CN105588887B - Chloride test working solution and detection method and application in Power Plant Water Vapor - Google Patents
Chloride test working solution and detection method and application in Power Plant Water Vapor Download PDFInfo
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- CN105588887B CN105588887B CN201410659596.6A CN201410659596A CN105588887B CN 105588887 B CN105588887 B CN 105588887B CN 201410659596 A CN201410659596 A CN 201410659596A CN 105588887 B CN105588887 B CN 105588887B
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- 238000001514 detection method Methods 0.000 title claims abstract description 62
- 239000012224 working solution Substances 0.000 title claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 20
- 238000012360 testing method Methods 0.000 title claims abstract description 17
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 4
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- 238000005342 ion exchange Methods 0.000 claims description 49
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- 239000002131 composite material Substances 0.000 claims description 23
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- 150000001450 anions Chemical class 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
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- 239000000203 mixture Substances 0.000 claims description 7
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- 238000002798 spectrophotometry method Methods 0.000 claims description 6
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- LJBWEZVYRBKOCI-UHFFFAOYSA-N 2,4,6-triaminoquinazoline Chemical group N1=C(N)N=C(N)C2=CC(N)=CC=C21 LJBWEZVYRBKOCI-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
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- 230000008859 change Effects 0.000 description 6
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides chloride test working solution and detection method and application in a kind of Power Plant Water Vapor.The working solution includes eluent and reaction reagent, and the eluent is Na2CO3‑NaHCO3Buffer solution eluent, Na2CO3And NaHCO3Concentration be 0.001 0.05mol/L；The reaction reagent includes 0.001wt%~0.05wt% developers, 0.1wt%~5.0wt% ferric perchlorates, preferably perchloric acid or nitric acid less than 1.0v%, perchloric acid, and methanol 5.0v%~15v%, surplus is high purity water.Present invention also offers the detection method using chlorion in above-mentioned working solution detection Power Plant Water Vapor and application.The method achieve trace chloro ion in Power Plant Water Vapor, automatically, quickly measure, detection are limited to 0.5 μ g/L.
Description
Technical field
The present invention relates to the detection of Power Plant Water Vapor, specifically, is related to chloride test work in a kind of Power Plant Water Vapor
Liquid and detection method and application.
Background technology
In recent years, put into operation with the continuous of fired power generating unit of high parameter Large Copacity, to unit thermodynamic system steam product
Matter requires more and more stricter.Chlorion is that maximum anion is endangered in water-steam system, the chlorion containing μ g/L levels in steam
Just it is enough the integrality for destroying oxidation on metal surface thing diaphragm.Therefore, trace chloro ion content in Power Plant Water Vapor is carried out accurate
Really detection is very necessary.Chlorion in steam and make-up water is provided in American Electric Power research institute (EPRI) steam-purity value directive/guide
Content should be less than 3.0 μ g/L.Domestic standard《GB-T12145-2008 thermal power generation units and apparatus of steam power plants Water Vapor Quality》
In set hydrogen conductivity Con trolling index, by the on-line monitoring of hydrogen conductivity, the anion-content being indirectly controlled in steam,
And chloride ion content is not specified, reason is the domestic effective ways for still lacking Accurate Determining trace chloro ion at present.
At present, domestic and international traditional accurate method of detection trace chloro ion only has the chromatography of ions.But because of ion color
Spectrometer is expensive, maintenance cost is high and maintenance workload is bigger, requires higher to running environment, is widely used at present
Test and study in the lab analysis of scientific research institutions, but it is seldom in the application of power plant.So develop a kind of inexpensive, fast
Fast detection method that is accurate, being easily achieved trace chloro ion in the industrial pure water system (such as Power Plant Water Vapor system) of onlineization monitoring
With very important Research Significance and practical value.
Using flowing injecting analysis technology (Flow Injection Analysis, abbreviation FIA) determine water in Micro Amounts of Chlorine from
The existing achievement in research of son, it is successfully used for the measure of trace chlorine in boiler water in thermal power plants.FIA is combined with AAS
The content of trace chlorine in power plant's stove water is determined, the detection of this method is limited to 20 μ g/L, RSD and is less than 0.89%, and the rate of recovery is
100%-105%, analyze speed are 60-120 samples/h.
FIA technologies are combined with the Ion-exchange pretreatment method of sample, the development in trace analysis chemistry has accounted for phase
When big proportion, and many aspects have turned into the forward position of FIA technologies development.FIA- ON-LINE ION-EXCHANGEs preenrichment-spectrophotometric
There has been no pertinent literature and achievement to report in trace chloro ion analysis context of detection for method, and one of key technology condition of this method to be
Colour reagent, it is the key factor for determining this method in detection underwater trace chloride ion content (being less than 5.0 μ g/L) feasibility
One of.
At present, determining the research of trace chloro ion and application for water sample pre-concentration has two kinds：Prior art 1 is a kind of cloudy
The pre-concentration of water sample in ion chromatography；Prior art 2 is for a kind of offline manual Ion-exchange pretreatment method and herein
On the basis of the continuous flow method ON-LINE ION-EXCHANGE preenrichment method realized, the eluent composition and concentration that two methods use, because
Technology path is different, so its composition and concentration are essentially different.
