CN101603969A - Flow-injection quick analysis system for hexavalent chromium water quality - Google Patents
Flow-injection quick analysis system for hexavalent chromium water quality Download PDFInfo
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- CN101603969A CN101603969A CNA2009101817733A CN200910181773A CN101603969A CN 101603969 A CN101603969 A CN 101603969A CN A2009101817733 A CNA2009101817733 A CN A2009101817733A CN 200910181773 A CN200910181773 A CN 200910181773A CN 101603969 A CN101603969 A CN 101603969A
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Abstract
The present invention relates to a kind of flow-injection quick analysis system for hexavalent chromium water quality, comprise the water sample source, current-carrying liquid storage bottle, syringe pump, indicator storage bottle, peristaltic pump, reaction tube and the photoelectricity flow cell that connect by capillary pipeline, be connected with a current-carrying liquid T-valve, the first sampling six-way valve and the second sampling six-way valve in the capillary pipeline, two sampling six-way valves have sampling or measure two transition states, and are promptly changeable by the valve gap of in good time rotation two 6 valves.Water sample and indicator diphenylcarbazide solution adopt the kapillary of fixed length to be connected into system respectively, and the two spreads in current-carrying liquid and react and generates red liquid, by the photoelectric colorimetry of photoelectricity flow cell, records chromic content in the water sample.Water sample is quantitatively accurate, and testing result is accurate, the reappearance height; Failure rate is very low, and easily is automated, and can be used for the express-analysis of chromic laboratory or to the on-line monitoring of Environmental Water or discharge water.
Description
Technical field
The present invention relates to the chromic flow-injection quick analysis system for hexavalent chromium water quality of a kind of flow injection and spectrophotometric analysis, be used for water source content of 6-valence Cr ions such as surface water or factory's discharge water and carry out express-analysis or on-line monitoring, belong to chemical analysis and monitoring water environment analysis field.
Background technology
Hexavalent chromium compound is widely used in metal plating, process hides electron trade and various metal industry, is used for the anticorrosive in absorption heat pump, industrial freezer and the heat exchanger for refrigerator in the colorant, cooling water recirculation system of pigment in addition.The sexavalent chrome bio-toxicity is very big, can cause vomiting when alimentary canal is invaded, abdomen is painful, can produce dermatitis and eczema when skin is invaded, and carcinogenic danger is arranged when long-term or short term contact or suction.Excessive (surpassing 10ppm) sexavalent chrome has lethal effect to aquatic organism, experiment shows, sexavalent chrome in the contaminated potable water can be carcinogenic, after animal is drunk and contains chromic water, sexavalent chrome can be absorbed by the cell of many tissues and organ in the body, edible by hexavalent chromium polluted food and water source, can cause in various degree damage to human body.Therefore, must strictly monitor chromic content in surface water and the relevant enterprise discharge water,, avoid producing harm so that in time corresponding countermeasure is taked at the water source that sexavalent chrome is exceeded standard.
At present, measure chromic instrument and mainly contain spectrophotometric method, atomic spectroscopy, polarography, flow injection analysis, electrochemical process, chemoluminescence method, neutron activation method, isotope dilution mass spectrometry, X-ray diffraction method and resonance scattering method.Polarography and directly current method can directly measure the sexavalent chrome of ultramicron (analysis precision can reach (10
-3Mg/L), though neutron activation method and isotope dilution mass spectrometry are highly sensitive, selectivity is high, because of being subjected to condition restriction, these methods do not obtain widespread usage as yet.Other big multi-methods are difficult to popularize use owing to instrument costs an arm and a leg.
Flow Injection Analysis is a kind of new express-analysis technology, has simply, changes fast and automatically the characteristics that degree is high and save indicator, and development in recent years is very fast, and present most automatic water quality monitoring systems have all used the flow injection technology.Exist serviceable life short but be used to detect chromic flow injection analyzer at present, shortcomings such as failure rate height.
Summary of the invention
The purpose of this invention is to provide a kind of flow-injection quick analysis system for hexavalent chromium water quality online or the laboratory express-analysis that is used for, have simple to operate, constant flow, detect examination fast, the precision advantages of higher.
