CN104860352B - A kind of method calcined ammonium vanadate and prepare high-purity vanadium pentoxide - Google Patents
A kind of method calcined ammonium vanadate and prepare high-purity vanadium pentoxide Download PDFInfo
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Abstract
The present invention relates to the preparation field of vanadic anhydride, discloses a kind of method calcined ammonium vanadate and prepare high-purity vanadium pentoxide.The method that calcining ammonium vanadate provided by the invention prepares high-purity vanadium pentoxide can be using ammonium vanadate as raw material, by including ammonium vanadate is crushed into granularity less than 5 μm, then the step of atomization oxygen-enriched air roasting is carried out after being mixed with oxidant, purity is made and is more than 99.9%, the vanadic anhydride of high-purity of the nitrogen content less than 0.001 weight % and low nitrogen content, the method technique that calcining ammonium vanadate provided by the invention prepares high-purity vanadium pentoxide simultaneously is easy to use, it is low for equipment requirements, it is easy to operate, wide adaptation range, cost is low, with good Social benefit and economic benefit.
Description
Technical field
The present invention relates to the preparation field of vanadic anhydride, in particular it relates to which a kind of calcining ammonium vanadate prepares high-purity five
The method of V 2 O.
Background technology
Vanadium is a kind of important metallic element, has many premium properties, is widely used in every field.Generation
The vanadium that 85% is there are about in boundary is applied to steel industry, and remaining 15% is mainly used in aerometal, vanadium cell, chemical industry, oxidation
In the industries such as agent., it is necessary to five oxidations two of high-purity when in applied to industries such as vanadium cell, vananum, catalysis, nuclear energy
Vanadium, wherein higher to requirement of nitrogen, means suitable is less than 0.001 weight %.The rotary kiln dinectly bruning used at present
Ammonium vanadate prepares the technique of vanadic anhydride, and nitrogen content can reach 0.02 weight % in vanadic anhydride.
Publication No. CN101811734A, entitled " a kind of method of producing vanadium pentoxide by microwave calcinations of ammonium metavanadate "
Chinese patent application in, be fitted into after ammonium metavanadate and vanadium pentoxide powder are separately dried in microwave reactor, five oxidation
Two vanadium weight account for the 10-50% of gross weight, microwave frequency 2.45GHz, power 0-80kW, 50-550 DEG C of calcining heat, time 5-
30min, calcination product purity are 98.5 weight %.
Publication No. CN102502829A, entitled " a kind of ammonium metavanadate calcining and decomposing prepares high purity vanadic anhydride
In the Chinese patent application of production technology ", the life that a kind of ammonium metavanadate calcining and decomposing prepares high-purity vanadium pentoxide is disclosed
Production. art, it is that high-purity ammonium metavanadate powder is positioned in rustless steel container, and it is controllable that material container is placed in into low vacuum
In atmosphere reacting furnace, dehydration and deamination processing and calcined oxide processing are carried out, to obtain high-purity vanadium pentoxide.The technique is given birth to
For pentoxide content up to more than 99.5%, tetravalence content of vanadium is less than 0.20% in the high-purity vanadium pentoxide of production.
It can not all cause in above-mentioned technique all without the method for individually abjection nitrogen in the technique of calcining ammonium vanadate at present
Nitrogen content in final products in vanadic anhydride is less than 0.001 weight %.
The content of the invention
In order to solve in the technique of existing calcining ammonium vanadate, the purity of vanadium pentoxide of acquisition is low, and nitrogen content is high, it is impossible to
The defects of fully meeting the application in the industries such as vanadium cell, vananum, catalysis, nuclear energy, the present invention propose a kind of calcining vanadium
The method that sour ammonium prepares high-purity vanadium pentoxide.
The present inventor after research it was unexpectedly observed that ammonium vanadate is crushed into granularity less than 5 μm, then with oxidation
Agent (such as H2O2The aqueous solution) purity of vanadium pentoxide that be prepared after atomization oxygen-enriched air roasting is more than after mixing
99.9%, nitrogen content is less than 0.001 weight %, in the technique for overcoming existing calcining ammonium vanadate, the vanadic anhydride of acquisition
Purity is low, and nitrogen content is high, it is impossible to the defects of fully meeting the application in the industries such as vanadium cell, vananum, catalysis, nuclear energy, from
And complete the present invention.
The invention provides a kind of method calcined ammonium vanadate and prepare high-purity vanadium pentoxide, this method is included vanadic acid
Ammonium is crushed to granularity less than 5 μm, and atomization oxygen-enriched air roasting is carried out after then being mixed with oxidant.
