CN101063653A - Improved SiO2 analytic instrument - Google Patents
Improved SiO2 analytic instrument Download PDFInfo
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- CN101063653A CN101063653A CNA2007100573554A CN200710057355A CN101063653A CN 101063653 A CN101063653 A CN 101063653A CN A2007100573554 A CNA2007100573554 A CN A2007100573554A CN 200710057355 A CN200710057355 A CN 200710057355A CN 101063653 A CN101063653 A CN 101063653A
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- instrument
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- cuvette
- sio
- silicon
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Abstract
This invention relates to one improved SiO2 analysis device, which comprises the following technique keys: setting one layer of film in front of light window and analysis glass lens and the film is filtered under 820 nanometer wavelength; the film is insolvent to water in 0. 1 percent of acid liquid; the said film is of optical resin lens or amidogen nethyl formate film; this invention can set reaction pool in color comparison container with control value set in between.
Description
Technical field
The invention belongs to analytical instrumentation techniques, particularly improved SiO
2Analytical instrument.
Background technology
In the GB rules, to sio
2Analysis and measure and to continue to use ammonium molybdate or sodium molybdate in acid solution for many years always, generate yellow silicon molybdenum complex with silicon in the water, with 1-amino, beta naphthal, 4-sulfonic acid (being called for short 1,2,4 acid) reductive agent the silicon molybdenum complex is reduced into silicon molybdenum blue, uses its silicon content of silicate analysis-e/or determining, its reaction is:
4MoO2-4+6H
+→MO
4O2-13+3H
2O
H
2SiO
4+ 3MoO2-13+6H
+→ H
2[Si (Mo
3O
10)
4] molybdenum yellow+3H
2O
H
4[Si(Mo
3O
10)
4]+2→H
6[H
2SiMo
12O
10]+2
At present, test sio both domestic and external
2Instrument be not always the case, as U.S. SWAN, German AQUACON, Britain ABB, domestic Beijing China electricity, Hua Keyi, Beijing row's cloud, Ministry of Nuclear Industry five etc., but using best at present is French POLYMETRON9210 silicon table, in introduction China in 2004, so far existing historical more than 3 years, in this time more than 3 years, large quantities of large-scale units have newly been gone up in the whole nation, because the online silicon table of French POLYMETRON8891 uses better in China, also more stable, therefore large-scale unit is at chemical silicon (SiO
2) the selecting for use of table, mostly adopt 9210 series of the new research and development of French POLYMETRON.
Its measuring principle is based under acidity 1.2～1.3pH value, silicon in the water and sodium molybdate generate molybdenum yellow, utilize oxalic acid to make masking agent, with phosphate radical, iron plasma hidden after, after in solution, adding iron ammonium sulfate, make water medium-Si, Mo Huang be transformed into silicon molybdenum blue, generate stable blue color base compound, carry out opto-electronic conversion with the 820nm wavelength, thereby measure the size of aqueous solution mesosilicic acid salt content.
Instrument is made up of four parts substantially:
1) control diagnostic system
It is the brain and the heart of instrument, because the instrument internal memory is bigger, operating speed is very fast, and imported a large amount of deal with data, and making the instrument operation use function and obtained giving full play to, instrument has multiple menu, select for use for the user, can deserve to be called a smart instrumentation preferably, cut off the water supply as instrument, it is dirty that medicament is used a certain amount of back sample, reagent problem, check errors, mark liquid, advance medicine or the like problem, instrument can both be diagnosed voluntarily, and gives a warning or point out, and prevents that misdata from generating.
2) sample introduction and measuring system
Sampling system is a 200mL sample introduction cup, it can be in process of the test, automatically select to handle water sample, the multichannel water sample reaches in process of the test and does not interfere with each other, make the water sample that enters cuvette always fresh, allow representative water sample enter Measuring glass, and carry out water sample at any time and measure, the Measuring glass volume is 9mL; It is Measuring glass be again the dosing cuvette, its machining precision is very high, and is equipped with the constant wavelength list of 820nm wavelength light source, use fiber optic transmission, carry out the water sample colorimetric, water and light source output are kept apart, make water, electricity reach separation, this also is the big invention in design of this instrument.
