CN108333174A - A kind of analysis method of achievable vanadium solution concentration on-line checking - Google Patents
A kind of analysis method of achievable vanadium solution concentration on-line checking Download PDFInfo
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- CN108333174A CN108333174A CN201810042577.7A CN201810042577A CN108333174A CN 108333174 A CN108333174 A CN 108333174A CN 201810042577 A CN201810042577 A CN 201810042577A CN 108333174 A CN108333174 A CN 108333174A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
Abstract
The present invention provides a kind of analysis method of achievable vanadium solution concentration on-line checking, includes the following steps：Standard working curve makes：Using ultraviolet-visible spectrophotometry, extinction data in N number of vanadium concentration data and the standard spectrum diagram curve of corresponding concentration are obtained, draw absorbance concentration curve；The on-line checking of full vanadium concentration in solution to be detected：The solution to be detected of certain volume is pipetted, pH to 79 is adjusted；Excess hydrogen peroxide is added；Sulfuric acid solution is added；To be not added with the blank solution of solution to be detected as reference, the absorbance value for the solution to be detected that determination step obtains calculates full vanadium concentration in sample according to standard working curve；The full vanadium concentration is multiplied by solution extension rate to be detected, finally obtains the full vanadium concentration in solution to be detected.The analysis method that vanadium solution concentration on-line checking can be achieved in the present invention can vanadium ion concentration simple, quickly, in Accurate Determining vanadium metallurgical process sample or production discharge water.
Description
Technical field
The present invention relates to vanadium measurement of concetration technology more particularly to a kind of analysis sides of achievable vanadium solution concentration on-line checking
Method.
Background technology
In the national standard and environmental standard about Water-quality control, the detection of content of vanadium mainly uses in water sample method
Including graphite furnace atomic absorption spectrometry and tantalum reagent (BPHA) extraction spectrophotometric method.Sampling Graphite Furnace Atomic Absorption is divided light
Degree method advantage is detection sensitivity height, strong antijamming capability, the disadvantage is that instrument and equipment price height, daily maintenance and cost of use
Height, the exhaust gas generated in detection process are absorbed and are disposed, and environmental pollution can be led to by being directly entered air.Tantalum reagent
(BPHA) it is detection linear wide, strong antijamming capability the advantages of extraction spectrophotometric method, the disadvantage is that detection cycle is long, another party
Face, it is poisonous and hazardous organic and inorganic chemical reagent, generated detection discard solution are formed using multiple types in detection process
Pollution source.
In the examination criterias such as the metallurgical standard used in vanadium smelter or professional standard, the measurement of content of vanadium mainly uses
Method be mainly potassium permanganate (or ammonium persulfate) oxidation-ferrous ammonium sulfate titration, this method is used for the matter of vanadium metallurgy
Amount control detects different links, including raw material detection, process control detection and intermediate and control of product quality detection, lacks
Point is low less than the sample solution of 1g/L detection precision for vanadium concentration, and the poisonous and hazardous of multiple types is used in detection process
Organic and inorganic chemical reagent improves detection devil liquor recovery difficulty and cost, and also solution causes the secondary pollution of environment.
The method for directly measuring content of vanadium in solution using spectrophotometry is described in some patents, mainly utilizes four
Valence vanadium is detected the absorption characteristic of special wavelength light, if vanadium exists in the form of pentavalent vanadium in solution, needs to pass through reduction
Reaction converts vanadium to tetravalence vanadium and is detected, and needs to restore process conversion by initial oxidation if vanadium exists with trivalent vanadium
It is detected for tetravalence vanadium, the control of the conditions such as acid-base value of solution and oxidation appropriate, the selection of reducing agent in conversion process
It is complex, therefore this method only has vanadium energy-accumulating medium detection application report.Document has been reported that vanadium can be used as stabilizer and show
Toner (2- (3,5- bis- Bromo-2-pyridylazo) -5- diethylaminophenols) is combined, and is directly detected in precipitation using spectrophotometry
Trace Hydrogen Peroxide content, this method still have it is more using reagent, the shortcomings of complex process.
Therefore, exploitation is a kind of simple and practicable, is capable of the method for on-line checking solution vanadium concentration, can reduce artificial intensity,
The generation that chemical pollutant can be reduced is significant for vanadium chemistry industry.
Invention content
It is an object of the present invention to for the problem that in current solution content of vanadium assay method it is complicated, can not be extensively using,
It is proposed that a kind of analysis method of achievable vanadium solution concentration on-line checking, this method can simple, quick, Accurate Determining vanadium metallurgy mistakes
Vanadium ion concentration in journey sample or production discharge water.