The method that calcining ammonium vanadate provided by the invention prepares high-purity vanadium pentoxide can be made using ammonium vanadate as raw material
Obtain the vanadic anhydride that purity is more than high-purity of the 99.9%, nitrogen content less than 0.001 weight % and low nitrogen content.This hair simultaneously
Method technique that the calcining ammonium vanadate of bright offer prepares high-purity vanadium pentoxide is easy to use, low for equipment requirements, operation side
Just, wide adaptation range, cost are low, have good Social benefit and economic benefit.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of method calcined ammonium vanadate and prepare high-purity vanadium pentoxide, this method is included vanadic acid
Ammonium is crushed to granularity less than 5 μm, and atomization oxygen-enriched air roasting is carried out after then being mixed with oxidant.
In accordance with the present invention it is preferred that the oxidant can contain H2O2。
It is further preferred that the oxidant can be H2O2The aqueous solution.Preferably, the H2O2The aqueous solution body
Fraction is 10-30 volume %, preferably 15-25 volumes %, further preferred 20 volume %.
According to the present invention, the weight ratio of the ammonium vanadate and oxidant can be 1：(0.1-1), preferably 1：(0.2-0.8),
Further preferred 1：(0.4-0.6), still further preferably 1:0.5.Wherein, the weight ratio of the ammonium vanadate and oxidant refers to vanadium
The weight ratio of material of the sour ammonium with playing oxidation in the oxidant used.
According to the present invention, when the oxidant is H2O2The aqueous solution when, the ammonium vanadate and H2O2Weight ratio can be
1：(0.1-1), preferably 1：(0.2-0.8), further preferred 1：(0.4-0.6), still further preferably 1:0.5.
According to the present invention, the operation that the ammonium vanadate mixes with oxidant can be carried out in magnetic stirring apparatus.The vanadium
The condition that sour ammonium mixes with oxidant includes：Time can be 10-60min, preferably 20-50min；Temperature can be 10-80 DEG C,
It is preferred that 20-60 DEG C.
According to the present invention, the ammonium vanadate can be ammonium poly-vanadate and/or ammonium metavanadate.When the ammonium vanadate is more vanadic acid
When ammonium and ammonium metavanadate, the ratio between ammonium poly-vanadate and ammonium metavanadate is not limited, can be mixed with any part by weight
Use.The ammonium poly-vanadate or ammonium metavanadate can be with commercially available.For example, ammonium poly-vanadate can be purchased from Liaoyang perseverance industry chemical industry
The commodity of Co., Ltd, ammonium metavanadate can be the commodity purchased from Liaoyang Heng Ye Chemical Co., Ltd.s.
In accordance with the present invention it is preferred that ammonium vanadate is crushed to granularity less than 4 μm.
According to the present invention, described that ammonium vanadate is crushed into granularity less than 5 μm, preferably smaller than 4 μm of operation is including the use of height
Pressure nitrogen crushes in jet mill crusher to ammonium vanadate particle.The jet mill crusher can with commercially available, such as
Can be the QLMR-400G type airflow millings purchased from Jilin Xindake Electrical and Mechanical Technology Co., Ltd..The high pressure nitrogen
Pressure can be 0.6-1.0MPa, preferably 0.7-0.8Mpa.In the high pressure nitrogen, the content of nitrogen is not less than 99.9 bodies
Product %.The temperature of the crushing is not particularly limited, can be carried out under normal temperature (such as 18-30 DEG C).The time of the crushing
Can be 5-60min, preferably 10-40min.
In accordance with the present invention it is preferred that the ammonium vanadate particle before being crushed using high pressure nitrogen in jet mill crusher
Granularity be less than 0.2mm, further preferred 0.05-0.15mm.
According to the present invention, the operation of the atomization oxygen-enriched air roasting can be：By the ammonium vanadate obtained according to aforementioned operation with
The mixture of oxidant is atomized after being mixed with oxygen-containing gas, is then calcined.In the oxygen-containing gas, the body of oxygen
Fraction is not less than 90 volume %, preferably not less than 99.9 volume %.The condition of the oxygen-enriched air roasting includes：Temperature can be
550-600 DEG C, preferably 560-590 DEG C, time can be 0.2-2h, preferably 0.6-1.4h.
The operation of the atomization can be carried out in atomizer.The atomizer can be with commercially available.For example, the atomization
Device can be the ZS-30Z type industry atomizers purchased from Hangzhou Zheng Dao electric equipments Co., Ltd.
In the present invention：
The purity of vanadic anhydride product refer in the vanadic anhydride product that finally obtains the weight of vanadic anhydride with
The ratio of the gross weight of the product.
Nitrogen content in vanadic anhydride product refer in the vanadic anhydride product that finally obtains the weight of nitrogen with
The ratio of the gross weight of the product.
Below will the present invention will be described in detail by specific embodiment.