3) quantitative remedy-adding system
Be to constitute by each 50 μ L precision metering pumps, make the quite accurate of Time Calculation control by computer instruction, this is manually can't be obtained, also be that artificial test is incomparable, its precision will substantially exceed artificial dosing and sampling, and after each test, equally clean three cuvettes by artificial test after, just carry out sample introduction work.
4) behind access 485 interfaces, staff's labour intensity has been saved in the remote controlled and operation of this instrument, and this instrument compliance with environmental protection requirements, saved the reagent consumption on the basis that precision improves, every month every kind of reagent consumption only be 1L, this also be other tables count can not compare.
In sum, this instrument is world first-class from function, structure, design, manufacturing, can reach the top product in the world.But each instrument from researching and developing manufacturing, all has one from being tested to this process of application, and this instrument is no exception.Have only through on-line operation, allow the product of customer's approval, just can deserve to be called first-class product.Finding now, is present best sio immediately
2Instrument also there are the following problems:
We know that silicate is in measuring process, the ordinary test chamber is done a test and is removed that reagent is prepared, scrubbed glass apparatus, this plurality of processes of taking a sample, merely from adding reagent, a general reagent dosing process can reach 14 minutes, and in-line meter is as carrying out work by this time, and in-site measurement is too slow, in order to shorten instrument measurement cycle length, general producer multiselect reaches this purpose with shortening the reagent reaction time in the instrument.Though a large amount of tests have been done to instrument by producer before dispatching from the factory, its precision of instrument is also very high but at the scene; But after dispatching from the factory, when carrying out commerical test, not like that just.
Our factory is bought two 9210 silicon tables simultaneously from summer in 2004, and 3,4 units are respectively joined an instrument, monitor stove water simultaneously, saturated vapour, three measuring points of superheated vapor.Count factory from table and debug so far, instrument can not normally move, and sees the following form:
Above data are as can be seen: instrument displayed value data will be higher than testing laboratory's data.Generally to get same time water sample, differ from 2 times in the time of good, differ from 3～4 times in the time of bad, bigger sometimes.
Summary of the invention
For solving the problems of the prior art, the present invention has passed through a large amount of experiments and demonstration.
We once did the test of mark liquid, marked liquid and measured value maximum error 3.5% as can be seen, obviously were not mark liquid problems, and in order to address this problem, we have done the test of oxalic acid joining day.Oxalic acid changes little to the hidden effect of phosphate radical iron, and this moment, stove water silicon was more approaching with the operation measured value, and during by 4 minutes and 23 seconds, SiO after the instrument setting program time
2Reach 48.2ppb and exceed normal value.If carry out dosing by this time, can or can not influence mark liquid and measure, we have done the test of mark liquid again for this reason, and different time adds the influence of silicon mark liquid:
| 4 | 211 | 204 | 204 | 204 |
From showing data as can be seen, conversion time adds, and oxalic acid has no effect to silicon mark liquid.
Propose for this reason, online silicon table is in conjunction with power plant's situation, have aquation phosphate radical lime stone interference problem in water and the steam, the agent prescription table B that is now using according to the agent prescription table C of the former as can be seen factory of Test Summary and China power plant is very accurate to the measurement data of mark liquid, and reaction is also than comparatively fast.
Go out from above experimental analysis, at first be little silicon table mark stove water respectively, saturated vapour, superheated vapor, four water samples, the different reagent of difference. former factory 9210 prescriptions are R1 sulfuric acid sodium molybdate .R2 oxalic acid, the R3 iron ammonium sulfate as can be seen, stove water and mark liquid and China's agent prescription are more approaching frequently, and steam differs bigger, has both made to deduct different agent prescriptions, and different balance check 1.8 values also differ bigger. compare the more of stove water difference with 9210 table meters, do a #3 unit saturated vapour test for this reason again and seen the above table problem of .#3 unit discovery, based on little silicon table data, dosing behind the volume pump is big 3.5 times on the instrument numerical value, compared greatly 9.5 times with the indication of 9210 instrument. experimental error is introduced by volume pump and cuvette respectively substantially certainly, does an experiment in detail again according to this result.