To achieve the above object, the technical solution adopted by the present invention is：A kind of achievable vanadium solution concentration on-line checking
Analysis method includes the following steps：
Step (1) standard working curve makes：The vanadium standard solution (simple substance vanadium solution) for measuring N number of different volumes (also may be used
Choose the vanadium standard solution of N number of isometric various concentration)；Be added solution adjust pH to 7-9, sequentially add hydrogenperoxide steam generator and
The addition of sulfuric acid solution, the hydrogen peroxide should be able to meet：Low price vanadium ion present in solution to be detected is all aoxidized
For positive pentavalent vanadium ion, positive pentavalent vanadium ion formed vanadyl with hydrogen peroxide, and solution is in faint yellow；The sulfuric acid solution adds
Enter the light brown that amount can make solution colour in stabilization, vanadium further reacts formation with excessive hydrogen peroxide surely in solution to be detected
Fixed crosses vanadyl key；The vanadium standard solution of N number of different volumes is added into water constant volume；Using ultraviolet-visible spectrophotometry, obtain N number of
Extinction data in vanadium concentration data and the standard spectrum diagram curve of corresponding concentration draw absorbance-concentration curve, i.e. standard work
Make curve, by obtaining linear equation after matched curve：C=aA+b
In formula:
The vanadium concentration of C-solution to be measured, unit mg/L；
A-solution 480nm absorbance values to be measured；
A-linear gradient；
B-linear intercept；
The on-line checking of full vanadium concentration in step (2) solution to be detected：
(2-1) is pipetted in the solution to container to be detected of certain volume, and suitable quantity of water dilution is added, acid solution or alkali soluble is added
Liquid adjusts pH value of solution to be detected to 7-9；
Excess hydrogen peroxide is added in (2-2), and the addition of the hydrogen peroxide should be able to meet：To exist in solution to be detected
Low price vanadium ion be all oxidized to positive pentavalent vanadium ion；Positive pentavalent vanadium ion formed vanadyl with hydrogen peroxide；
Sulfuric acid solution is added in (2-3), and vanadium in solution to be detected is made further to react formation stabilization with excessive hydrogen peroxide
Cross vanadyl key, add water constant volume；
(2-4) is to be not added with the blank solution of solution to be detected【The identical excessive peroxide with step (2-2) and (2-3) is added
Change hydrogen and sulfuric acid solution】As reference, the absorbance value for the solution to be detected that determination step (2-3) obtains, the characteristic absorption
The a length of 400-550nm of spike；
(2-5) calculates full vanadium concentration in sample according to step (1) standard working curve；The full vanadium concentration is multiplied by be detected
Solution extension rate finally obtains the full vanadium concentration in solution to be detected.
Further, the N is more than or equal to 5, preferably 5-9.
Further, the aqueous slkali is sodium hydroxide solution, and the acid solution is sulfuric acid solution.
Further, the mass concentration ratio upper limit of various ions and vanadium is as follows in the solution to be detected：Cr:V<2, Cu:V
<20, Fe:V<20, W:V<20, Mo:V<8.Since in high purity vanadium chemical field, every foreign ion is all strictly controlled,
Therefore, in practical operation, detect solution in content of vanadium when, can by certain method by Control of Impurities in a certain concentration model
In enclosing, ensure that the industrial applications of vanadium solution concentration on-line detection method of the present invention are realized.High-purity vanadium chemistry neck is fully investigated
The influence for the various foreign ions comparison color method that domain is related to, it is determined that the ratio upper limit of itself and the mass concentration of vanadium：Cr:V<2,
Cu:V<20, Fe:V<20, W:V<20, Mo:V<8；Such as content of vanadium is 100mg/L, in the upper limit, the detection of vanadium misses every impurity
Difference is no more than 10%.
Further, it after step (2-3), stands 3-5min and forms stable light brown to solution to be detected, then measure
Its absorbance value.
Further, the characteristic absorption peak wavelength is 430-510nm, at that wavelength, the absorption of other impurities element
Minimum and vanadyl absorbance excessively is larger.Integrated interference factor and cross vanadyl absorbance and consider, at 450nm vanadyl absorbance it is big,
There is interference, become smaller more than vanadyl absorbance is crossed after 500nm, and part of impurity elements interference also increases, error increases.It is more preferably special
Sign absorption peak wavelength is 480~500nm.
Further, full vanadium concentration range is 4mg/L~800mg/L in vanadium standard solution.Use vanadium solution of the present invention
Minimum concentration on-line detection method can detectable concentration be accurately the content of vanadium of 4mg/L, and highest can detectable concentration be accurately 800mg/L
Content of vanadium.
Further, vanadium concentration and absorbance standard working curve linear equation：C=32.329A-0.0621.
