CN102849795A - Preparation of high-purity vanadium pentoxide - Google Patents
Preparation of high-purity vanadium pentoxide Download PDFInfo
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- CN102849795A CN102849795A CN201110195832XA CN201110195832A CN102849795A CN 102849795 A CN102849795 A CN 102849795A CN 201110195832X A CN201110195832X A CN 201110195832XA CN 201110195832 A CN201110195832 A CN 201110195832A CN 102849795 A CN102849795 A CN 102849795A
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Abstract
A preparation of high-purity vanadium pentoxide comprises the following steps: 1, alkali dissolution: adding crude ammonium metavanadate to deionized water, and adding 98% sodium hydroxide to completely dissolve the ammonium metavanadate; 2, impurity removal: adding a mixed reagent of Al2(SO4)3, MgCl2 and Na2CO3 to remove impurities; 3, primary filtration: filtering through adopting a vacuum filtering machine; 4, oxidation and modification: adding an oxidant NaClO3 to oxidize a small amount of low-valence vanadium into pentavalent vanadium, and adjusting the pH value to 7.5-8.5; 5, heavy metal ion removal: adding a sulfidizing agent to generate insoluble heavy metal ion sulfides; 6, secondary filtration; 7, ammonia precipitation: adding an ammonium salt or ammonia water to precipitate NH4VO3; and 8, dehydration and deamination: adopting centrifuge dehydration to obtain NH4VO3 powder, and calcining the NH4VO3 in a deamination furnace to obtain the high-purity vanadium pentoxide. The purity of the produced vanadium pentoxide can reach above 99.9%, and the quality is stable, so the preparation completely accords with production requirements of high-end products.
Description
Technical field
The present invention relates to a kind of production method of high-purity vanadium pentoxide, belong to the hydrometallurgy category.
Background technology
Vanadium is multivalence attitude element, and its valence state is at V
2+To V
5+Between conversion.
Efficiently, this characteristic that green, emerging energy storage device all-vanadium flow battery utilizes vanadium just, adopt all-vanadium ionic solution as the positive and negative electrode electrolytic solution of vanadium cell, be V at anode
4+/ V
5+, be V in battery cathode
2+/ V
3+Discharge and recharge mutual conversion; The quality of vanadium ion electrolyte property directly affects the performance of vanadium cell.In order to realize its high quality, long lifetime, the working condition that energy efficiency is high, stable, normal operation purity is produced its electrolytic solution at the Vanadium Pentoxide in FLAKES more than 99.9%.
Also be to utilize this characteristic of vanadium as catalyzer in chemosynthesis industry, such as the phthalate anhydride catalyzer, hexanodioic acid catalyzer, maleic anhydride catalyst, hexylene glycol decarburization catalyzer etc., the Vanadium Pentoxide in FLAKES that uses in these catalyzer requires extremely low foreign matter content, and the purity of its Vanadium Pentoxide in FLAKES must be more than 99.5%.
The production of high purity vanadic anhydride, present domestic cleaners such as Tai-Ace S 150, calcium chloride, oxalic acid, sulphosalicylic acid that mostly adopt, the respectively content of silicon, phosphorus, iron in the decline vanadium in different pH values.Its technical process is long, and work consuming is many, and production cost is high, and the Vanadium Pentoxide in FLAKES product purity does not all reach the requirement that some high-end products are used vanadium mostly.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of high-purity vanadium pentoxide, and purpose is to produce the high-purity vanadium pentoxide that can be used in electrolyte of vanadium redox battery and chemical reagent, organic catalyst compound etc.
The objective of the invention is to be achieved through the following technical solutions: a kind of preparation of high-purity vanadium pentoxide is characterized in that: described production method may further comprise the steps:
1. thick ammonium meta-vanadate alkali is molten: thick ammonium meta-vanadate adds in the deionized water, when being heated to 50～60 ℃, adds the sheet alkali more than 98%, continues to be heated to 70～80 ℃, and it is dissolved fully, and the pH value of solution is at 8.5-9.