Flow-injection quick analysis system for hexavalent chromium water quality of the present invention is by the water sample source, current-carrying liquid reservoir, syringe pump, indicator reservoir, peristaltic pump, reaction tube and the photoelectricity flow cell that connect by capillary pipeline, be connected with a plurality of cross-over valves in the said capillary pipeline, said cross-over valve comprises a current-carrying liquid T-valve V6, the first sampling six-way valve V4 and the second sampling six-way valve V5, and the annexation of each cross-over valve is as follows:
First interface of said T-valve links to each other with current-carrying liquid bottle, and second interface links to each other with syringe pump P1, and second interface and first, the 3rd interface are selected one and communicated;
Said first the sampling six-way valve in, first interface with link to each other with water sample by a peristaltic pump, the 3rd interface links to each other with the 3rd interface of current-carrying liquid T-valve V6; The 4th interface links to each other successively with reaction tube, flow cell, and the 6th interface is a waste liquid outlet;
Among the said second sampling six-way valve V5, first interface links to each other with the indicator bottle by a peristaltic pump, is connected with indicator capillary quantity tube between second interface and the 5th interface, and the 6th interface is a waste liquid outlet; Between second interface of the 3rd interface and the first sampling six-way valve V4 and the 4th interface and first sample and be connected with the capillary sampling pipe of a fixed length between the 5th interface of six-way valve V4 respectively;
Two sampling six-way valves have sampling or measure two transition states:
During the sampling attitude, the break-make relation is in two sampling six-way valve V4, the V5 valve separately: between first and second interface, the 3rd with the 4th interface between, the 5th with the 6th interface between communicate disconnection respectively between the second and the 3rd interface, between the 4th and the 5th interface respectively;
During measurement state, the break-make relation is in two sampling six-way valve V4, the V5 valve separately: disconnection respectively between first and second interface, between the 3rd and the 4th interface, between the 5th and the 6th interface, second with the 3rd interface between, the 4th with the 5th interface between communicate respectively.
System of the present invention also is provided with water sample electrovalve V1 and standard specimen electrovalve V2, and wherein the 3rd interface of water sample electrovalve V1 connects the water sample source, and second interface links to each other with first interface of the first sampling six-way valve by peristaltic pump P2; The first, the 3rd interface of standard specimen electrovalve V2 connects a standard specimen source respectively, and second interface links to each other with first interface of water sample electrovalve V1; Second interface in two electrovalves is selected one with the first, the 3rd interface separately respectively and is communicated.
Said current-carrying liquid is the mixed solution of phosphoric acid,diluted and dilute sulfuric acid, and wherein sulfuric acid and concentration of phosphoric acid are respectively 2.5%.
Said developer is a diphenylcarbazide solution.
Said syringe pump is the electronic constant current syringe pump of being made by the pottery of acid corrosion-resistant and/or stainless steel material.
Internal diameter capillaceous is generally at 0.5-1mm.
Native system is current-carrying liquid with the dilute acid soln, by constant flow pump current-carrying liquid is injected pipeline capillaceous continuously, under current-carrying liquid promotes, quantitatively water sample and diphenylcarbazide are pushed and advance and limited diffusion in current-carrying liquid, sexavalent chrome and indicator diphenylcarbazide react in the water sample, product is a red liquid, after reacted sample enters the colorimetric flow cell, under the rayed of 540nm wavelength, detect, because red product absorbs maximum to the light of 540nm wavelength, and is absorbed with difference under the different concentration.According to the changing value that sees through light intensity, obtain to have the response curve of corresponding peak height and peak width, utilize peak height or peak width, through comparing, calculate and try to achieve chromic content in the water sample with blank.Because the flow velocity of current-carrying liquid is constant, in certain remaining time, the disperse state of sample in current-carrying liquid has the height reappearance, so measurement result is accurate, the reappearance height; With its peak width information, measure highly sensitively, and have very wide measurement range (water sample of chromium content 4～1000mg/L all can be measured); The water sample of the each incision of Flow Injection Analysis method is micro-, have only about 100 μ L, so the consumption of reagent is very extremely low, and can reacts at normal temperatures, need not heating, has saved operation cost greatly.Native system is used for timings such as the source water of rivers and lakes, water factory or industrial discharge water or carries out chromic on-line monitoring at random, easy and obtain instant analysis data apace, particularly for the great water pollution accident of spy's property sent out, can in time find, in time report, in time handle, striven for valuable time for removing a hidden danger.
This sexavalent chrome analytic system constant flow rate, adopt the capillary sampling pipe of fixed length, water sample is quantitatively accurate, adopt the multi-channel sampling valve, easy to operate, only need the valve gap of rotation two sampling valves in good time, sampling pipe and indicator quantity tube can be connected into system, and make diphenylcarbazide between two sections quantified sample water, and can accelerate the two phase counterdiffusion and reaction, shorten the reaction time.Native system is finished a water sample detection analysis and is only needed several minutes, realizes real time on-line monitoring truly.Native system is simple in structure, and failure rate is very low, and easily is automated.