The analysis method of vanadium solution concentration on-line checking can be achieved in the present invention, will be contained in vanadium solution by the way that hydrogen peroxide is added
Some low price vanadium ions are uniformly converted into pentavalent vanadium ion；Excessive hydrogen peroxide will form stable peroxide with pentavalent vanadium ion
Vanadium key, the variation that vanadyl key feature optical absorption intensity is crossed using ultraviolet-visible spectrophotometer measurement solution are measured in solution always
Vanadium concentration.Vanadium ion concentration has the wider range of linearity with photon absorbing intensity, and by on-line dilution appropriate, this method can be quick
Complete the vanadium solution on-line checking to various concentration.Vanadium solution concentration on-line detection method step science of the present invention, rationally, and it is existing
There is technology to compare to has the following advantages：
1) method provided by the invention can be used for the content of vanadium of continuous, automatic detection solution, be particularly suitable for vanadium chemistry work
Continuous process in industry, the detection of vanadium in wastewater concentration, can be significantly reduced cost of labor in being handled such as the resin vanadium removal of waste water, drop
Low labor intensity.
2) reagent that the present invention uses, which easily takes, is easy to get, and no special chemical reagent, generated detection waste liquid can directly be flow back to
It detects in sample, is not necessarily to otherwise processed.
3) detection process is without organic reagent and other toxic reagent applications, method high sensitivity, and the range of linearity is wide.
4) hydrogen peroxide, which is made, in vanadium solution concentration on-line detection method of the present invention is not only oxidant but also is used as color developing agent application
Micro content of vanadium in solution is directly detected in UV-VIS spectrophotometry.
To sum up, vanadium solution concentration on-line detection method of the present invention can be used for the prison of vanadium metallurgical process sample vanadium ion concentration
It surveys, the real time monitoring of vanadium ion concentration in water is discharged especially suitable for production, is with a wide range of applications in vanadium field of metallurgy.
Description of the drawings
Fig. 1 was vanadyl molecular structure；
Fig. 2 content of vanadium is 89mg/L solution UV, visible light optical wavelength-absorbance curve, adds hydrogen peroxide color developing effect pair
Than；
Fig. 3 series concentrations (3.6,8.9,17.9,35.7,89.3,178.5,357.0,535.5,714.0, with V2O5Contain
Amount calculates, and unit is：Mg/L wavelength (400nm~550nm)-absorbance change curve of vanadium standard sample solution)；
It is curve that Fig. 4, which is that standard solution absorbance changes with vanadium concentration at 480nm,；
Fig. 5 may interfere with the outer visible spectrophotometric scanning absorbance-wavelength curve of element (Cr, Fe, Cu, W, Mo).
Specific implementation mode
The present invention is further described with reference to embodiments：
Embodiment 1
Present embodiment discloses a kind of analysis methods of achievable vanadium solution concentration on-line checking, include the following steps：
1, instrument and reagent
1.2 instrument
Ultraviolet-uisible spectrophotometer：PE Lambda 35
1.2 reagent
1.2.1 sulfuric acid solution：AR 1+1
1.2.2 sodium hydroxide solution：AR 0.1g/ml
1.2.3 hydrogen peroxide:AR 30%
1.2.4 vanadium standard solution：Simple substance content of vanadium 1000mg/L (standard solution certificate number GSB04-1759-2004)
2, hydrogen peroxide contrast experiment
1.1 accurate titles pipette two parts of 0.5ml vanadium standard solution (1.2.4), are respectively placed in 100ml volumetric flasks, 30- is added
50ml water flush volume bottles, then 1ml sodium hydroxide solutions (1.2.2) are separately added into, portion addition 0.2ml hydrogen peroxide (1.2.3),
Portion is not added with, then is separately added into 10ml sulfuric acid solutions (1.2.1), and often adding a kind of reagent will fully shake up, then with water constant volume,
It shakes up, place 3-5min, solution is existed using the solution of non-mark-on liquid as reference liquid using 1cm cuvettes in stable light brown
Colorimetric at 480nm.
1.2 full content of vanadium are in two parts of solution of 89mg/L, if the comparison of hydrogen peroxide color developing effect is added and sees Fig. 2.
The drafting of 3 standard curves
3.1 series concentration vanadium standard solution are prepared
It is accurate to claim to pipette 0,0.2ml, 0.5ml, 1.0ml, 2.0ml, 5.0ml, 10.0ml, 20.0ml, 30.0ml, 40.0ml
In 100ml volumetric flasks 30-50ml water flush volume bottles are added, then be separately added into 1ml hydroxides in vanadium standard solution (1.2.4)
Sodium solution (1.2.2), 0.2ml hydrogen peroxide (1.2.3), 10ml sulfuric acid solutions (1.2.1), often adding a kind of reagent will fully shake
It is even, then with water constant volume, shake up, place 3-5min, solution forms stabilization in stable light brown, i.e. pentavalent vanadium ion with hydrogen peroxide
Cross vanadyl key (see Fig. 1).Volume is the standard solution vanadium concentration of 100mL with V2O5Content calculation, computational methods are shown in formula
(1), the vanadium concentration of prepared serial solution be respectively 0,0.36,0.89,1.79,3.57,8.93,17.85,35.70,
53.55,71.40 (unit is：mg/100mL).