2. removal of impurities: in solution, add Al
2(SO
4)
3, MgCl
2And Na
2CO
3Mix reagent, stir 30～40min, left standstill 1-2 hour.
3. once filter: the mixing solutions after will leaving standstill pumps into vacuum filter and filters, and impurity is separated, and obtains vanadium solution.
4. oxidation: the solution after removal of impurities is filtered places reactor, adds oxygenant NaClO
3Solution or hydrogen peroxide, add-on are V in the solution
2O
50.2～0.25% of quality heats 50～60 ℃ and also constantly stirs 2-4 after individual hour, gets the pentavalent vanadium solution.
5. modified: adding with analytical pure sulfuric acid and deionized water in gained pentavalent vanadium solution is 7.5-8.5 by the sulphuric acid soln adjusting pH value that 1: 1 volume is made into, and leaves standstill 4～8 hours.
6. heavy-metal ion removal: add vulcanizing agent as cleaner, generate the heavy metal ion sulfide of indissoluble.Meanwhile, the metal ion of low price is (such as Fe
2+) after oxidation, be converted into high volence metal ion (such as Fe
3+), at this moment there is hydrolysis reaction that Fe occurs
2++ 2OH
-→ FeOOH ↓+H
+
7. secondary filtration: adopt vacuum filter that vanadium solution is filtered again, obtain pure vanadium solution.
8. ammonium is heavy: with the saturated solution of ammonium salt or ammoniacal liquor by ammonium ion and vanadium ion 1.2-2: 1 ratio joins in the pure vanadium solution, and stirring 30～40min separates out NH
4VO
3Precipitation.
9. the dehydration, deamination: with the NH that separates out
4VO
3Stir pulp, pump into centrifuge dewatering, obtain NH
4VO
3White powder.And it is sent into the calcination of deamination stove decompose deamination, obtain the orange-yellow Vanadium Pentoxide in FLAKES of high purity.
In 1: 2～3 adding deionized waters, ammonium meta-vanadate is soluble in the basic solution of heat described thick ammonium meta-vanadate take solid-to-liquid ratio, and solubleness is low in cold water, is heated to 50～60 ℃, and its reaction process is:
NH
4VO
3+NaOH→NaVO
3+NH
3↑+H
2O
Heat while stirring, the consumption of sheet alkali is pressed the cubage of ammonium meta-vanadate, dissolves fully to ammonium meta-vanadate, and solution is alkalescence.
Described preparation process water is the deionized water that drinking public water supply obtains by mixed-bed resin absorption.
The service temperature of the filtered liquid of described vacuum filter is 50～60 ℃.
Its service temperature of described reactor is no more than 80 ℃, and pressure is normal pressure, and the mechanical stirring rotating speed is 125～140r/min.
420～500 ℃ of described deamination furnace operating temperature, the time is 6-7 hour.
Contain a certain amount of impurity (comprising: Fe, Pb, Al, Ca, Cu, Mn, Cr, Cd, Si, P, As plasma) in the described thick ammonium meta-vanadate, under alkaline condition, add a certain amount of Al
2(SO
4)
3+ MgSO
4+ Na
2CO
3Mixture, the separation that can solve hetero-ion.The one, generate the alkali formula precipitation of insoluble (such as Fe
3+, Pb
2+, Cu
2+, Cr
3+, Cd
2+Deng); Two have the precipitations such as following carbonate, phosphoric acid salt to occur:
Ca
2++CO
2 2-→CaCO
3↓
Mn
2++CO
3 2-→MnCO
3↓
Mg
2++PO
4 3-→Mg
3(PO
4)
2↓
The 3rd, As, Si etc. are at Al
2(SO
4)
3To become the cotton-shaped network of wrapping up under the flocculation agent effect in precipitation; Stable through leaving standstill, the vanadium solution that obtains certain purity is filtered in clarification.
