CN105366722B - The method of normal temperature extraction production high purity vanadic anhydride - Google Patents
The method of normal temperature extraction production high purity vanadic anhydride Download PDFInfo
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- CN105366722B CN105366722B CN201510871635.3A CN201510871635A CN105366722B CN 105366722 B CN105366722 B CN 105366722B CN 201510871635 A CN201510871635 A CN 201510871635A CN 105366722 B CN105366722 B CN 105366722B
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000605 extraction Methods 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 238000001704 evaporation Methods 0.000 claims abstract description 30
- 230000008020 evaporation Effects 0.000 claims abstract description 27
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 230000001376 precipitating effect Effects 0.000 claims abstract description 23
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000012459 cleaning agent Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000011109 contamination Methods 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 20
- 239000012498 ultrapure water Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000284 extract Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 NH4NO3 Chemical compound 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Disclosed by the invention is the method for normal temperature extraction production high purity vanadic anhydride.The present invention solve preparation method in the prior art intermediate raw material unit consumption increase, technological process it is tediously long, and product quality it is not high the problem of.The present invention includes：（1）Industrial ammonium metavanadate or/and industrial vanadic anhydride are slowly added in extractant, selective dissolving ammonium metavanadate or/and vanadic anhydride form and contain vanadium solution；Precipitating reagent is added in containing vanadium solution makes contamination precipitation；（2）Filtrate is obtained after filter operation；（3）Filtrate heating evaporation, the pH of liquid is adjusted to 16, then obtain solid-liquid mixed liquor by crystallisation by cooling after evaporation；（4）Solid-liquid mixed liquor is subjected to separation of solid and liquid, solid cleans filtering with cleaning agent；（5）Solid after filtering is toasted 2 12 hours at a temperature of 400 600 DEG C, and finished product is made after then cooling down.The present invention has the advantages that technique is simple, cost is low, quality good.
Description
Technical field
The present invention relates to the preparation method of high purity vanadic anhydride, and in particular to be high-purity five oxidation of normal temperature extraction production
The method of two vanadium.
Background technology
In the technique that vanadic anhydride is extracted from navajoite stone, five in desorbed solution obtained by after roasting ion exchange
Contain Fe in V 2 O product+2、Pb+4、Cu+2、Cr+3、Cd+2、S1-2、As-2、K+1、Na+1Etc. plurality of impurities, ability need to be purified
Obtain the vanadic anhydride product of high-purity.High purity vanadic anhydride is widely used in the fields such as Aero-Space, vanadium cell, has
Wide market prospects.
The method of purification of high purity vanadic anhydride is carried out under neutral or weak basic condition mostly in the prior art, at this
Preparation process under part is too tediously long, although by crystallizing twice, its purity only only reaches 99.0%.This method is in normal temperature
Under the conditions of can effectively obtain high purity vanadic anhydride, its purity can reach more than 99.9%, very high purity, and use normal temperature
The method of acid extract crystallization, its operation is easier, and the additional substance consumed in technical process is less, and cost is cheaper.
Publication number CN 101456587A patent provides " a kind of production method of high purity vanadic anhydride ", its feature
It is to use NaOH, Na2CO3As precipitating reagent, make substantial amounts of cation generation precipitation, then use KClO3As oxidant, at 90 DEG C
The Low Valent Vanadium in solution is oxidized to vanadic anhydride at a temperature of left and right, finally with dilute sulfuric acid adjust solution pH value, after filtering
Calcining obtains the higher vanadic anhydride product of purity under oxidation environment.This method rotation calcining link is high to equipment requirement,
Investment is big, and heating oxidation operation energy consumption is higher, and the cation for adding precipitating reagent and oxidant is difficult to remove in the later stage, refining effect
Typically, product quality is difficult to control to.
The content of the invention
Increase it is an object of the invention to the intermediate raw material unit consumption for overcoming preparation method in the prior art, technological process it is superfluous
It is long, and product quality it is not high the problem of；A kind of side of the normal temperature extraction production high purity vanadic anhydride solved the above problems is provided
Method.
