CN1523347A - Trace quantity sodium ion automatic rapid determination method and apparatus - Google Patents
Trace quantity sodium ion automatic rapid determination method and apparatus Download PDFInfo
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- CN1523347A CN1523347A CNA031339719A CN03133971A CN1523347A CN 1523347 A CN1523347 A CN 1523347A CN A031339719 A CNA031339719 A CN A031339719A CN 03133971 A CN03133971 A CN 03133971A CN 1523347 A CN1523347 A CN 1523347A
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- 238000000034 method Methods 0.000 title abstract description 23
- 229910001415 sodium ion Inorganic materials 0.000 title abstract description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000005070 sampling Methods 0.000 claims abstract description 27
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 11
- 239000012498 ultrapure water Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 49
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 43
- 229910052708 sodium Inorganic materials 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000012670 alkaline solution Substances 0.000 claims description 30
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 26
- 239000002699 waste material Substances 0.000 claims description 14
- 229940043279 diisopropylamine Drugs 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 8
- 230000035945 sensitivity Effects 0.000 claims description 8
- 238000003556 assay Methods 0.000 claims description 6
- 229920002379 silicone rubber Polymers 0.000 claims description 6
- 239000004945 silicone rubber Substances 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 210000003296 saliva Anatomy 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 2
- 238000013500 data storage Methods 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 13
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 62
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- -1 polyethylene Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
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- 229910000851 Alloy steel Inorganic materials 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001067 superalloy steel Inorganic materials 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
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- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a trace Na ion quickly determining method, applied to water quality analysis and monitoring. Under the action of peristaltic pump, one path of ultrapure water enters pipeline meeting through carrying liquor pump line, flow path and bypass pipeline, the other path fully alkalizes through the alkali liquor flow path to enter the pipeline meeting, the ultrapure water joins the alkali liquor to fully alkalize in the reacting coiled pipe and then enters current electrochemical detector, the blank signal value of the electrode potential signal produced between Na selective electrode and reference electrode is displayed by the Na ion processor and the recorder records the base line of the blank value; a water sample to be measured enters quantitative sampling ring through the lead-in pipe in the sampling position of the filling valve, when the filling valve switches filling position, the filled water sample stuff is uniformly alkalized to enter the current electrochemical detector, the electrode potential signal produced between the Na selective electrode and reference electrode is displayed by the Na ion processor and output to the recorder, which records the real testing curve.
Description
Technical field
The present invention relates to the automatic rapid assay methods of trace sodion and realize the determinator of this method.Belong to chemical analysis and quantitative technical field.The present invention is applicable to the fast measuring of trace sodion in the boiler feed water, steam, condensate water, generator cooling-water of thermal power plant, the water quality management that the sun bed goes out saliva, nuclear power station secondary cooling water, semi-conductor industry etc.
Background technology
The size of sodium ions content is the important level of control that the PWR nuclear power station prevents the metal alkaline embrittlement, also is an important indicator of thermal power plant's steam quality.If carry the impurity that some contain sodium in the steam,, will in steam turbine, cause the resultant fault of uniform corrosion, spot corrosion, stress corrosion, corrosion fatigue and these several situations as NaOH, sodium chloride, sodium sulphate etc.Spot corrosion, stress corrosion, corrosion fatigue often cause the damage of components of steam turbine, cause very large economy loss, and cause prolong stop time.The U.S. once carried out investigation to the operation unit that 193 single-machine capacities surpass 100MW, find the steam turbine corrosion that causes by impurity in the steam and the stopping accident that causes unexpectedly up to 4.6%, the parts of damage comprise alloy steel, stainless steel, or even the superalloy steel.Therefore, in order to prevent fouling, salt crust, the corrosion of metal parts in the relieving system guarantees the security of system economical operation, prolongs the time between overhauls(TBO) and the serviceable life of heat power equipment, and sodium content is strictly controlled and monitors in the Power Plant Water Vapor system.
In addition, along with developing rapidly of power industry, constantly the putting into operation of high parameter, high capacity unit, the Na ion concentration lower control limit in steam and the water supply system is also more and more lower.Stipulate as GB GB12145-1999 steam quality standard: steam sodium ions content＜5 μ g/L; Expectation sodium ions content value＜3 μ g/L; Boiler feed water sodium ions content＜10 μ g/L, expectation sodium ions content＜5 μ g/L; Condensate water sodium ions content＜5 μ g/L.Conventional trace sodium determination method, as the chromatography of ions, flame atomic absorption method and ICP method, sample needs pre-concentration to handle, and complicated operation, and apparatus expensive can not be monitored in real time; Simple ion selective electrode method and gravimetric method, disturbing factor are difficult for eliminating, and the measurement result error is big, accuracy is low, and poor reproducibility has been difficult to satisfy the demand.