As can be seen from the above table, when normally moving dosing, indicated value is 90.9, after manual dosing was poured cuvette into again, the instrument displayed value was 23.2, when two extraordinarily go into tartrate after indicated value be 11.5, data 23.2 are comparatively desirable as can be seen from above numerical value, very approaching with measured value, we have done the interference experiment of cuvette phosphate radical again for this reason
See the following form:
0＝8.9 S＝850
As can be seen from the above table, former cuvette experimental error is very big, can reach 1920ppb, and numerical stability proves that according to experimental result the anti-phosphate radical interference performance of former cuvette is poor after changing cuvette about 50ppb, is unsuitable for using in power plant.The data that new and old cuvette is in operation are listed in the table below below:
From above data as can be seen, new ware and former ware ratio, stove water number be according to can descending nearly one times, still exceeds one times but compare with measured value. and from the steam data, new ware and old ware have descended four to five times but they are still than measured value value height than data.
Therefore we have done following experiment again:
Data that the #3 unit is surveyed are not for adding the data of coating cuvette, and data that the #4 unit is surveyed are for adding the data of coating cuvette.Not too big from the difference of new as can be seen ware of above data and old ware, still there is several times error between 9210 instrument displayed values and the measured value as can be seen.
Cuvette reflective mirror error experiments sees the following form;
| Stove water | Saturated vapour | Superheated vapor | |||||||
| 9210 table indications | Measured value | The reflective mirror error | 9210 table indications | Measured value | The reflective mirror error | 9210 table indications | Measured value | The reflective mirror error | * reflective mirror error |
| 31.4 | 8.7 | 13.3 | 3.52 | 1.2 | 0.9 | 3.12 | 0.1 | 4.7 | 0.6 |
| PH＝9.04 | PH＝9.1 | PH＝9.12 | |||||||
| Remarks: * experimentizes for adding R1 immediately after taking a sample, and the reflective mirror error experimentizes for the sampling back adds R1 after static 5 minutes | |||||||||
From above data as can be seen, the interference of reflective mirror in experiment is still very big, and max value of error can reach 4.7ppb, as changing experimental arrangement, add R1 after the sampling immediately and can make interference obviously be reduced to 0.6ppb, the surface area that 9210 cuvettes contact with aqueous solution is 10.362cm
2, and the area of reflex reflector lens is 4.9cm
2, 47.3% of the shared cuvette internal surface area of reflex reflector lens, the error that big like this ratio causes to experiment is conspicuous, it carries out in 1/2 glassware as experiment.In last table experiment, institute's water sampling is 100ml, tests in polypropylene vial, and long-pending with water engaging surface is 110.02cm
2, the reflex reflector lens area is 4.9cm
2Their ratio is 6.29%, and the actual error of its error ratio 9210 table in experiment is low 7.51 times like this
Conclusion: all in all above, all there is error in new and old cuvette, comes from that reflex reflector lens causes in alkaline solution due to the dissolving in the cuvette, and excessive because of the less reflex reflector lens proportion of cuvette volume, the experiment that equals silicon is to carry out in 1/2 glass container.Found the place of problem, we propose to use the resin reflex reflector lens instead again through repeatedly experiment, and the metal cuvette is all used the technical scheme of the new ware of band coating instead.
And POLYMETRON9210 silicon table, when test routine begins, after cuvette washes three times, sample can reach clock more than 4 minutes rest time in cuvette, and the stove water, steam that contain NaOH can cause very big test error to test in the time of this clock more than 4 minutes, and data see the following form:
There is deviation the verification mark liquid time with normal Measuring Time, differs nearly 20 seconds
Checking time (dosing)
The R1----R2------R3-------colorimetric
0 4.05 minutes 4.25 minutes 5.25
Measuring Time (dosing)
The R1----R2------R3-------colorimetric
0 4.23 minutes 4.48 minutes 5.58 minutes
Whether reagent zero point accurately is the key of decision accuracy of instrument height, and we adopt:
Pure no silicon water (positive dosing)=reagent zero point (desirable zero point);
Double reagent (extinction value)-single times reagent (extinction value)=reagent zero point.
So just can make instrument zero more accurate, make the precision of instrument higher.
Sample introduction overflow cup should be done and improve, and adds solenoid valve control siphon to reach the purpose of metering.Cuvette metering is 8 milliliters at every turn, causes the overflow of water medicine after adding 750 μ L medicines, influence measuring accuracy, after solenoid valve is opened, solution above the emptying, below solution be 7 milliliters of comparatively ideals.
