatively ring L by the plating mercury solution in electrolytic cell T through 0 interface in interface 1, the center of hyperchannel sequence valve V5.After quantitatively ring L is full of, forward hyperchannel sequence valve V5 to 5, peristaltic pump P2 rotating, is injected into by 0, hyperchannel sequence valve V5 center interface, interface 5 the plating mercury solution quantitatively encircling in L in plating mercury solution reagent bottle K, repeat 4 times, the plating mercury solution in electrolytic cell T is all reclaimed; Again the 4th solenoid valve V4 is adjusted to 2-3 position logical, hyperchannel sequence valve V5 first forwards 1 to, peristaltic pump P2 reversion, distilled water is injected in electrolytic cell T, and distilled water stream is: interface 1 → interface 2 of interface 3 → interface 2 → peristaltic pump P2 → liquid level detector I → T-valve V6 of the 4th solenoid valve V4 → quantitatively encircle 0, L → hyperchannel sequence valve V5 center interface → interface 1 → electrolytic cell T.
5. former water treatment
The 1-2 position of the first solenoid valve V1 is logical, and the 1-2 position of the second solenoid valve V2 is logical; Start syringe pump Pl to sucking state, former water sample is in interface 1 → interface 2 → syringe pump Pl chamber of interface 1 → interface 2 → the second solenoid valve V2 of the first solenoid valve V1; It is logical that the second solenoid valve V2 is adjusted to 2-3 position, syringe pump Pl is to injecting state, and former water sample in push chamber, injects in adsorption column D by interface 2, the interface 3 of the second solenoid valve V2, nanofiber in post carries out enrichment to lead ion, and waste water is discharged by interface 2 to the interface 1 of the 3rd solenoid valve V3.Make the 2-3 position of the first solenoid valve V1 logical, the 1-2 position of the second solenoid valve V2 is logical, eluent is drawn in syringe pump Pl, then make the 2-3 position of the second solenoid valve V2 logical, the 1-2 position of the 3rd solenoid valve V3 is logical, eluent is injected adsorption column D by syringe pump Pl, adsorption column is carried out to wash-out, the eluting water flowing out from adsorption column is pretreated detection sample water, be collected in sample water storage bottle E, this step can enriched lead ion, improve the concentration that detects lead ion in sample, to improve detection sensitivity.
6. sample water sample introduction program
T-valve V6 is that 1-2 position is logical, and the 4th solenoid valve V4 is that 1-2 position is logical, and hyperchannel sequence valve V5 forwards 1 to, and peristaltic pump P2 forward rotates, and the distilled water in electrolytic cell T is discharged to (the upper sample of distilled water in electrolytic cell T adds after detecting).Then hyperchannel sequence valve V5 forwards 2 to, peristaltic pump P2 forward, sample water is injected quantitatively ring L through following route: 0, interface 2 → center interface of sample water storage bottle E → hyperchannel sequence valve V5 → quantitatively encircle L, treat that liquid level detector I detects water sample, stops peristaltic pump P2.T-valve V6 is adjusted to 2-3 position logical, peristaltic pump P2 reversion, gets rid of unnecessary sample water (former road is back to sample water storage bottle E); Then the 1-2 position of T-valve V6 is logical, and hyperchannel sequence valve V5 forwards 1 to, and peristaltic pump P2 reversion, is injected into through 0, hyperchannel sequence valve V5 center interface, interface 1 water sample quantitatively encircling in L in electrolytic cell T, and water sample injects complete.
7. current-carrying liquid sample introduction program
The 1-2 position of T-valve V6 is logical, and hyperchannel sequence valve V5 forwards 3 to, and peristaltic pump P2 forward is injected quantitatively ring L current-carrying liquid from current-carrying liquid bottle, treats that liquid level detector I detects current-carrying liquid, and peristaltic pump P2 reversion, gets rid of unnecessary current-carrying liquid; Peristaltic pump P2 reversion, is injected into the current-carrying liquid quantitatively encircling in L in electrolytic cell T, and the method repeats 4 times, and the current-carrying liquid that quantitatively encircles tetra-times of amounts of L is joined in electrolytic cell T.