In formula：C-standard solution (1.2.4) vanadium elemental concentration, unit mg/L；
When V1-drafting standard curve, standard solution (1.2.4) volume, unit mL are accurately pipetted；
181.88-vanadic anhydride molecular weight；
101.88-elemental vanadium atomic weight；
1000-milliliters and liter conversion coefficient；
3.2 various concentration vanadium standard solution wavelength-absorbance curve scanning
It is molten to series concentration vanadium standard at 400-550nm using 1cm cuvettes using the solution of non-mark-on liquid as reference liquid
Liquid carries out length scanning, obtains various concentration vanadium standard solution wavelength-absorbance curve scanning spectrogram, sees Fig. 3.
Standard working curve between 3.3 absorbances-vanadium concentration of standard solution is drawn
Reading the corresponding absorbance value of various concentration vanadium standard solution at wavelength 480nm (is respectively：0.013、0.030、
0.057,0.112,0.278,0.554,1.106,1.658,2.211), using absorbance as ordinate, with a concentration of abscissa of vanadium
Draw absorbance with vanadium concentration increase and change standard working curve, see Fig. 4, by linear regression analysis obtain absorbance and
V2O5The calculation formula (2) mutually calculated between content
Y=ax+b ... ... ... (2)
In formula:
The vanadium concentration of y-solution to be measured, unit mg/100mL；
X-solution 480nm absorbance values to be measured；
A-linear gradient (a=32.329)；
B-linear intercept (b=-0.0621)；
Embodiment 2
Present embodiment discloses a kind of analysis methods of achievable vanadium solution concentration on-line checking, include the following steps：
1, instrument and reagent
1.1 instrument
Ultraviolet-uisible spectrophotometer：PE Lambda 35
1.2 reagent
1.2.1 sulfuric acid solution：AR 1+1
1.2.2 sodium hydroxide solution：AR 0.1g/ml
1.2.3 hydrogen peroxide:AR 30%
1.2.4 vanadium standard solution：Simple substance content of vanadium 1000mg/L (standard solution certificate number GSB04-1759-2004)
1.2.5 potassium bichromate：AR
1.2.6 ferric sulfate：AR
1.2.7 copper sulphate：AR
1.2.8 ammonium tungstate：AR
1.2.9 ammonium molybdate：AR
2, impurity interference experiment
2.1 vanadium standard solution UV, visible light spectrophotometric absorbance curves
It is accurate to claim to pipette 0.2ml vanadium standard solution (1.2.4) in 100ml volumetric flasks, 30-50ml water flush volumes are added
Bottle, then it is separately added into 1ml sodium hydroxide solutions (1.2.2), 0.2ml hydrogen peroxide (1.2.3), 10ml sulfuric acid solutions (1.2.1), often
Adding a kind of reagent will fully shake up, then with water constant volume, content of vanadium is with V2O5It is calculated as 36mg/100mL.It shakes up, place 3-
5min, solution is in stable light brown.Using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes at 400-550nm
Length scanning is carried out to series concentration vanadium standard solution.
2.2 chromium interference experiments
2.2.1 6,100ml volumetric flasks are taken, 30-50ml water is separately added into, then are separately added into 1ml sodium hydroxide solutions
(1.2.2)；
2.2.2 0.2829g potassium bichromates (1.2.5) are accurately weighed in 100ml beakers, with being transferred to after water dissolution
In 100ml volumetric flasks, constant volume shakes up, and chromium content is 1000mg/L in this solution；
2.2.3 pipette respectively again 0,1.0ml, 2.0ml, 5.0ml, 10.0ml, 20.0ml potassium bichromate solution (2.1.2) in
In 100ml volumetric flasks (2.1.1), it is separately added into 0.2ml hydrogen peroxide (1.2.3), 10ml sulfuric acid solutions (1.2.1), often adds one
Kind of reagent will fully shake up, then with water constant volume, at this time in solution chromium concn be respectively 10mg/L, 20mg/L, 50mg/L,
100mg/L、200mg/L；
2.2.4 it shakes up, place 5min, using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes in 400-550nm
Place carries out length scanning.
2.3 ferro element interference experiments
2.3.1 6,100ml volumetric flasks are taken, 30-50ml water is separately added into, then are separately added into 1ml sodium hydroxide solutions
(1.2.2)；
2.3.2 0.3580g ferric sulfate (1.1.6) is accurately weighed in 100ml beakers, with being transferred to 100ml after water dissolution
In volumetric flask, constant volume shakes up, and iron content is 1000mg/L in this solution；
2.3.3 0,10ml, 20ml, 30ml, 40ml, 50.0ml ferrum sulfuricum oxydatum solutum (2.2.2) is pipetted respectively again in 100ml to hold
In measuring bottle (2.1.1), it is separately added into 0.2ml hydrogen peroxide (1.1.3), 10ml sulfuric acid solutions (1.1.1), often adds a kind of reagent all
Fully to shake up, then with concentration of iron in water constant volume at this time solution be respectively 100mg/L, 200mg/L, 300mg/L, 400mg/L,
500mg/L；
2.3.4 it shakes up, place 5min, using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes in 400-550nm
Place carries out length scanning.