To reach above-mentioned purpose, technical scheme is as follows：
The method of normal temperature extraction production high purity vanadic anhydride, including：
（1）Industrial ammonium metavanadate or/and industrial vanadic anhydride are slowly added in extractant under agitation, choosing
The dissolving ammonium metavanadate or/and vanadic anhydride of selecting property, form and contain vanadium solution；Precipitating reagent is added in containing vanadium solution makes impurity sink
Form sediment；
（2）Filtrate is obtained after filter operation；
（3）Filtrate heating evaporation, the pH of liquid is adjusted to 1-6, then obtain solid-liquid by crystallisation by cooling and mix after evaporation
Close liquid；
（4）Solid-liquid mixed liquor is subjected to separation of solid and liquid, solid cleans filtering with cleaning agent；
（5）Solid after filtering is toasted at a temperature of 400-600 DEG C, and finished product is then made after cooling.Filtering
The baking time at a temperature of 400-600 DEG C of solid afterwards is 2-12 hours.
The high purity vanadic anhydride produced by the present invention, its production cost only only has 6000-8000 yuan/ton, into
This is cheap, and effect is notable.
The extractant is made up of one or more formulas in A1- A5；
A1:By mass percent concentration be 0.5-3.0% Peracetic acid, 1.0-6.0% ammonia, 91.0-98.5% high purity water
Composition；
A2:It is 0.6-6.0% hydrogen peroxide, 1.0-9.0% ammonia, 85.0-98.4% high purity water groups by mass percent concentration
Into；
A3:It is that 0.2-6.0% ethamine and 94.0-99.8% high purity water are constituted by mass percent concentration；
A4:It is that 0.2-8.0% methylamine and 92.0-99.8% high purity water are constituted by mass percent concentration；
A5:It is that 0.2-5.0% ethylenediamine and 95.0-99.8% high purity water are constituted by mass percent concentration.
The precipitating reagent is by Na2CO3、(NH4)2CO3(NH4)2One or more compositions in S；Described every liter molten containing vanadium
Na in liquid2CO3(NH4)2CO3Addition be 0.2-6.0g, (NH4)2S addition is 0.6-6.0g.
After extract is extracted, most foreign metal ion is can remove, can be by then after the processing for passing through precipitating reagent
Remaining micro metal ion becomes Precipitation.Key reaction is as follows:
Fe+2+S-2=FeS↓Cu+2+S-2=CuS↓
Pb+2+S-2=PbS↓Cr+2+S-2=CrS↓
Cd+2+S-2=CdS↓Ca+2+CO3-2=CaCO3↓。
The cleaning agent is made up of the one or more in Na2CO3, NH4NO3, acetone and ethanol；Wherein, Na2CO3Concentration
For 10g-80g/L, NH4NO3Concentration is that 10-70g/L, acetone concentration are 10g-80g/L, and concentration of alcohol is 40g-120g/L.
The step（1）Detailed process it is as follows：
Industrial ammonium metavanadate or/and industrial vanadic anhydride are slowly added in extractant under agitation, selection
Property dissolving ammonium metavanadate or/and vanadic anhydride, formed contain vanadium solution；Precipitating reagent stirring 10-30 is added in containing vanadium solution
Minute, then vacuum filter is carried out after standing 30-60 minute realize separation of solid and liquid, the screen pack of vacuum filter is 800-5000
Mesh.
In order to preferably cost-effective, the additive loss added is reduced, and effectively reduce the waste liquid of discharge, the step
（3）It is middle when the filtrate of vacuum filter is evaporated, turn into ammoniacal liquor after the gas condensation of filtrate evaporation, then recycling is circulated
Use.
In order to be able to preferably separate out ammonium metavanadate and vanadic anhydride in filtrate, the step（3）The steaming of middle filtrate
Hair amount is the 10-40% of filtrate cumulative volume, and its pH value is adjusted to 1-5 by acid after evaporation, then again by crystallisation by cooling, until
Untill crystalline solid is separated out completely, solid-liquid mixed liquor is obtained.
As a preferred embodiment, the acid of the regulation pH value is the nitric acid that mass percent concentration is 10-70%.
In order to preferably improve the purity of product, the step（4）Detailed process it is as follows：By vacuum filter by solid-liquid
Mixed liquor carries out separation of solid and liquid, cleans solid 3-8 times with cleaning agent, vacuum filter, vacuum filter are carried out during cleaning
Screen pack be 800-5000 mesh.
Further, the step（5）Middle finished product is packed after levigate.