Chromatography of ions in prior art 1 is one kind of high performance liquid chromatography, is mainly used in anion, cation analysis
Detection.The chromatography of ions is selectively good, high sensitivity, can determine multicomponent simultaneously, by optimizing analysis system and analysis condition,
Test limit is up to 10-12G/L or lower.
Trace chloro ion detects in ion exchange resin enrichment-spectrophotometry Power Plant Water Vapor in prior art 2
Method, this method devise a kind of offline Ion-exchange pretreatment system, and leacheate used is 110mmol/L Na2CO3-
35mmol/L NaHCO3.After the high-purity water samples of 1000mL (1~10 μ g/L) are enriched with this method, then it is condensed into elution
After 25mL, the concentration of its chlorion up to 40~400 μ g/L, with the chlorine in mercuric thiocyanate spectrophotometry eluent from
Son, for this method in the range of 20~400 μ g/L, standard curve is linearly preferable.
A certain amount of water sample is taken to flow through specific device (built-in ion exchange resin), chlorion is quantitatively enriched on resin,
It is eluted from resin from tens times smaller than volume of water sample of eluent again, so as to reach enrichment concentration chlorion
Purpose.Then directly the chlorion in concentration sample is measured with spectrophotometer.
The method for continuous measuring and device of trace chloro ion in a kind of high purity water are developed based on the analysis method, it includes
Water sample enrichment facility and the photodetector system being attached thereto, concentration systems are based on ion exchange principle and are enriched with trace in high-purity water sample
The chlorion of amount, when water sample chloride ion content is more than 20 μ g/L, water sample is directly entered photodetector system and measured；Water sample
When middle chloride ion content is less than 20 μ g/L, system carries out the concentration of Chloride Ion In Water, elution by enrichment facility is automatically switched to,
Eluent measures into electro-optical system, so as to which the Monitoring lower-cut of chlorion is down to below 1.0 μ g/L.This method it is automatic
It is relatively low to change level, carries out being enriched with-elution action using traditional high-order static pressure mode, the control to concentration rate uses offline hand
Work determines, it is difficult to accurately controls concentration rate, detection method is still Manual analysis method；Eluent used in this method is
110mmol/L Na2CO3-35mmol/LNaHCO3。
The content of the invention
It is an object of the present invention to provide chloride test working solution in a kind of Power Plant Water Vapor.
It is another object of the present invention to provide a kind of chloride test method in Power Plant Water Vapor.
A further object of the present invention is in the application in offer methods described in Power Plant Water Vapor in trace chloro ion detection.
For the above-mentioned purpose, the invention provides a kind of automatic quick detection working solution of chlorion in Power Plant Water Vapor, institute
Stating working solution includes eluent and reaction reagent, and the eluent is Na2CO3-NaHCO3Buffer solution eluent, Na2CO3With
NaHCO3Concentration be 0.001-0.05mol/L；The reaction reagent include 0.001wt%~0.05wt% developers,
0.1wt%~5.0wt% ferric perchlorates, preferably perchloric acid or nitric acid less than 1.0v%, perchloric acid, methanol 5.0v%~
15v%, surplus are high purity water；It is preferred that the developer is mercuric thiocyanate.
According to working solution of the present invention, the pH value of reaction reagent is 1.0~3.0.
According to working solution of the present invention, in the Na2CO3-NaHCO3Na in buffer solution eluent2CO3And NaHCO3
Mol ratio be 4:1.
Above-mentioned percetage by weight, percentage by volume are calculated according on the basis of the gross weight of reaction reagent, cumulative volume respectively
Obtain, above-mentioned Na2CO3-NaHCO3Buffer solution is Na2CO3-NaHCO3The aqueous solution.The mesh of above-mentioned addition perchloric acid or nitric acid
Be adjust reaction reagent pH value be 1.0~3.0.
According to working solution of the present invention, the chlorion component to be measured being enriched with need to elute progress from resin phase
On-line checking, the performance of eluent have a major impact to the sensitivity finally detected and analyze speed.Sum up, to eluent
The requirement of performance has following several respects：
1st, using eluting peak peak as reading position during detection in the online preconcentration of flowing injecting analysis technology, because
This, elution is faster, and peak is narrower, and peak value is higher, and concentration coefficient is also bigger.This requires eluent to be desorbed from sorptive medium rapidly
Determinand；
2nd, the occlusion and desorption performance that eluent can not be to sorptive medium in continuous several times elution have a significant effect, it is desirable to
Sorbent can be recycled hundreds of times, have no significant change；
3rd, using spectrophotomelric assay, the optical property and chemical property of eluent are considered simultaneously, and eluent should have
Interfacial refraction rate difference between the sample remained in resin after good UV permeabilities, eluent and dress sample is as far as possible with treating
The refractive index close of test specimens, to reduce the interference to detection signal.