2.4 copper interference experiments
2.4.1 6,100ml volumetric flasks are taken, 30-50ml water is separately added into, then are separately added into 1ml sodium hydroxide solutions
(1.2.2)；
2.4.2 0.2512g copper sulphate (1.1.7) is accurately weighed in 100ml beakers, with being transferred to 100ml after water dissolution
In volumetric flask, constant volume shakes up, and iron content is 1000mg/L in this solution；
2.4.3 0,10ml, 20ml, 30ml, 40ml, 50.0ml copper-bath (2.3.2) is pipetted respectively again in 100ml to hold
In measuring bottle (2.1.1), it is separately added into 0.2ml hydrogen peroxide (1.1.3), 10ml sulfuric acid solutions (1.1.1), often adds a kind of reagent all
Fully to shake up, then with copper concentration in water constant volume at this time solution be respectively 100mg/L, 200mg/L, 300mg/L, 400mg/L,
500mg/L；
2.4.4 it shakes up, place 5min, using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes in 400-550nm
Place carries out length scanning.
2.5 wolfram element interference experiments
2.5.1 6,100ml volumetric flasks are taken, 30-50ml water is separately added into, then are separately added into 1ml sodium hydroxide solutions
(1.2.2)；
2.5.2 0.1379g ammonium tungstates (1.1.8) are accurately weighed in 100ml beakers, with being transferred to 100ml after water dissolution
In volumetric flask, constant volume shakes up, and iron content is 1000mg/L in this solution；
2.5.3 0,10ml, 20ml, 30ml, 40ml, 50.0ml ammonium tungstate solution (2.4.2) is pipetted respectively again in 100ml to hold
In measuring bottle (2.1.1), it is separately added into 0.2ml hydrogen peroxide (1.1.3), 10ml sulfuric acid solutions (1.1.1), often adds a kind of reagent all
Fully to shake up, then with tungsten concentration in water constant volume at this time solution be respectively 100mg/L, 200mg/L, 300mg/L, 400mg/L,
500mg/L；
2.5.4 it shakes up, place 5min, using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes in 400-550nm
Place carries out length scanning.
2.6 molybdenum element interference experiments
2.1.1 6,100ml volumetric flasks are taken, 30-50ml water is separately added into, then are separately added into 1ml sodium hydroxide solutions
(1.2.2)；
2.6.2 0.1840g ammonium molybdates (1.1.9) are accurately weighed in 100ml beakers, with being transferred to 100ml after water dissolution
In volumetric flask, constant volume shakes up, and iron content is 1000mg/L in this solution；
2.6.3 pipette respectively again 0,1.0ml, 2.0ml, 5.0ml, 10.0ml, 20.0ml ammonium molybdate solution (2.5.2) in
In 100ml volumetric flasks (2.1.1), it is separately added into 0.2ml hydrogen peroxide (1.1.3), 10ml sulfuric acid solutions (1.1.1), often adds one
Kind of reagent will fully shake up, then with water constant volume, at this time in solution chromium concn be respectively 10mg/L, 20mg/L, 50mg/L,
100mg/L、200mg/L；
2.6.4 it shakes up, place 5min, using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes in 400-550nm
Place carries out length scanning.
3, impurity element interference effect is analyzed
Respectively choose chromium concn be 100mg/L, concentration of iron 500mg/L, copper concentration 500mg/L, tungsten concentration 500mg/
L, molybdenum concentration is a concentration of for the scanning curve and vanadium of the UV, visible light spectrophotometric 400-550nm range of wavelengths of 200mg/L
The scanning curve of the sample solution of 3.6mg/L compares to obtain Fig. 5.
Embodiment 3
Present embodiment discloses a kind of analysis methods of achievable vanadium solution concentration on-line checking, include the following steps：
1, standard curve making
1.1 reagent
1.1.1 sulfuric acid solution：AR 1+1
1.1.2 sodium hydroxide solution：AR 0.1g/ml
1.1.3 hydrogen peroxide:AR 30%
1.1.4 vanadium standard solution：Simple substance content of vanadium 1000mg/L (standard solution certificate number GSB04-1759-2004)
1.2 instrument
Ultraviolet-uisible spectrophotometer：The general analysis general T6 new centuries
1.3 series concentration vanadium standard solution are prepared
1.3.1 it is accurate claim to pipette 0,0.2ml, 0.5ml, 1.0ml, 2.0ml, 5.0ml, 10.0ml, 20.0ml, 30.0ml,
In 100ml volumetric flasks 30-50ml water flush volume bottles are added, then be separately added into 1ml in 40.0ml vanadium standard solution (1.1.4)
Sodium hydroxide solution (1.1.2), 0.2ml hydrogen peroxide (1.1.3), 10ml sulfuric acid solutions (1.1.1), often adding a kind of reagent will
Fully shake up, then with water constant volume, shake up, place 3-5min, solution is in stable light brown.Volume is the standard solution of 100mL
Vanadium concentration is with V2O5Content calculation, computational methods are shown in formula (1), the vanadium concentration of prepared serial solution is respectively 0,0.36,
0.89,1.79,3.57,8.93,17.85,35.70,53.55,71.40 (unit is：mg/100mL).
