CN104058455A - Vanadium sulfate preparation method - Google Patents
Vanadium sulfate preparation method Download PDFInfo
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- CN104058455A CN104058455A CN201310513341.4A CN201310513341A CN104058455A CN 104058455 A CN104058455 A CN 104058455A CN 201310513341 A CN201310513341 A CN 201310513341A CN 104058455 A CN104058455 A CN 104058455A
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- acetone
- vitriol oil
- vanadylic sulfate
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Abstract
The invention discloses a vanadium sulfate preparation method which comprises redox reaction of vanadyl sulfate and acetone in the presence of concentrated sulfuric acid. The vanadium sulfate preparation method has the characteristics of simple operation and short reaction period, due to the reduction of electric energy consumption and no use of zinc powder, the production cost is reduced. In addition, vanadium sulfate prepared by the method can exist in a solid form, and the cost of transportation is saved.
Description
Technical field
The present invention relates to a kind of preparation method of Vanadosulfuric acid.
Background technology
Vanadosulfuric acid is the important component part of the electrolytic solution of all-vanadium flow battery, and V electrolyte is generally made up of in sulphuric acid soln equimolar Vanadosulfuric acid and vanadylic sulfate.Vanadosulfuric acid consumption in all-vanadium flow battery is large, has great application prospect.
At present, preparing Vanadosulfuric acid has three kinds of methods: first method is electrolysis Vanadium Pentoxide in FLAKES in sulphuric acid soln, first obtains vanadylic sulfate, and continuation electrolysis obtains the mixing solutions of vanadylic sulfate and Vanadosulfuric acid; Second method is to obtain vanadous oxide with Vanadium Pentoxide in FLAKES reduction, will in vanadous oxide vitriolization, obtain Vanadosulfuric acid solution; The third method is the mixture that obtains Low Valent Vanadium with zinc powder reduction Vanadium Pentoxide in FLAKES, after separating, obtains hydroxide two vanadium, and hydroxide two vanadium are oxidized to hydroxide three vanadium in air, will in hydroxide three vanadium vitriolizations, obtain Vanadosulfuric acid solution.First method is to prepare at present the main method of Vanadosulfuric acid, but the method time is long and power consumption is large; The solution impurity that second method obtains is many, is mixing vanadylic sulfate; The third method complicated operation, productive rate is low, and needs a large amount of zinc powders in reaction, has increased reaction cost.
CN102394308A has described the method that obtains Vanadosulfuric acid by the sulphuric acid soln of electrolysis Vanadium Pentoxide in FLAKES, in the method by repeatedly by the solution that contains vanadylic sulfate and Vanadosulfuric acid through diaphragm electrolysis operation, final vanadylic sulfate solution and the Vanadosulfuric acid solution that obtains high density, but the method complicated process of preparation.
CN103199293A has described and has obtained hydroxide three vanadium with zinc powder reduction Vanadium Pentoxide in FLAKES separation of oxygenated, and hydroxide three vanadium after filtration, repeatedly vitriolization obtains the method for Vanadosulfuric acid again after washing, has used a large amount of zinc powders in the method, and production cost is improved.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect of prior art, a kind of preparation method of new Vanadosulfuric acid is provided.
The preparation method who the invention provides a kind of Vanadosulfuric acid, the method comprises: under the vitriol oil exists, vanadylic sulfate and acetone are carried out to redox reaction.
The feature that the present invention has is simple to operate, reaction time is short, because reaction process power consumption is few and without zinc powder, therefore reduced production cost.In addition, Vanadosulfuric acid of the present invention can exist with solid form, has also saved transportation cost.
Embodiment
The preparation method who the invention provides a kind of Vanadosulfuric acid, the method comprises: under the vitriol oil exists, vanadylic sulfate and acetone are carried out to redox reaction.
According to the present invention, in described Vanadosulfuric acid, the valency of v element is 3, and the chemical formula of described Vanadosulfuric acid can be V
2(SO
4)
3; In described vanadylic sulfate, the valency of vanadium is 4, and the chemical formula of described vanadylic sulfate can be VOSO
4xH
2o, that is, described vanadylic sulfate can contain x crystal water, and wherein, x can be the integer of 0-9.In order to reduce production costs, do not affect the effect of reaction simultaneously, preferably, described vanadylic sulfate contains 3 crystal water.Described vanadylic sulfate can make by the method for this area routine, for example, can reduce the Vanadium Pentoxide in FLAKES of vitriol oil activation with glycerine and make, also can be by commercially available.