In following examples and comparative example：
Ammonium metavanadate is the commodity purchased from Liaoyang Heng Ye Chemical Co., Ltd.s, and its constituent is as shown in table 1：
Ammonium metavanadate composition (the unit of table 1：Weight %)
Ammonium poly-vanadate is the commodity purchased from Liaoyang Heng Ye Chemical Co., Ltd.s, and its constituent is as shown in table 2：
Ammonium poly-vanadate composition (the unit of table 2：Weight %)
The purity of vanadic anhydride product is according to GB/T 6609.10-2004《Aluminum oxide chemical analysis method and physical
Can assay method benzoylphenylhydroxylamine extraction spectrphotometric method for measuring pentoxide content》Measure.
Nitrogen content in vanadic anhydride product is according to GB/T 24583.3-2009《The measure of nitrogen content of vanadium-nitrogen alloy is steamed
Evaporate-neutralization titration》Measure.
Embodiment 1
At a temperature of 25 DEG C, ammonium metavanadate of the 600g particle diameters less than 0.18mm is placed in the feed bin of jet mill crusher,
The pressure of high pressure nitrogen is controlled to collect less than 5 μm of ammonium metavanadate particle in 0.8MPa, impact 20min, then screening.
The ammonium metavanadate particle of 100g acquisitions is weighed, is 10% hydrogen peroxide with volume fraction under room temperature (25 DEG C)
The aqueous solution (the H containing 10g2O2) mixed in magnetic stirring apparatus, incorporation time 10min.Then by above-mentioned ammonium vanadate and dioxygen
The mixture of the aqueous solution of water after the oxygen mix that volume fraction is 99.9% in atomizer with being atomized.After atomization
Material is calcined 2h in combustion furnace at 550 DEG C, obtains high-purity powdery vanadic anhydride product.
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.98%, and nitrogen content is 0.0009 weight %.
Embodiment 2
At a temperature of 15 DEG C, ammonium metavanadate of the 600g particle diameters less than 0.15mm is placed in the feed bin of jet mill crusher,
The pressure of high pressure nitrogen is controlled to collect less than 5 μm of ammonium metavanadate particle in 1.0MPa, impact 10min, then screening.
The ammonium metavanadate particle of 100g acquisitions is weighed, is 30% hydrogen peroxide with volume fraction under room temperature (25 DEG C)
The aqueous solution (the H containing 100g2O2) mixed in magnetic stirring apparatus, incorporation time 10min.Then by above-mentioned ammonium vanadate with it is double
The mixture of the aqueous solution of oxygen water after the oxygen mix that volume fraction is 99.9% in atomizer with being atomized.After being atomized
Material be calcined 0.2h at 600 DEG C in combustion furnace, obtain high-purity powdery vanadic anhydride product.
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.99%, nitrogen content 0.0008%.
Embodiment 3
In addition to following operating parameter, operating method is the same as embodiment 1.
Ammonium metavanadate of the 600g particle diameters used in embodiment 1 less than 0.15mm is changed into 300g particle diameters less than 0.15mm's
The mixture of the ammonium poly-vanadate of metavanadic acid and 300g particle diameters less than 0.20mm.Water by volume fraction for 10% hydrogen peroxide simultaneously
Solution changes the aqueous solution (H containing 20g for the hydrogen peroxide that volume fraction is 15% into2O2)。
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.98%, nitrogen content 0.0008%.
Embodiment 4
In addition to following operating parameter, operating method is the same as embodiment 2.
Ammonium metavanadate of the 600g particle diameters used in embodiment 2 less than 0.15mm is changed into 600g particle diameters less than 0.20mm's
Ammonium poly-vanadate.Change the aqueous solution for the hydrogen peroxide that volume fraction is 30% into the hydrogen peroxide that volume fraction is 25% water-soluble simultaneously
Liquid (the H containing 80g2O2)。
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.99%, nitrogen content 0.0007%.
Embodiment 5
In addition to following operating parameter, operating method is the same as embodiment 2.
Change the aqueous solution for the hydrogen peroxide that the volume fraction used in embodiment 2 is 30% into pair that volume fraction is 20%
The aqueous solution (the H containing 40g of oxygen water2O2)。
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.99%, nitrogen content 0.0007%.
Embodiment 6
In addition to following operating parameter, operating method is the same as embodiment 5.
Use the aqueous solution for the hydrogen peroxide that the volume fraction in embodiment 5 is 30% so that contain in the aqueous solution of hydrogen peroxide
There is 60g H2O2。
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.99%, nitrogen content 0.0006%.
Embodiment 7
In addition to following operating parameter, operating method is the same as embodiment 1.
The material after atomization is calcined into 2h at 550 DEG C in combustion furnace to be changed to be calcined 1.4h at 560 DEG C.
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.99%, nitrogen content 0.0006%.
Embodiment 8
In addition to following operating parameter, operating method is the same as embodiment 2.