In formula：C-standard solution (1.2.4) vanadium elemental concentration, unit mg/L；
When V1-drafting standard curve, standard solution (1.2.4) volume, unit mL are accurately pipetted；
181.88-vanadic anhydride molecular weight；
101.88-elemental vanadium atomic weight；
1000-milliliters and liter conversion coefficient；
1.3.2 series concentration vanadium standard absorbance value measures
Using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes at 480nm colorimetric, obtain various concentration standard
The corresponding absorbance value of solution.Using light absorption value as abscissa, with a concentration of ordinate of the vanadium of standard solution, it is bent to draw standard work
Line.Absorbance and V are obtained by linear regression analysis2O5The calculation formula (2) mutually calculated between content
Y=ax+b ... ... ... (2)
In formula:
The vanadium concentration of y-solution to be measured, unit mg/100mL；
X-solution 480nm absorbance values to be measured；
A-linear gradient (a=32.329)；
B-linear intercept (b=-0.0621)；
2, sample detects
2.1 sample (the full vanadium of case prediction for full content of vanadium in liquid more than 50g/L (in terms of vanadic anhydride)
Content is in 70g/L or so), 0.25ml samples are accurately pipetted, in 100ml volumetric flasks, 30-50ml water flush volume bottles are added,
It is suitable with standard curve that appropriate sodium hydroxide solution (1.1.2) adjusting pH value of solution is added, then is separately added into 0.2ml hydrogen peroxide
(1.1.3), 10ml sulfuric acid solutions (1.1.1), often adding a kind of reagent will fully shake up, then with water constant volume, shake up, place 3-
5min, solution in stable light brown, using 1cm cuvettes at 480nm colorimetric, reference is done with the blank solution for sample of not adding an examination of
Liquid measures sample absorbance：0.552.
2.2 calculating
Full content of vanadium (g/L) is calculated by formula (2), in terms of vanadic anhydride：
In formula：A-sample solution absorbance (does reference) with the blank solution for sample of not adding an examination of；
A-absorptivity；
B-intercept；
V-sample stoste volume, unit mL；
1-sample constant volume to be checked (is usually 100mL with standard solution constant volume ratio:100mL=1).
2.3 are computed, and the full content of vanadium of sample is 71.14g/L in the case (in terms of vanadic anhydride).
Embodiment 4
Present embodiment discloses a kind of analysis methods of achievable vanadium solution concentration on-line checking, include the following steps：
1, standard curve making
1.1 reagent
1.1.1 sulfuric acid solution：AR 1+1
1.1.2 sodium hydroxide solution：AR 0.1g/ml
1.1.3 hydrogen peroxide:AR 30%
1.1.4 vanadium standard solution：Simple substance content of vanadium 1000mg/L (standard solution certificate number GSB04-1759-2004).
1.2 instrument
Ultraviolet-uisible spectrophotometer：The general analysis general T6 new centuries
1.3.1 row concentration vanadium standard solution is prepared
It is accurate to claim to pipette 0,0.2ml, 0.5ml, 1.0ml, 2.0ml, 5.0ml, 10.0ml, 20.0ml, 30.0ml, 40.0ml
In 100ml volumetric flasks 30-50ml water flush volume bottles are added, then be separately added into 1ml hydroxides in vanadium standard solution (1.1.4)
Sodium solution (1.1.2), 0.2ml hydrogen peroxide (1.1.3), 10ml sulfuric acid solutions (1.1.1), often adding a kind of reagent will fully shake
It is even, then with water constant volume, shake up, place 3-5min, solution is in stable light brown.Volume is the standard solution vanadium concentration of 100mL
With V2O5Content calculation, computational methods are shown in formula (1), the vanadium concentration of prepared serial solution is respectively 0,0.36,0.89,
1.79,3.57,8.93,17.85,35.70,53.55,71.40 (unit is：mg/100mL).