Current, the Trace Sodium ion determination adopts GB GB12155-89 " sodion dynamic method " in the water samples such as power plant boiler feedwater, steam, condensate water, and the National Standard Method operating process is as follows: select for use and add dynamically cup electrode (FC) of basifier.Be installed on the fixed support by Fig. 1,, lay another support so that place tygon voltage stabilizing bucket (SP) in the about 100-200mm eminence of ionization electrode cup (FC).The polyethylene pipe kapillary of 2-3mm is as fixing U trap, and sebific duct or the polyethylene pipe with wall thickness 3mm is connected with pole cup (FC) by figure then.Need be used alternatingly with the tygon voltage stabilizing bucket (SP) of five 1000-2000ml during mensuration.Deposit pNa4, pNa5 titer, I level reagent water (PW) basifier (AR) and water sample (S) respectively.Diisopropylamine solution (1+80) is annotated in basifier container (AR), and be placed on the place than the high 200-300mm of pole cup (FC), the addition of diisopropylamine should make pH＞10.5 of water sample (S).With I level reagent water (PW) with the flow velocity of 50ml/min by pole cup (FC), drip diisopropylamine solution (AR) simultaneously, make draining pH＞10.5 of pole cup (FC).When changing solution, clamp U trap at any time, in order to avoid siphon is destroyed,, reduce error at measurment simultaneously for fear of mutual pollution, sampling and location should be special-purpose with vessel, do not obscure mutually.Behind sodion meter (Mt) the energized preheating 0.5h, perform the operations such as zeroing, temperature compensation and full scale correction of instrument on request, make instrument be in stand-by state.Install sodium electrodes selective (WE) and mercurous chloride electrode (RE).When measuring a plurality of water samples (S), pole cup (FC) with water sample (S) flushing of transferring pH, is not located separately.Each sample of said method is measured about 10min consuming time, the about 500ml of each sample consumption.
The subject matter that prior art exists is the preliminary work trouble, complicated operation, the general staff is difficult to grasp, analysis speed is slow, and sample, I level reagent water (PW) and basifier (AR) consumption are big, and the analysis stream from pressurizing vessel (SP) to waste discharge mouth (W) cleans very time-consuming and difficult, when high na concn sample changeover becomes to hang down the na concn sample, mutual cross pollution usually takes place, and the precision of analysis result, reappearance and accuracy are all very poor, can't realize automatic express-analysis.
Summary of the invention
The objective of the invention is to develop a kind of device that is used for the method for automatic fast measuring trace sodion and realizes this method; solve the subject matter that prior art exists; simplify the operation course; simplify apparatus structure; reduce sample and basifier consumption; improve economy; be beneficial to environmental protection; eliminate the cross pollution in the prior art mensuration process; improve analysis speed and automatization level; improve precision and accuracy; develop a kind of novel full-automatic trace sodion analytical equipment on this basis, realize that the device of this method will be used for the water analysis and the monitoring in fields such as thermal power plant effectively.
Technical scheme of the present invention is made up of measuring principle and assay method and determinator.
Measuring principle of the present invention: when water sample with the volume of denier and higher velocity flow during through the sensitive membrane surface of sodium electrodes selective, carry out ion-exchange and set up certain electrode potential between film and water sample, the film potential of this film can be represented with Nernst equation:
E=E
0+ 2.3026 (RT/nF) lg a
Na+In the formula, E
0Be standard electrode potential (V) that R is mol gas constant 8.134 (Jmol
-1K
-1), F is Faraday constant 96486 (Cmol
-1), T is thermodynamic temperature (K), n is the electron number that transmits in the electrode reaction, a
Na+Activity (molL for the Na+ ion
-1).
The contrast electrode of an other maintenance constant potential is inserted in the sample flow simultaneously, constitutes and measure battery:
△ E=E '
0+ Slga
Na+In the formula, △ E is for measuring cell potential poor (V), E '
0For cutting square potential difference (PD) (V), S is this special slope of energy, a
Na +Be Na
+Activity (the molL of ion
-1).The electrical potential energy of measuring this battery obtains the activity of tested sodion.The current potential of sodium ion electrode changes with the activity of sodion in the sample.With a high impedance millivoltmeter or ionometer can obtain with water in the corresponding electrode potential of sodion activity.