The present invention compared with prior art, with advantages below and beneficial effect：
1st, the present invention has that technique is simple, the low feature of cost, and the cost of finished product per ton is in 6000-8000 members in the present invention
Left and right；Simultaneously using the method for the present invention, part extract also can be recycled；
2nd, good product quality of the invention, the purity of finished product of the present invention can reach more than 99.9%, significantly larger than prior art
In other methods for being purified.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The method of normal temperature extraction production high purity vanadic anhydride, detailed process is as follows：
（1）The industrial ammonium metavanadates of 1000g are weighed first, configure extract；
Extract contains the hydrogen peroxide of volume hundred to 2.0%, 1.6% ammonia and 97.4% high purity water；
Industrial ammonium metavanadate is slowly added in 30 liters of extracts, the stirring and dissolving under normal temperature condition, treat industrial vanadium partially
After sour ammonium has all dissolved, stand 1-6 hours and obtain containing vanadium solution；
The normal temperature condition of this in the present invention is 5~35 DEG C, and the normal temperature condition of this in the present embodiment is 25 DEG C.
（2）First 200- is used with 1000 milliliters of G4 sand core filters after having filtered to carrying out vacuum filter containing vanadium solution
800ml high-purity water washing 2-8 times；
Then under agitation, 20g solid Na is added2CO3With the Na that 20ml mass percents are 30%2S, continues
Stirring 30 minutes, stands 24 hours, carries out vacuum filter with G4 sand core filters afterwards and obtains filtrate.
（3）Filtrate is placed in evaporation recover and is evaporated by filtering after finishing, and after evaporation capacity is cumulative volume 30%, uses
Mass percent is neutralized for 20% nitric acid, filtrate pH is reached 2, the liquid after neutralization is water-cooled in cooler
To room temperature, until ammonium metavanadate is all separated out, solid-liquid mixed liquor is obtained.Turn into ammoniacal liquor after liquid condensation after evaporation, recovery is followed
Ring is used.
（4）Solid-liquid mixed liquor after cooling carries out vacuum filter, and it is 0.1% with 30 mass per liter percentages to have filtered rear
NH4NO3Cleaning fluid cleaned under conditions of vacuum filter.
（5）High-purity ammonium metavanadate is placed in Muffle furnace after having cleaned, calcination 4 is carried out under 550 DEG C of temperature conditionss
Hour, after calcination is complete, room temperature is rapidly cooled to, can be packed with the sieving of 100 mesh sub-sieves in dustless environment is dried.
Take out 1.0g samples and carry out impurity analysis, product quality reaches 99.91% after testing.
Embodiment 2
The present embodiment and the difference of embodiment 1 are that the composition of the extract of this in the present embodiment, precipitating reagent and cleaning agent is not
Together, and precipitating reagent specific addition step it is different, and the condition of reaction is different, specific to set as follows：
（1）The industrial ammonium metavanadates of 1000g are weighed first, configure extract：Extract contains mass percent concentration
2.5% hydrogen peroxide, 2.0% ammonia and 95.5% high purity water.Then industrial ammonium metavanadate is slowly added into 25 liters of extracts
In, precipitating reagent is added while extract is added and is stirred, the precipitating reagent includes 1.5g/L Na2CO3And 0.6g/L
(NH4)2S, after ammonium metavanadate is completely dissolved, the solution containing vanadium is obtained after standing 6 hours.
（2）Vacuum filter, which is carried out, with the husky core filters of 1000 milliliters of G4 obtains filtrate.
（3）Filtrate feeding evaporation recover is evaporated recovery, after evaporator evaporation goes out total liquid volume 20%, stops
Evaporation, opens evaporator lid and adds the nitric acid that a certain amount of concentration is 50% under agitation, liquid pH value is readjusted prices to 6, moved
Enter coolant water by liquid cooling to room temperature, stand 24 hours, untill ammonium metavanadate crystallization is all separated out, obtain solid-liquid
Mixed liquor（By analyzing, V in liquid2O5Concentration is considered as less than 1g/ml successfully to be crystallized）.Turn into ammonia after liquid condensation after evaporation
Water, recycling use.
（4）Ammonium metavanadate crystal and liquid mixture are sent in the husky core filters of 2000ML G4 and carried out with vacuum filtration process
Filtering, is that the high-purity aqueous cleaning of 5% acetone is cleaned 10 times with about 20 liters of mass percent concentrations after filtering is finished.
（5）High-purity ammonium metavanadate crystal is sent in square silica crucible after having cleaned, silica crucible is positioned over Muffle furnace
In, dried 8 hours at a temperature of 450 DEG C.Room temperature is quickly cooled to afterwards, then the high purity vanadic anhydride powder of rufous is used
The sub-sieve sieving of 100 mesh, you can packed, analysis detection purity of vanadium pentoxide is 99.92%.