In this detection method and system, Na has been selected2CO3-NaHCO3Buffer solution is as eluent.Na2CO3-NaHCO3
Buffer solution is the conventional leacheate of ion chromatography.Although ion chromatography and the mesh of FIA ON-LINE post enrichment
Difference, ion chromatography is that various ingredients are separated on post, it is each reached separation.And this analysis method be will be to be measured
Chlorion in liquid is separated and is enriched on post, and other anion in prepare liquid can be also enriched in post, as long as after elution not
The chemical spectrophotomelric assay can of chlorion is disturbed, does not pursue the separation between chlorion and other anion.In ion color
In spectrum analysis, Na2CO3-NaHCO3Buffer solution has the superperformance of different component in separation, elution post, so, the present invention adopts
Use Na2CO3-NaHCO3Eluent of the buffer solution as FIA ON-LINE post enrichment system.It will be appreciated, however, that from
Detector used in sub- red, orange, green, blue, yellow (ROGBY) is electric conductivity detector, and used in the present invention is UV, visible light spectrophotometric detector, because of detection
Principle is different, and the elution technique requirement to component to be measured in evaporating column is also different, and concentration column performance is also different, so, ion color
Spectrum leacheate used is not suitable for flowing injecting analysis technology-ON-LINE ION-EXCHANGE enrichment-AAS.So the present invention is right
The selection of eluent composition, eluent composition is not only considered to " enrichment " of the chlorion in post, the influence of " elution " performance,
It is also contemplated that the influence to chemical reaction and optical detection performance after post.
If Na2CO3-NaHCO3Na in buffer solution eluent2CO3And NaHCO3Concentration when being all higher than 0.05mol/L, find
After eluent contacts mixing with reaction reagent, a large amount of bubbles in pipeline be present, into detector after unstability of base line is fixed, noise is big,
Sometimes even result in detection signal and fluctuate very big, severe jamming measure, its result is as shown in Figure 5；If Na2CO3-NaHCO3Buffering
Na in liquid eluent2CO3And NaHCO3Concentration be respectively less than 0.001mol/L, find eluting peak sensitivity decrease, peak width increase,
Influence detection sensitivity and analysis efficiency.
The invention provides trace chloro ion detection method in a kind of pure aquatic system, methods described is to use above-mentioned Water of Power Plant
The automatic quick detection of chlorion is carried out with working solution in vapour, and the process employs flowing injecting analysis technology-online ion to hand over
Change enrichment-spectrophotometric analysis method.
According to method of the present invention, ON-LINE ION-EXCHANGE enrichment ion exchange column effective dimensions used is：Internal diameter
For 1.0~3.0mm, length is 10~30mm, and volume is 50~200 μ L, and filler is strong-base anion-exchange resin；It is enriched with dense
Water sample flow during contracting is less than 5.0ml/min, and elution flow quantity is less than 5.0ml/min during elution, and elution time is 2~10min；
Reaction reagent flow is less than 5.0ml/min；Reaction temperature is room temperature.
According to method of the present invention, anion exchange resin of the present invention can be that strong alkalinity anion exchanges tree
Fat or weak-base anion-exchange resin；Wherein further preferably the anion exchange resin is that strong alkalinity anion exchanges tree
Fat；
According to method strong-base anion-exchange resin of the present invention can be the conventional strong basicity the moon in this area from
Sub-exchange resin, for example quaternary ammonium group anionoid resin, guanidine radicals quasi-alkali anion exchange resin；For example domestic D201 again
Type strong-base anion-exchange resin, the D204 types strong-base anion-exchange resin D254 of company (Zhejiang win honour for), 717 highly basic
Property I types anion exchange resin, U.S. Amberlite IRA-400 types strong-base anion-exchange resin, Germany
LewatitM500 types strong-base anion-exchange resin, the DIAION of MitsubishiTMSerial strong-base anion-exchange resin,
DOWEXTMSerial strong-base anion-exchange resin, for example DiaionTMThe I types and II types strong alkalinity anion of series exchange tree
Fat, the two structural formula difference are as follows：
According to method of the present invention, the particle diameter of the further preferably described anion exchange resin of the present invention is 100
~400 mesh.
According to method of the present invention, methods described further preferably comprises the following steps：
(1) enrichment process：Water sample is through ion exchange column, the resin anion (R.A.) in chlorion and ion exchange column in water sample
Ion exchange is carried out to be enriched in resin, meanwhile, eluent flows through reaction coil pipe and enters detector after converging with reaction reagent
Detected, obtain background signal；
(2) elution and detection process：After the completion of enrichment process, eluent inversely washes the chlorion being enriched on resin
Take off, reacted after being mixed with reaction reagent into reaction tray pipe, then flow through detector and detected；
It is preferred that methods described also includes the equilibrium process of exchanging column resin before enrichment process：Order uses pure water and elution
Liquid cleans to exchanging column resin so that the cation exchange groups of exchanging column resin reach balance with eluent composition.