The rule (see figure 6) that meets linear equation in electrode potential and the water sample between the Trace Sodium ion concentration, the Na ion concentration of 10-100 μ g/L and the expression formula between the response signal are Y
1=kX
1+ b
1The Na ion concentration of 0-10 μ g/L and the expression formula between the response signal are Y
2=kX
2+ b
2As long as determine the electrode potential of denier sodion in the water sample, just can obtain the concentration value of sodion.
Assay method of the present invention is under the dynamic action of peristaltic pump, one road ultrapure water by current-carrying liquid pump pipe, current-carrying liquid stream, shunt valve, enter the pipeline point of function combinations piece; Another road is that ultrapure water passes through alkaline solution pump line, alkaline solution stream, the semi-permeable diaphragm alkalization pipe that enters the alkalization device is fully alkalized by basifier, become alkaline solution, after pipeline point, ultrapure water and the alkaline solution that enters the function combinations piece converges, fully alkalization in the reaction coil pipe of function combinations piece, export the formula electrochemical detector that circulates through the reaction coil pipe, between sodium electrodes selective and contrast electrode, produce the electrode potential signal, be transferred to the sodion processor, show the blank signal value after treatment, and write down the baseline of blank value by registering instrument; Under the dynamic action of peristaltic pump, a water sample to be measured, by the sample ingress pipe, when " sampling location " of sample fillup valve, enter valve quantitative sampling ring and carry out the unnecessary water sample of quantitative collection water sample (0.8ml) through the outflow of sampling ring outlet stream to the first waste discharge mouth; When the sample fillup valve converted " injection phase " to, the water sample in the quantitative sampling ring was injected in the current-carrying liquid stream; " the water sample plug " that injects converges by the pipeline point and the alkaline solution of function combinations piece, enter after converging in the reaction tray pipe, " water sample plug ", fully alkalization even in the reaction coil pipe by alkaline solution, hydrogen ion is to the interference of sodion mensuration in the elimination " water sample plug "; " water sample plug " is through the outlet of reaction coil pipe then, the formula that circulates electrochemical detector, at first vertically contact with the sensitive membrane surface of sodium electrodes selective, the generating electrodes reaction, can increase the sensitivity of electrode like this, flow through temperature sensor and contrast electrode again, flow out from the second waste discharge mouth at last; Sodion in " water sample plug " produces the electrode potential signal between sodium electrodes selective and contrast electrode, transfer to the sodion processor, two cover linear equations according to storage, measured value is judged and the equation conversion automatically, show reading after treatment, and note measured curve, temperature sensor output temperature compensating signal by registering instrument.
Determinator of the present invention is made up of peristaltic pump, current-carrying liquid pump pipe, current-carrying liquid stream, alkaline solution pump line, alkaline solution stream, sample ingress pipe, sampling ring outlet stream, the first waste discharge mouth, sample fillup valve, quantitative sampling ring, shunt valve, alkalization device, semi-permeable diaphragm alkalization pipe, basifier, alkaline solution outlet, function combinations piece, pipeline point, reaction coil pipe, reaction coil pipe outlet, flow type electrochemical detector, sodium electrodes selective, temperature sensor, contrast electrode, sodion processor, registering instrument, the second waste discharge mouth.Peristaltic pump after the startup, under its powered, one road current-carrying liquid pump plumber does, and is connected by the shunt valve of current-carrying stream with the sample fillup valve, and its outlet is connected with the reaction coil pipe pipeline point of function combinations piece; Another road alkaline solution pump line is connected with the semi-permeable diaphragm alkalization pipe of alkalization device by the alkaline solution stream, and the outlet of alkaline solution is connected with the pipeline point of function combinations piece, and the outlet of reaction coil pipe is connected with the flow type electrochemical detector; The lead output electrode electric potential signal of sodium electrodes selective and contrast electrode is to the sodion processor, and can be in the two cover linear equations that store automatically, judges automatically and equation conversion and showing according to measured value; The sodion processor exports deal with data to registering instrument by lead, the record measured curve.