Description of drawings
Fig. 1 is the structural representation that flow-injection quick analysis system for hexavalent chromium water quality is in the measurement state.
Fig. 2 is the structural representation that flow-injection quick analysis system for hexavalent chromium water quality is in sample states.
Each label table is shown among the figure: V1-water sample electrovalve, V2-standard specimen electrovalve, V4, V5-sampling six-way valve, V6-current-carrying liquid T-valve, P1-current-carrying liquid syringe pump, P2-water sample peristaltic pump, P3-indicator peristaltic pump, Ls, Ls '-sampling pipe, L
X-indicator quantity tube, F-reaction tube, G-photoelectricity flow cell, S-sample water source, B1, B2-standard specimen water source, H--current-carrying liquid storage bottle, M-indicator storage bottle, W1, W2-waste liquid bottle.
Embodiment
Example structure and test process below in conjunction with this flow injection of description of drawings express-analysis sexavalent chrome system.
Below the pipeline of each embodiment be internal diameter 0.8mm, the polytetrafluoroethylene capillary of external diameter 2.5mm;
The indicator compound method is as follows:
(1) indicator diphenyl phosphinylidyne two hydrazines
(molecular formula is C to take by weighing 2g diphenyl phosphinylidyne two hydrazines
13H
14N
4O), be dissolved in 200ml acetone, add water and be settled to 500ml.
Need store in the brown bottle after this solution preparation and keep in Dark Place, can not use after look deepens.
(2) current-carrying liquid
Under agitation slowly add the phosphoric acid of 50ml and the sulfuric acid of 50ml in 1000ml distilled water, adding distil water is settled to 2000ml then.
(3) chromium standard stock solution
Take by weighing 110 ℃ of potassium dichromate (K of dry 2 hours down
2Cr
2O
7) 0.2829 ± 0.0001g, after the water dissolving, move in the 1000ml volumetric flask, be diluted with water to graticule, shake up.This solution contains sexavalent chrome 100mg/L.The standard specimen water that contains chromium is obtained by this stock solution dilution.
As Fig. 1, Fig. 2, sampling valve six-way valve V4 and V5, valve seat are provided with six interfaces 1～6, and the inboard of valve gap is provided with three arc grooves, and the end of three arc grooves can correspondingly overlap on six interfaces on the valve seat; The rotation valve gap can make deep-slotted chip breaker turn over a radian at interval, thus the annexation of change over valve V4, V5; Quantitative sampling pipe Ls and Ls ' are the kapillaries of two sections fixed length, and Ls is connected between the interface 3 of the interface 2 of valve V4 and valve V5, and Ls ' is connected between the interface 4 of the interface 5 of valve V4 and valve V5; Indicator diphenyl phosphinylidyne two hydrazidines buret L
XBe connected between the interface 2 and interface 5 of V5; The rotation valve gap makes deep-slotted chip breaker move a radian at interval, can be with Ls, Ls ' and L
XAnnexation in system becomes the sample states of Fig. 2 from the measurement sample state exchange of Fig. 1.
Before native system uses, with current-carrying liquid system is cleaned earlier, operating process is as follows:
T-valve V6 goes to interface 2 and communicates with 1, starts ceramic injection pump P1 to sucking attitude, sucks current-carrying liquid to the chamber of syringe pump P1 from current-carrying liquid storage bottle H, is filled the back termination of pumping; Subsequently T-valve V6 is gone to interface 2 and communicates with 3 (shown position), transfer to as shown in Figure 1 measurement state, start ceramic injection pump P1, make the following stream of current-carrying liquid injection syringe pump P1 chamber in to injecting attitude with annotating sample valve V4 and V5:
P1 → V6 interface 2,3 → V4 interface 3,2 → sampling pipe L
s→ V5 interface 3,2 → indicator quantity tube L
X→ V5 interface 5,4 → sampling pipe L
s' → V4 interface 5,4 → reaction tube → flow cell G → waste liquid bottle W2; Current-carrying liquid is to cleaning from above stream.Cleaning finishes, termination of pumping P1, and system cleans and finishes.