The material after atomization is calcined into 0.2h at 600 DEG C in combustion furnace to be changed to be calcined 0.6h at 590 DEG C.
After testing, the purity of the vanadic anhydride product of acquisition reaches 99.99%, nitrogen content 0.0006%.
Comparative example 1
In addition to following operating parameter, operating method is the same as embodiment 1.
The ammonium metavanadate particle of 100g acquisitions is weighed, directly in the presence of volume fraction is 99.9% oxygen, is being burnt
2h is calcined in stove at 550 DEG C, obtains high-purity powdery vanadic anhydride product.
After testing, the purity of the vanadic anhydride product of acquisition is 97.89%, nitrogen content 0.002%.
Comparative example 2
In addition to following operating parameter, operating method is the same as embodiment 2.
The ammonium metavanadate particle of 100g acquisitions is weighed, directly in the presence of volume fraction is 99.9% oxygen, is being burnt
0.2h is calcined in stove at 600 DEG C, obtains high-purity powdery vanadic anhydride product.
After testing, the purity of the vanadic anhydride product of acquisition is 98.25%, nitrogen content 0.003%.
As can be seen here, the method for preparing high-purity vanadium pentoxide using calcining ammonium vanadate provided by the invention can obtain
The vanadic anhydride product of higher purity and lower nitrogen content, meets in the industries such as vanadium cell, vananum, catalysis, nuclear energy
The requirement of purity and nitrogen content to vanadic anhydride product.And documents 1-2 before ammonium vanadate is calcined due to not adopting
The operation mixed with hydrogen peroxide and ammonium vanadate, the purity of the vanadic anhydride product obtained substantially reduces and nitrogen content substantially rises
It is high, it is impossible to meet the application in the industries such as vanadium cell, vananum, catalysis, nuclear energy.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
- A kind of 1. method calcined ammonium vanadate and prepare high-purity vanadium pentoxide, it is characterised in that this method is included ammonium vanadate Granularity is crushed to less than 5 μm, atomization oxygen-enriched air roasting is carried out after then being mixed with oxidant；The oxidant is 10-30 volumes % H2O2The aqueous solution；The condition that the ammonium vanadate mixes with oxidant includes：Time is 10-60min；Temperature is 10-80 DEG C； The condition of the oxygen-enriched air roasting includes：Temperature is 550-600 DEG C；Time is 0.2-2h.
- 2. according to the method for claim 1, wherein, the oxidant is 15-25 volumes % H2O2The aqueous solution.
- 3. according to the method for claim 1, wherein, the weight ratio of the ammonium vanadate and oxidant is 1：(0.1-1).
- 4. according to the method for claim 1, wherein, the weight ratio of the ammonium vanadate and oxidant is 1：(0.2-0.8).
- 5. according to the method for claim 1, wherein, the weight ratio of the ammonium vanadate and oxidant is 1：(0.4-0.6).
- 6. method according to claim 1 or 2, wherein, the ammonium vanadate and H2O2Weight ratio be 1：(0.1-1).
- 7. method according to claim 1 or 2, wherein, the ammonium vanadate and H2O2Weight ratio be 1：(0.2-0.8).
- 8. method according to claim 1 or 2, wherein, the ammonium vanadate and H2O2Weight ratio be 1：(0.4-0.6).
- 9. according to the method for claim 1, wherein, the condition that the ammonium vanadate mixes with oxidant includes：Time is 20- 50min；Temperature is 20-60 DEG C.
- 10. according to the method for claim 1, wherein, the ammonium vanadate is crushed to granularity less than 4 μm.
- 11. according to the method for claim 1, wherein, the broken operation is milled including the use of high pressure nitrogen in air-flow Ammonium vanadate particle is crushed in broken machine.
- 12. according to the method for claim 11, wherein, the pressure of the high pressure nitrogen is 0.6-1.0MPa.
- 13. according to the method for claim 11, wherein, the pressure of the high pressure nitrogen is 0.7-0.8Mpa.
- 14. according to the method described in claim 11,12 or 13, wherein, in the high pressure nitrogen, the content of nitrogen is not less than 99.9 volume %.
- 15. according to the method for claim 1, wherein, the condition of the oxygen-enriched air roasting includes：Temperature is 560-590 DEG C；When Between be 0.6-1.4h.
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| CN108545774A (en) * | 2018-03-30 | 2018-09-18 | 武汉理工大学 | Porous vanadic anhydride micron ball electrode material and its preparation method and application |
| CN108358242B (en) * | 2018-04-17 | 2020-03-31 | 中国科学院过程工程研究所 | Preparation method of vanadium pentoxide with nitrogen element content less than one hundred thousand |
| CN108975400A (en) * | 2018-10-11 | 2018-12-11 | 攀钢集团钒钛资源股份有限公司 | The method that wet-treating ammonium vanadate prepares vanadic anhydride |
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