Described removal of heavy metal ions utilizes atomic absorption analyzer to analyze the solution of oxidation after modified, if still there is certain heavy metal ion M
N+(such as Ni, Zn etc.) then adopt vulcanizing agent [such as (NH
4)
2S] reduce and remove, following precipitin reaction: 2M will occur
N++ nS
2-→ M
2Sn ↓ sulfide precipitation condition is: normal temperature precipitation 50min～60min, [S
2-]=1～1.2 * 10
-2Mol/L.
Described deamination is with NH
4VO
3White powder is inserted in the deamination stove, and the control temperature is at 420～500 ℃, and calcination 6～7 hours obtains orange-yellow high-purity vanadium pentoxide.
Its breakdown is:
The invention has the beneficial effects as follows: the Vanadium Pentoxide in FLAKES purity of 1, producing is high, impurity is few, and more than the purity to 99.9%, steady quality meets the production requirement of some high-end products fully; 2, technical process is short, equipment is simple, cost is low, high efficiency, is fit to the industrial production of mass-producing.
Description of drawings
Fig. 1 is preparation method's of the present invention process flow sheet
Embodiment
Description below by to specific embodiment is described in further detail the specific embodiment of the present invention.
Embodiment 1:
1) thick ammonium meta-vanadate 200kg (is contained V
2O
568%) add in the 500kg deionized water, be heated to 50 ℃, add 48kg sheet alkali (98.5%), the limit edged stirs, and heats gradually to 80 ℃, and approximately the 40min ammonium meta-vanadate dissolves fully.
2) add Al
2(SO
4)
3+ MgSO
4+ Na
2CO
3Mixture 15kg carries out the vanadium solution removal of impurities, stirs 20min, again through natural sedimentation, clarification 2 hours.
3) the removal of impurities mixed solution being pumped into vacuum filter filters.
4) filtered liquid is pumped in the reactor, add in the vanadium solution and use 0.3kg99%NaClO
3The solution of preparation stirs while adding the limit and heats and to 60 ℃ vanadium solution is carried out oxidation, and sampling detects after 4 hours, can't check the Low Valent Vanadium ion.
5) in reactor, add gradually with analytical pure sulfuric acid solution (1+1), stir while adding limit test, PH=8 to the solution.
6) use the atomic absorption instrument analytical solution, the Ni ion of trace is only arranged, do not carry out heavy metal and process, directly vanadium solution is pumped into vacuum filter and filter.
7) in the vanadium solution of secondary filtration, adding by 260kg powder NH
4Cl stirs while adding with the saturated solution of deionized water preparation, mixing speed 130r/min, and continuously stirring 35min staticly settles 1.5 hours, gets the supernatant liquor check, and it contains vanadium concentration is 0.02g/L.
8) take out 2/3 supernatant liquor, start agitator and stir, make it reach more uniform fluid slurry, then pump into centrifuge dewatering with underflow pump, namely get white ammonium meta-vanadate.
9) this ammonium meta-vanadate is sent in the full-automatic stainless steel deamination stove, the control temperature is at 450 ℃, and calcination 6 hours is incubated 5 hours, obtains orange-yellow Vanadium Pentoxide in FLAKES powder, inspection by sampling, V
2O
5Content is 99.91%.
Embodiment 2:
1) thick ammonium meta-vanadate 300kg (is contained V
2O
562%) add in the 900kg deionized water, be heated to 50 ℃, add 65kg sheet alkali (98.5%), stir while adding, and heat gradually to 75 ℃, approximately the 35min ammonium meta-vanadate dissolves fully.
2) add Al
2(SO
4)
3+ MgSO
4+ Na
2CO
3Mixture 25kg carries out the vanadium solution removal of impurities, stirs 30min, again through natural sedimentation, clarification 2 hours.
3) the removal of impurities mixed solution being pumped into vacuum filter filters.
4) filtered liquid is pumped in the reactor, add in the vanadium solution and use 0.45kg99%NaClO
3The solution of preparation stirs while adding the limit and heats and to 60 ℃ vanadium solution is carried out oxidation, and sampling detects after 4 hours, can't check the Low Valent Vanadium ion.
