CN103868910A - Method for detecting ingredients of vanadyl sulfate product - Google Patents

Method for detecting ingredients of vanadyl sulfate product Download PDF

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CN103868910A
CN103868910A CN201410085741.4A CN201410085741A CN103868910A CN 103868910 A CN103868910 A CN 103868910A CN 201410085741 A CN201410085741 A CN 201410085741A CN 103868910 A CN103868910 A CN 103868910A
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content
sulfate
vanadic sulfate
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vanadic
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成勇
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Abstract

The invention provides a method for detecting the ingredients of a vanadyl sulfate product. The method comprises the following steps: completely dissolving weighed vanadyl sulfate samples by water under a heating condition, and diluting and making up to volume to obtain a to-be-tested solution; simultaneously determining the content of a vanadium element and the content of a sulfur element in the to-be-tested solution by using inductively coupled plasma atomic emission spectrometry; and calculating the content of a vanadyl sulfate compound and the content of total sulfate radicals in the vanadyl sulfate samples, so as to obtain the content of free sulfate radicals in the vanadyl sulfate samples by a subtraction method. By adopting the method, the content of the ingredients such as all vanadium, vanadyl sulfate, sulfate radicals and free sulfate radicals in the vanadyl sulfate can be simultaneously measured one time, and the method is efficient, fast and accurate.