In formula：C-standard solution (1.2.4) vanadium elemental concentration, unit mg/L；
V1When-drafting standard curve, standard solution (1.2.4) volume, unit mL are accurately pipetted；
181.88-vanadic anhydride molecular weight；
101.88-elemental vanadium atomic weight；
1000-milliliters and liter conversion coefficient；
1.3.2 series concentration vanadium standard absorbance value measures
Using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes at 480nm colorimetric, obtain various concentration standard
The corresponding absorbance value of solution.Using light absorption value as abscissa, with a concentration of ordinate of the vanadium of standard solution, it is bent to draw standard work
Line.Absorbance and V are obtained by linear regression analysis2O5The calculation formula (2) mutually calculated between content
Y=ax+b ... ... ... (2)
In formula:
The vanadium concentration of y-solution to be measured, unit mg/100mL；
X-solution 480nm absorbance values to be measured；
A-linear gradient (a=32.329)；
B-linear intercept (b=-0.0621)；
2, sample detects
2.1 for full content of vanadium in liquid, in the sample of 3g/L~50g/L (in terms of vanadic anhydride), (case is predicted complete
Content of vanadium is in 3g/L or so), 10.00ml samples are accurately pipetted, in 100ml volumetric flasks, 30-50ml water flush volumes are added
Bottle, appropriate sodium hydroxide solution (1.1.2) is added, and to adjust pH value of solution suitable with standard curve, then is separately added into 0.2ml hydrogen peroxide
(1.1.3), 10ml sulfuric acid solutions (1.1.1), often adding a kind of reagent will fully shake up, then with water constant volume, shake up, place
3-5min, solution in stable light brown, using 1cm cuvettes at 480nm colorimetric, done and joined with the blank solution for sample of not adding an examination of
Than liquid, sample absorbance is measured：0.958.
2.2 calculating
Full content of vanadium (g/L) is calculated by formula (2), in terms of vanadic anhydride：
In formula：A-sample solution absorbance (does reference) with the blank solution for sample of not adding an examination of；
A-absorptivity；
B-intercept；
V-sample stoste volume, unit mL；
1-sample constant volume to be checked (is usually 100mL with standard solution constant volume ratio:100mL=1).
2.3 are computed, and the full content of vanadium of sample is 3.09g/L in the case (in terms of vanadic anhydride).
Embodiment 5
Present embodiment discloses a kind of analysis methods of achievable vanadium solution concentration on-line checking, include the following steps：
1, standard curve making
1.1 reagent
1.1.1 sulfuric acid solution：AR 1+1
1.1.2 sodium hydroxide solution：AR 0.1g/ml
1.1.3 hydrogen peroxide:AR 30%
1.1.4 vanadium standard solution：Simple substance content of vanadium 1000mg/L (standard solution certificate number GSB04-1759-2004)
1.2 instrument
Ultraviolet-uisible spectrophotometer
1.3 row concentration vanadium standard solution are prepared
It is accurate to claim to pipette 0,0.2ml, 0.5ml, 1.0ml, 2.0ml, 5.0ml, 10.0ml, 20.0ml, 30.0ml, 40.0ml
In 100ml volumetric flasks 30-50ml water flush volume bottles are added, then be separately added into 1ml hydroxides in vanadium standard solution (1.1.4)
Sodium solution (1.1.2), 0.2ml hydrogen peroxide (1.1.3), 10ml sulfuric acid solutions (1.1.1), often adding a kind of reagent will fully shake
It is even, then with water constant volume, shake up, place 3-5min, solution is in stable light brown.Volume is the standard solution vanadium concentration of 100mL
With V2O5Content calculation, computational methods are shown in formula (1), the vanadium concentration of prepared serial solution is respectively 0,0.36,0.89,
1.79,3.57,8.93,17.85,35.70,53.55,71.40 (unit is：mg/100mL).
In formula：C-standard solution (1.2.4) vanadium elemental concentration, unit mg/L；
V1When-drafting standard curve, standard solution (1.2.4) volume, unit mL are accurately pipetted；
181.88-vanadic anhydride molecular weight；
101.88-elemental vanadium atomic weight；
1000-milliliters and liter conversion coefficient；
1.3.2 series concentration vanadium standard absorbance value measures
Using the solution of non-mark-on liquid as reference liquid, using 1cm cuvettes at 480nm colorimetric, obtain various concentration standard
The corresponding absorbance value of solution.Using light absorption value as abscissa, with a concentration of ordinate of the vanadium of standard solution, it is bent to draw standard work
Line.Absorbance and V are obtained by linear regression analysis2O5The calculation formula (2) mutually calculated between content
Y=ax+b ... ... ... (2)
In formula:
The vanadium concentration of y-solution to be measured, unit mg/100mL；
X-solution 480nm absorbance values to be measured；
A-linear gradient (a=32.329)；
B-linear intercept (b=-0.0621)；
2, sample detects
2.1 for full content of vanadium in liquid, in the sample of 3g/L or less (in terms of vanadic anhydride), (case predicts full vanadium
Content is in 0.1g/L or so), 25.00ml samples are accurately pipetted, in 100ml volumetric flasks, 30-50ml water flush volumes are added
Bottle, appropriate sodium hydroxide solution (1.1.2) is added, and to adjust pH value of solution suitable with standard curve, then is separately added into 0.2ml hydrogen peroxide
(1.1.3), 10ml sulfuric acid solutions (1.1.1), often adding a kind of reagent will fully shake up, then with water constant volume, shake up, place
3-5min, solution in stable light brown, using 1cm cuvettes at 480nm colorimetric, done and joined with the blank solution for sample of not adding an examination of
Than liquid, sample absorbance is measured：0.063.