Embodiment 3
The present embodiment and the difference of embodiment 2 are that the composition of the extract of this in the present embodiment, precipitating reagent and cleaning agent is not
Together, and reaction condition it is different, specific operation process is as follows：
（1）The industrial vanadic anhydrides of 1000g are weighed first, configure extract：Extract contains mass percent concentration
0.6% Peracetic acid, 3.6% ammonia and 95.8% high purity water.Then slowly stir at room temperature and add industrial vanadic anhydride
Enter in 25 liters of extracts, continue agitated liquid afterwards and add precipitating reagent, the precipitating reagent includes 0.3g/L（NH4）2CO3 、
0.2g/L （NH4）2S, after vanadic anhydride has all dissolved, stops stirring, stands 3 hours.
（2）Vacuum filter is carried out with the husky core filters of 1000ML G4.
（3）Filtrate feeding evaporation recover is evaporated recovery after having filtered, after liquid evaporation falls the 15% of cumulative volume
Stop evaporation, can be recycled after evaporating the cold liquid reclaimed as extract.Under agitation with 25% HNO3Liquid will be evaporated
PH is adjusted to 2, then send chiller water to be cooled to room temperature, treats five oxygen in all precipitations of ammonium metavanadate crystal, detection remaining liq
It is qualified to change two vanadium concentration less than 1g/L.
（4）The husky core filters of 2000ML G4 are sent to carry out vacuum filter solidliquid mixture, after having filtered, with containing 30g/L
10 liters of the high-purity aqueous solution of ethanol cleaning solidliquid mixture 6 times, cleans with 5L high purity waters solid-liquid mixture 3 times again afterwards.
（5）By in cleaned high-purity ammonium metavanadate feeding rectangle silica crucible, dried 5 hours at a temperature of 500 DEG C, it
The high purity vanadic anhydride that room temperature obtains rufous is rapidly decreased to afterwards, is packed with the sub-sieve sieving of 100 mesh.
The purity content that above-mentioned finished product obtains vanadic anhydride through analysis detection is 99.95%, wherein, impurity Si contents are
1ppm, Fe content are 8ppm.
Embodiment 4
The present embodiment and embodiment 1-3 difference are the composition of the extract of this in the present embodiment, precipitating reagent and cleaning agent
Near or above the upper limit of the ratio range in claims, specific operation process is as follows：
（1）The industrial vanadic anhydrides of 1000g are weighed first, configure extract：Extract contains mass percent concentration
6.6% hydrogen peroxide, 9% ammonia and 84.4% high purity water.Then slowly stir at room temperature and add industrial vanadic anhydride
In 15 liters of extracts, continue agitated liquid afterwards and add precipitating reagent, the precipitating reagent includes 9.0/L（NH4）2CO3 、6.6g/L
（NH4）2S, after vanadic anhydride has all dissolved, stops stirring, stands 2 hours.
（2）Vacuum filter is carried out with the husky core filters of 1000ML G4.
（3）Filtrate feeding evaporation recover is evaporated recovery after having filtered, after liquid evaporation falls the 35% of cumulative volume
Stop evaporation, can be recycled after evaporating the cold liquid reclaimed as extract.Under agitation with 68% HNO3Liquid will be evaporated
PH is adjusted to 5, then send chiller water to be cooled to room temperature, treats five oxygen in all precipitations of ammonium metavanadate crystal, detection remaining liq
It is qualified to change two vanadium concentration less than 1g/L.
（4）The husky core filters of 2000ML G4 are sent to carry out vacuum filter solidliquid mixture, after having filtered, with containing 70g/L
NH4NO310 liters of high-purity aqueous solution cleaning solidliquid mixture 6 times, cleans with 5L high purity waters solid-liquid mixture 3 times again afterwards.
（5）By in cleaned high-purity ammonium metavanadate feeding rectangle silica crucible, dried 6 hours at a temperature of 600 DEG C, it
The high purity vanadic anhydride that room temperature obtains rufous is rapidly decreased to afterwards, is packed with the sub-sieve sieving of 100 mesh.
The purity content that above-mentioned finished product obtains vanadic anhydride through analysis detection is 99.2%, wherein, impurity Si contents are
20ppm, Fe content are 50ppm.