Description

A kind of method that detects vanadic sulfate product composition
Technical field
The invention belongs to vanadic sulfate product and detect analysis technical field, specifically, the present invention relates to a kind of method that can simultaneously measure full vanadium in vanadic sulfate sample, vanadic sulfate, total sulfate radical, free sulfuric acid radical content.
Background technology
In general, vanadic sulfate is main mordant, catalyzer, reductive agent as yarn fabric in the past, or as pottery, the colorant of glass, and vanadic sulfate also can be used for treating the illness such as diabetes, hyperlipemia in medical procedures.At present, along with the fast development of new energy technology in world wide and application thereof, all-vanadium flow battery (vanadium electricity liquid) using vanadic sulfate as electrolytic solution, due to can degree of depth high current density discharge, have that power is large, capacity is large, efficiency is high, the life-span is long, can momentary charge, safe, low cost and other advantages.Vanadium cell application is very wide, there is boundless application prospect in wind-power electricity generation, photovoltaic generation, peak load regulation network, electric automobile etc. field, can be used as the standby power supply at mansion, airport, programme-controlled exchange station etc., or as the supporting energy storage device of the clean electric power generation such as wind-force, sun power system, and provide electric power and for fields such as peak load regulation networks for submarine, ocean-going vessel.Therefore, the development of vanadic sulfate and application receive much attention.
In the prior art, main traditional chemical analysis method potentiometric titration or the content of oxidation-reduction method titration measuring vanadium, barium sulphate gravimetric determination sulfate radical and determination of acid-basetitration free sulfuric acid of adopting, the major defect of its existence is determination method corresponding to each material, trivial operations step is many, sense cycle is long, and labour intensity is large, and manpower consumption is many, especially gravimetric method is because ageing reaction etc. is consuming time longer, and whole testing process conventionally need to approximately 24 hours.
Summary of the invention
The object of the invention is to solve at least one in prior art above shortcomings.
For example, the object of the present invention is to provide a kind of method that can disposablely simultaneously measure in vanadic sulfate the component contents such as full vanadium, vanadic sulfate, sulfate radical and free sulphur acid group.
The invention provides a kind of method that detects vanadic sulfate product composition, said method comprising the steps of: water will take vanadic sulfate sample dissolution to completely under heating condition, after water dilution constant volume, form solution to be measured; Directly adopt ICP-AES to measure v element in solution to be measured and the content of element sulphur simultaneously; According to the v element content recording, calculate the content of vanadic sulfate compound in vanadic sulfate sample by the molecular formula of vanadic sulfate, according to the element sulphur content recording, calculate the content of total sulfate radical in vanadic sulfate sample by sulfate radical molecular formula; According to the vanadic sulfate compounds content calculating, by the molecular formula of vanadic sulfate, calculate the content of existing sulfate radical in vanadic sulfate compound molecule, pass through minusing, from total sulfate radical content, deduct existing sulfate radical content in vanadic sulfate compound molecule, obtain the content of vanadic sulfate sample Free Sulfuric Acid root.
In one exemplary embodiment of the present invention, the step of described formation solution to be measured comprises: take 0.5～1.0g vanadic sulfate sample, add 15～20mL water heating to boil to sample and dissolve completely, dilute to volume in 100～200mL volumetric flask after cooling with water.
In one exemplary embodiment of the present invention, in the described step of simultaneously measuring v element in solution to be measured and element sulphur content, the detected parameters of ICP-AES is set to: RF power 1250W, assisted gas flow velocity 1.0L/min, peristaltic pump pump speed 70r/min, height of observation 11.4mm, atomizer pressure 0.25MPa, measure 10～20s integral time, and select element analysis spectrum line to be: V240.488nm, S182.034nm.
Compared with prior art, beneficial effect of the present invention comprises: can disposablely measure in vanadic sulfate the component contents such as full vanadium, vanadic sulfate, sulfate radical and free sulphur acid group simultaneously; There is efficient quick, simple to operate, manpower consumption is little, the short step of flow process is few, be no more than 15min proving time, performance index are good.
Embodiment
Hereinafter, describe the present invention in detail and detect the method for vanadic sulfate product composition in connection with exemplary embodiment.
In one exemplary embodiment of the present invention, the method that detects vanadic sulfate product composition can be measured the content of full vanadium, vanadic sulfate, sulfate radical and free sulphur acid group in vanadic sulfate sample simultaneously.Specifically, the method for detection vanadic sulfate product composition comprises the following steps:
A) take vanadic sulfate sample, directly complete with water heating for dissolving, and it is to be measured to dilute using water the vanadic sulfate sample solution of preparing as pre-service after constant volume;
B) directly adopt inductively coupled plasma atomic emission spectrum (ICP-OES) to measure vanadium in prepared vanadic sulfate sample solution and the content of element sulphur simultaneously;
The content of the v element (V) c) obtaining according to mensuration, and by the compound molecule formula (VOSO of vanadic sulfate 4), calculate the concentration content of contained vanadic sulfate compound in vanadic sulfate sample;