Described balance is：When using high purity water as water sample, during the entire process of carrying out " enrichment ", " elution ", work station is remembered
The signal of record be stable baseline (" background " for ensuring ion exchange column is zero, in ion exchange column the cation exchange groups of resin with
Poised state is reached between eluent constituent concentration).
According to method of the present invention, methods described still further preferably comprises the following steps：
(1) enrichment process：Water sample is driven through multiple valve by pump B, into ion exchange column, chlorion in water sample with from
Resin anion (R.A.) in sub- exchange column carries out ion exchange and is enriched in resin, meanwhile, pump A driving eluents and reaction reagent
After converging by the road in composite module, flow through reaction coil pipe and detected into detector, detection signal is carried out by work station
Data acquisition and processing (DAP), obtain background signal；
(2) elution and detection process：After the completion of enrichment process, eluent elutes the chlorion being enriched on resin
Come, reacted after being mixed with reaction reagent in composite module into reaction tray pipe, then flow through detector and detected.
According to method of the present invention, the present invention further preferably enrichment concentration when water sample flow for 0.5~
5.0ml/min；
It is 1.0~3.0ml/min to elute flow quantity during according to method of the present invention, further preferably elution；
According to method of the present invention, the present invention further preferably reaction reagent flow is 1.0~3.0ml/min.
Wherein, the present invention can also use cellulose or nylon wire to seal the inlet and outlet of ion exchange column, to prevent
Resin flows out.
According to method of the present invention, described pump can be peristaltic pump.
According to method of the present invention, the pump speed of methods described still further preferably peristaltic pump is less than 70rmp.
According to method of the present invention, the pump speed of methods described still further preferably peristaltic pump is 20~60rmp.
According to method of the present invention, the pump line internal diameter of methods described still further preferably peristaltic pump is less than or equal to
1.5mm；Wherein it is more preferably 0.5~1.5mm.
According to method of the present invention, the length that methods described still further preferably reacts coil pipe is less than 500cm, internal diameter
Less than 1.0mm.
According to method of the present invention, the length that methods described still further preferably reacts coil pipe is 150~450cm.
According to method of the present invention, the internal diameter that methods described still further preferably reacts coil pipe is 0.5mm.
According to method of the present invention, still further preferably water sample, eluent and reaction reagent flow through methods described
The internal diameter of pipeline is 1.0mm.
According to method of the present invention, still further preferably described detector is UV-vis spectroscopy to methods described
Detector, light path are 10~50mm, and pond body product is 10~100 μ L.
According to method of the present invention, described multiple valve can be 8 channel valves.
Method of the present invention can be specially：
(1) exchange column " balance " process：As shown in Figure 1, multiple valve is in " sampling " state, and exchange column is located in advance
Reason.Cleaning and the balance of post are swapped with high purity water, eluent respectively；
The effect being finally reached is：When using high purity water as water sample, during the entire process of carrying out " enrichment ", " elution ", work
The signal recorded of standing is stable baseline, it is ensured that " background " of exchange column is zero, the cation exchange groups of resin and elution in exchange column
Poised state is reached between liquid constituent concentration, analysis result is shown in Fig. 4；
(2) enrichment process：As shown in Figure 1, multiple valve is in " sampling " state, and water sample is driven by peristaltic pump B by the road
Into (from bottom to top) ion exchange column, the resin in the chlorion and exchange column in water sample carries out ion exchange and is enriched in tree
In fat post；Meanwhile peristaltic pump A driving eluents converge in composite module by the road with reaction reagent, pass through reaction coil pipe and enter
Enter detector to be detected, detection signal carries out real-time data acquisition and processing by work station；Detection signal now is baseline
Signal, analysis result are shown in Fig. 4；
(3) elution and detection process：After the completion of " sampling (enrichment) " process, multiple valve, which is automatically brought to, " to be injected and (washes
It is de-) " state, the position of valve is as shown in Figure 2；Eluent enters ion exchange column from top to bottom, by the chlorine being enriched on resin from
Son is eluted out, and is mixed in composite module with reaction reagent, is reacted into reaction coil pipe, then flows through detector and examined
Survey, waste liquid is discharged into waste liquid barrel；In whole elution process, the detection signal of chlorine ion concentration is adopted in real time by work station in eluent
Collection, analysis result are shown in Fig. 4.
Under above-mentioned optimal experiment condition, the detection sensitivity highest of this method.
On the other hand, the application present invention also offers the method for the invention in Water of Power Plant in chloride test.
Wherein when the pH value of power plant's water sample is less than when 10, phosphate content is less than 3.0mg/L to measure typically without dry
Disturb.