In the present invention, the described vitriol oil refers to the vitriol oil and the oleum of this area routine, the oleum that the vitriol oil that concentration is 70-99% and concentration are greater than 100%.For in reducing reaction cost, make reaction conditions gentleness, under preferable case, the concentration of the described vitriol oil is 70-98.3 % by weight.
According to method of the present invention, the consumption of described vanadylic sulfate and the vitriol oil can be selected and change in wider scope, for example, the mol ratio of described vanadylic sulfate and the vitriol oil can be 2:1-2, the mol ratio of described vanadylic sulfate and acetone also can change in relative broad range, for example, the mol ratio of described vanadylic sulfate and acetone can be 2:3-35.
According to method of the present invention, under preferable case, the mol ratio of vanadylic sulfate, the vitriol oil and acetone is 2:(1-1.1): (5-10).
According to method of the present invention, for fear of the volatilization of acetone, preferably, described reaction is carried out in encloses container, and described reaction conditions can comprise: temperature is 60-80 DEG C, and pressure is 1.5-2kPa, and the reaction times is 1-3h.In the present invention, pressure refers to absolute pressure.
According to method of the present invention, in order to remove acetone residual in Vanadosulfuric acid and to obtain dry Vanadosulfuric acid solid, under preferable case, described method also comprises the product solvent wash obtaining after reaction dry.
In the present invention, " solvent " refers to the classes of agents that can dissolve each other with acetone but do not react with Vanadosulfuric acid.The present invention has no particular limits described solvent, for example, can be one or more in the conventional solvents such as ethyl acetate, butylacetate, methyl alcohol and ethanol.In order to reduce costs, avoid the volatilization pollution on the environment of a large amount of solvents simultaneously, under preferable case, described solvent is ethanol and ethyl acetate, the mol ratio of ethanol and ethyl acetate can be 1:1-5.
In the present invention, the method that reacted product is washed has no particular limits, as long as can remove acetone residual in product.For example, can first filter for product is placed in to strainer, obtain filter residue, and repetitive operation solvent submergence filter residue, the process that allows solvent naturally flow out.
According to method of the present invention, with number of times >=2 o'clock of solvent wash reaction product, can remove acetone residual in Vanadosulfuric acid.
In the present invention, described dry method is the method for this area routine, for example, can be normal pressure freeze-day with constant temperature method, desiccant dryness method and hypobaric drying method.In order to improve drying rate, and solvent is volatilized completely, under preferable case, described dry employing hypobaric drying method, described dry temperature can be 40-100 DEG C, is preferably 60-80 DEG C.
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
In following examples, vanadylic sulfate, purchased from Pan Gangfan industry company, contains 3 crystal water, and acetone is 0.788g/cm in the density of normal temperature
3.
Embodiment 1
Get the vitriol oil, 200mL (2.71mol) acetone of 217.05g (1mol) vanadylic sulfate, 51.6g (0.5mol) 95% in the airtight pressure vessel of 1.5kPa, be heated to 60 DEG C of isothermal reaction 1h, the ethanol of the cooling rear 1:1 with 400mL and ethyl acetate mixture washing three times, and the solid obtaining after washing oven dry at 60 DEG C, vacuum is obtained to light green solid.Detect and learn by analysis with reference to the method described in the embodiment 1 of CN102879391A, this solid is the Vanadosulfuric acid existing with trivalent vanadium form, and its purity is 99.95%.
Embodiment 2
Get 217.05g (1mol) vanadylic sulfate, 52.5g(0.525mol) 98% the vitriol oil, 250mL (3.40mol) acetone be in the airtight pressure vessel of 1.7kPa, be heated to 70 DEG C of isothermal reaction 2h, the cooling rear ethanol with 450mL1:2 and ethyl acetate mixture washing three times, and the solid obtaining after washing oven dry at 65 DEG C, vacuum is obtained to light green solid.Detect and learn by analysis with reference to the method described in the embodiment 1 of CN102879391A, this solid is the Vanadosulfuric acid existing with trivalent vanadium form, and its purity is 99.95%.