8. process of measurement
By electrochemical workstation H, in the galvanochemistry working software in panel computer G, select anodic stripping voltammetry, sedimentation potential is-1.1 V, sedimentation time is 150 s, selected cleaning current potential is-0.3 V, and the time is 15s, and Voltammetry lead is divided into two processes:
(1) enrichment process: under certain impressed voltage, first the lead ion in solution is reduced and is deposited on electrode surface, forms intermetallics.
(2) process in leaching: after deposition process finishes, also oppositely apply scanning voltage tranquillization a moment, the at this moment just Fast Stripping from electrode of lead of deposition, thus obtain very large Stripping Currents.
In reaction equation, B is electrode material.
By above-mentioned anodic stripping voltammetry method, replicate determination three times, utilizes galvanochemistry working software in panel computer G to calculate the value of plumbous stripping peak area; Then in electrolytic cell T, add mark liquid (each mark-on 50 μ L) with micro-sampling pump P3, analyze by anodic stripping voltammetry again, utilize galvanochemistry working software to calculate the numerical value of peak area, mark-on is once more afterwards, obtain equally the mark peak area at stripping peak afterwards, adopt the standard addition method computing formula in galvanochemistry working software, calculate concentration plumbous in water sample.
After making sample, the 1-2 position of T-valve V6 is logical, and hyperchannel sequence valve V5 forwards 1 to, and the 1-2 position of the 4th solenoid valve V4 is logical, and peristaltic pump P2 forward is discharged the waste liquid in electrolytic cell T.
9. cleaning procedure
The 1-2 position of T-valve V6 is logical, hyperchannel sequence valve V5 forwards 1 to, the 2-3 position of the 4th solenoid valve V4 is logical, peristaltic pump P2 reversion, distilled water is through following route injection electrolytic cell T: interface 1 → interface 2 of interface 3 → interface 2 → peristaltic pump P2 → liquid level detector I → T-valve V6 of the 4th solenoid valve V4 → quantitatively encircle 0, L → hyperchannel sequence valve V5 center interface → interface 1 → electrolytic cell T, distilled water is to cleaning with upper pipeline and electrolytic cell T of flowing through.Then the 4th solenoid valve V4 is adjusted to 1-2 position logical, peristaltic pump P2 forward, is back to former the distilled water in electrolytic cell T road the interface 2 of the 4th solenoid valve V4, discharges subsequently from interface 1, and distilled water cleans complete.Then forward hyperchannel sequence valve V5 to 4, peristaltic pump P2 forward, from cleaning fluid storage bottle J, suck cleaning fluid, through 0, interface 4 → center of hyperchannel sequence valve V5 interface → quantitatively encircle L, detect after solution until liquid level detector I, hyperchannel sequence valve V5 forwards 1 to, peristaltic pump P2 reversion, the cleaning fluid quantitatively encircling in L is injected in electrolytic cell T, repeats 4 times, in electrolytic cell T, inject 4 times to the long-pending cleaning fluid of quantitative ring body.Then select time-current method the galvanochemistry working software in panel computer G, adopts potentiostatic method to clean the mercury film on working electrode B1, and selected to clean current potential be-1.5 V, and scavenging period is 60 s, makes mercury film on working electrode B1 by wash-out.Then by peristaltic pump P2 forward, the cleaning fluid in electrolytic cell T is discharged through interface 2 → interface 1 of 0, interface 1 → center of hyperchannel sequence valve V5 interface → quantitatively encircle interface 2 → interface 1 → liquid level detector I → peristaltic pump P2 → four solenoid valve V4 of L → T-valve V6.
10. descend the preparation routine of task
Passage sequence valve V5 forwards 1 to, the 4th solenoid valve V4 is that 2-3 position is logical, peristaltic pump P2 reversion, by distilled water through interface 1 → interface 2 of interface 3 → interface 2 → peristaltic pump P2 → liquid level detector I → T-valve V6 of the 4th solenoid valve V4 → quantitatively encircle 0, L → hyperchannel sequence valve V5 center interface → interface 1 → electrolytic cell T.Termination of pumping, system, in preparing, is carried out plating mercury for next sample detection and is prepared.
The present embodiment test data sees the following form:
Detect the data of water sample with plumbous automatic on-line monitoring instrument
National standard method: atomic absorption spectrophotometry (GB/T 7475-1987)
Adopt close that lead concentration numerical value that sequential injection detection method of the present invention and pick-up unit record and National Standard Method record, show that sequential injection detects water quality lead and has higher accuracy and go interference.