The content of the element sulphur (S) d) obtaining according to mensuration, and by sulfate radical molecular formula (SO 4 2-), calculate in vanadic sulfate sample the concentration content of total sulfate radical;
E) according to the concentration content that calculates vanadic sulfate compound in the sample that obtains, with and the molecular formula (VOSO of compound 4), calculate the content of existing sulfate radical in vanadic sulfate compound molecule;
F) by minusing, from total sulfate radical content, deduct existing sulfate radical content in vanadic sulfate compound molecule, thereby calculate the concentration content of vanadic sulfate sample Free Sulfuric Acid root;
Preferably, take 0.5～1.0g vanadic sulfate sample, add 15～20mL water heating to boil to sample and dissolve completely, dilute to volume in 100～200mL volumetric flask with water after cooling.Then adopt ICP-AES (ICP-OES) directly to measure v element in vanadic sulfate sample solution prepared by pre-service and the concentration content of element sulphur.Wherein, ICP-OES detected parameters being set is: RF power 1250W, assisted gas flow velocity 1.0L/min, peristaltic pump pump speed 70r/min, height of observation 11.4mm, atomizer pressure 0.25MPa, mensuration 10～20s integral time.Select element analysis spectrum line: V240.488nm, S182.034nm.Then, directly measure the v element that obtains and the concentration content of element sulphur according to ICP-OES, and in conjunction with the compound molecule formula of vanadic sulfate and sulfate radical, indirect calculation goes out the concentration content of vanadic sulfate, total sulfate radical and free sulphur acid group respectively.
In this exemplary embodiment, the v element content that ICP-OES directly measures is the full content of vanadium in vanadic sulfate sample; According to v element content (W v) and the molecular formula (VOSO of vanadic sulfate compound 4), indirect calculation obtains the concentration content of vanadic sulfate compound in vanadic sulfate sample
Figure BDA0000475029920000031
also be
Figure BDA0000475029920000032
according to the concentration content of the vanadic sulfate compound calculating
Figure BDA0000475029920000033
and molecular formula (VOSO 4) calculate the content of existing sulfate radical in vanadic sulfate compound
Figure BDA0000475029920000034
also be
Figure BDA0000475029920000035
according to element sulphur content (W s) and the molecular formula (SO4) of sulfate radical compound, indirect calculation goes out the concentration content of existing total sulfate radical in vanadic sulfate sample
Figure BDA0000475029920000036
also be
Figure BDA0000475029920000037
adopt minusing to calculate the concentration content of free sulphur acid group
Figure BDA0000475029920000038
the concentration content of total sulfate radical
Figure BDA0000475029920000039
deduct the concentration content of existing sulfate radical in vanadic sulfate compound molecule
Figure BDA00004750299200000310
calculate the concentration content of free sulphur acid group
Figure BDA00004750299200000311
also,
Figure BDA00004750299200000312
Generally speaking, the present invention can disposablely obtain the content of the chemical compositions such as vanadic sulfate in vanadic sulfate sample, total sulfur root, free sulphur acid group simultaneously, and method is simple, quick, cost is low.
Below in conjunction with concrete example, the specific embodiment of the present invention is further described.
Take 0.5～1.0g vanadic sulfate sample, add 15～20mL water heating to boil to sample and dissolve completely, dilute to volume in 100～200mL volumetric flask with water after cooling.Then adopt ICP-AES (ICP-OES) directly to measure v element in vanadic sulfate sample solution prepared by pre-service and the concentration content of element sulphur.Wherein, ICP-OES detected parameters being set is: RF power 1250W, assisted gas flow velocity 1.0L/min, peristaltic pump pump speed 70r/min, height of observation 11.4mm, atomizer pressure 0.25MPa, mensuration 10～20s integral time.Select element analysis spectrum line: V240.488nm, S182.034nm.
Result is calculated: the ICP-OES measurement result of v element is exactly the content of full vanadium in vanadic sulfate sample; Measure the vanadium obtaining, the content of element sulphur according to above-mentioned ICP-OES, and calculate respectively the content of vanadic sulfate, total sulfate radical, free sulphur acid group by following computing formula (1)～(4).
W VOSO 4 = W V × VOSO 4 V = W V × 163 51 = W V × 3.1961 - - - ( 1 )
Figure BDA0000475029920000042
In formula:
W v---the content of the v element that ICP-OES records, %;
W s---the content of the element sulphur that ICP-OES records, %;
Figure BDA0000475029920000045
---the content of vanadic sulfate in vanadic sulfate sample, %;
Figure BDA0000475029920000046
---the content of sulfate radical in vanadic sulfate compound molecule, %;
Figure BDA0000475029920000047
---the content of total sulfate radical in vanadic sulfate sample, %;
Figure BDA0000475029920000048
---the content of vanadic sulfate sample Free Sulfuric Acid root, %;
example 1
In example of the present invention, ICP-OES is the U.S. match iCAP6300 of Mo Feishier company type inductively coupled plasma atomic emission spectrometer.
Take 0.5g vanadic sulfate sample, add 15mL water heating to boil to sample and dissolve completely, dilute to volume in 100mL volumetric flask with water after cooling.Then adopt ICP-AES (ICP-OES) directly to measure v element in vanadic sulfate sample solution prepared by pre-service and the concentration content of element sulphur.Wherein, ICP-OES detected parameters being set is: RF power 1250W, assisted gas flow velocity 1.0L/min, peristaltic pump pump speed 70r/min, height of observation 11.4mm, atomizer pressure 0.25MPa, mensuration 10～20s integral time.Select element analysis spectrum line: V240.488nm, S182.034nm.
According to the result of the vanadium of direct mensuration, element sulphur, then calculate the concentration content of vanadic sulfate, total sulfate radical and free sulphur acid group according to above-mentioned formula (1)～(4).