Embodiment 5
The present embodiment and embodiment 1-4 difference are the composition of the extract of this in the present embodiment, precipitating reagent and cleaning agent
The lower limit for the ratio range being near or below in claims, specific operation process is as follows：
（1）The industrial vanadic anhydrides of 1000g are weighed first, configure extract：Extract contains mass percent concentration
0.3% ethamine and 99.7% high purity water.Then slowly stirring adds 60 liters of oxidations two of extract dissolving industry five at room temperature
Vanadium, continues agitated liquid and adds precipitating reagent, the precipitating reagent includes 0.1/L afterwards（NH4）2CO3、0.1g/L （NH4）2S, is treated
After vanadic anhydride has all dissolved, stop stirring, stand 2 hours.
（2）Vacuum filter is carried out with the husky core filters of 1000ML G4.
（3）Filtrate feeding evaporation recover is evaporated recovery after having filtered, after liquid evaporation falls the 10% of cumulative volume
Stop evaporation, can be recycled after evaporating the cold liquid reclaimed as extract.Under agitation with 12% HNO3Liquid will be evaporated
PH is adjusted to 5, then send chiller water to be cooled to room temperature, treats five oxygen in all precipitations of ammonium metavanadate crystal, detection remaining liq
It is qualified to change two vanadium concentration less than 1g/L.
（4）The husky core filters of 2000ML G4 are sent to carry out vacuum filter solidliquid mixture, after having filtered, with containing 10g/L
10 liters of the high-purity aqueous solution of acetone cleaning solidliquid mixture 6 times, cleans with 5L high purity waters solid-liquid mixture 3 times again afterwards.
（5）By in cleaned high-purity ammonium metavanadate feeding rectangle silica crucible, dried 6 hours at a temperature of 400 DEG C, it
The high purity vanadic anhydride that room temperature obtains rufous is rapidly decreased to afterwards, is packed with the sub-sieve sieving of 100 mesh.
The purity content that above-mentioned finished product obtains vanadic anhydride through analysis detection is 99.70%, wherein, impurity Si contents are
5ppm, Fe content are 15ppm, and this embodiment supplies consumption is larger, no economic benefit.
Embodiment 6
The present embodiment is that the proportioning of the extract of this in the present embodiment is different from the difference of embodiment 1, should in the present embodiment
The composition of extract is as follows：
A1:0.6% Peracetic acid, 3.2% ammonia, 97.1% high purity water；
Or A3:3% methylamine and 97% high purity water；
Or A5:1.5% ethylenediamine and 98.5% high purity water.
Analysis detection is carried out to the finished product obtained using above-mentioned different component and the extract of proportioning, vanadic anhydride is obtained
Purity content situation it is as follows：
Using above-mentioned A1 constituents extract when, the purity content of the vanadic anhydride is 99.92%, wherein, it is miscellaneous
Matter Si contents are 6ppm, and Fe contents are 16ppm；
Using above-mentioned A3 constituents extract when, the purity content of the vanadic anhydride is 99.91%, wherein, it is miscellaneous
Matter Si contents are 8ppm, and Fe contents are 15ppm；
Using above-mentioned A5 constituents extract when, the purity content of the vanadic anhydride is 99.89%, wherein, it is miscellaneous
Matter Si contents are 9ppm, and Fe contents are 18ppm.
Above-described embodiment is only the preferred embodiments of the present invention, not limiting the scope of the invention, as long as using
The design principle of the present invention, and the change for carrying out non-creativeness work on this basis and making, all should belong to the present invention's
Within protection domain.
Claims (8)
1. the method for normal temperature extraction production high purity vanadic anhydride, it is characterised in that including：
(1) industrial ammonium metavanadate or/and industrial vanadic anhydride are slowly added in extractant, selective dissolving metavanadic acid
Ammonium or/and vanadic anhydride, form and contain vanadium solution；Precipitating reagent is added in containing vanadium solution makes contamination precipitation；
(2) filtrate is obtained after filter operation；
(3) filtrate heating evaporation, the pH of liquid is adjusted to 1-6, then obtain solid-liquid mixed liquor by crystallisation by cooling after evaporation；
(4) solid-liquid mixed liquor is subjected to separation of solid and liquid, solid cleans filtering with cleaning agent；
(5) solid after filtering is toasted at a temperature of 400-600 DEG C, and finished product is then made after cooling；
The extractant is made up of one or more formulas in A1-A5；
A1:By mass percent concentration be 0.5-3.0% Peracetic acid, 1.0-6.0% ammonia, 91.0-98.5% high purity water group
Into；
A2:It is that 0.6-6.0% hydrogen peroxide, 1.0-9.0% ammonia, 85.0-98.4% high purity waters are constituted by mass percent concentration；
A3:It is that 0.2-6.0% ethamine and 94.0-99.8% high purity water are constituted by mass percent concentration；
A4:It is that 0.2-8.0% methylamine and 92.0-99.8% high purity water are constituted by mass percent concentration；
A5:It is that 0.2-5.0% ethylenediamine and 95.0-99.8% high purity water are constituted by mass percent concentration；
The precipitating reagent is by (NH4)2CO3(NH4)2One or more compositions in S；Described every liter contains (NH in vanadium solution4)2CO3Addition be 0.2-6g, (NH4)2S addition is 0.6-6g.