Enter sampling routine then.As Fig. 2, electrovalve V1 is in the state that interface 2 as shown communicates with 3, and valve V4 and V5 go to the sampling attitude, starts peristaltic pump P2, water sample S is carried by peristaltic pump P2, by interface 3, the interface 1 of 2 → V4, the 2 → sampling pipe L of following flow path (referring to Fig. 2): S → V1
sThe interface 3 of → V5,4 → sampling pipe L
sThe interface 5 of ' → V4,6 → waste liquid bottle W1, sampling pipe L at this moment
sAnd L
s' all filled with water sample.Start peristaltic pump P3 simultaneously, indicator M passes through by the following stream of Fig. 2 through pump P3: the interface 1 of current-carrying liquid M → valve V5,2 → indicator quantity tube L
XThe interface 5 of → valve V5,6 → waste liquid bottle W1, quantity tube L at this moment
XPromptly filled with indicator M (diphenyl phosphinylidyne two hydrazine solutions).
Then enter process of measurement.Stop peristaltic pump P2 and P3, and valve V4 and V5 are gone to measurement state as Fig. 1, start syringe pump P1 once more, make current-carrying liquid once more by interface 2,3 → V4 interface 3, the 2 → sampling pipe L of following flow path: P1 → V6
sThe interface 3 of → V5,2 → indicator quantity tube L
X→ V5 interface 5,4 → sampling pipe L
s' → V4 interface 5,4 → reaction tube F → photoelectricity flow cell G → waste liquid bottle W2; Liquid in the above stream distributes with the order of " current-carrying liquid ‖ water sample ‖ indicator ‖ water sample ‖ current-carrying liquid ", be that indicator is between two sections water samples, in by current-carrying liquid progradation, water sample spreads gradually and mixes in gradient with indicator, react, reaction produces red product, its red depth of color is directly proportional with chromium content in the water, the two finishes at reaction tube F internal reaction, reacted water sample is advanced photoelectricity flow cell G, by wavelength is the 540nm light source irradiation, acquisition has the response curve of corresponding peak height and peak width, with peak height or peak width through with the standard specimen water test curve ratio of known chromium concn, promptly draw chromic content in the water sample by calculating.
Standard specimen water is the water of known hexavalent chromium concentration, its flow injection spectrophotomelric assay process is the same, just sampling process transfers to interface 2 with water sample electrovalve V1 and communicates with 1, and, during mark sample B1, standard specimen electrovalve V2 transfers to interface 2 and communicates with 3, and during mark sample B2, standard specimen electrovalve V2 transfers to interface 2 and communicates with 1.
Following table be with the Flow Injection Analysis system of present embodiment detect two standard specimens and three water samples the detection data:
From last table as seen, it is very approaching that water sample detects gained with this Flow Injection Analysis system hexavalent chromium concentration and manual titrimetry record the hexavalent chromium concentration value, illustrate that native system test sexavalent chrome is quick and accurate.
Claims (5)
1. flow-injection quick analysis system for hexavalent chromium water quality, comprise the water sample source, current-carrying liquid storage bottle, syringe pump, indicator storage bottle, peristaltic pump, reaction tube and the photoelectricity flow cell that connect by capillary pipeline, it is characterized in that said indicator is a diphenylcarbazide, be connected with a plurality of cross-over valves in the capillary pipeline, said cross-over valve comprises a current-carrying liquid T-valve, the first sampling six-way valve and the second sampling six-way valve, and the annexation of each cross-over valve is as follows:
First interface of said T-valve links to each other with current-carrying liquid bottle, and second interface links to each other with syringe pump, and second interface and first, the 3rd interface are selected one and communicated;
Said first the sampling six-way valve in, first interface with link to each other with water sample by a peristaltic pump, the 3rd interface links to each other with the 3rd interface of current-carrying liquid T-valve; The 4th interface links to each other successively with reaction tube, flow cell, and the 6th interface is a waste liquid outlet;
In the said second sampling six-way valve, first interface links to each other with the indicator bottle by a peristaltic pump, is connected with indicator capillary quantity tube between second interface and the 5th interface, and the 6th interface is a waste liquid outlet; Between second interface of the 3rd interface and the first sampling six-way valve and the 4th interface and first sample and to be connected with the capillary sampling pipe of a fixed length between the 5th interface of six-way valve respectively;
Two sampling six-way valves have sampling or measure two transition states:
During the sampling attitude, the break-make relation is in the two sampling six-way valves valves separately: between first and second interface, the 3rd with the 4th interface between, the 5th with the 6th interface between communicate disconnection respectively between the second and the 3rd interface, between the 4th and the 5th interface respectively;
During measurement state, the break-make relation of the valve inner joint of two sampling six-way valves is: disconnection respectively between first and second interface, between the 3rd and the 4th interface, between the 5th and the 6th interface, second with the 3rd interface between, the 4th with the 5th interface between communicate respectively.