example 2
Except following difference, all the other all adopt the method identical with example 1 to measure the vanadic sulfate sample of example 2: vanadic sulfate sample takes 1.0g, add 20mL water heating to boil to sample and dissolve completely, dilute to volume in 200mL volumetric flask after cooling with water.
example 3
Except following difference, all the other all adopt the method identical with example 1 to measure the vanadic sulfate sample of example 2: vanadic sulfate sample takes 1.0g, add 20mL water heating to boil to sample and dissolve completely, dilute to volume in 100mL volumetric flask after cooling with water.
example 4
Except following difference, all the other all adopt the method identical with example 1 to measure the vanadic sulfate sample of example 2: vanadic sulfate sample takes 0.5g, add 15mL water heating to boil to sample and dissolve completely, dilute to volume in 100mL volumetric flask after cooling with water.
example 5
Except following difference, all the other all adopt the method identical with example 1 to measure the vanadic sulfate sample of example 2: vanadic sulfate sample takes 0.8g, add 18mL water heating to boil to sample and dissolve completely, dilute to volume in 200mL volumetric flask after cooling with water.
example 6
Except following difference, all the other all adopt the method identical with example 1 to measure the vanadic sulfate sample of example 2: vanadic sulfate sample takes 0.6g, add 15mL water heating to boil to sample and dissolve completely, dilute to volume in 100mL volumetric flask after cooling with water.
example 7
Except following difference, all the other all adopt the method identical with example 1 to measure the vanadic sulfate sample of example 2: vanadic sulfate sample takes 0.7g, add 16mL water heating to boil to sample and dissolve completely, dilute to volume in 200mL volumetric flask after cooling with water.
example 8
Except following difference, all the other all adopt the method identical with example 1 to measure the vanadic sulfate sample of example 2: vanadic sulfate sample takes 0.9g, add 20mL water heating to boil to sample and dissolve completely, dilute to volume in 100mL volumetric flask after cooling with water.
precision test situation
To example 1, example 3, example 5 and example 7, amount to four vanadic sulfate samples and carry out respectively independently clearing up for 8 times preparation detection sample solution, determination of elemental analysis and result calculating, 8 measurement results are carried out to statistical treatment, assess precision of the present invention according to relative standard deviation (RSD%).Measurement result is in table 1.
Table 1 analytical approach precision (n=8) %
Figure BDA0000475029920000061
From table 1, RSD(relative standard deviation) be not more than 1.0%, show that invention has good precision, the preparation of sample solution and Instrument measuring reappearance are good.
result control test situation
This example is respectively to example 2, example 4 and example 8, and the content of the full vanadium in three vanadic sulfate samples, total sulfate radical is tested altogether.Then adopt the redox titration analytical approach of traditional classical (, chemical method in table 2) measure, also in mixture of sulfuric phosphoric acid medium with ammonium persulfate by V(III) or V(IV) be all oxidized to V(V), taking N-benzene for ortho-aminobenzoic acid as indicator, with iron ammonium sulfate standard solution titration V(V), calculate the content of v element in sample according to the concentration of ferrous titrimetric standard solution and consumption thereof; And the concentration content of the total sulfate ion of employing barium sulphate gravimetric determination.Two kinds of method measurement results contrast with the measurement result of this method ICP-OES and contrast in table 2.
Table 2 standard model testing result control test (%)
Figure BDA0000475029920000062
Table 2 is visible, and the result that this method is measured full vanadium, total sulfate radical in vanadic sulfate sample is consistent with the contrast of traditional classical chemical analysis method, shows that the present invention has high accuracy and reliability.
In sum, method of the present invention, with water-soluble solution vanadic sulfate sample, adopts ICP-AES directly to measure contained vanadium, element sulphur in vanadic sulfate simultaneously, thereby directly obtains the content of full vanadium in vanadic sulfate sample; Then, by the concentration of total sulfate radical in the molecular formula indirect calculation sulfuric acid oxidation of element sulphur content and sulfate radical compound; Calculate the concentration content of vanadic sulfate by the content of v element and the molecular formula of vanadic sulfate compound, and then by the proportionate relationship of sulfate radical in vanadic sulfate compound molecule formula, calculate the concentration content of the sulfate radical existing in vanadic sulfate compound, the content that finally deducts sulfate radical in compound with the content of total sulfate radical, final indirect calculation obtains the concentration content of free sulfuric acid; Whole measurement and calculation completes automatically by ICP-OES detecting instrument is disposable, can directly or indirectly measure the content that has obtained full vanadium, sulfate radical and free sulfuric acid in vanadic sulfate sample simultaneously, analytical approach has efficient quick, simple to operate, manpower consumption is little, and the short step of flow process is few, is no more than 15min proving time, performance index are good, completely meet vanadic sulfate product quality is quick and precisely checked and the requirement of controlling.
Although described the present invention in conjunction with exemplary embodiment above, those of ordinary skill in the art should be clear, in the case of not departing from the spirit and scope of claim, can carry out various amendments to above-described embodiment.