Another further aspect, it is described present invention also offers the automatic rapid detection system of trace chloro ion in a kind of Power Plant Water Vapor
System includes：Reaction reagent bottle 1, eluent bottle 2, water sample bottle 3, flow injection analyzer 14, composite module 6, reaction coil pipe 9 and
Detector 10；Wherein flow injection analyzer 14 includes pump A4, pump B5, ion exchange column 8 and multiple valve 7；Wherein reaction examination
Agent bottle 1 is connected by pipeline via pump A4 with multiple valve 7, and water sample bottle 3 is connected by pipeline via pump B5 with multiple valve 7,
Composite module 6 sets at least two entrances and one outlet, the entering via pump A4 and composite module 6 by pipeline of eluent bottle 2
Mouth connection, multiple valve 7 are connected by pipeline with 6 another entrance of composite module, and the outlet of composite module 6 passes through pipeline and reaction
The entrance of coil pipe 9 is connected, and the outlet of reaction coil pipe 9 is connected by pipeline with detector 10, the inlet and outlet of ion exchange column 8 difference
It is connected by pipeline with multiple valve 7.
According to the automatic rapid detection system of trace chloro ion in Power Plant Water Vapor of the present invention, wherein be appreciated that
It is that described flow injection analyzer 14 also includes programming Control system.
According to system of the present invention, the multiple valve can be the conventional multiple valve of prior art, for example for
Following multiple valve：In original state (multiple valve is in " sampling " state) water sample can be made to pass through pipeline by water sample bottle 3
Enter ion exchange column 8 from bottom to top via pump B5, reaction reagent is by reaction reagent bottle 1 by pipeline via pump A4 and eluent
Collected by eluent bottle 2 by pipeline via pump A4 in composite module 6, and (multiple valve is in " injection in working condition
(elution) " state) eluent can be made to enter ion exchange column 8 from top to bottom via pump A4 by pipeline by eluent bottle 2, then
Enter composite module 6 via pipeline, converged with reaction reagent by reaction reagent bottle 1 by pipeline via pump A4 into composite module 6
The multiple valve of collection.
According to system of the present invention, the multiple valve can be the existing skill for the arbitrary structures for meeting above-mentioned condition
The multiple valve of art, the present invention are preferably eight channel valves.
According to system of the present invention, the pump A4 and pump B5 are peristaltic pump.
According to system of the present invention, the system also includes peace and quiet water bottle 11 and discharging of waste liquid end 13, described peace and quiet
Water bottle is connected by pipeline with multiple valve, and the discharging of waste liquid end 13 is connected by pipeline with detector 10.
According to system of the present invention, the system also includes work station 12, the work station 12 and the electricity of detector 10
Connection.
Described work station is this area conventional equipment, can be used for the testing result of detector is handled and shown
Show, it might even be possible to which the input of data is carried out to be controlled to equipment such as detectors by alternating interface between man and computer.
According to system of the present invention, the detector 10 is UV-vis spectroscopy detector.
Described UV-vis spectroscopy detector can be UV-vis spectroscopy detector any in the prior art, this
Invention institute is 10~50mm preferably using light path, the UV-vis spectroscopy detector that pond body product is 10~100 μ L.
According to system of the present invention, the filler in the ion exchange column 8 is resin anion (R.A.).
According to system of the present invention, resin anion (R.A.) of the present invention is the anion tree of prior art any conventional
Fat, can be for example strong-base anion-exchange resin or weak-base anion-exchange resin；Wherein further preferred described the moon
Ion exchange resin is strong-base anion-exchange resin；
According to system of the present invention, the particle diameter of the further preferably described anion exchange resin of the present invention is 100
~400 mesh.
According to the system described in any one of the present invention, the internal diameter of ion exchange column 8 is 1.0~3.0mm, length 10
~30mm.
According to the system described in any one of the present invention, the length that the system preferably reacts coil pipe is less than 500cm, internal diameter
Less than 1.0mm.
According to the system described in any one of the present invention, the reaction length of coil pipe 9 is 150~450cm, and internal diameter is
0.5mm。
According to the system described in any one of the present invention, the internal diameter for the pipeline that water sample, eluent and reagent flow through is
1.0mm。
According to the system described in any one of the present invention, wherein the pump line internal diameter of present invention pump described preferably wherein is less than etc.
In 1.5mm
Wherein further preferred pump line internal diameter is 0.5~1.5mm.
It is understood that whole pipelines that pipeline described here connects between each component of the present invention, i.e. water sample, washing
The pipeline that de- liquid and reaction reagent flow through.
In Power Plant Water Vapor provided by the invention in the automatic quick detection working solution of chlorion, its eluent is Na2CO3-
NaHCO3Buffer solution, suitable for non-neutral industrial technology underwater trace chloride ion conductor, trace in such as Power Plant Water Vapor sample
Chloride ion conductor.Na2CO3-NaHCO3Buffer solution eluent has certain resiliency, the change of water sample pH value to the pH value of water sample
The pH value control condition that chemically reacts after enriching column " enrichment ", " elution " performance and post is not interfered with.