5) in reactor, add gradually with analytical pure sulfuric acid solution (1+1), stir while adding limit test, PH=8 to the solution.
6) after atomic absorption instrument is to liquor analysis, add (NH
4)
2S (98%) 0.67kg carries out removal of heavy metal ions, stirs 10min, leaves standstill 60min.Then mixing solutions being pumped into vacuum filter filters.
7) in the vanadium solution of secondary filtration, adding by 340kg powder NH
4Cl stirs while adding with the saturated solution of deionized water preparation, mixing speed 130r/min, and continuously stirring 40min staticly settles 2 hours, gets the supernatant liquor check, and it contains vanadium concentration is 0.01g/L.
8) take out 2/3 supernatant liquor, start agitator and stir, make it reach more uniform fluid slurry, then pump into centrifuge dewatering with underflow pump, namely get white ammonium meta-vanadate.
9) this ammonium meta-vanadate is sent in the full-automatic stainless steel deamination stove, the control temperature is at 420 ℃, and calcination 7 hours is incubated 6 hours, obtains orange-yellow Vanadium Pentoxide in FLAKES powder, inspection by sampling, V
2O
5Content is 99.93%.
Claims (6)
1. the preparation of a high-purity vanadium pentoxide is characterized in that: described preparation method may further comprise the steps:
1. thick ammonium meta-vanadate alkali is molten: thick ammonium meta-vanadate adds in the deionized water, when being heated to 50～60 ℃, adds the sheet alkali more than 98%, continues to be heated to 70～80 ℃, and it is dissolved fully, and the pH value of solution is at 8.5-9.
2. removal of impurities: in solution, add Al
2(SO
4)
3, MgCl
2And Na
2CO
3Mix reagent, stir 30～40min, left standstill 1-2 hour.
3. once filter: the mixing solutions after will leaving standstill pumps into vacuum filter and filters, and impurity is separated, and obtains vanadium solution.
4. oxidation: the solution after removal of impurities is filtered places reactor, adds oxygenant NaClO
3Solution or hydrogen peroxide, add-on are V in the solution
2O
50.2～0.25% of quality heats 50～60 ℃ and also constantly stirs 2-4 after individual hour, gets the pentavalent vanadium solution.
5. modified: adding with analytical pure sulfuric acid and deionized water in gained pentavalent vanadium solution is 7.5-8.5 by the sulphuric acid soln adjusting pH value that 1: 1 volume is made into, and leaves standstill 4～8 hours.
6. heavy-metal ion removal: in vanadium solution, add vulcanizing agent as the heavy metal ion precipitation agent, generate the heavy metal ion sulfide of indissoluble.
7. secondary filtration: adopt vacuum filter that vanadium solution is filtered again, obtain pure vanadium solution.
8. ammonium is heavy: with the saturated solution of ammonium salt or ammoniacal liquor by ammonium ion and vanadium ion 1.2-2: 1 ratio joins in the pure vanadium solution, and stirring 30～40min separates out NH
4VO
3Precipitation.
9. the dehydration, deamination: with the NH that separates out
4VO
3Stir pulp, pump into centrifuge dewatering, obtain NH
4VO
3Powder, and it is sent into the calcination of deamination stove decompose deamination, high-purity vanadium pentoxide obtained.
2. the according to claim 1 preparation of described a kind of high-purity vanadium pentoxide is characterized in that: the ratio of described thick ammonium meta-vanadate and deionized water is 1: 2～3.
According to claim 1 with the preparation of 2 described a kind of high-purity vanadium pentoxides, it is characterized in that: described preparation process water is the deionized water that drinking public water supply obtains by mixed-bed resin absorption.
4. the according to claim 1 preparation of described a kind of high-purity vanadium pentoxide is characterized in that: the service temperature of the filtered liquid of described vacuum filter is 50～60 ℃.