Embodiment 3
Get 217.05g (1mol) vanadylic sulfate, 55g(0.55mol) 98% the vitriol oil, 300mL (4.08mol) acetone be in the airtight pressure vessel of 1.8kPa, be heated to 80 DEG C of isothermal reaction 1h, the cooling rear ethanol with 500mL1:4 and ethyl acetate mixture washing three times, and the solid obtaining after washing oven dry at 70 DEG C, vacuum is obtained to light green solid.Detect and learn by analysis with reference to the method described in the embodiment 1 of CN102879391A, this solid is the Vanadosulfuric acid existing with trivalent vanadium form, and its purity is 99.95%.
Embodiment 4
Get 217.05g (1mol) vanadylic sulfate, 55g(0.55mol) 98% the vitriol oil, 300mL (4.08mol) acetone be in the airtight pressure vessel of 2.0kPa, be heated to 60 DEG C of isothermal reaction 3h, the cooling rear ethanol with 400mL1:5 and ethyl acetate mixture washing three times, and the solid obtaining after washing oven dry at 75 DEG C, vacuum is obtained to light green solid.Detect and learn by analysis with reference to the method described in the embodiment 1 of CN102879391A, this solid is the Vanadosulfuric acid existing with trivalent vanadium form, and its purity is 99.95%.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. a preparation method for Vanadosulfuric acid, the method comprises: under the vitriol oil exists, vanadylic sulfate and acetone are carried out to redox reaction.
2. method according to claim 1, wherein, the mol ratio of vanadylic sulfate, the vitriol oil and acetone is 2:(1-2): (3-35).
3. method according to claim 2, wherein, the mol ratio of vanadylic sulfate, the vitriol oil and acetone is 2:(1-1.1): (5-10).
4. according to the method described in any one in claim 1-3, wherein, the concentration of the described vitriol oil is 70-98.3 % by weight.
5. according to the method described in any one in claim 1-3, wherein, described reaction is carried out in encloses container, and the condition of described reaction comprises: temperature is 60-80 DEG C, and pressure is 1.5-2kPa, and the reaction times is 1-3h.
6. according to the method described in any one in claim 1-3, wherein, described method also comprises: by the product solvent wash obtaining after reaction dry.
7. method according to claim 6, wherein, described solvent is ethanol and ethyl acetate.
8. method according to claim 7, wherein, the mol ratio of ethanol and ethyl acetate is 1:1-5.
9. method according to claim 6, wherein, described dry temperature is 60-80 DEG C.
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| CN201310513341.4A CN104058455A (en) | 2013-10-25 | 2013-10-25 | Vanadium sulfate preparation method |
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| CN201310513341.4A CN104058455A (en) | 2013-10-25 | 2013-10-25 | Vanadium sulfate preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518263A (en) * | 2019-08-22 | 2019-11-29 | 浙江大学 | The direct hydrazine fuel cell of the homogeneous auxiliary catalysis of vanadic sulfate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202463A (en) * | 1997-06-17 | 1998-12-23 | 蔡晨波 | Process for high-yield synthesis of high content vanadylic sulfate |
| JPH1111949A (en) * | 1997-06-17 | 1999-01-19 | Shinko Kagaku Kogyo Kk | Production of vanadium (iii) sulfate and its sulfuric acid aqueous solution |
| CN103043721A (en) * | 2012-12-25 | 2013-04-17 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing vanadyl sulfate |
| CN103199293A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadium sulfate solution for vanadium cell |
-
2013
- 2013-10-25 CN CN201310513341.4A patent/CN104058455A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202463A (en) * | 1997-06-17 | 1998-12-23 | 蔡晨波 | Process for high-yield synthesis of high content vanadylic sulfate |
| JPH1111949A (en) * | 1997-06-17 | 1999-01-19 | Shinko Kagaku Kogyo Kk | Production of vanadium (iii) sulfate and its sulfuric acid aqueous solution |
| CN103043721A (en) * | 2012-12-25 | 2013-04-17 | 攀钢集团攀枝花钢钒有限公司 | Method for preparing vanadyl sulfate |
| CN103199293A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadium sulfate solution for vanadium cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518263A (en) * | 2019-08-22 | 2019-11-29 | 浙江大学 | The direct hydrazine fuel cell of the homogeneous auxiliary catalysis of vanadic sulfate |
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Application publication date: 20140924 |