In summary, the inventive method uses flow injection-ON-LINE ION-EXCHANGE enrichment-AAS, there is provided one
Trace chloro ion detection working solution and analysis method and system in automatic, quick, accurate, the reliable Power Plant Water Vapor of kind.FIA skills
The automation mechanized operation that the high sample treatment efficiency of art and height are reappeared, sample concentrating process and detection means can directly be existed
Line connects and analysis method is turned into an entirety, whole analysis process is completed in an enclosed system.The online ions of FIA-
Exchanging concentration method enables the Pro-concentration with ion exchange process method under the conditions of manual operations to have great change, not only avoid sample and is operating
Multiple transfer in container, so as to greatly reduce human error, and save sample and reaction reagent, more convenient operation, letter
It is clean.Importantly, FIA on line concentration systems make " enrichment " and " elution " process of test substance realize height reappear from
Dynamicization operates, and whole analysis system is in automatic detection state all the time, in real time analysis system during detection " enrichment "
The change procedure of detection signal during blank baseline and " elution ", the quantitative concentration effect for objectively reflecting exchange column, from
And manual uncertain factor and human error are eliminated, improve the reliability and accuracy of detection data.Pass through control
The experiment conditions such as enrichment time processed, enrichment rate, eluate concentration, elution flow rate, obtain concentration effect that height reappears and compared with
High concentration rate.
Brief description of the drawings
Fig. 1 is the embodiment of trace chloro ion detecting system one (original state) in Power Plant Water Vapor of the invention；
Fig. 2 is the embodiment of trace chloro ion detecting system one (working condition) in Power Plant Water Vapor of the invention；
Fig. 3 is ion exchange column schematic diagram；Wherein, 81 be PTFE tube, and 82 be uniform bore diameter nipple, and 83 be O-shaped close
Seal, 84 be nylon wire, and 85 be fiber, and 86 be resin extender, and 87 be lucite cylinder；
Fig. 4 is present system detection signal spectrogram；
Fig. 5 is Na2CO3-NaHCO3Na in buffer solution eluent2CO3And NaHCO3Concentration when being all higher than 0.05mol/L,
Present system detection signal spectrogram；
Fig. 6 is the measure schematic diagram of working curve under the conditions of different water sample enrichment times.
Embodiment
The implementation process of the present invention and caused beneficial effect are described in detail below by way of specific embodiment, it is intended to which help is read
Reader more fully understand the present invention essence and feature, not as to this case can practical range restriction.
1. equipment
The system includes：Reaction reagent bottle 1, eluent bottle 2, water sample bottle 3, pump A4, pump B5, composite module 6, multichannel
Valve 7, exchange column 8, reaction coil pipe 9, detector 10, peace and quiet water bottle 11, work station 12 and discharging of waste liquid end 13；Wherein reaction reagent
Bottle 1 is connected by pipeline via pump A4 with multiple valve 7, and water sample bottle 3 is connected by pipeline via pump B5 with multiple valve 7, is washed
De- liquid bottle 2 is connected by pipeline via pump A4 with the entrance of composite module 6, and multiple valve 7 is another by pipeline and composite module 6
Entrance is connected, and the outlet of composite module 6 be connected by pipeline with the reaction entrance of coil pipe 9, the outlet of reaction coil pipe 9 by pipeline and
Detector 10 is connected, and the exchange column 8 is imported and exported to be connected by pipeline with multiple valve 7 respectively, and the peace and quiet water bottle passes through pipe
Road is connected with multiple valve, and the discharging of waste liquid end 13 is connected by pipeline with detector 10, the work station 12 and detector
10 electrical connections.Wherein described multiple valve is eight channel valves.Wherein described pump A4 and pump B5 is peristaltic pump.The detector 10 is
UV-vis spectroscopy detector.
Wherein ion exchange column is as shown in Figure 3；Wherein, 81 be PTFE tube, and 82 be uniform bore diameter nipple, and 83 be O-shaped
Sealing ring, 84 be nylon wire, and 85 be fiber, and 86 be resin extender, and 87 be lucite cylinder.
The multiple valve can be such that water sample is entered from bottom to top via pump B5 by pipeline by water sample bottle 3 in original state
Exchange column 8, reaction reagent by reaction reagent bottle 1 by pipeline via pump A4 and eluent by eluent bottle 2 by pipeline via
Pump A4 collects in composite module 6, and working condition can make eluent by eluent bottle 2 by pipeline via pump A4 from upper
And it is lower enter exchange column 8, then enter composite module 6 via pipeline, with reaction reagent by reaction reagent bottle 1 by pipeline via pump
A4 collects into composite module 6.The internal diameter of the pipeline is 1.0mm.
2. analysis process
The present invention system multiple valve position be mounted with fill anion exchange resin ion exchange column (such as Fig. 1,
Shown in 2), current-carrying solution is eluent, establishes FIA- ON-LINE ION-EXCHANGEs preenrichment-spectrophotometric analysis system.A pumps, B
Pump and 8 channel valves are the critical pieces of flow injection analyzer, and the instrument can carry out the programming of operation sequence, setting pump speed, adopt
Sample (enrichment) time, injection (elution) time etc., sample " collection " and " injection " are automatically switched by setup program, are realized whole
The Automated condtrol of pipe-line system.