2. the method for normal temperature extraction production high purity vanadic anhydride according to claim 1, it is characterised in that the cleaning
Agent is by NH4NO3, one or more compositions in acetone and ethanol；Wherein, NH4NO3Concentration is that 10g-70g/L, acetone concentration are
10g-80g/L, concentration of alcohol is 40g-120g/L.
3. the method for normal temperature extraction production high purity vanadic anhydride according to claim 1, it is characterised in that the step
(1) detailed process is as follows：
Industrial ammonium metavanadate or/and industrial vanadic anhydride are slowly added in extractant under agitation, it is selective
Ammonium metavanadate or/and vanadic anhydride are dissolved, is formed and contains vanadium solution；Precipitating reagent is added in containing vanadium solution to stir 10-30 minutes,
Vacuum filter is carried out after standing 30-60 minutes again and realizes separation of solid and liquid, the screen pack of vacuum filter is 800-5000 mesh.
4. the method for normal temperature extraction production high purity vanadic anhydride according to claim 1, it is characterised in that the step
(3) when the filtrate of filtering is evaporated in, ammoniacal liquor is turned into after the gas condensation of filtrate evaporation, then recycling circulation makes
With.
5. the method for normal temperature extraction production high purity vanadic anhydride according to claim 1, it is characterised in that the step
(3) evaporation capacity of filtrate is the 10-40% of filtrate cumulative volume in, adjusts its pH value to 1-5 by acid after evaporation, then passes through again
Crystallisation by cooling, untill crystalline solid is separated out completely, obtains solid-liquid mixed liquor.
6. the method for normal temperature extraction production high purity vanadic anhydride according to claim 5, it is characterised in that the regulation
The acid of pH value is the nitric acid that mass percent concentration is 10-70%.
7. the method for normal temperature extraction production high purity vanadic anhydride according to claim 1, it is characterised in that the step
(4) detailed process is as follows：Solid-liquid mixed liquor is carried out by separation of solid and liquid by vacuum filter, solid 3-8 is cleaned with cleaning agent
It is secondary, vacuum filter is carried out during cleaning, the screen pack of vacuum filter is 800-5000 mesh.
8. the method for normal temperature extraction production high purity vanadic anhydride according to claim 1, it is characterised in that the step
(5) finished product is packed after levigate in.
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| CN201510871635.3A CN105366722B (en) | 2015-12-02 | 2015-12-02 | The method of normal temperature extraction production high purity vanadic anhydride |
| PCT/CN2016/079544 WO2017092217A1 (en) | 2015-12-02 | 2016-04-18 | Method for producing high-purity vanadium pentoxide by room temperature extraction |
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| CN106966431B (en) * | 2017-05-15 | 2018-10-16 | 天津市风船化学试剂科技有限公司 | A kind of preparation method of the high-purity ammonium metavanadate of 4N assigned stages |
| CN107500357A (en) * | 2017-10-10 | 2017-12-22 | 攀钢集团研究院有限公司 | The preparation method of vanadic anhydride |
| CN111484076A (en) * | 2020-04-22 | 2020-08-04 | 承德新新钒钛储能科技有限公司 | Method for recovering high-purity vanadium from failure vanadium electrolyte |
| CN111778390A (en) * | 2020-07-08 | 2020-10-16 | 辽宁石化职业技术学院 | Purification method for producing vanadium pentoxide by sodium roasting |
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| CN102849795B (en) * | 2011-07-02 | 2014-12-17 | 全喆 | Preparation of high-purity vanadium pentoxide |
| CN103112897A (en) * | 2013-03-08 | 2013-05-22 | 贵州遵义汇兴铁合金有限责任公司 | Method for simultaneously extracting vanadium, aluminum and potassium from stone coal |
| CN104692461A (en) * | 2015-02-16 | 2015-06-10 | 河北钢铁股份有限公司承德分公司 | Method for preparing high-purity powdered vanadium oxide |
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