In the determinator of the present invention, each ingredient architectural feature is as follows:
The sample fillup valve can automatic or manual work, form with the sampling stream by injecting stream, the volume of quantitative sampling ring can change between 0.1-2.0ml as required, if the volume that injects water sample is less than 0.8ml and be not to resemble SCX when going out saliva and belonging to highly acid, current-carrying liquid stream can replace with the alkaline solution stream, becomes single pipeline determinator (see figure 4); Adopt 6 holes, 3 groove fillup valves, shunt valve can; If room temperature changes little, temperature sensor can; Peristaltic pump can adopt more than the triple channel, also can use ram pump, and the single pipeline determinator can adopt two passage pumps; The ventilative tubing that semi-permeable diaphragm alkalization pipe should have the semi-permeable diaphragm function, as silicone rubber tube, internal diameter 0.5-1.0mm all can more than the long 10cm; The function combinations piece has the three-port structure function; The reaction coil pipe can adopt polyethylene pipe, polyfluortetraethylene pipe, polyvinyl chloride pipe, internal diameter 0.5-1.0mm, and length 50-200cm makes and injects the water sample plug current-carrying liquid that alkalized and fully alkalize; The flow type electrochemical detector can adopt difformity and unlike material; The sodium electrodes selective can be to sodium electrode various types of electrodes selectively, as: glass sodium electrode (23-8S type, 2801 types, 200048 types), combined type glass-membrane electrode or flow type sodium electrode; Temperature sensor can be the various sensors with temperature sensing function, as TDS-110 type temperature sensor, DS18B20 type one line system digital temperature sensor etc.; Contrast electrode can be the various electrodes with reference function, as Hg/HgCl
2Electrode, Ag/AgCl electrode or ion-selective electrode; The sodion processor can be high resistant millivoltmeter or ionometer, and as DWG-9323A type sodion meter etc., it can store two cover linear equations; Because the electrode potential signal has a range of linearity during greater than 10 μ g/L at Na ion concentration, when less than 10 μ g/L, flex point occurs, break away from the original range of linearity, enter another range of linearity, so when tested Na ion concentration is in 10-1000 μ g/L scope, use linear equation Y
1=kX
1+ b
1Expression; When tested Na ion concentration during, use linear equation Y less than 10 μ g/L
2=kX
2+ b
2Expression; Registering instrument can be various types of registering instruments, as desk-top self-balancing recorder etc.; Current-carrying liquid should be that conductivity is the following pure water of 0.06 μ s/cm; Basifier can adopt diisopropylamine, ammoniacal liquor, diethylamine and dimethylamine etc.; The alkalization device alkalizes ultrapure water current-carrying liquid and injection " sample plug " with alkaline solution, make its pH＞more than 10.5;
Sodium electrodes selective in the flow type electrochemical detector of the present invention can be changed, and when being replaced by electrodes such as chlorine, fluorine, hydrogen, then this determinator can be finished the mensuration with the corresponding ion concentration of electrode.
Determinator of the present invention can be used single-chip microcomputer and computer control (see figure 5), wherein peristaltic pump, sample fillup valve by secondary single chip computer AT 89C52 control, its interface is connected with host computer host scm AT89C52; The calculating of host scm control concentration, temperature compensation, millivolt output and result show; Host scm is connected by interface RS232 with the host computer computing machine, can finish operations such as data storage, data processing, s operation control, printout.
Basic fundamental parameter of the present invention is: measurement range 0-10 μ g/L Na
+10-100 μ g/L Na
+Relative standard deviation RSD＜1%; Linearly dependent coefficient r＞0.9990; Analysis speed 50 samples/h; Sample consumption 0.8ml/ time; The reagent consumption 100ml/ month; Escape hole waste liquor PH＞11.0.
Advantage of the present invention and good effect are: easy and simple to handle, finding speed is fast, favorable reproducibility; After device energising of the present invention was stable, analysis operation only was left a step in the sample water that the insertion of sample ingress pipe is different.The mixing of the alkalization of the sampling of valve and injection, current-carrying and sample, sample and alkaline solution, electrode electro Chemical reaction, stream cleaning, electrode cleaning, mensuration etc. are to carry out automatically entirely.Thus, the present invention is a kind of new assay method, full-automatic trace sodion analytical approach and device fast of comprising.
A) with semi-permeable diaphragm alkalization pipe unit current-carrying liquid and detected water sample automatic alkalization and accurately alkalization have been realized;
B) realized automatic alkalization traceization (basifier consumption: the 100ml/ month);
C) this semi-permeable diaphragm alkalization pipe only allows gas or diffusion of vapor to see through, and ion can not spread and see through, so, avoided the impurity in the basifier (sodium etc.) to enter analytical equipment, eliminated basifier self and contained of the interference of sodium amount, also can not cause unnecessary dilution analytical equipment to measuring.
D) realized measuring the trace sodion under the sealing state fully, environment is to measuring a difficult problem of disturbing when having solved off-line analysis.
E) realized that electrode cleans automatically, the sodium electrodes selective can remain cleaning, state to be measured.