2. flow-injection quick analysis system for hexavalent chromium water quality according to claim 1, it is characterized in that being provided with water sample electrovalve and standard specimen electrovalve, wherein the 3rd interface of water sample electrovalve connects the water sample source, and second interface links to each other by first interface of peristaltic pump with the first sampling six-way valve; The first, the 3rd interface of standard specimen electrovalve connects a standard specimen source respectively, and second interface links to each other with first interface of water sample electrovalve; Second interface in two electrovalves is selected one with the first, the 3rd interface separately respectively and is communicated.
3. flow-injection quick analysis system for hexavalent chromium water quality according to claim 1 is characterized in that said current-carrying liquid is the mixed solution of phosphoric acid,diluted and dilute sulfuric acid, and wherein sulfuric acid and concentration of phosphoric acid are respectively 2.5%.
4. flow-injection quick analysis system for hexavalent chromium water quality according to claim 1 is characterized in that said syringe pump is the electronic constant current syringe pump of pottery and/or stainless steel.
5. according to claim 1 or 2 or 3 or 4 described flow-injection quick analysis system for hexavalent chromium water quality, it is characterized in that internal diameter capillaceous is 0.5-1mm.
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|---|---|---|---|
| CNA2009101817733A CN101603969A (en) | 2009-07-23 | 2009-07-23 | Flow-injection quick analysis system for hexavalent chromium water quality |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101793902A (en) * | 2010-03-29 | 2010-08-04 | 河海大学 | Device for fluidly injecting and rapidly analyzing residual chlorine of water quality and analysis method thereof |
| CN102200539A (en) * | 2011-03-29 | 2011-09-28 | 江苏德林环保技术有限公司 | Online analytical device for nickel ions of water quality through flow injection |
| CN102226770A (en) * | 2011-03-30 | 2011-10-26 | 江苏德林环保技术有限公司 | Flow injection analysis device for nitrite or nitrate in water |
| CN102375074A (en) * | 2010-08-20 | 2012-03-14 | Abb技术有限公司 | Chemical analysis apparatus |
| CN102980860A (en) * | 2012-11-21 | 2013-03-20 | 中国科学院烟台海岸带研究所 | Full-automatic quick measurement system and method for water quality hexavalent chromium |
| CN104977265A (en) * | 2015-07-15 | 2015-10-14 | 厦门市吉龙德环境工程有限公司 | Analyzer and analytical method for soluble sulfides in water sample |
| CN109580480A (en) * | 2017-09-28 | 2019-04-05 | 株式会社岛津制作所 | Total phosphorus determination device |
| WO2020228507A1 (en) * | 2019-05-16 | 2020-11-19 | 山东省科学院海洋仪器仪表研究所 | High-precision seawater ph in-situ measurement system and method based on integrated valve-terminal apparatus |
-
2009
- 2009-07-23 CN CNA2009101817733A patent/CN101603969A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101793902A (en) * | 2010-03-29 | 2010-08-04 | 河海大学 | Device for fluidly injecting and rapidly analyzing residual chlorine of water quality and analysis method thereof |
| CN102375074A (en) * | 2010-08-20 | 2012-03-14 | Abb技术有限公司 | Chemical analysis apparatus |
| CN102375074B (en) * | 2010-08-20 | 2015-02-18 | Abb技术有限公司 | Chemical analysis apparatus |
| CN102200539A (en) * | 2011-03-29 | 2011-09-28 | 江苏德林环保技术有限公司 | Online analytical device for nickel ions of water quality through flow injection |
| CN102226770A (en) * | 2011-03-30 | 2011-10-26 | 江苏德林环保技术有限公司 | Flow injection analysis device for nitrite or nitrate in water |
| CN102980860A (en) * | 2012-11-21 | 2013-03-20 | 中国科学院烟台海岸带研究所 | Full-automatic quick measurement system and method for water quality hexavalent chromium |
| CN102980860B (en) * | 2012-11-21 | 2014-10-22 | 中国科学院烟台海岸带研究所 | Full-automatic quick measurement system and method for water quality hexavalent chromium |
| CN104977265A (en) * | 2015-07-15 | 2015-10-14 | 厦门市吉龙德环境工程有限公司 | Analyzer and analytical method for soluble sulfides in water sample |
| CN109580480A (en) * | 2017-09-28 | 2019-04-05 | 株式会社岛津制作所 | Total phosphorus determination device |
| WO2020228507A1 (en) * | 2019-05-16 | 2020-11-19 | 山东省科学院海洋仪器仪表研究所 | High-precision seawater ph in-situ measurement system and method based on integrated valve-terminal apparatus |
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Open date: 20091216 |