Claims (3)

1. a method that detects vanadic sulfate product composition, is characterized in that, said method comprising the steps of:
Under heating condition, water will take vanadic sulfate sample dissolution to completely, after water dilution constant volume, form solution to be measured;
Directly adopt ICP-AES to measure v element in solution to be measured and the content of element sulphur simultaneously;
According to the v element content recording, calculate the content of vanadic sulfate compound in vanadic sulfate sample by the molecular formula of vanadic sulfate, according to the element sulphur content recording, calculate the content of total sulfate radical in vanadic sulfate sample by sulfate radical molecular formula;
According to the vanadic sulfate compounds content calculating, by the molecular formula of vanadic sulfate, calculate the content of existing sulfate radical in vanadic sulfate compound molecule, pass through minusing, from total sulfate radical content, deduct existing sulfate radical content in vanadic sulfate compound molecule, obtain the content of vanadic sulfate sample Free Sulfuric Acid root.
2. the method for detection vanadic sulfate product composition according to claim 1, it is characterized in that, the step of described formation solution to be measured comprises: take 0.5～1.0g vanadic sulfate sample, add 15～20mL water heating to boil to sample and dissolve completely, dilute to volume in 100～200mL volumetric flask with water after cooling.
3. the method for detection vanadic sulfate product composition according to claim 1, it is characterized in that, in the described step of simultaneously measuring v element in solution to be measured and element sulphur content, the detected parameters of ICP-AES is set to: RF power 1250W, assisted gas flow velocity 1.0L/min, peristaltic pump pump speed 70r/min, height of observation 11.4mm, atomizer pressure 0.25MPa, measure 10～20s integral time, and select element analysis spectrum line to be: V240.488nm, S182.034nm.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104655610A (en) * 2015-01-28 2015-05-27 攀钢集团研究院有限公司 Analysis method and determination method of oxalate ion content in vanadyl oxalate
CN105043829A (en) * 2015-06-03 2015-11-11 马钢(集团)控股有限公司 Preparation method of sample used for metallic calcium chemical analysis
CN108037114A (en) * 2018-02-07 2018-05-15 四川星明能源环保科技有限公司 A kind of detection method of the component of the method for detecting impurities of vanadic sulfate and the hydrate of vanadium containing tetravalence
CN111458257A (en) * 2020-04-03 2020-07-28 青岛天祥食品集团有限公司 Method for detecting content of filter aid and phospholipid in pressed peanut oil filter residue

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104655610A (en) * 2015-01-28 2015-05-27 攀钢集团研究院有限公司 Analysis method and determination method of oxalate ion content in vanadyl oxalate
CN104655610B (en) * 2015-01-28 2018-05-01 攀钢集团研究院有限公司 The analysis method and assay method of vanadyl oxalate oxalate ion concentration
CN105043829A (en) * 2015-06-03 2015-11-11 马钢(集团)控股有限公司 Preparation method of sample used for metallic calcium chemical analysis
CN108037114A (en) * 2018-02-07 2018-05-15 四川星明能源环保科技有限公司 A kind of detection method of the component of the method for detecting impurities of vanadic sulfate and the hydrate of vanadium containing tetravalence
CN111458257A (en) * 2020-04-03 2020-07-28 青岛天祥食品集团有限公司 Method for detecting content of filter aid and phospholipid in pressed peanut oil filter residue

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Application publication date: 20140618