2.2 calculating
Full content of vanadium (g/L) is calculated by formula (2), in terms of vanadic anhydride：
In formula：A-sample solution absorbance (does reference) with the blank solution for sample of not adding an examination of；
A-absorptivity；
B-intercept；
V-sample stoste volume, unit mL；
1-sample constant volume to be checked (is usually 100mL with standard solution constant volume ratio:100mL=1).
2.3 are computed, and the full content of vanadium of sample is 0.08g/L in the case (in terms of vanadic anhydride).
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (8)
1. a kind of analysis method of achievable vanadium solution concentration on-line checking, which is characterized in that include the following steps：
Step (1) standard working curve makes：
Measure the vanadium standard solution of N number of different volumes, aqueous slkali be added and adjusts pH to 7-9, sequentially add hydrogenperoxide steam generator and
The addition of sulfuric acid solution, the hydrogen peroxide should be able to meet：Low price vanadium ion present in solution to be detected is all aoxidized
For positive pentavalent vanadium ion, positive pentavalent vanadium ion formed vanadyl with hydrogen peroxide, and solution is in faint yellow；The sulfuric acid solution adds
Enter the light brown that amount can make solution colour in stabilization, vanadium further reacts formation with excessive hydrogen peroxide surely in solution to be detected
Fixed crosses vanadyl key；The vanadium standard solution of N number of different volumes is added into water constant volume；Using ultraviolet-visible spectrophotometry, obtain N number of
Extinction data in vanadium concentration data and the standard spectrum diagram curve of corresponding concentration draw absorbance-concentration curve, i.e. standard work
Make curve, by obtaining linear equation after matched curve：C=aA+b；
In formula:
The vanadium concentration of C-solution to be measured, unit mg/L；
A-solution 480nm absorbance values to be measured；
A-linear gradient；
B-linear intercept；
The on-line checking of full vanadium concentration in step (2) solution to be detected：
(2-1) is pipetted in the solution to container to be detected of certain volume, and suitable quantity of water dilution is added, acid solution or aqueous slkali tune is added
Whole pH value of solution to be detected is to 7-9；
Excess hydrogen peroxide is added in (2-2), and the addition of the hydrogen peroxide should be able to meet：It will be low present in solution to be detected
Valence vanadium ion is all oxidized to positive pentavalent vanadium ion；Positive pentavalent vanadium ion formed vanadyl with hydrogen peroxide；
Sulfuric acid solution is added in (2-3), and the addition of the sulfuric acid solution can make solution colour in stable brown, solution to be detected
Middle vanadium is further reacted with excessive hydrogen peroxide forms stable vanadyl key excessively, adds water constant volume；
The suction of (2-4) to be not added with the solution to be detected that the blank solution of solution to be detected is obtained as reference, determination step (2-3)
Shading value, the characteristic absorption peak wavelength are 400-550nm；
(2-5) calculates full vanadium concentration in sample according to step (1) standard working curve；The full vanadium concentration is multiplied by solution to be detected
Extension rate finally obtains the full vanadium concentration in solution to be detected.
2. vanadium solution concentration on-line detection method according to claim 1, which is characterized in that the N is more than or equal to 5.
3. vanadium solution concentration on-line detection method according to claim 1, which is characterized in that the aqueous slkali is sodium hydroxide
Solution, the acid solution are sulfuric acid solution.
4. vanadium solution concentration on-line detection method according to claim 1, which is characterized in that various in the solution to be detected
The mass concentration ratio upper limit of ion and vanadium is as follows：Cr:V<2, Cu:V<20, Fe:V<20, W:V<20, Mo:V<8.
5. vanadium solution concentration on-line detection method according to claim 1, which is characterized in that after step (2-3), stand 3-
5min forms stable light brown to solution to be detected, then measures its absorbance value.
6. vanadium solution concentration on-line detection method according to claim 1, which is characterized in that the characteristic absorption peak wavelength is
430-510nm。
7. vanadium solution concentration on-line detection method according to claim 1, which is characterized in that full vanadium concentration in vanadium standard solution
Range is 4mg/L~800mg/L.
8. vanadium solution concentration on-line detection method according to claim 1, which is characterized in that the linear equation：C=
32.329A-0.0621。
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