Claims (4)
1. a sequential injection detects the device of water quality lead online, it is characterized in that comprising electrolytic cell (T), syringe pump (P1), peristaltic pump (P2), micro-sampling pump (P3), the first solenoid valve (V1), the second solenoid valve (V2), the 3rd solenoid valve (V3), the 4th solenoid valve (V4), hyperchannel sequence valve (V5), T-valve (V6), electrochemical workstation (H) and panel computer (G), each parts are linked to be system by high molecule plastic flexible pipe, and its annexation is as follows:
In electrolytic cell (T), be inserted with working electrode (B1), contrast electrode (B2) and auxiliary electrode (B3), described each electrode is connected with the corresponding interface of electrochemical workstation (H) respectively; Electrochemical workstation (H) is connected with panel computer (G);
The first solenoid valve (V1) the 1st interface connect water sample source, the first solenoid valve the 2nd interface be connected with the 1st interface of the second solenoid valve (V2), the interface 3 of the first solenoid valve (V1) be eluent export;
The 2nd interface of the second solenoid valve (V2) is connected with syringe pump, and the interface 3 of the second solenoid valve (V2) connects adsorption column (D), is filled with sorbing material polystyrene-dithizone nanofiber in the interior adsorption column of adsorption column (D);
The 1st interface of the 3rd solenoid valve (V3) is waste liquid outlet, and the 2nd interface connects adsorption column (D) outlet, and interface 3 connects sample water storage bottle (E);
The 4th solenoid valve (V4) the 1st interface be waste liquid outlet, the 4th solenoid valve V4 the 2nd interface be connected with the 1st interface of T-valve (V6) through peristaltic pump (P2), the interface 3 of the 4th solenoid valve V4 is distilled water import;
Hyperchannel sequence valve (V5) comprises a hub-interface and the 1st ~ 5th interface and that selection communicates with it thereof around; Between the 2nd interface of described hub-interface and T-valve (V6), be connected quantitatively to encircle (L); The annexation of other each interface of hyperchannel sequence valve (V5) is as follows: the 1st interface connects electrolytic cell (T), the 2nd interface connects sample water storage bottle, interface 3 connects current-carrying liquid storage bottle (F), the 4th interface connects cleaning fluid storage bottle (J), and the 5th interface connects plating mercury solution storage bottle (K); The outlet of micro-sampling pump (P3) is connected with electrolytic cell.
2. sequential injection according to claim 1 detects the device of water quality lead online, it is characterized in that described high molecule plastic flexible pipe is internal diameter 1.1 ~ 1.3 mm, the polyfluortetraethylene pipe of external diameter 2.5 ~ 3.0 mm.
3. sequential injection according to claim 1 and 2 detects the device of water quality lead online, it is characterized in that described quantitative ring (L) for internal diameter be 2.0 mm, external diameter is 3.75 mm, length is the polyfluortetraethylene pipe of 2 m.
4. sequential injection according to claim 3 detects the device of water quality lead online, and the internal diameter that it is characterized in that the polyfluortetraethylene pipe that connects micro-sampling pump (P3) is 0.8 mm, and external diameter is 1.6 mm.
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| CN105699467B (en) * | 2016-01-15 | 2018-11-13 | 刘文涛 | A kind of improved electrochemical analysis method and application |
| CN107860614B (en) * | 2017-11-22 | 2024-02-23 | 江苏蓝创智能科技股份有限公司 | Quantitative metering device of water quality detector |
| CN107991365A (en) * | 2017-11-27 | 2018-05-04 | 宇星科技发展(深圳)有限公司 | A kind of on-line cleaning method for the heavy metal on-line computing model working electrode based on anodic stripping voltammetry |
| CN107884465B (en) * | 2017-12-08 | 2023-09-22 | 自然资源部第二海洋研究所 | Online monitoring system and method for early warning of red tide |
| CN109406431A (en) * | 2018-12-13 | 2019-03-01 | 凯铭科技(杭州)有限公司 | A kind of liquid channel system and its control method of unit dosage |
| US20210033624A1 (en) * | 2019-07-29 | 2021-02-04 | Guiyang Li | Online Measurement of Titer in Antibody Production |
| CN111174099A (en) * | 2019-12-19 | 2020-05-19 | 江苏国技仪器有限公司 | Multi-range water quality analyzer flow path system and accurate quantification method |
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