Exchange column " balance " process：As shown in Figure 1, multiple valve is in " sampling " state (original state) to flow, to from
Sub- exchange column is pre-processed.Cleaned, balanced and cleaning process with high purity water, eluent, high purity water respectively, is finally reached
Effect be：When using high purity water as water sample, during the entire process of carrying out " enrichment ", " elution ", the signal of work station record is steady
Fixed baseline, it is ensured that " background " of ion exchange column is zero, and the cation exchange groups of resin and eluent composition are dense in ion exchange column
Poised state is reached between degree.
" enrichment " process：As shown in Figure 1, multiple valve is in " sampling " state (original state) to flow.Water sample is by the road
(from bottom to top) ion exchange column is driven into by peristaltic pump B, the resin in chlorion and ion exchange column in water sample is carried out
Ion exchange is enriched in resin column.Meanwhile peristaltic pump A driving eluents converge in composite module by the road with reaction reagent
Close, pass through reaction coil pipe and detected into detector, detection signal carries out real-time data acquisition and processing by work station.This
When detection signal be background signal.
" elution " process：After the completion of " sampling (enrichment) " process, multiple valve is automatically brought to " injection (elution) " state
(working condition), the position of valve are as shown in Figure 2.Eluent enters ion exchange column, the chlorine that will be enriched on resin from top to bottom
Ion elution comes out, and is mixed in composite module with reaction reagent, is reacted into reaction coil pipe, then flows through detector progress
Detection, waste liquid are discharged into waste liquid barrel.In whole elution process, the detection signal of chlorine ion concentration is adopted in real time by work station in eluent
Collection.
Embodiment is shown in Table 1：
The embodiment of table 1
Under these experimental conditions, in the range of 5.0~100 μ g/L, standard work has been carried out according to aforesaid operations step
The measure of curve.Fig. 6 show different enrichment times and (is followed successively by embodiment 1 (10min), embodiment 2 (20min) and embodiment 3
(30min)) under the conditions of the standard working curve that determines, it can be seen that linear regression coeffficient is both greater than 0.999, linear good.
Test example
1st, the measure of standard working curve
A series of chlorion titers are prepared in the range of 5.0~100 μ g/L, it is rich under the conditions of above-mentioned 3 embodiments
The collection time is followed successively by 10 minutes, 20 minutes, 30 minutes, the standard working curve in this concentration range is determined, as a result such as Fig. 6 institutes
Show.From fig. 6 it can be seen that three working curve peak heights with and standard liquid chlorine ion concentration be in good linear relationship, during enrichment
Between it is longer, the slope of curve is higher, and the sensitivity of method is higher.
2nd, the measure of reappearance
Using the experiment condition of embodiment 1, parallel determination 7 times is distinguished to 5.0 μ g/L and 30 μ g/L chlorion standard liquid
More than, the reappearance of this method is determined, measurement result is shown in Table 2.Relative standard deviation is respectively 3.68% He
2.09%, less than 5.0%, the reappearance of this method is good.
The reappearance measurement result of table 2
3rd, the measure of lower limit is detected
In the method, detection limit refers to the peak height for the analyte being clearly discernible on work station signal record figure
Lower limit, it is generally recognized that the response signal peak height that be able to be distinguished, minimum should be 3 times of baseline noise, be analyzed corresponding to this signal
The concentration of thing.The detection limit of this method is respectively：
CDetection limit, 10min=1.0 μ g/L；
CDetection limit, 20min=0.50 μ g/L
The other performance index of this method are shown in Table 3.
The performance indications of this method of table 3
4th, practical application
Trace chloro ion content in some Power Plant Water Vapor samples is measured using this project approach, the results are shown in Table 4.
The measurement result of trace chloro ion in the Power Plant Water Vapor of table 4
From testing result as can be seen that this project establish Power Plant Water Vapor in trace chloro ion detection method and chromatography of ions
Method is compared, and relatively, variation tendency is consistent for testing result.Because of the difference of detection method, data processing method etc., this item purpose
There is some difference with the chromatography of ions for testing result.For chloride ion content be more than 5.0 μ g/L sample, relative error ±
Within 10%, 5.0 μ g/L sample is less than for chlorinity, relative error is within ± 20%.
5th, the measure of the rate of recovery
In order to verify influence of the disturbing factor that may be present to measured value in water sample, various concentrations are added into water sample
Standard sample carries out the measure of the rate of recovery, measurement result such as table 5.
The measure of the rate of recovery of table 5
As seen from Table 5, the measured value of the rate of recovery illustrates that the ion in water sample, pH etc. do not have in the range of 95-110%
Interference is formed to detection, demonstrates the accuracy and reliability of this method.
Claims (20)
1. one kind is using chlorion in flow injection-ON-LINE ION-EXCHANGE enrichment-spectrophotometric analysis method detection Power Plant Water Vapor
With working solution, it is characterised in that the working solution includes eluent and reaction reagent；
The eluent is Na2CO3-NaHCO3Buffer solution eluent, Na2CO3And NaHCO3Concentration be 0.001~
0.05mol/L；
The reaction reagent includes 0.001wt%~0.05wt% developers, 0.1wt%~5.0wt% ferric perchlorates, is less than
1.0v% perchloric acid or nitric acid, methanol 5.0v%~15v%, surplus are high purity water.