F) since the water sample consumption by quantitative sampling ring traceization, the iron in the steam sample can not pollute the sodium electrodes selective; Because the present invention measures under the physics non-equilibrium state, the sample introduction of traceization makes iron dirt (Fe (OH)
3) be difficult to form, even form, also be difficult to be adsorbed on its surface, so the present invention has eliminated Fe (OH) owing to arrhea the time weak point on sodium electrodes selective surface
3Sediment has prolonged the serviceable life of sodium electrodes selective to the influence (the iron dirt can make electrode reaction speed reduce and maybe can't work) on electrode activity surface.
G) since the contrast electrode among the present invention near the second waste discharge mouth of stream, away from the sodium electrodes selective, the internal-filling liquid KC1 (mercurous chloride electrode) of contrast electrode is eliminated fully to the interference of measuring trace sodium and being produced.
H) fast (40-60 sample/h of analysis speed of the present invention; The GB12155-89 method is 6 samples/h), favorable reproducibility (RSD＜0.86%).
J) the basifier consumption of conventional online sodion meter is the 3-51/ month, and basifier consumption of the present invention only is the 100ml/ month, promptly only is the former about 1/50.The present invention greatly reduces alkali consumption, has improved economy, is more conducive to environmental protection.
K) amount of samples significantly reduces (0.8ml/ time; The GB12155-89 method is 500ml/ time), reduced operating personnel's working strength.
The present invention is specially adapted to trace Na in stove water, feedwater, steam, condensate water, make-up water, the water outlet of sun bed of fuel-burning power plant
+Mensuration; Scientific domain involved in the present invention has multiple subjects such as chemical instruments, analytical chemistry, boiler water processing, electronics, is the synthetic study achievement of boundary science of reporting to the leadship after accomplishing a task, and has very important Practical significance and social effect.
Description of drawings
Fig. 1 GB12155-89 " sodion dynamic method " synoptic diagram
S sample, PNa4 titer, PNa5 titer, PW I level reagent water (ultrapure water), AR basifier, SP stable container, FR flowmeter, FC pole cup, WE sodium electrodes selective, RE contrast electrode, MT sodion meter, T thermometer, FO among the figure
1, FO
2Overflow, W waste discharge mouth.
The automatic fast measuring device of Fig. 2 trace sodion synoptic diagram
1 peristaltic pump among the figure, 2 current-carrying liquid pump pipes, 2a current-carrying liquid stream, 3 alkaline solution pump lines, 3a alkalization stream stream, 4 sample ingress pipes, 5 sampling ring outlet stream, 6 first waste discharge mouths, 7 sample fillup valves, 8 quantitative sampling rings, 9 shunt valves, 10 alkalization devices, 11 semi-permeable diaphragms alkalization pipe, 12 basifiers, 13 alkaline solution outlets, 14 function combinations pieces, 15 pipeline points, 16 reaction coil pipes, 17 reaction coil pipe outlets, 18 flow type electrochemical detectors, 19 sodium electrodes selectives (WE), 20 temperature sensors, 21 contrast electrodes, 22 sodion processors, 23 registering instruments, 24 second waste discharge mouths, 25 computing machines, 26 host scms, 27 pairs of single-chip microcomputers.
Fig. 3 flow type electrochemical detector of the present invention structural representation
The automatic fast measuring device of Fig. 4 single tube of the present invention road trace sodion synoptic diagram
Fig. 5 determinator single-chip microcomputer of the present invention and computer control synoptic diagram
Fig. 6 embodiment 1 trace sodion canonical plotting
Fig. 7 embodiment 1 trace sodion physical record curve map
Fig. 8 embodiment 2 sampling volumes are to the curve map of sensitivity influence
Fig. 9 embodiment 3 current-carrying flows are to the curve map of peak height influence
Figure 10 embodiment 4 alkalization length of tube are to the curve map of pH value of solution influence
Figure 11 embodiment 5 diisopropylamine concentration are to the curve map of peak height influence
Figure 12 embodiment 6 alkalization thickness of pipe are to the curve map of alkalization influential effect
Figure 13 embodiment 7 reaction tray length of tube are to the curve map of peak height influence
Embodiment
In conjunction with the accompanying drawings embodiments of the invention are further described:
Utilize method of the present invention and device (see figure 2) that trace sodion in certain power plant's stove water and the steam is measured.Experiment condition: basifier (12) is 60% diisopropylamine; Semi-permeable diaphragm alkalization pipe (11) has used long 65cm, internal diameter 0.6mm, the silicone rubber tube with semi-permeable diaphragm function; It is the following ultrapure water of 0.06 μ s/cm that current-carrying liquid has used conductivity; Reaction coil pipe (16) has used long 200cm, the polyethylene pipe of internal diameter 0.5mm; Function combinations piece (14) and flow type electrochemical detector (18) (see figure 3) have used the organic glass material to make; Sodium electrodes selective (19) has used 23-8S type glass sodium electrode; Contrast electrode (21) has used 001S type mercurous chloride electrode; Temperature sensor (20) is a TDS-110 type temperature sensor; Sodion processor (22) is a DWG-9323A type ionometer; Registering instrument (23) is the desk-top self-balancing recorder of XWT-100.