In actual measurement, silicate (sio
2) optical window or lens in the analyser are glassware, his transmittance is fine, and antiacid erosion is also fine, but at silicate (sio
2) just different in the analysis.Because lens or optical window are glasswares, sio
2Composition is very high, and it can cause corrosion in alkaline solution, at (sio
2) it can generate the yellow silicon molybdenum complex of one deck with ammonium molybdate or sodium molybdate in the analysis, after adding reductive agent in the solution, the yellow complex that this one deck forms on optical window or lens can be reduced into the dynamic silicon molybdenum blue film of this one deck of silicon molybdenum blue and generate, because and sio in the solution
2Be same color, therefore can cause the measurement of silicon more than 3 times and disturb.Through test findings in a few years, this is the fact that can not argue.
Therefore technical scheme of the present invention is as follows:
SiO of the present invention
2The improvement of analytical instrument, its technology is at SiO
2Before the glass lens of analytical instrument, the optical window skim is set, film the seeing through of light 100% under 820 nano wave lengths.
Film can not be 0.1% acidity owing to aqueous solution in the analytical test process, causes the damage of film, should possess corrosion resistant characteristic.Diameter requires to make according to optical window, also can adopt transmittance to use optical resin lens preferably usually, and its thickness is 1.2mm, and transmittance is fine, and wearing quality is also fine, or adopts urethanes to cross film.
The present invention is corrosion-resistant at glass lens and optical window surface plating one deck, does not influence the film-urethanes film of transmittance again, perhaps adopts optical resin lens, and solution and glass lens, optical window are isolated, and does not participate in reagent reacting.Effect of the present invention is remarkable, be embodied in after optical flat reflective mirror or glass optics lens light window plate one deck urethanes film or the poly-acetoacetic ester optical mirror slip of dress lastblock, detected solution and glass lens are kept apart, after in measuring solution, adding ammonium molybdate, because glass lens or reflective mirror do not participate in reagent reacting, reagent only with solution in silicon dioxde reaction, such result who surveys is real dioxide-containing silica.Do not isolate with solution as glass lens or reflective mirror, the participation reagent reacting can make and react the same silicon molybdenum blue of silicon dioxide product in generation and the sample on glass lens or the reflective mirror, causes measurement result higher.
We have found the place of problem, therefore the problem that solves be cuvette problem, so under the situation that cuvette is not changed, we propose a technical scheme of dealing with problems, as shown in Figure 1, a reagent reacting pond is set before cuvette, in reaction tank, adds R1 sulfuric acid sodium molybdate, the sample after advancing quantitatively again, the dosing process is all carried out in reaction tank, will be minimum so that disturb.Enter cuvette through solenoid control again after reaching requirement, fast detecting can avoid the dissolving of cuvette to disturb like this.
A kind of improved SiO of the present invention
2Analytical instrument, its technology are to be provided with reaction tank before cuvette, are provided with operation valve between reaction tank and the cuvette and are connected.
Now external producer is as Britain ABB Kent company, French Pohle Mei Telong, and U.S. SWAN company, the lens and the optical window of man of the homemade silicon of German Ou Ke AQUACON and all Watch Factory cuvettes are optical glass, cause the silicon table at micro-SiO
2After manually in polypropylene vial, testing in measured result and the laboratory in the measurement, move to colorimetric in the spectrophotometer again, nearly three times of difference, fail the reason of the problem of finding out for over ten years always, existing national power plant, environmental protection, chemical fiber factory, what use in a large number all is import water analysis instrument, and a silicon meter price is all about 160,000 yuan, but the numerical value of surveying too big with data error that the laboratory is surveyed, through test in a large number for many years, finally find the existence of this problem, and this problem is resolved
Embodiment
Embodiment 1: adopts urethanes film optical coating technology, spends and be 1.2mm, and the use on French POLYMETRON9210 silicon table, test result and adopt spectrophotometer manual analysis result to be compared as follows table before and after improving:
Embodiment 2: adopt and installing optical resin lens additional before the lens of French POLYMETRON9210 silicon table and reflective mirror, film the seeing through of light 100% under 820 nano wave lengths.Test result and employing spectrophotometer manual analysis result are compared as follows table before and after the process modification::
Behind the embodiment 3:9210 silicon table reprogramming, with cancellation former 4 minutes sample introduction rest times, it is as follows to add the sample test data of intaking again behind the R1 sulfuric acid sodium molybdate earlier:
Embodiment 4: Beijing China electric HD-2011 silicon table system does not have the instrument of reaction tank, it is to react and colorimetric after directly adding reagent in cuvette, so instrument error is bigger, adds a reaction tank before cuvette for this reason, make because reaction tank is a macromolecular compound, do not contain SiO
2, therefore in course of reaction, do not have SiO
2Ooze out and cause interference, reaction finishes the back shifts out reaction tank by internally piloted valve and enters cuvette and carry out colorimetric, because the time is short, also can not cause corrosion to disturb by the contrast colors ware.Data see the following form:
#3 machine on April 26th, 2007
Embodiment 5: the instrument of French Pohle Mei Telong 9210, it is to react and colorimetric after directly adding reagent in cuvette, so instrument error is bigger, adds a reaction tank before cuvette for this reason, makes because reaction tank is a macromolecular compound, does not contain SiO
2, therefore in course of reaction, do not have SiO
2Ooze out and cause interference, reaction finishes the back shifts out reaction tank by internally piloted valve and enters cuvette and carry out colorimetric, because the time is short, also can not cause corrosion to disturb by the contrast colors ware.9210 measurement data after reaction tank is installed in improvement additional see the following form:
Claims (6)
1. improved SiO
2Analytical instrument is characterized in that at SiO
2Before the glass lens of analytical instrument, the optical window skim is set, film the seeing through of light 100% under 820 nano wave lengths.
2. SiO as claimed in claim 1
2The improvement of analytical instrument is characterized in that described film can not be 0.1% acidity owing to aqueous solution.
3. improved SiO as claimed in claim 1
2Analytical instrument is characterized in that described film is an optical resin lens.
4. improved SiO as claimed in claim 1
2Analytical instrument is characterized in that described film is the urethanes plated film.
5. improved SiO as claimed in claim 1
2Analytical instrument is characterized in that described film thickness is 1.2mm.
6. improved SiO
2Analytical instrument is characterized in that being provided with reaction tank before cuvette, be provided with operation valve between reaction tank and the cuvette and be connected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100573554A CN101063653A (en) | 2007-05-17 | 2007-05-17 | Improved SiO2 analytic instrument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100573554A CN101063653A (en) | 2007-05-17 | 2007-05-17 | Improved SiO2 analytic instrument |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101063653A true CN101063653A (en) | 2007-10-31 |
Family
ID=38964816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100573554A Pending CN101063653A (en) | 2007-05-17 | 2007-05-17 | Improved SiO2 analytic instrument |
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| Country | Link |
|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106338508A (en) * | 2016-11-03 | 2017-01-18 | 大唐东北电力试验研究所有限公司 | Online silicon dioxide analyzer and method for analyzing content of silicon dioxide in water |
| CN106404773A (en) * | 2016-11-03 | 2017-02-15 | 大唐东北电力试验研究所有限公司 | Detection method for measuring silicon content in water body and silicon dioxide content analysis device |
| CN106596429A (en) * | 2016-12-19 | 2017-04-26 | 攀钢集团江油长城特殊钢有限公司 | Method for measuring silicon dioxide in fluorine-containing samples |
| CN115356327A (en) * | 2022-10-19 | 2022-11-18 | 北京市农林科学院智能装备技术研究中心 | Nutrient solution detection device, method and system |
-
2007
- 2007-05-17 CN CNA2007100573554A patent/CN101063653A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106338508A (en) * | 2016-11-03 | 2017-01-18 | 大唐东北电力试验研究所有限公司 | Online silicon dioxide analyzer and method for analyzing content of silicon dioxide in water |
| CN106404773A (en) * | 2016-11-03 | 2017-02-15 | 大唐东北电力试验研究所有限公司 | Detection method for measuring silicon content in water body and silicon dioxide content analysis device |
| CN106596429A (en) * | 2016-12-19 | 2017-04-26 | 攀钢集团江油长城特殊钢有限公司 | Method for measuring silicon dioxide in fluorine-containing samples |
| CN106596429B (en) * | 2016-12-19 | 2019-11-15 | 攀钢集团江油长城特殊钢有限公司 | The measuring method of silica in fluorine-containing sample |
| CN115356327A (en) * | 2022-10-19 | 2022-11-18 | 北京市农林科学院智能装备技术研究中心 | Nutrient solution detection device, method and system |
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