2. working solution according to claim 1, it is characterised in that the developer is mercuric thiocyanate.
3. working solution according to claim 1, it is characterised in that the pH value of the reaction reagent is 1.0~3.0.
4. working solution according to claim 1, it is characterised in that in the Na2CO3-NaHCO3In buffer solution eluent
Na2CO3And NaHCO3Mol ratio be 4:1.
5. working solution according to claim 1, it is characterised in that the reaction reagent include 0.001wt%~
0.05wt% developers, 0.1wt%~5.0wt% ferric perchlorates, the perchloric acid less than 1.0v%, methanol 5.0v%~15v%,
Surplus is high purity water.
6. a kind of chloride test method in Power Plant Water Vapor, it is characterised in that methods described is using any one of claim 1-5
Chloride test is carried out with working solution in described Power Plant Water Vapor, rich the process employs flow injection-ON-LINE ION-EXCHANGE
Collection-spectrophotometric analysis method.
7. according to the method for claim 6, it is characterised in that ON-LINE ION-EXCHANGE enrichment ion exchange column used
Effective dimensions is：Internal diameter is 1.0~3.0mm, and length is 10~30mm, and volume is 50~200 μ L, and filler is chromatographic grade anion
Exchanger resin, water sample flow during enrichment concentration are less than 5.0ml/min, and elution flow quantity is less than 5.0ml/min during elution, elution
Time is 2~10min；Reaction reagent flow is less than 5.0ml/min；Reaction temperature is room temperature.
8. according to the method for claim 6, it is characterised in that ON-LINE ION-EXCHANGE enrichment ion exchange column used
Filler is strong-base anion-exchange resin, and water sample flow during enrichment concentration is 0.5~5.0ml/min, eluent during elution
Flow is 1.0~3.0ml/min, and reaction reagent flow is 1.0~3.0ml/min.
9. according to the method for claim 6, it is characterised in that methods described comprises the following steps：
(1) enrichment process：Through ion exchange column, the resin anion (R.A.) in chlorion and ion exchange column in water sample is carried out water sample
Ion exchange is enriched in resin, meanwhile, eluent flows through reaction coil pipe and carried out into detector after converging with reaction reagent
Detection, obtains background signal；
(2) elution and detection process：After the completion of enrichment process, eluent inversely elutes the chlorion being enriched on resin
Come, reacted after being mixed with reaction reagent into reaction tray pipe, then flow through detector and detected.
10. according to the method for claim 9, it is characterised in that the length for reacting coil pipe is less than 500cm, and internal diameter is less than
1.0mm。
11. according to the method for claim 10, it is characterised in that the length for reacting coil pipe is 150~450cm, and internal diameter is
0.5mm。
12. according to the method for claim 9, it is characterised in that the pipeline that water sample, eluent and reaction reagent flow through it is interior
Footpath is 1.0mm.
13. according to the method for claim 9, it is characterised in that methods described also includes exchange column tree before enrichment process
The equilibrium process of fat：Order is cleaned using pure water and eluent to exchanging column resin so that the exchange base of exchanging column resin
Group reaches balance with eluent composition.
14. according to the method for claim 9, it is characterised in that this method comprises the following steps：
(1) enrichment process：Water sample is driven through multiple valve by pump B, and into ion exchange column, the chlorion in water sample is handed over ion
The resin anion (R.A.) changed in post carries out ion exchange and is enriched in resin, meanwhile, pump A driving eluents are with reaction reagent through pipe
After road is converged in composite module, flow through reaction coil pipe and detected into detector, detection signal carries out data by work station
Collection and processing, obtain background signal；
(2) elution and detection process：After the completion of enrichment process, the chlorion being enriched on resin is eluted out by eluent,
Reacted after being mixed with reaction reagent in composite module into reaction tray pipe, then flow through detector and detected.
15. according to the method for claim 14, it is characterised in that the pump A, pump B are peristaltic pump.
16. according to the method for claim 15, it is characterised in that the pump speed of peristaltic pump is small less than 70rmp, pump line internal diameter
In equal to 1.5mm.
17. according to the method for claim 16, it is characterised in that the pump speed of peristaltic pump is 20~60rmp, and pump line internal diameter is
0.5~1.5mm.
18. according to the method for claim 9, it is characterised in that described detector is UV-vis spectroscopy detector,
Light path is 10~50mm, and pond body product is 10~100 μ L.
19. application of the method described in claim any one of 6-18 in power plant's water sample in chloride test.
20. application according to claim 19, it is characterised in that the pH value of power plant's water sample is less than 10, and phosphate radical contains
Amount is less than 3.0mg/L.
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| CN203858201U (en) * | 2014-05-30 | 2014-10-01 | 华北电力科学研究院有限责任公司 | Automatic rapid detection system for trace chloride ions in power plant water vapour |
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| CN203858201U (en) * | 2014-05-30 | 2014-10-01 | 华北电力科学研究院有限责任公司 | Automatic rapid detection system for trace chloride ions in power plant water vapour |
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