The sodion typical curve of two analyst coverages that obtain (0.5-10 μ g/L; 10-100 μ g/L) as shown in Figure 6, the physical record curve of its standard specimen and reappearance curve are as shown in Figure 7.As shown in table 1 to the data that certain power plant's stove water and steam sample record.Sodium content in the 1-3 stove stove water is respectively 86.9,83.4,93.8 μ g/L; Sodium content in No. 1 stove superheated vapor 1 and 2 is respectively 10,9.6 μ g/L; Sodium content in the saturated vapour of No. 3 stoves is 5.5 μ g/L.Relative standard deviation (RSD, the index of reflection reappearance quality)＜0.86%; As seen the present invention can satisfy the needs that the trace sodion is measured in the Lu Shui of power plant, the steam fully.
Table 1
| Sample | Sampling amount (ml) | Addition (ml) | Measured value | Theoretical value | The recovery |
| Stove | ?50(86.9μg/LNa) | 50(60μg/L) | ????77.1 | ????73.5 | ??105％ |
| | ?50(83.4μg/LNa) | 50(60μg/L) | ????74.8 | ????71.7 | ??104％ |
| | ?50(93.8μg/LNa) | 50(60μg/L) | ????78.3 | ????76.9 | ??102％ |
| | ?50(10μg/LNa) | 50(6μg/L) | ????8.1 | ????8.0 | ??101％ |
| | ?50(9.6μg/LNa) | 50(6μg/L) | ????8.0 | ????7.8 | ??103％ |
| Saturated vapour | ?50(5.5μg/LNa) | 50(6μg/L) | ????6.0 | ????5.8 | ??103％ |
In order to check accuracy of the present invention and reliability, do recovery experiment with the stove water water sample and the steam water sample of power plant, its result is as shown in table 1.The recovery that records is respectively 102-105% (stove water), 101-103% (steam) result is satisfactory.
Present embodiment is at room temperature to measure the influence of sampling volume to sensitivity with the sodion titer of variable concentrations respectively.As can be seen from Figure 8, along with the increase of sampling volume, sensitivity increases gradually; When sampling volume reaches 0.80ml when above, the increase of peak height tends towards stability.
Present embodiment is to measure the influence of current-carrying flow to sensitivity.When using single pipeline analytical equipment (Fig. 4), the current-carrying flow to the influence of response peak height as shown in Figure 9.Three curves are peak heights of surveying with the sodium standard sample of variable concentrations respectively among the figure.Along with the increase of current-carrying flow, peak height increases, but after the current-carrying flow reached 3.0ml/min, peak height increased slowly.
Present embodiment is to measure the influence of alkalization length of tube to carrier fluid pH.In order to eliminate H
+To Na
+The interference of measuring, the present invention improve the pH value of current-carrying liquid as the basifier of this device with diisopropylamine.The alkalization pipe is silicone rubber tube (Φ 0.6mm), and its length has been carried out preferably.Experimental result as shown in figure 10.Along with the increase of alkalization length of tube, the pH value of alkalization back current-carrying liquid also increases gradually; When alkalization after length of tube reaches 60cm, the pH value of solution reaches more than 11, when having satisfied trace sodion mensuration to the requirement of pH.
Present embodiment is to measure the influence of diisopropylamine basifier concentration to peak height.Specimen is respectively the sodium titer of 100,50,10,5 μ g/L.The result who obtains as shown in figure 11.Along with the increase of basifier concentration, peak height also increases gradually, and after basifier concentration reached 50%, peak height increase trend reduced.
Present embodiment is the correlationship of measuring between alkalization thickness of pipe and the current-carrying pH value of solution value.Experiment condition is, basifier is 60% diisopropylamine, and as semi-permeable diaphragm alkalization pipe, its length 46cm, wall thickness are respectively 0.35,0.5,0.6,0.75 and 0.85mm to silicon as sebific duct.Experimental result as shown in figure 12.Along with the increase of alkalization thickness of pipe, the current-carrying liquid pH value that is alkalized also reduces gradually; Obviously, this is because during the increase of alkalization thickness of pipe, the cause that can cause the gas permeability of silicone rubber tube to reduce.The internal diameter of selecting for use of the present invention is 1.2mm, and external diameter is 2.4mm, and promptly thickness is the silicone rubber tube do alkalization pipe of 0.6mm.