5. the according to claim 1 preparation of described a kind of high-purity vanadium pentoxide is characterized in that: its service temperature of described reactor is no more than 80 ℃, and pressure is normal pressure, and the mechanical stirring rotating speed is 125～140r/min.
6. the according to claim 1 preparation of described a kind of high-purity vanadium pentoxide is characterized in that: 420～500 ℃ of described deamination furnace operating temperature, the time is 6-7 hour.
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| CN102849795B CN102849795B (en) | 2014-12-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366722A (en) * | 2015-12-02 | 2016-03-02 | 雅安市中甫新能源开发有限公司 | Normal temperature extraction method for producing high-purity vanadium pentoxide |
| WO2018129868A1 (en) | 2017-01-11 | 2018-07-19 | 中国科学院过程工程研究所 | System for extracting vanadium from leaching solution containing vanadium chromium silicon and for preparing vanadium pentoxide and processing method therefor |
| CN111302396A (en) * | 2020-04-20 | 2020-06-19 | 承德燕北冶金材料有限公司 | Preparation method of vanadium pentoxide |
| CN112542603A (en) * | 2021-01-04 | 2021-03-23 | 贵州义信矿业有限公司 | Method for preparing energy storage vanadium electrolyte by using low-purity vanadium pentoxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336177B (en) * | 2018-12-11 | 2020-12-29 | 联和能源投资控股有限公司 | Method for cleanly producing high-purity vanadium pentoxide by using hydrogen peroxide and ammonia water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239740A (en) * | 2008-03-07 | 2008-08-13 | 昆明理工大学 | Method for producing vanadium pentoxide jointly from vanadium-containing stone coal mine and fluorite |
| CN101274777A (en) * | 2007-03-26 | 2008-10-01 | 吉首大学 | A method for extracting vanadium pentoxide from vanadium-containing liquid |
| CN101456587A (en) * | 2008-10-17 | 2009-06-17 | 芜湖人本合金有限责任公司 | Production method of high-purity vanadium pentoxide |
-
2011
- 2011-07-02 CN CN201110195832.XA patent/CN102849795B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274777A (en) * | 2007-03-26 | 2008-10-01 | 吉首大学 | A method for extracting vanadium pentoxide from vanadium-containing liquid |
| CN101239740A (en) * | 2008-03-07 | 2008-08-13 | 昆明理工大学 | Method for producing vanadium pentoxide jointly from vanadium-containing stone coal mine and fluorite |
| CN101456587A (en) * | 2008-10-17 | 2009-06-17 | 芜湖人本合金有限责任公司 | Production method of high-purity vanadium pentoxide |
Non-Patent Citations (3)
| Title |
|---|
| 朱文祥: "《无机化合物制备手册》", 30 September 2006, 化学工业出版社 * |
| 舒万艮: "《有色金属精细化工产品生产与应用》", 31 December 1995, 中南工业大学出版社 * |
| 陈津等: "《冶金环境工程》", 30 April 2009, 中南大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105366722A (en) * | 2015-12-02 | 2016-03-02 | 雅安市中甫新能源开发有限公司 | Normal temperature extraction method for producing high-purity vanadium pentoxide |
| WO2017092217A1 (en) * | 2015-12-02 | 2017-06-08 | 四川行之智汇知识产权运营有限公司 | Method for producing high-purity vanadium pentoxide by room temperature extraction |
| WO2018129868A1 (en) | 2017-01-11 | 2018-07-19 | 中国科学院过程工程研究所 | System for extracting vanadium from leaching solution containing vanadium chromium silicon and for preparing vanadium pentoxide and processing method therefor |
| CN111302396A (en) * | 2020-04-20 | 2020-06-19 | 承德燕北冶金材料有限公司 | Preparation method of vanadium pentoxide |
| CN112542603A (en) * | 2021-01-04 | 2021-03-23 | 贵州义信矿业有限公司 | Method for preparing energy storage vanadium electrolyte by using low-purity vanadium pentoxide |
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