Present embodiment is the influence of assaying reaction coil lengths to sensitivity.The main effect of reaction coil pipe is that the sample plug of injection is fully alkalized by alkaline current-carrying liquid.When using the single pipeline analytic system (Fig. 4), if the reaction tray length of tube is too short, the sample plug can not fully alkalize, thereby can influence the accurate response of sodium electrode pair sodion; If the reaction tray length of tube is long, dispersion degree increases, and can cause the decline of sensitivity again.So, under above-mentioned preferred condition, in the scope of 50-250cm, having carried out preferably with internal diameter 0.5mm polyethylene pipe, length, the result is as shown in figure 13.When the reaction tray length of tube is 200cm, the peak value of response maximum.
Present embodiment, the present invention and international GB12155-89 " sodion dynamic method " compare, and its result is as shown in table 2.(60 samples/h), sample consumption aspect this method such as (0.8ml/ samples) are far superior to National Standard Method (8-10 sample/h, 500ml/ sample) at analysis speed in discovery; National Standard Method is the interference of sodion in the wayward environment when measuring trace sodium, and influence is normally measured and caused measured value higher, even can't measure.
In addition, the basifier consumption of conventional online sodion meter is the 5L/ month, and the basifier consumption of this method only is the 0.1L/ month, promptly only is the former about 1/50.So, if develop a kind of novel industrial online sodion analyser, can reduce alkali consumption greatly based on the present invention, improve economy, and be more conducive to environmental protection.
Table 2
| Sample | The present invention | The GB12155-89 dynamic method |
| ????1 | ????5.5μg/L | ????7μg/L |
| ????2 | ????9.6μg/L | ????12μg/L |
| ????3 | ????86.9μg/L | ????88μg/L |
| ????4 | ????93.8μg/L | ????98μg/L |
| Analysis speed | 40-60 sample/h | 6-10 sample/h |
| Amount of samples | 0.8ml/ sample | The 100-500ml/ sample |
| Precision (RSD) | ????0.86％ | ????5％ |
Claims (5)
1, the automatic rapid assay methods of a kind of trace sodion, it is characterized in that: under the dynamic action of peristaltic pump (1), one road ultrapure water (PW) by current-carrying liquid pump pipe (2), current-carrying liquid stream (2a), shunt valve (9), enter the pipeline point (15) of function combinations piece (14); Another road is that ultrapure water (PW) is by alkaline solution pump line (3), alkaline solution stream (3a), the semi-permeable diaphragm alkalization pipe (11) that enters alkalization device (10) is by fully alkalization of basifier (12), become alkaline solution, enter the pipeline point (15) of function combinations piece (14), after ultrapure water current-carrying and alkaline solution converge, fully alkalization in the reaction coil pipe (16) of function combinations piece (14), through reaction coil pipe outlet (17) the formula electrochemical detector (18) that circulates, between sodium electrodes selective (19) and contrast electrode (21), produce electrode potential signal Es, be transferred to sodion processor (22), show the blank signal value after treatment, and write down the baseline of blank value by registering instrument (23); Under the dynamic action of peristaltic pump (1), a water sample S to be measured, by sample ingress pipe (4), flow into quantitative sampling ring (8), a certain amount of water sample S (0.8ml) when " sampling location " of sample fillup valve (6), unnecessary water sample exports stream (5) to the first waste discharge mouth (6) through sampling ring and flows out; When sample fillup valve (7) converts " injection phase " to, water sample plug in the quantitative sampling ring (8) is injected in the current-carrying liquid stream (1), " the water sample plug " that injects converges with alkaline solution by the pipeline point (15) of function combinations piece (14), enter reaction tray pipe (16) after converging, " water sample plug ", fully alkalization even in reaction coil pipe (16) by alkaline solution, hydrogen ion is to the interference of sodion mensuration in the elimination " water sample plug "; " water sample plug " is through reaction coil pipe outlet (17) the formula electrochemical detector (18) that circulates then, at first vertically contact with the sensitive film surface of sodium electrodes selective (19), the generating electrodes reaction, can increase the sensitivity of electrode like this, flow through temperature sensor (20) and contrast electrode (21) again, flow out from the second waste discharge mouth (24) at last; Sodion in " water sample plug " produces electrode potential signal Es between sodium electrodes selective (19) and contrast electrode (21), transfer to sodion processor (22), two cover linear equations according to storage, measured value is judged and the equation conversion automatically, show reading after treatment, and by registering instrument (23) output measured curve, temperature sensor (20) output temperature compensating signal Ts.
2, the automatic fast measuring device of a kind of trace sodion is characterized in that: by peristaltic pump (1), current-carrying liquid pump pipe (2), current-carrying liquid stream (2a), alkaline solution pump line (3), alkaline solution stream (3a), sample ingress pipe (4) sampling ring outlet stream (5), the first waste discharge mouth (6), sample fillup valve (7), quantitative sampling ring (8), shunt valve (9), alkalization device (10), semi-permeable diaphragm alkalization pipe (11), basifier (12), alkaline solution outlet (13), function combinations piece (14), pipeline point (15), reaction coil pipe (16), reaction coil pipe outlet (17), flow type electrochemical detector (18), sodium electrodes selective (19), temperature sensor (20), contrast electrode (21), sodion processor (22), registering instrument (23), the second waste discharge mouth (24) is formed.Peristaltic pump after the startup (1), under its powered, the work of one road current-carrying liquid pump pipe (2) is connected with the shunt valve (9) of sample fillup valve (7) by current-carrying stream (2a), and its outlet is connected with reaction coil pipe (16) the pipeline point (15) of function combinations piece (14); Another road alkaline solution pump line (3), be connected with the semi-permeable diaphragm alkalization pipe (11) of alkalization device (10) by alkaline solution stream (3a), the outlet of alkaline solution (13) is connected with the pipeline point (15) of function combinations piece (14), and reaction coil pipe outlet (17) is connected with flow type electrochemical detector (18); The lead output electrode electric potential signal Es of sodium electrodes selective (19) and contrast electrode (21) to sodion processor (22), and can judge and equation conversion and demonstration according to measured value in the two cover linear equations that store automatically automatically; Sodion processor (22) exports deal with data to registering instrument (23) by lead, the record measured curve.
3, the automatic fast measuring device of trace sodion as claimed in claim 2 is characterized in that: sample fillup valve (7) but automatic or manual work, by injecting stream and the sampling stream is formed; When injecting water sample S and do not resemble going out saliva and belonging to highly acid of SCX less than 0.8ml, current-carrying liquid stream (2a) can replace with alkaline solution stream (3a), become the single pipeline determinator; When adopting 6 holes, 3 groove fillup valves (7), shunt valve (9) can; Peristaltic pump (1) can adopt two passages or triple channel or ram pump; Semi-permeable diaphragm alkalization pipe (11) can adopt silicone rubber tube, internal diameter 0.5-1.0mm; Function combinations piece (14) has three-port structure; Reaction coil pipe (16) can adopt tygon, polyfluortetraethylene pipe, polyvinyl chloride pipe, internal diameter 0.5-1.0mm; Sodium electrodes selective (19) can adopt simple glass film sodium electrode (23-8S type, 2801 types, 200048 types), combined type glass-membrane electrode or flow type sodium electrode; Temperature sensor can be various sensors such as the TDS-110 sensor with temperature sensing function, DS18820 type one line system digital temperature sensor; Contrast electrode (21) can be various electrodes such as the Hg/HgCl with reference function
2Electrode, Ag/AgCl electrode or ion-selective electrode; Sodion processor (22) can adopt high resistant millivoltmeter or DWG-9323A type sodion meter; Registering instrument (23) can adopt all kinds registering instrument such as desk-top self-balancing recorder; Basifier (12) in the alkalization device (10) can adopt diisopropylamine, ammoniacal liquor, diethylamine and dimethylamine.
4, the automatic fast measuring device of trace sodion as claimed in claim 2, it is characterized in that: the sodium electrodes selective (19) in flow type electrochemical detector (18) can be changed, when being replaced by electrodes such as chlorine, fluorine, hydrogen, this determinator can be finished the mensuration with the corresponding ion concentration of electrode.
5, the automatic fast measuring device of trace sodion as claimed in claim 2, it is characterized in that: determinator can be used single-chip microcomputer (26,27) and computing machine (25) control, wherein peristaltic pump (1), sample fillup valve (7) are by secondary single-chip microcomputer (27) AT89C52 control, and its interface is connected with host computer host scm (26) AT89C52; The calculating of host scm (26) control concentration, temperature compensation, millivolt output and result show; Host scm (26) is connected by interface RS232 with host computer computing machine (25), can finish operations such as data storage, data processing, s operation control and printout.
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